Photoionization of 2,3-dimethyl-2-butanol (thexyl alcohol): Interaction between the charged and expelled fragments

Abstract Photoionization studies of ($ CH_{3} $)2CHC($ CH_{3} $)2OH (tert-hexyl alcohol, also called thexyl alcohol) exhibit four fragmentations below 10 eV. As with other tertiary alcohols, no molecular ion is detected. The only ion observed at threshold corresponds to propane loss. Examination of...
Ausführliche Beschreibung

Gespeichert in:

Autor*in:	Traeger, John C. [verfasserIn] Morton, Thomas Hellman

Format:	E-Artikel
Sprache:	Englisch

Erschienen:	2004

Schlagwörter:	Bond Order Bond Dissociation Energy Neutral Complex Appearance Energy Thexyl

Anmerkung:	© American Society for Mass Spectrometry 2004

Übergeordnetes Werk:	Enthalten in: Journal of the American Society for Mass Spectrometry - Washington, DC : ACS Publications, 1990, 15(2004), 7 vom: 01. Juli, Seite 989-997
Übergeordnetes Werk:	volume:15 ; year:2004 ; number:7 ; day:01 ; month:07 ; pages:989-997

Links:	Volltext

DOI / URN:	10.1016/j.jasms.2004.03.016

Katalog-ID:	SPR031488714

Internformat


LEADER	01000caa a22002652 4500
001	SPR031488714
003	DE-627
005	20230331083333.0
007	cr uuu---uuuuu
008	201007s2004 xx \|\|\|\|\|o 00\| \|\|eng c
024	7		\|a 10.1016/j.jasms.2004.03.016 \|2 doi
035			\|a (DE-627)SPR031488714
035			\|a (SPR)j.jasms.2004.03.016-e
040			\|a DE-627 \|b ger \|c DE-627 \|e rakwb
041			\|a eng
100	1		\|a Traeger, John C. \|e verfasserin \|4 aut
245	1	0	\|a Photoionization of 2,3-dimethyl-2-butanol (thexyl alcohol): Interaction between the charged and expelled fragments
264		1	\|c 2004
336			\|a Text \|b txt \|2 rdacontent
337			\|a Computermedien \|b c \|2 rdamedia
338			\|a Online-Ressource \|b cr \|2 rdacarrier
500			\|a © American Society for Mass Spectrometry 2004
520			\|a Abstract Photoionization studies of ($ CH_{3} $)2CHC($ CH_{3} $)2OH (tert-hexyl alcohol, also called thexyl alcohol) exhibit four fragmentations below 10 eV. As with other tertiary alcohols, no molecular ion is detected. The only ion observed at threshold corresponds to propane loss. Examination of a deuterated analogue, ($ CH_{3} $)2CHC($ CD_{3} $)2OH, shows only loss of $ C_{3} %$ H_{7} $D, implying that the fragment ion has the structure of ionized acetone enol. There is no evidence for reversible deuterium transposition, as has been reported for isotopomers of the homologous secondary alcohol ($ CH_{3} $)2CHCH($ CH_{3} $)OH. Propane loss from thexyl alcohol is attributed to intermediacy of ion-neutral complexes containing isopropyl radical and O-protonated acetone. Simple cleavage to give O-protonated acetone has an appearance energy 18 kJ $ mol^{−1} $ higher than that of propane loss. Thermochemical estimates and ab initio calculations both predict that methyl loss should have a lower threshold than the fragmentation leading to isopropyl loss, but experiments show the appearance energy to be 6 kJ $ mol^{−1} $ higher. This is consistent with previous reports of reverse activation barriers for methyl cleavages. Finally, formation of tert-hexyl cation, ($ CH_{3} $)2CHC($ CH_{3} $)2+, is observed with an appearance energy comparable to that of methyl loss, substantially below that predicted for OH radical expulsion from the molecular ion. The comparatively low threshold of this fragmentation is ascribed to ion-pair formation (concomitant with hydroxide ion) directly from an electronically excited neutral. Interactions between charged and neutral fragments (including energetics, bond orders <1, and electrical charges on molecular fragments) are explored using a combination of DFT and ab initio methods, along with topological analysis using the Atoms in Molecules approach.
650		4	\|a Bond Order \|7 (dpeaa)DE-He213
650		4	\|a Bond Dissociation Energy \|7 (dpeaa)DE-He213
650		4	\|a Neutral Complex \|7 (dpeaa)DE-He213
650		4	\|a Appearance Energy \|7 (dpeaa)DE-He213
650		4	\|a Thexyl \|7 (dpeaa)DE-He213
700	1		\|a Morton, Thomas Hellman \|4 aut
773	0	8	\|i Enthalten in \|t Journal of the American Society for Mass Spectrometry \|d Washington, DC : ACS Publications, 1990 \|g 15(2004), 7 vom: 01. Juli, Seite 989-997 \|w (DE-627)320598799 \|w (DE-600)2019911-9 \|x 1879-1123 \|7 nnns
773	1	8	\|g volume:15 \|g year:2004 \|g number:7 \|g day:01 \|g month:07 \|g pages:989-997
856	4	0	\|u https://dx.doi.org/10.1016/j.jasms.2004.03.016 \|z lizenzpflichtig \|3 Volltext
912			\|a GBV_USEFLAG_A
912			\|a SYSFLAG_A
912			\|a GBV_SPRINGER
912			\|a GBV_ILN_20
912			\|a GBV_ILN_22
912			\|a GBV_ILN_23
912			\|a GBV_ILN_24
912			\|a GBV_ILN_31
912			\|a GBV_ILN_32
912			\|a GBV_ILN_39
912			\|a GBV_ILN_40
912			\|a GBV_ILN_60
912			\|a GBV_ILN_62
912			\|a GBV_ILN_63
912			\|a GBV_ILN_65
912			\|a GBV_ILN_69
912			\|a GBV_ILN_70
912			\|a GBV_ILN_73
912			\|a GBV_ILN_74
912			\|a GBV_ILN_95
912			\|a GBV_ILN_100
912			\|a GBV_ILN_101
912			\|a GBV_ILN_105
912			\|a GBV_ILN_110
912			\|a GBV_ILN_120
912			\|a GBV_ILN_138
912			\|a GBV_ILN_150
912			\|a GBV_ILN_151
912			\|a GBV_ILN_152
912			\|a GBV_ILN_161
912			\|a GBV_ILN_170
912			\|a GBV_ILN_187
912			\|a GBV_ILN_213
912			\|a GBV_ILN_224
912			\|a GBV_ILN_230
912			\|a GBV_ILN_285
912			\|a GBV_ILN_293
912			\|a GBV_ILN_370
912			\|a GBV_ILN_602
912			\|a GBV_ILN_647
912			\|a GBV_ILN_702
912			\|a GBV_ILN_2001
912			\|a GBV_ILN_2003
912			\|a GBV_ILN_2004
912			\|a GBV_ILN_2005
912			\|a GBV_ILN_2006
912			\|a GBV_ILN_2007
912			\|a GBV_ILN_2009
912			\|a GBV_ILN_2010
912			\|a GBV_ILN_2011
912			\|a GBV_ILN_2014
912			\|a GBV_ILN_2015
912			\|a GBV_ILN_2020
912			\|a GBV_ILN_2021
912			\|a GBV_ILN_2025
912			\|a GBV_ILN_2026
912			\|a GBV_ILN_2027
912			\|a GBV_ILN_2031
912			\|a GBV_ILN_2034
912			\|a GBV_ILN_2037
912			\|a GBV_ILN_2038
912			\|a GBV_ILN_2039
912			\|a GBV_ILN_2044
912			\|a GBV_ILN_2049
912			\|a GBV_ILN_2050
912			\|a GBV_ILN_2055
912			\|a GBV_ILN_2056
912			\|a GBV_ILN_2059
912			\|a GBV_ILN_2061
912			\|a GBV_ILN_2064
912			\|a GBV_ILN_2065
912			\|a GBV_ILN_2068
912			\|a GBV_ILN_2070
912			\|a GBV_ILN_2086
912			\|a GBV_ILN_2106
912			\|a GBV_ILN_2108
912			\|a GBV_ILN_2110
912			\|a GBV_ILN_2111
912			\|a GBV_ILN_2112
912			\|a GBV_ILN_2113
912			\|a GBV_ILN_2116
912			\|a GBV_ILN_2118
912			\|a GBV_ILN_2119
912			\|a GBV_ILN_2122
912			\|a GBV_ILN_2129
912			\|a GBV_ILN_2143
912			\|a GBV_ILN_2144
912			\|a GBV_ILN_2147
912			\|a GBV_ILN_2148
912			\|a GBV_ILN_2152
912			\|a GBV_ILN_2153
912			\|a GBV_ILN_2188
912			\|a GBV_ILN_2190
912			\|a GBV_ILN_2232
912			\|a GBV_ILN_2336
912			\|a GBV_ILN_2507
912			\|a GBV_ILN_2522
912			\|a GBV_ILN_4012
912			\|a GBV_ILN_4035
912			\|a GBV_ILN_4037
912			\|a GBV_ILN_4046
912			\|a GBV_ILN_4112
912			\|a GBV_ILN_4125
912			\|a GBV_ILN_4126
912			\|a GBV_ILN_4242
912			\|a GBV_ILN_4246
912			\|a GBV_ILN_4249
912			\|a GBV_ILN_4251
912			\|a GBV_ILN_4305
912			\|a GBV_ILN_4306
912			\|a GBV_ILN_4307
912			\|a GBV_ILN_4313
912			\|a GBV_ILN_4322
912			\|a GBV_ILN_4323
912			\|a GBV_ILN_4324
912			\|a GBV_ILN_4325
912			\|a GBV_ILN_4326
912			\|a GBV_ILN_4328
912			\|a GBV_ILN_4333
912			\|a GBV_ILN_4334
912			\|a GBV_ILN_4335
912			\|a GBV_ILN_4338
912			\|a GBV_ILN_4367
912			\|a GBV_ILN_4393
912			\|a GBV_ILN_4700
951			\|a AR
952			\|d 15 \|j 2004 \|e 7 \|b 01 \|c 07 \|h 989-997

Indexfelder

author_variant	j c t jc jct t h m th thm
matchkey_str	article:18791123:2004----::htinztoo2dmty2uaoteyachlneatobtenhca
hierarchy_sort_str	2004
publishDate	2004
allfields	10.1016/j.jasms.2004.03.016 doi (DE-627)SPR031488714 (SPR)j.jasms.2004.03.016-e DE-627 ger DE-627 rakwb eng Traeger, John C. verfasserin aut Photoionization of 2,3-dimethyl-2-butanol (thexyl alcohol): Interaction between the charged and expelled fragments 2004 Text txt rdacontent Computermedien c rdamedia Online-Ressource cr rdacarrier © American Society for Mass Spectrometry 2004 Abstract Photoionization studies of ($ CH_{3} $)2CHC($ CH_{3} $)2OH (tert-hexyl alcohol, also called thexyl alcohol) exhibit four fragmentations below 10 eV. As with other tertiary alcohols, no molecular ion is detected. The only ion observed at threshold corresponds to propane loss. Examination of a deuterated analogue, ($ CH_{3} $)2CHC($ CD_{3} $)2OH, shows only loss of $ C_{3} %$ H_{7} $D, implying that the fragment ion has the structure of ionized acetone enol. There is no evidence for reversible deuterium transposition, as has been reported for isotopomers of the homologous secondary alcohol ($ CH_{3} $)2CHCH($ CH_{3} $)OH. Propane loss from thexyl alcohol is attributed to intermediacy of ion-neutral complexes containing isopropyl radical and O-protonated acetone. Simple cleavage to give O-protonated acetone has an appearance energy 18 kJ $ mol^{−1} $ higher than that of propane loss. Thermochemical estimates and ab initio calculations both predict that methyl loss should have a lower threshold than the fragmentation leading to isopropyl loss, but experiments show the appearance energy to be 6 kJ $ mol^{−1} $ higher. This is consistent with previous reports of reverse activation barriers for methyl cleavages. Finally, formation of tert-hexyl cation, ($ CH_{3} $)2CHC($ CH_{3} $)2+, is observed with an appearance energy comparable to that of methyl loss, substantially below that predicted for OH radical expulsion from the molecular ion. The comparatively low threshold of this fragmentation is ascribed to ion-pair formation (concomitant with hydroxide ion) directly from an electronically excited neutral. Interactions between charged and neutral fragments (including energetics, bond orders <1, and electrical charges on molecular fragments) are explored using a combination of DFT and ab initio methods, along with topological analysis using the Atoms in Molecules approach. Bond Order (dpeaa)DE-He213 Bond Dissociation Energy (dpeaa)DE-He213 Neutral Complex (dpeaa)DE-He213 Appearance Energy (dpeaa)DE-He213 Thexyl (dpeaa)DE-He213 Morton, Thomas Hellman aut Enthalten in Journal of the American Society for Mass Spectrometry Washington, DC : ACS Publications, 1990 15(2004), 7 vom: 01. Juli, Seite 989-997 (DE-627)320598799 (DE-600)2019911-9 1879-1123 nnns volume:15 year:2004 number:7 day:01 month:07 pages:989-997 https://dx.doi.org/10.1016/j.jasms.2004.03.016 lizenzpflichtig Volltext GBV_USEFLAG_A SYSFLAG_A GBV_SPRINGER GBV_ILN_20 GBV_ILN_22 GBV_ILN_23 GBV_ILN_24 GBV_ILN_31 GBV_ILN_32 GBV_ILN_39 GBV_ILN_40 GBV_ILN_60 GBV_ILN_62 GBV_ILN_63 GBV_ILN_65 GBV_ILN_69 GBV_ILN_70 GBV_ILN_73 GBV_ILN_74 GBV_ILN_95 GBV_ILN_100 GBV_ILN_101 GBV_ILN_105 GBV_ILN_110 GBV_ILN_120 GBV_ILN_138 GBV_ILN_150 GBV_ILN_151 GBV_ILN_152 GBV_ILN_161 GBV_ILN_170 GBV_ILN_187 GBV_ILN_213 GBV_ILN_224 GBV_ILN_230 GBV_ILN_285 GBV_ILN_293 GBV_ILN_370 GBV_ILN_602 GBV_ILN_647 GBV_ILN_702 GBV_ILN_2001 GBV_ILN_2003 GBV_ILN_2004 GBV_ILN_2005 GBV_ILN_2006 GBV_ILN_2007 GBV_ILN_2009 GBV_ILN_2010 GBV_ILN_2011 GBV_ILN_2014 GBV_ILN_2015 GBV_ILN_2020 GBV_ILN_2021 GBV_ILN_2025 GBV_ILN_2026 GBV_ILN_2027 GBV_ILN_2031 GBV_ILN_2034 GBV_ILN_2037 GBV_ILN_2038 GBV_ILN_2039 GBV_ILN_2044 GBV_ILN_2049 GBV_ILN_2050 GBV_ILN_2055 GBV_ILN_2056 GBV_ILN_2059 GBV_ILN_2061 GBV_ILN_2064 GBV_ILN_2065 GBV_ILN_2068 GBV_ILN_2070 GBV_ILN_2086 GBV_ILN_2106 GBV_ILN_2108 GBV_ILN_2110 GBV_ILN_2111 GBV_ILN_2112 GBV_ILN_2113 GBV_ILN_2116 GBV_ILN_2118 GBV_ILN_2119 GBV_ILN_2122 GBV_ILN_2129 GBV_ILN_2143 GBV_ILN_2144 GBV_ILN_2147 GBV_ILN_2148 GBV_ILN_2152 GBV_ILN_2153 GBV_ILN_2188 GBV_ILN_2190 GBV_ILN_2232 GBV_ILN_2336 GBV_ILN_2507 GBV_ILN_2522 GBV_ILN_4012 GBV_ILN_4035 GBV_ILN_4037 GBV_ILN_4046 GBV_ILN_4112 GBV_ILN_4125 GBV_ILN_4126 GBV_ILN_4242 GBV_ILN_4246 GBV_ILN_4249 GBV_ILN_4251 GBV_ILN_4305 GBV_ILN_4306 GBV_ILN_4307 GBV_ILN_4313 GBV_ILN_4322 GBV_ILN_4323 GBV_ILN_4324 GBV_ILN_4325 GBV_ILN_4326 GBV_ILN_4328 GBV_ILN_4333 GBV_ILN_4334 GBV_ILN_4335 GBV_ILN_4338 GBV_ILN_4367 GBV_ILN_4393 GBV_ILN_4700 AR 15 2004 7 01 07 989-997
spelling	10.1016/j.jasms.2004.03.016 doi (DE-627)SPR031488714 (SPR)j.jasms.2004.03.016-e DE-627 ger DE-627 rakwb eng Traeger, John C. verfasserin aut Photoionization of 2,3-dimethyl-2-butanol (thexyl alcohol): Interaction between the charged and expelled fragments 2004 Text txt rdacontent Computermedien c rdamedia Online-Ressource cr rdacarrier © American Society for Mass Spectrometry 2004 Abstract Photoionization studies of ($ CH_{3} $)2CHC($ CH_{3} $)2OH (tert-hexyl alcohol, also called thexyl alcohol) exhibit four fragmentations below 10 eV. As with other tertiary alcohols, no molecular ion is detected. The only ion observed at threshold corresponds to propane loss. Examination of a deuterated analogue, ($ CH_{3} $)2CHC($ CD_{3} $)2OH, shows only loss of $ C_{3} %$ H_{7} $D, implying that the fragment ion has the structure of ionized acetone enol. There is no evidence for reversible deuterium transposition, as has been reported for isotopomers of the homologous secondary alcohol ($ CH_{3} $)2CHCH($ CH_{3} $)OH. Propane loss from thexyl alcohol is attributed to intermediacy of ion-neutral complexes containing isopropyl radical and O-protonated acetone. Simple cleavage to give O-protonated acetone has an appearance energy 18 kJ $ mol^{−1} $ higher than that of propane loss. Thermochemical estimates and ab initio calculations both predict that methyl loss should have a lower threshold than the fragmentation leading to isopropyl loss, but experiments show the appearance energy to be 6 kJ $ mol^{−1} $ higher. This is consistent with previous reports of reverse activation barriers for methyl cleavages. Finally, formation of tert-hexyl cation, ($ CH_{3} $)2CHC($ CH_{3} $)2+, is observed with an appearance energy comparable to that of methyl loss, substantially below that predicted for OH radical expulsion from the molecular ion. The comparatively low threshold of this fragmentation is ascribed to ion-pair formation (concomitant with hydroxide ion) directly from an electronically excited neutral. Interactions between charged and neutral fragments (including energetics, bond orders <1, and electrical charges on molecular fragments) are explored using a combination of DFT and ab initio methods, along with topological analysis using the Atoms in Molecules approach. Bond Order (dpeaa)DE-He213 Bond Dissociation Energy (dpeaa)DE-He213 Neutral Complex (dpeaa)DE-He213 Appearance Energy (dpeaa)DE-He213 Thexyl (dpeaa)DE-He213 Morton, Thomas Hellman aut Enthalten in Journal of the American Society for Mass Spectrometry Washington, DC : ACS Publications, 1990 15(2004), 7 vom: 01. Juli, Seite 989-997 (DE-627)320598799 (DE-600)2019911-9 1879-1123 nnns volume:15 year:2004 number:7 day:01 month:07 pages:989-997 https://dx.doi.org/10.1016/j.jasms.2004.03.016 lizenzpflichtig Volltext GBV_USEFLAG_A SYSFLAG_A GBV_SPRINGER GBV_ILN_20 GBV_ILN_22 GBV_ILN_23 GBV_ILN_24 GBV_ILN_31 GBV_ILN_32 GBV_ILN_39 GBV_ILN_40 GBV_ILN_60 GBV_ILN_62 GBV_ILN_63 GBV_ILN_65 GBV_ILN_69 GBV_ILN_70 GBV_ILN_73 GBV_ILN_74 GBV_ILN_95 GBV_ILN_100 GBV_ILN_101 GBV_ILN_105 GBV_ILN_110 GBV_ILN_120 GBV_ILN_138 GBV_ILN_150 GBV_ILN_151 GBV_ILN_152 GBV_ILN_161 GBV_ILN_170 GBV_ILN_187 GBV_ILN_213 GBV_ILN_224 GBV_ILN_230 GBV_ILN_285 GBV_ILN_293 GBV_ILN_370 GBV_ILN_602 GBV_ILN_647 GBV_ILN_702 GBV_ILN_2001 GBV_ILN_2003 GBV_ILN_2004 GBV_ILN_2005 GBV_ILN_2006 GBV_ILN_2007 GBV_ILN_2009 GBV_ILN_2010 GBV_ILN_2011 GBV_ILN_2014 GBV_ILN_2015 GBV_ILN_2020 GBV_ILN_2021 GBV_ILN_2025 GBV_ILN_2026 GBV_ILN_2027 GBV_ILN_2031 GBV_ILN_2034 GBV_ILN_2037 GBV_ILN_2038 GBV_ILN_2039 GBV_ILN_2044 GBV_ILN_2049 GBV_ILN_2050 GBV_ILN_2055 GBV_ILN_2056 GBV_ILN_2059 GBV_ILN_2061 GBV_ILN_2064 GBV_ILN_2065 GBV_ILN_2068 GBV_ILN_2070 GBV_ILN_2086 GBV_ILN_2106 GBV_ILN_2108 GBV_ILN_2110 GBV_ILN_2111 GBV_ILN_2112 GBV_ILN_2113 GBV_ILN_2116 GBV_ILN_2118 GBV_ILN_2119 GBV_ILN_2122 GBV_ILN_2129 GBV_ILN_2143 GBV_ILN_2144 GBV_ILN_2147 GBV_ILN_2148 GBV_ILN_2152 GBV_ILN_2153 GBV_ILN_2188 GBV_ILN_2190 GBV_ILN_2232 GBV_ILN_2336 GBV_ILN_2507 GBV_ILN_2522 GBV_ILN_4012 GBV_ILN_4035 GBV_ILN_4037 GBV_ILN_4046 GBV_ILN_4112 GBV_ILN_4125 GBV_ILN_4126 GBV_ILN_4242 GBV_ILN_4246 GBV_ILN_4249 GBV_ILN_4251 GBV_ILN_4305 GBV_ILN_4306 GBV_ILN_4307 GBV_ILN_4313 GBV_ILN_4322 GBV_ILN_4323 GBV_ILN_4324 GBV_ILN_4325 GBV_ILN_4326 GBV_ILN_4328 GBV_ILN_4333 GBV_ILN_4334 GBV_ILN_4335 GBV_ILN_4338 GBV_ILN_4367 GBV_ILN_4393 GBV_ILN_4700 AR 15 2004 7 01 07 989-997
allfields_unstemmed	10.1016/j.jasms.2004.03.016 doi (DE-627)SPR031488714 (SPR)j.jasms.2004.03.016-e DE-627 ger DE-627 rakwb eng Traeger, John C. verfasserin aut Photoionization of 2,3-dimethyl-2-butanol (thexyl alcohol): Interaction between the charged and expelled fragments 2004 Text txt rdacontent Computermedien c rdamedia Online-Ressource cr rdacarrier © American Society for Mass Spectrometry 2004 Abstract Photoionization studies of ($ CH_{3} $)2CHC($ CH_{3} $)2OH (tert-hexyl alcohol, also called thexyl alcohol) exhibit four fragmentations below 10 eV. As with other tertiary alcohols, no molecular ion is detected. The only ion observed at threshold corresponds to propane loss. Examination of a deuterated analogue, ($ CH_{3} $)2CHC($ CD_{3} $)2OH, shows only loss of $ C_{3} %$ H_{7} $D, implying that the fragment ion has the structure of ionized acetone enol. There is no evidence for reversible deuterium transposition, as has been reported for isotopomers of the homologous secondary alcohol ($ CH_{3} $)2CHCH($ CH_{3} $)OH. Propane loss from thexyl alcohol is attributed to intermediacy of ion-neutral complexes containing isopropyl radical and O-protonated acetone. Simple cleavage to give O-protonated acetone has an appearance energy 18 kJ $ mol^{−1} $ higher than that of propane loss. Thermochemical estimates and ab initio calculations both predict that methyl loss should have a lower threshold than the fragmentation leading to isopropyl loss, but experiments show the appearance energy to be 6 kJ $ mol^{−1} $ higher. This is consistent with previous reports of reverse activation barriers for methyl cleavages. Finally, formation of tert-hexyl cation, ($ CH_{3} $)2CHC($ CH_{3} $)2+, is observed with an appearance energy comparable to that of methyl loss, substantially below that predicted for OH radical expulsion from the molecular ion. The comparatively low threshold of this fragmentation is ascribed to ion-pair formation (concomitant with hydroxide ion) directly from an electronically excited neutral. Interactions between charged and neutral fragments (including energetics, bond orders <1, and electrical charges on molecular fragments) are explored using a combination of DFT and ab initio methods, along with topological analysis using the Atoms in Molecules approach. Bond Order (dpeaa)DE-He213 Bond Dissociation Energy (dpeaa)DE-He213 Neutral Complex (dpeaa)DE-He213 Appearance Energy (dpeaa)DE-He213 Thexyl (dpeaa)DE-He213 Morton, Thomas Hellman aut Enthalten in Journal of the American Society for Mass Spectrometry Washington, DC : ACS Publications, 1990 15(2004), 7 vom: 01. Juli, Seite 989-997 (DE-627)320598799 (DE-600)2019911-9 1879-1123 nnns volume:15 year:2004 number:7 day:01 month:07 pages:989-997 https://dx.doi.org/10.1016/j.jasms.2004.03.016 lizenzpflichtig Volltext GBV_USEFLAG_A SYSFLAG_A GBV_SPRINGER GBV_ILN_20 GBV_ILN_22 GBV_ILN_23 GBV_ILN_24 GBV_ILN_31 GBV_ILN_32 GBV_ILN_39 GBV_ILN_40 GBV_ILN_60 GBV_ILN_62 GBV_ILN_63 GBV_ILN_65 GBV_ILN_69 GBV_ILN_70 GBV_ILN_73 GBV_ILN_74 GBV_ILN_95 GBV_ILN_100 GBV_ILN_101 GBV_ILN_105 GBV_ILN_110 GBV_ILN_120 GBV_ILN_138 GBV_ILN_150 GBV_ILN_151 GBV_ILN_152 GBV_ILN_161 GBV_ILN_170 GBV_ILN_187 GBV_ILN_213 GBV_ILN_224 GBV_ILN_230 GBV_ILN_285 GBV_ILN_293 GBV_ILN_370 GBV_ILN_602 GBV_ILN_647 GBV_ILN_702 GBV_ILN_2001 GBV_ILN_2003 GBV_ILN_2004 GBV_ILN_2005 GBV_ILN_2006 GBV_ILN_2007 GBV_ILN_2009 GBV_ILN_2010 GBV_ILN_2011 GBV_ILN_2014 GBV_ILN_2015 GBV_ILN_2020 GBV_ILN_2021 GBV_ILN_2025 GBV_ILN_2026 GBV_ILN_2027 GBV_ILN_2031 GBV_ILN_2034 GBV_ILN_2037 GBV_ILN_2038 GBV_ILN_2039 GBV_ILN_2044 GBV_ILN_2049 GBV_ILN_2050 GBV_ILN_2055 GBV_ILN_2056 GBV_ILN_2059 GBV_ILN_2061 GBV_ILN_2064 GBV_ILN_2065 GBV_ILN_2068 GBV_ILN_2070 GBV_ILN_2086 GBV_ILN_2106 GBV_ILN_2108 GBV_ILN_2110 GBV_ILN_2111 GBV_ILN_2112 GBV_ILN_2113 GBV_ILN_2116 GBV_ILN_2118 GBV_ILN_2119 GBV_ILN_2122 GBV_ILN_2129 GBV_ILN_2143 GBV_ILN_2144 GBV_ILN_2147 GBV_ILN_2148 GBV_ILN_2152 GBV_ILN_2153 GBV_ILN_2188 GBV_ILN_2190 GBV_ILN_2232 GBV_ILN_2336 GBV_ILN_2507 GBV_ILN_2522 GBV_ILN_4012 GBV_ILN_4035 GBV_ILN_4037 GBV_ILN_4046 GBV_ILN_4112 GBV_ILN_4125 GBV_ILN_4126 GBV_ILN_4242 GBV_ILN_4246 GBV_ILN_4249 GBV_ILN_4251 GBV_ILN_4305 GBV_ILN_4306 GBV_ILN_4307 GBV_ILN_4313 GBV_ILN_4322 GBV_ILN_4323 GBV_ILN_4324 GBV_ILN_4325 GBV_ILN_4326 GBV_ILN_4328 GBV_ILN_4333 GBV_ILN_4334 GBV_ILN_4335 GBV_ILN_4338 GBV_ILN_4367 GBV_ILN_4393 GBV_ILN_4700 AR 15 2004 7 01 07 989-997
allfieldsGer	10.1016/j.jasms.2004.03.016 doi (DE-627)SPR031488714 (SPR)j.jasms.2004.03.016-e DE-627 ger DE-627 rakwb eng Traeger, John C. verfasserin aut Photoionization of 2,3-dimethyl-2-butanol (thexyl alcohol): Interaction between the charged and expelled fragments 2004 Text txt rdacontent Computermedien c rdamedia Online-Ressource cr rdacarrier © American Society for Mass Spectrometry 2004 Abstract Photoionization studies of ($ CH_{3} $)2CHC($ CH_{3} $)2OH (tert-hexyl alcohol, also called thexyl alcohol) exhibit four fragmentations below 10 eV. As with other tertiary alcohols, no molecular ion is detected. The only ion observed at threshold corresponds to propane loss. Examination of a deuterated analogue, ($ CH_{3} $)2CHC($ CD_{3} $)2OH, shows only loss of $ C_{3} %$ H_{7} $D, implying that the fragment ion has the structure of ionized acetone enol. There is no evidence for reversible deuterium transposition, as has been reported for isotopomers of the homologous secondary alcohol ($ CH_{3} $)2CHCH($ CH_{3} $)OH. Propane loss from thexyl alcohol is attributed to intermediacy of ion-neutral complexes containing isopropyl radical and O-protonated acetone. Simple cleavage to give O-protonated acetone has an appearance energy 18 kJ $ mol^{−1} $ higher than that of propane loss. Thermochemical estimates and ab initio calculations both predict that methyl loss should have a lower threshold than the fragmentation leading to isopropyl loss, but experiments show the appearance energy to be 6 kJ $ mol^{−1} $ higher. This is consistent with previous reports of reverse activation barriers for methyl cleavages. Finally, formation of tert-hexyl cation, ($ CH_{3} $)2CHC($ CH_{3} $)2+, is observed with an appearance energy comparable to that of methyl loss, substantially below that predicted for OH radical expulsion from the molecular ion. The comparatively low threshold of this fragmentation is ascribed to ion-pair formation (concomitant with hydroxide ion) directly from an electronically excited neutral. Interactions between charged and neutral fragments (including energetics, bond orders <1, and electrical charges on molecular fragments) are explored using a combination of DFT and ab initio methods, along with topological analysis using the Atoms in Molecules approach. Bond Order (dpeaa)DE-He213 Bond Dissociation Energy (dpeaa)DE-He213 Neutral Complex (dpeaa)DE-He213 Appearance Energy (dpeaa)DE-He213 Thexyl (dpeaa)DE-He213 Morton, Thomas Hellman aut Enthalten in Journal of the American Society for Mass Spectrometry Washington, DC : ACS Publications, 1990 15(2004), 7 vom: 01. Juli, Seite 989-997 (DE-627)320598799 (DE-600)2019911-9 1879-1123 nnns volume:15 year:2004 number:7 day:01 month:07 pages:989-997 https://dx.doi.org/10.1016/j.jasms.2004.03.016 lizenzpflichtig Volltext GBV_USEFLAG_A SYSFLAG_A GBV_SPRINGER GBV_ILN_20 GBV_ILN_22 GBV_ILN_23 GBV_ILN_24 GBV_ILN_31 GBV_ILN_32 GBV_ILN_39 GBV_ILN_40 GBV_ILN_60 GBV_ILN_62 GBV_ILN_63 GBV_ILN_65 GBV_ILN_69 GBV_ILN_70 GBV_ILN_73 GBV_ILN_74 GBV_ILN_95 GBV_ILN_100 GBV_ILN_101 GBV_ILN_105 GBV_ILN_110 GBV_ILN_120 GBV_ILN_138 GBV_ILN_150 GBV_ILN_151 GBV_ILN_152 GBV_ILN_161 GBV_ILN_170 GBV_ILN_187 GBV_ILN_213 GBV_ILN_224 GBV_ILN_230 GBV_ILN_285 GBV_ILN_293 GBV_ILN_370 GBV_ILN_602 GBV_ILN_647 GBV_ILN_702 GBV_ILN_2001 GBV_ILN_2003 GBV_ILN_2004 GBV_ILN_2005 GBV_ILN_2006 GBV_ILN_2007 GBV_ILN_2009 GBV_ILN_2010 GBV_ILN_2011 GBV_ILN_2014 GBV_ILN_2015 GBV_ILN_2020 GBV_ILN_2021 GBV_ILN_2025 GBV_ILN_2026 GBV_ILN_2027 GBV_ILN_2031 GBV_ILN_2034 GBV_ILN_2037 GBV_ILN_2038 GBV_ILN_2039 GBV_ILN_2044 GBV_ILN_2049 GBV_ILN_2050 GBV_ILN_2055 GBV_ILN_2056 GBV_ILN_2059 GBV_ILN_2061 GBV_ILN_2064 GBV_ILN_2065 GBV_ILN_2068 GBV_ILN_2070 GBV_ILN_2086 GBV_ILN_2106 GBV_ILN_2108 GBV_ILN_2110 GBV_ILN_2111 GBV_ILN_2112 GBV_ILN_2113 GBV_ILN_2116 GBV_ILN_2118 GBV_ILN_2119 GBV_ILN_2122 GBV_ILN_2129 GBV_ILN_2143 GBV_ILN_2144 GBV_ILN_2147 GBV_ILN_2148 GBV_ILN_2152 GBV_ILN_2153 GBV_ILN_2188 GBV_ILN_2190 GBV_ILN_2232 GBV_ILN_2336 GBV_ILN_2507 GBV_ILN_2522 GBV_ILN_4012 GBV_ILN_4035 GBV_ILN_4037 GBV_ILN_4046 GBV_ILN_4112 GBV_ILN_4125 GBV_ILN_4126 GBV_ILN_4242 GBV_ILN_4246 GBV_ILN_4249 GBV_ILN_4251 GBV_ILN_4305 GBV_ILN_4306 GBV_ILN_4307 GBV_ILN_4313 GBV_ILN_4322 GBV_ILN_4323 GBV_ILN_4324 GBV_ILN_4325 GBV_ILN_4326 GBV_ILN_4328 GBV_ILN_4333 GBV_ILN_4334 GBV_ILN_4335 GBV_ILN_4338 GBV_ILN_4367 GBV_ILN_4393 GBV_ILN_4700 AR 15 2004 7 01 07 989-997
allfieldsSound	10.1016/j.jasms.2004.03.016 doi (DE-627)SPR031488714 (SPR)j.jasms.2004.03.016-e DE-627 ger DE-627 rakwb eng Traeger, John C. verfasserin aut Photoionization of 2,3-dimethyl-2-butanol (thexyl alcohol): Interaction between the charged and expelled fragments 2004 Text txt rdacontent Computermedien c rdamedia Online-Ressource cr rdacarrier © American Society for Mass Spectrometry 2004 Abstract Photoionization studies of ($ CH_{3} $)2CHC($ CH_{3} $)2OH (tert-hexyl alcohol, also called thexyl alcohol) exhibit four fragmentations below 10 eV. As with other tertiary alcohols, no molecular ion is detected. The only ion observed at threshold corresponds to propane loss. Examination of a deuterated analogue, ($ CH_{3} $)2CHC($ CD_{3} $)2OH, shows only loss of $ C_{3} %$ H_{7} $D, implying that the fragment ion has the structure of ionized acetone enol. There is no evidence for reversible deuterium transposition, as has been reported for isotopomers of the homologous secondary alcohol ($ CH_{3} $)2CHCH($ CH_{3} $)OH. Propane loss from thexyl alcohol is attributed to intermediacy of ion-neutral complexes containing isopropyl radical and O-protonated acetone. Simple cleavage to give O-protonated acetone has an appearance energy 18 kJ $ mol^{−1} $ higher than that of propane loss. Thermochemical estimates and ab initio calculations both predict that methyl loss should have a lower threshold than the fragmentation leading to isopropyl loss, but experiments show the appearance energy to be 6 kJ $ mol^{−1} $ higher. This is consistent with previous reports of reverse activation barriers for methyl cleavages. Finally, formation of tert-hexyl cation, ($ CH_{3} $)2CHC($ CH_{3} $)2+, is observed with an appearance energy comparable to that of methyl loss, substantially below that predicted for OH radical expulsion from the molecular ion. The comparatively low threshold of this fragmentation is ascribed to ion-pair formation (concomitant with hydroxide ion) directly from an electronically excited neutral. Interactions between charged and neutral fragments (including energetics, bond orders <1, and electrical charges on molecular fragments) are explored using a combination of DFT and ab initio methods, along with topological analysis using the Atoms in Molecules approach. Bond Order (dpeaa)DE-He213 Bond Dissociation Energy (dpeaa)DE-He213 Neutral Complex (dpeaa)DE-He213 Appearance Energy (dpeaa)DE-He213 Thexyl (dpeaa)DE-He213 Morton, Thomas Hellman aut Enthalten in Journal of the American Society for Mass Spectrometry Washington, DC : ACS Publications, 1990 15(2004), 7 vom: 01. Juli, Seite 989-997 (DE-627)320598799 (DE-600)2019911-9 1879-1123 nnns volume:15 year:2004 number:7 day:01 month:07 pages:989-997 https://dx.doi.org/10.1016/j.jasms.2004.03.016 lizenzpflichtig Volltext GBV_USEFLAG_A SYSFLAG_A GBV_SPRINGER GBV_ILN_20 GBV_ILN_22 GBV_ILN_23 GBV_ILN_24 GBV_ILN_31 GBV_ILN_32 GBV_ILN_39 GBV_ILN_40 GBV_ILN_60 GBV_ILN_62 GBV_ILN_63 GBV_ILN_65 GBV_ILN_69 GBV_ILN_70 GBV_ILN_73 GBV_ILN_74 GBV_ILN_95 GBV_ILN_100 GBV_ILN_101 GBV_ILN_105 GBV_ILN_110 GBV_ILN_120 GBV_ILN_138 GBV_ILN_150 GBV_ILN_151 GBV_ILN_152 GBV_ILN_161 GBV_ILN_170 GBV_ILN_187 GBV_ILN_213 GBV_ILN_224 GBV_ILN_230 GBV_ILN_285 GBV_ILN_293 GBV_ILN_370 GBV_ILN_602 GBV_ILN_647 GBV_ILN_702 GBV_ILN_2001 GBV_ILN_2003 GBV_ILN_2004 GBV_ILN_2005 GBV_ILN_2006 GBV_ILN_2007 GBV_ILN_2009 GBV_ILN_2010 GBV_ILN_2011 GBV_ILN_2014 GBV_ILN_2015 GBV_ILN_2020 GBV_ILN_2021 GBV_ILN_2025 GBV_ILN_2026 GBV_ILN_2027 GBV_ILN_2031 GBV_ILN_2034 GBV_ILN_2037 GBV_ILN_2038 GBV_ILN_2039 GBV_ILN_2044 GBV_ILN_2049 GBV_ILN_2050 GBV_ILN_2055 GBV_ILN_2056 GBV_ILN_2059 GBV_ILN_2061 GBV_ILN_2064 GBV_ILN_2065 GBV_ILN_2068 GBV_ILN_2070 GBV_ILN_2086 GBV_ILN_2106 GBV_ILN_2108 GBV_ILN_2110 GBV_ILN_2111 GBV_ILN_2112 GBV_ILN_2113 GBV_ILN_2116 GBV_ILN_2118 GBV_ILN_2119 GBV_ILN_2122 GBV_ILN_2129 GBV_ILN_2143 GBV_ILN_2144 GBV_ILN_2147 GBV_ILN_2148 GBV_ILN_2152 GBV_ILN_2153 GBV_ILN_2188 GBV_ILN_2190 GBV_ILN_2232 GBV_ILN_2336 GBV_ILN_2507 GBV_ILN_2522 GBV_ILN_4012 GBV_ILN_4035 GBV_ILN_4037 GBV_ILN_4046 GBV_ILN_4112 GBV_ILN_4125 GBV_ILN_4126 GBV_ILN_4242 GBV_ILN_4246 GBV_ILN_4249 GBV_ILN_4251 GBV_ILN_4305 GBV_ILN_4306 GBV_ILN_4307 GBV_ILN_4313 GBV_ILN_4322 GBV_ILN_4323 GBV_ILN_4324 GBV_ILN_4325 GBV_ILN_4326 GBV_ILN_4328 GBV_ILN_4333 GBV_ILN_4334 GBV_ILN_4335 GBV_ILN_4338 GBV_ILN_4367 GBV_ILN_4393 GBV_ILN_4700 AR 15 2004 7 01 07 989-997
language	English
source	Enthalten in Journal of the American Society for Mass Spectrometry 15(2004), 7 vom: 01. Juli, Seite 989-997 volume:15 year:2004 number:7 day:01 month:07 pages:989-997
sourceStr	Enthalten in Journal of the American Society for Mass Spectrometry 15(2004), 7 vom: 01. Juli, Seite 989-997 volume:15 year:2004 number:7 day:01 month:07 pages:989-997
format_phy_str_mv	Article
institution	findex.gbv.de
topic_facet	Bond Order Bond Dissociation Energy Neutral Complex Appearance Energy Thexyl
isfreeaccess_bool	false
container_title	Journal of the American Society for Mass Spectrometry
authorswithroles_txt_mv	Traeger, John C. @@aut@@ Morton, Thomas Hellman @@aut@@
publishDateDaySort_date	2004-07-01T00:00:00Z
hierarchy_top_id	320598799
id	SPR031488714
language_de	englisch
fullrecord	<?xml version="1.0" encoding="UTF-8"?><collection xmlns="http://www.loc.gov/MARC21/slim"><record><leader>01000caa a22002652 4500</leader><controlfield tag="001">SPR031488714</controlfield><controlfield tag="003">DE-627</controlfield><controlfield tag="005">20230331083333.0</controlfield><controlfield tag="007">cr uuu---uuuuu</controlfield><controlfield tag="008">201007s2004 xx \|\|\|\|\|o 00\| \|\|eng c</controlfield><datafield tag="024" ind1="7" ind2=" "><subfield code="a">10.1016/j.jasms.2004.03.016</subfield><subfield code="2">doi</subfield></datafield><datafield tag="035" ind1=" " ind2=" "><subfield code="a">(DE-627)SPR031488714</subfield></datafield><datafield tag="035" ind1=" " ind2=" "><subfield code="a">(SPR)j.jasms.2004.03.016-e</subfield></datafield><datafield tag="040" ind1=" " ind2=" "><subfield code="a">DE-627</subfield><subfield code="b">ger</subfield><subfield code="c">DE-627</subfield><subfield code="e">rakwb</subfield></datafield><datafield tag="041" ind1=" " ind2=" "><subfield code="a">eng</subfield></datafield><datafield tag="100" ind1="1" ind2=" "><subfield code="a">Traeger, John C.</subfield><subfield code="e">verfasserin</subfield><subfield code="4">aut</subfield></datafield><datafield tag="245" ind1="1" ind2="0"><subfield code="a">Photoionization of 2,3-dimethyl-2-butanol (thexyl alcohol): Interaction between the charged and expelled fragments</subfield></datafield><datafield tag="264" ind1=" " ind2="1"><subfield code="c">2004</subfield></datafield><datafield tag="336" ind1=" " ind2=" "><subfield code="a">Text</subfield><subfield code="b">txt</subfield><subfield code="2">rdacontent</subfield></datafield><datafield tag="337" ind1=" " ind2=" "><subfield code="a">Computermedien</subfield><subfield code="b">c</subfield><subfield code="2">rdamedia</subfield></datafield><datafield tag="338" ind1=" " ind2=" "><subfield code="a">Online-Ressource</subfield><subfield code="b">cr</subfield><subfield code="2">rdacarrier</subfield></datafield><datafield tag="500" ind1=" " ind2=" "><subfield code="a">© American Society for Mass Spectrometry 2004</subfield></datafield><datafield tag="520" ind1=" " ind2=" "><subfield code="a">Abstract Photoionization studies of ($ CH_{3} $)2CHC($ CH_{3} $)2OH (tert-hexyl alcohol, also called thexyl alcohol) exhibit four fragmentations below 10 eV. As with other tertiary alcohols, no molecular ion is detected. The only ion observed at threshold corresponds to propane loss. Examination of a deuterated analogue, ($ CH_{3} $)2CHC($ CD_{3} $)2OH, shows only loss of $ C_{3} %$ H_{7} $D, implying that the fragment ion has the structure of ionized acetone enol. There is no evidence for reversible deuterium transposition, as has been reported for isotopomers of the homologous secondary alcohol ($ CH_{3} $)2CHCH($ CH_{3} $)OH. Propane loss from thexyl alcohol is attributed to intermediacy of ion-neutral complexes containing isopropyl radical and O-protonated acetone. Simple cleavage to give O-protonated acetone has an appearance energy 18 kJ $ mol^{−1} $ higher than that of propane loss. Thermochemical estimates and ab initio calculations both predict that methyl loss should have a lower threshold than the fragmentation leading to isopropyl loss, but experiments show the appearance energy to be 6 kJ $ mol^{−1} $ higher. This is consistent with previous reports of reverse activation barriers for methyl cleavages. Finally, formation of tert-hexyl cation, ($ CH_{3} $)2CHC($ CH_{3} $)2+, is observed with an appearance energy comparable to that of methyl loss, substantially below that predicted for OH radical expulsion from the molecular ion. The comparatively low threshold of this fragmentation is ascribed to ion-pair formation (concomitant with hydroxide ion) directly from an electronically excited neutral. Interactions between charged and neutral fragments (including energetics, bond orders <1, and electrical charges on molecular fragments) are explored using a combination of DFT and ab initio methods, along with topological analysis using the Atoms in Molecules approach.</subfield></datafield><datafield tag="650" ind1=" " ind2="4"><subfield code="a">Bond Order</subfield><subfield code="7">(dpeaa)DE-He213</subfield></datafield><datafield tag="650" ind1=" " ind2="4"><subfield code="a">Bond Dissociation Energy</subfield><subfield code="7">(dpeaa)DE-He213</subfield></datafield><datafield tag="650" ind1=" " ind2="4"><subfield code="a">Neutral Complex</subfield><subfield code="7">(dpeaa)DE-He213</subfield></datafield><datafield tag="650" ind1=" " ind2="4"><subfield code="a">Appearance Energy</subfield><subfield code="7">(dpeaa)DE-He213</subfield></datafield><datafield tag="650" ind1=" " ind2="4"><subfield code="a">Thexyl</subfield><subfield code="7">(dpeaa)DE-He213</subfield></datafield><datafield tag="700" ind1="1" ind2=" "><subfield code="a">Morton, Thomas Hellman</subfield><subfield code="4">aut</subfield></datafield><datafield tag="773" ind1="0" ind2="8"><subfield code="i">Enthalten in</subfield><subfield code="t">Journal of the American Society for Mass Spectrometry</subfield><subfield code="d">Washington, DC : ACS Publications, 1990</subfield><subfield code="g">15(2004), 7 vom: 01. Juli, Seite 989-997</subfield><subfield code="w">(DE-627)320598799</subfield><subfield code="w">(DE-600)2019911-9</subfield><subfield code="x">1879-1123</subfield><subfield code="7">nnns</subfield></datafield><datafield tag="773" ind1="1" ind2="8"><subfield code="g">volume:15</subfield><subfield code="g">year:2004</subfield><subfield code="g">number:7</subfield><subfield code="g">day:01</subfield><subfield code="g">month:07</subfield><subfield code="g">pages:989-997</subfield></datafield><datafield tag="856" ind1="4" ind2="0"><subfield code="u">https://dx.doi.org/10.1016/j.jasms.2004.03.016</subfield><subfield code="z">lizenzpflichtig</subfield><subfield code="3">Volltext</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_USEFLAG_A</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">SYSFLAG_A</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_SPRINGER</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_20</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_22</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_23</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_24</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_31</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_32</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_39</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_40</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_60</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_62</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_63</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_65</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_69</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_70</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_73</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_74</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_95</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_100</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_101</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_105</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_110</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_120</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_138</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_150</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_151</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_152</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_161</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_170</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_187</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_213</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_224</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_230</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_285</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_293</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_370</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_602</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_647</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_702</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2001</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2003</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2004</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2005</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2006</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2007</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2009</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2010</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2011</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2014</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2015</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2020</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2021</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2025</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2026</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2027</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2031</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2034</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2037</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2038</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2039</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2044</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2049</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2050</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2055</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2056</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2059</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2061</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2064</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2065</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2068</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2070</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2086</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2106</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2108</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2110</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2111</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2112</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2113</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2116</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2118</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2119</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2122</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2129</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2143</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2144</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2147</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2148</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2152</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2153</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2188</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2190</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2232</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2336</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2507</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2522</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4012</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4035</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4037</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4046</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4112</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4125</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4126</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4242</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4246</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4249</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4251</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4305</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4306</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4307</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4313</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4322</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4323</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4324</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4325</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4326</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4328</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4333</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4334</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4335</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4338</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4367</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4393</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4700</subfield></datafield><datafield tag="951" ind1=" " ind2=" "><subfield code="a">AR</subfield></datafield><datafield tag="952" ind1=" " ind2=" "><subfield code="d">15</subfield><subfield code="j">2004</subfield><subfield code="e">7</subfield><subfield code="b">01</subfield><subfield code="c">07</subfield><subfield code="h">989-997</subfield></datafield></record></collection>
author	Traeger, John C.
spellingShingle	Traeger, John C. misc Bond Order misc Bond Dissociation Energy misc Neutral Complex misc Appearance Energy misc Thexyl Photoionization of 2,3-dimethyl-2-butanol (thexyl alcohol): Interaction between the charged and expelled fragments
authorStr	Traeger, John C.
ppnlink_with_tag_str_mv	@@773@@(DE-627)320598799
format	electronic Article
delete_txt_mv	keep
author_role	aut aut
collection	springer
remote_str	true
illustrated	Not Illustrated
issn	1879-1123
topic_title	Photoionization of 2,3-dimethyl-2-butanol (thexyl alcohol): Interaction between the charged and expelled fragments Bond Order (dpeaa)DE-He213 Bond Dissociation Energy (dpeaa)DE-He213 Neutral Complex (dpeaa)DE-He213 Appearance Energy (dpeaa)DE-He213 Thexyl (dpeaa)DE-He213
topic	misc Bond Order misc Bond Dissociation Energy misc Neutral Complex misc Appearance Energy misc Thexyl
topic_unstemmed	misc Bond Order misc Bond Dissociation Energy misc Neutral Complex misc Appearance Energy misc Thexyl
topic_browse	misc Bond Order misc Bond Dissociation Energy misc Neutral Complex misc Appearance Energy misc Thexyl
format_facet	Elektronische Aufsätze Aufsätze Elektronische Ressource
format_main_str_mv	Text Zeitschrift/Artikel
carriertype_str_mv	cr
hierarchy_parent_title	Journal of the American Society for Mass Spectrometry
hierarchy_parent_id	320598799
hierarchy_top_title	Journal of the American Society for Mass Spectrometry
isfreeaccess_txt	false
familylinks_str_mv	(DE-627)320598799 (DE-600)2019911-9
title	Photoionization of 2,3-dimethyl-2-butanol (thexyl alcohol): Interaction between the charged and expelled fragments
ctrlnum	(DE-627)SPR031488714 (SPR)j.jasms.2004.03.016-e
title_full	Photoionization of 2,3-dimethyl-2-butanol (thexyl alcohol): Interaction between the charged and expelled fragments
author_sort	Traeger, John C.
journal	Journal of the American Society for Mass Spectrometry
journalStr	Journal of the American Society for Mass Spectrometry
lang_code	eng
isOA_bool	false
recordtype	marc
publishDateSort	2004
contenttype_str_mv	txt
container_start_page	989
author_browse	Traeger, John C. Morton, Thomas Hellman
container_volume	15
format_se	Elektronische Aufsätze
author-letter	Traeger, John C.
doi_str_mv	10.1016/j.jasms.2004.03.016
title_sort	photoionization of 2,3-dimethyl-2-butanol (thexyl alcohol): interaction between the charged and expelled fragments
title_auth	Photoionization of 2,3-dimethyl-2-butanol (thexyl alcohol): Interaction between the charged and expelled fragments
abstract	Abstract Photoionization studies of ($ CH_{3} $)2CHC($ CH_{3} $)2OH (tert-hexyl alcohol, also called thexyl alcohol) exhibit four fragmentations below 10 eV. As with other tertiary alcohols, no molecular ion is detected. The only ion observed at threshold corresponds to propane loss. Examination of a deuterated analogue, ($ CH_{3} $)2CHC($ CD_{3} $)2OH, shows only loss of $ C_{3} %$ H_{7} $D, implying that the fragment ion has the structure of ionized acetone enol. There is no evidence for reversible deuterium transposition, as has been reported for isotopomers of the homologous secondary alcohol ($ CH_{3} $)2CHCH($ CH_{3} $)OH. Propane loss from thexyl alcohol is attributed to intermediacy of ion-neutral complexes containing isopropyl radical and O-protonated acetone. Simple cleavage to give O-protonated acetone has an appearance energy 18 kJ $ mol^{−1} $ higher than that of propane loss. Thermochemical estimates and ab initio calculations both predict that methyl loss should have a lower threshold than the fragmentation leading to isopropyl loss, but experiments show the appearance energy to be 6 kJ $ mol^{−1} $ higher. This is consistent with previous reports of reverse activation barriers for methyl cleavages. Finally, formation of tert-hexyl cation, ($ CH_{3} $)2CHC($ CH_{3} $)2+, is observed with an appearance energy comparable to that of methyl loss, substantially below that predicted for OH radical expulsion from the molecular ion. The comparatively low threshold of this fragmentation is ascribed to ion-pair formation (concomitant with hydroxide ion) directly from an electronically excited neutral. Interactions between charged and neutral fragments (including energetics, bond orders <1, and electrical charges on molecular fragments) are explored using a combination of DFT and ab initio methods, along with topological analysis using the Atoms in Molecules approach. © American Society for Mass Spectrometry 2004
abstractGer	Abstract Photoionization studies of ($ CH_{3} $)2CHC($ CH_{3} $)2OH (tert-hexyl alcohol, also called thexyl alcohol) exhibit four fragmentations below 10 eV. As with other tertiary alcohols, no molecular ion is detected. The only ion observed at threshold corresponds to propane loss. Examination of a deuterated analogue, ($ CH_{3} $)2CHC($ CD_{3} $)2OH, shows only loss of $ C_{3} %$ H_{7} $D, implying that the fragment ion has the structure of ionized acetone enol. There is no evidence for reversible deuterium transposition, as has been reported for isotopomers of the homologous secondary alcohol ($ CH_{3} $)2CHCH($ CH_{3} $)OH. Propane loss from thexyl alcohol is attributed to intermediacy of ion-neutral complexes containing isopropyl radical and O-protonated acetone. Simple cleavage to give O-protonated acetone has an appearance energy 18 kJ $ mol^{−1} $ higher than that of propane loss. Thermochemical estimates and ab initio calculations both predict that methyl loss should have a lower threshold than the fragmentation leading to isopropyl loss, but experiments show the appearance energy to be 6 kJ $ mol^{−1} $ higher. This is consistent with previous reports of reverse activation barriers for methyl cleavages. Finally, formation of tert-hexyl cation, ($ CH_{3} $)2CHC($ CH_{3} $)2+, is observed with an appearance energy comparable to that of methyl loss, substantially below that predicted for OH radical expulsion from the molecular ion. The comparatively low threshold of this fragmentation is ascribed to ion-pair formation (concomitant with hydroxide ion) directly from an electronically excited neutral. Interactions between charged and neutral fragments (including energetics, bond orders <1, and electrical charges on molecular fragments) are explored using a combination of DFT and ab initio methods, along with topological analysis using the Atoms in Molecules approach. © American Society for Mass Spectrometry 2004
abstract_unstemmed	Abstract Photoionization studies of ($ CH_{3} $)2CHC($ CH_{3} $)2OH (tert-hexyl alcohol, also called thexyl alcohol) exhibit four fragmentations below 10 eV. As with other tertiary alcohols, no molecular ion is detected. The only ion observed at threshold corresponds to propane loss. Examination of a deuterated analogue, ($ CH_{3} $)2CHC($ CD_{3} $)2OH, shows only loss of $ C_{3} %$ H_{7} $D, implying that the fragment ion has the structure of ionized acetone enol. There is no evidence for reversible deuterium transposition, as has been reported for isotopomers of the homologous secondary alcohol ($ CH_{3} $)2CHCH($ CH_{3} $)OH. Propane loss from thexyl alcohol is attributed to intermediacy of ion-neutral complexes containing isopropyl radical and O-protonated acetone. Simple cleavage to give O-protonated acetone has an appearance energy 18 kJ $ mol^{−1} $ higher than that of propane loss. Thermochemical estimates and ab initio calculations both predict that methyl loss should have a lower threshold than the fragmentation leading to isopropyl loss, but experiments show the appearance energy to be 6 kJ $ mol^{−1} $ higher. This is consistent with previous reports of reverse activation barriers for methyl cleavages. Finally, formation of tert-hexyl cation, ($ CH_{3} $)2CHC($ CH_{3} $)2+, is observed with an appearance energy comparable to that of methyl loss, substantially below that predicted for OH radical expulsion from the molecular ion. The comparatively low threshold of this fragmentation is ascribed to ion-pair formation (concomitant with hydroxide ion) directly from an electronically excited neutral. Interactions between charged and neutral fragments (including energetics, bond orders <1, and electrical charges on molecular fragments) are explored using a combination of DFT and ab initio methods, along with topological analysis using the Atoms in Molecules approach. © American Society for Mass Spectrometry 2004
collection_details	GBV_USEFLAG_A SYSFLAG_A GBV_SPRINGER GBV_ILN_20 GBV_ILN_22 GBV_ILN_23 GBV_ILN_24 GBV_ILN_31 GBV_ILN_32 GBV_ILN_39 GBV_ILN_40 GBV_ILN_60 GBV_ILN_62 GBV_ILN_63 GBV_ILN_65 GBV_ILN_69 GBV_ILN_70 GBV_ILN_73 GBV_ILN_74 GBV_ILN_95 GBV_ILN_100 GBV_ILN_101 GBV_ILN_105 GBV_ILN_110 GBV_ILN_120 GBV_ILN_138 GBV_ILN_150 GBV_ILN_151 GBV_ILN_152 GBV_ILN_161 GBV_ILN_170 GBV_ILN_187 GBV_ILN_213 GBV_ILN_224 GBV_ILN_230 GBV_ILN_285 GBV_ILN_293 GBV_ILN_370 GBV_ILN_602 GBV_ILN_647 GBV_ILN_702 GBV_ILN_2001 GBV_ILN_2003 GBV_ILN_2004 GBV_ILN_2005 GBV_ILN_2006 GBV_ILN_2007 GBV_ILN_2009 GBV_ILN_2010 GBV_ILN_2011 GBV_ILN_2014 GBV_ILN_2015 GBV_ILN_2020 GBV_ILN_2021 GBV_ILN_2025 GBV_ILN_2026 GBV_ILN_2027 GBV_ILN_2031 GBV_ILN_2034 GBV_ILN_2037 GBV_ILN_2038 GBV_ILN_2039 GBV_ILN_2044 GBV_ILN_2049 GBV_ILN_2050 GBV_ILN_2055 GBV_ILN_2056 GBV_ILN_2059 GBV_ILN_2061 GBV_ILN_2064 GBV_ILN_2065 GBV_ILN_2068 GBV_ILN_2070 GBV_ILN_2086 GBV_ILN_2106 GBV_ILN_2108 GBV_ILN_2110 GBV_ILN_2111 GBV_ILN_2112 GBV_ILN_2113 GBV_ILN_2116 GBV_ILN_2118 GBV_ILN_2119 GBV_ILN_2122 GBV_ILN_2129 GBV_ILN_2143 GBV_ILN_2144 GBV_ILN_2147 GBV_ILN_2148 GBV_ILN_2152 GBV_ILN_2153 GBV_ILN_2188 GBV_ILN_2190 GBV_ILN_2232 GBV_ILN_2336 GBV_ILN_2507 GBV_ILN_2522 GBV_ILN_4012 GBV_ILN_4035 GBV_ILN_4037 GBV_ILN_4046 GBV_ILN_4112 GBV_ILN_4125 GBV_ILN_4126 GBV_ILN_4242 GBV_ILN_4246 GBV_ILN_4249 GBV_ILN_4251 GBV_ILN_4305 GBV_ILN_4306 GBV_ILN_4307 GBV_ILN_4313 GBV_ILN_4322 GBV_ILN_4323 GBV_ILN_4324 GBV_ILN_4325 GBV_ILN_4326 GBV_ILN_4328 GBV_ILN_4333 GBV_ILN_4334 GBV_ILN_4335 GBV_ILN_4338 GBV_ILN_4367 GBV_ILN_4393 GBV_ILN_4700
container_issue	7
title_short	Photoionization of 2,3-dimethyl-2-butanol (thexyl alcohol): Interaction between the charged and expelled fragments
url	https://dx.doi.org/10.1016/j.jasms.2004.03.016
remote_bool	true
author2	Morton, Thomas Hellman
author2Str	Morton, Thomas Hellman
ppnlink	320598799
mediatype_str_mv	c
isOA_txt	false
hochschulschrift_bool	false
doi_str	10.1016/j.jasms.2004.03.016
up_date	2024-07-03T23:57:43.049Z
_version_	1803604263489765376
fullrecord_marcxml	<?xml version="1.0" encoding="UTF-8"?><collection xmlns="http://www.loc.gov/MARC21/slim"><record><leader>01000caa a22002652 4500</leader><controlfield tag="001">SPR031488714</controlfield><controlfield tag="003">DE-627</controlfield><controlfield tag="005">20230331083333.0</controlfield><controlfield tag="007">cr uuu---uuuuu</controlfield><controlfield tag="008">201007s2004 xx \|\|\|\|\|o 00\| \|\|eng c</controlfield><datafield tag="024" ind1="7" ind2=" "><subfield code="a">10.1016/j.jasms.2004.03.016</subfield><subfield code="2">doi</subfield></datafield><datafield tag="035" ind1=" " ind2=" "><subfield code="a">(DE-627)SPR031488714</subfield></datafield><datafield tag="035" ind1=" " ind2=" "><subfield code="a">(SPR)j.jasms.2004.03.016-e</subfield></datafield><datafield tag="040" ind1=" " ind2=" "><subfield code="a">DE-627</subfield><subfield code="b">ger</subfield><subfield code="c">DE-627</subfield><subfield code="e">rakwb</subfield></datafield><datafield tag="041" ind1=" " ind2=" "><subfield code="a">eng</subfield></datafield><datafield tag="100" ind1="1" ind2=" "><subfield code="a">Traeger, John C.</subfield><subfield code="e">verfasserin</subfield><subfield code="4">aut</subfield></datafield><datafield tag="245" ind1="1" ind2="0"><subfield code="a">Photoionization of 2,3-dimethyl-2-butanol (thexyl alcohol): Interaction between the charged and expelled fragments</subfield></datafield><datafield tag="264" ind1=" " ind2="1"><subfield code="c">2004</subfield></datafield><datafield tag="336" ind1=" " ind2=" "><subfield code="a">Text</subfield><subfield code="b">txt</subfield><subfield code="2">rdacontent</subfield></datafield><datafield tag="337" ind1=" " ind2=" "><subfield code="a">Computermedien</subfield><subfield code="b">c</subfield><subfield code="2">rdamedia</subfield></datafield><datafield tag="338" ind1=" " ind2=" "><subfield code="a">Online-Ressource</subfield><subfield code="b">cr</subfield><subfield code="2">rdacarrier</subfield></datafield><datafield tag="500" ind1=" " ind2=" "><subfield code="a">© American Society for Mass Spectrometry 2004</subfield></datafield><datafield tag="520" ind1=" " ind2=" "><subfield code="a">Abstract Photoionization studies of ($ CH_{3} $)2CHC($ CH_{3} $)2OH (tert-hexyl alcohol, also called thexyl alcohol) exhibit four fragmentations below 10 eV. As with other tertiary alcohols, no molecular ion is detected. The only ion observed at threshold corresponds to propane loss. Examination of a deuterated analogue, ($ CH_{3} $)2CHC($ CD_{3} $)2OH, shows only loss of $ C_{3} %$ H_{7} $D, implying that the fragment ion has the structure of ionized acetone enol. There is no evidence for reversible deuterium transposition, as has been reported for isotopomers of the homologous secondary alcohol ($ CH_{3} $)2CHCH($ CH_{3} $)OH. Propane loss from thexyl alcohol is attributed to intermediacy of ion-neutral complexes containing isopropyl radical and O-protonated acetone. Simple cleavage to give O-protonated acetone has an appearance energy 18 kJ $ mol^{−1} $ higher than that of propane loss. Thermochemical estimates and ab initio calculations both predict that methyl loss should have a lower threshold than the fragmentation leading to isopropyl loss, but experiments show the appearance energy to be 6 kJ $ mol^{−1} $ higher. This is consistent with previous reports of reverse activation barriers for methyl cleavages. Finally, formation of tert-hexyl cation, ($ CH_{3} $)2CHC($ CH_{3} $)2+, is observed with an appearance energy comparable to that of methyl loss, substantially below that predicted for OH radical expulsion from the molecular ion. The comparatively low threshold of this fragmentation is ascribed to ion-pair formation (concomitant with hydroxide ion) directly from an electronically excited neutral. Interactions between charged and neutral fragments (including energetics, bond orders <1, and electrical charges on molecular fragments) are explored using a combination of DFT and ab initio methods, along with topological analysis using the Atoms in Molecules approach.</subfield></datafield><datafield tag="650" ind1=" " ind2="4"><subfield code="a">Bond Order</subfield><subfield code="7">(dpeaa)DE-He213</subfield></datafield><datafield tag="650" ind1=" " ind2="4"><subfield code="a">Bond Dissociation Energy</subfield><subfield code="7">(dpeaa)DE-He213</subfield></datafield><datafield tag="650" ind1=" " ind2="4"><subfield code="a">Neutral Complex</subfield><subfield code="7">(dpeaa)DE-He213</subfield></datafield><datafield tag="650" ind1=" " ind2="4"><subfield code="a">Appearance Energy</subfield><subfield code="7">(dpeaa)DE-He213</subfield></datafield><datafield tag="650" ind1=" " ind2="4"><subfield code="a">Thexyl</subfield><subfield code="7">(dpeaa)DE-He213</subfield></datafield><datafield tag="700" ind1="1" ind2=" "><subfield code="a">Morton, Thomas Hellman</subfield><subfield code="4">aut</subfield></datafield><datafield tag="773" ind1="0" ind2="8"><subfield code="i">Enthalten in</subfield><subfield code="t">Journal of the American Society for Mass Spectrometry</subfield><subfield code="d">Washington, DC : ACS Publications, 1990</subfield><subfield code="g">15(2004), 7 vom: 01. Juli, Seite 989-997</subfield><subfield code="w">(DE-627)320598799</subfield><subfield code="w">(DE-600)2019911-9</subfield><subfield code="x">1879-1123</subfield><subfield code="7">nnns</subfield></datafield><datafield tag="773" ind1="1" ind2="8"><subfield code="g">volume:15</subfield><subfield code="g">year:2004</subfield><subfield code="g">number:7</subfield><subfield code="g">day:01</subfield><subfield code="g">month:07</subfield><subfield code="g">pages:989-997</subfield></datafield><datafield tag="856" ind1="4" ind2="0"><subfield code="u">https://dx.doi.org/10.1016/j.jasms.2004.03.016</subfield><subfield code="z">lizenzpflichtig</subfield><subfield code="3">Volltext</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_USEFLAG_A</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">SYSFLAG_A</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_SPRINGER</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_20</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_22</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_23</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_24</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_31</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_32</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_39</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_40</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_60</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_62</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_63</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_65</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_69</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_70</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_73</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_74</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_95</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_100</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_101</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_105</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_110</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_120</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_138</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_150</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_151</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_152</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_161</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_170</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_187</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_213</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_224</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_230</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_285</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_293</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_370</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_602</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_647</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_702</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2001</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2003</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2004</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2005</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2006</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2007</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2009</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2010</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2011</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2014</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2015</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2020</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2021</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2025</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2026</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2027</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2031</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2034</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2037</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2038</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2039</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2044</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2049</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2050</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2055</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2056</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2059</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2061</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2064</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2065</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2068</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2070</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2086</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2106</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2108</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2110</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2111</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2112</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2113</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2116</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2118</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2119</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2122</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2129</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2143</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2144</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2147</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2148</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2152</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2153</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2188</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2190</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2232</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2336</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2507</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_2522</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4012</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4035</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4037</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4046</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4112</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4125</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4126</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4242</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4246</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4249</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4251</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4305</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4306</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4307</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4313</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4322</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4323</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4324</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4325</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4326</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4328</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4333</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4334</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4335</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4338</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4367</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4393</subfield></datafield><datafield tag="912" ind1=" " ind2=" "><subfield code="a">GBV_ILN_4700</subfield></datafield><datafield tag="951" ind1=" " ind2=" "><subfield code="a">AR</subfield></datafield><datafield tag="952" ind1=" " ind2=" "><subfield code="d">15</subfield><subfield code="j">2004</subfield><subfield code="e">7</subfield><subfield code="b">01</subfield><subfield code="c">07</subfield><subfield code="h">989-997</subfield></datafield></record></collection>
score	7.4018393

Nicht das Richtige dabei?

Schreiben Sie uns!

Photoionization of 2,3-dimethyl-2-butanol (thexyl alcohol): Interaction between the charged and expelled fragments

Nicht das Richtige dabei?

Zugang & Verfügbarkeit

Vorhandene Bände

Nicht das Richtige dabei?