Generation of two isomers of C5H from the corresponding anions.: A theoretically motivated mass spectrometric study

被引:39
作者
Blanksby, SJ [1 ]
Dua, S [1 ]
Bowie, JH [1 ]
机构
[1] Univ Adelaide, Dept Chem, Adelaide, SA 5005, Australia
关键词
D O I
10.1021/jp990201t
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Molecular orbital calculations have predicted the stability of a range of connectivities for the radical C5H potential surface. The most energetically favorable of these include the linear C4CH geometry and two ring-chain structures HC2C3 and C2C3H The corresponding anions are also shown to be theoretically stable, and furthermore, a fourth isomer, C2CHC2, is predicted to be the most stable anion connectivity. These results have motivated experimental efforts. Methodologies for the generation of the non-ring-containing isomeric anions C4CH and C2CHC2 have been developed utilizing negative ion mass spectrometry. The absolute connectivities of the anions have been established using deuterium labeling, charge reversal, and neutralization reionization techniques. The success of the latter experiment confirms theoretical predictions of stability of the corresponding neutral species. This is the first reported observation of the neutral C2CHC2 species that calculations predict to be substantially less stable than the C4CH connectivity but still bound relative to isomerization processes.
引用
收藏
页码:5161 / 5170
页数:10
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共 69 条
[41]  
NGUYEN VG, 1996, J MASS SPECTROM, V31, P842
[42]   PHOTOELECTRON-SPECTROSCOPY OF RADICAL-ANIONS [J].
OAKES, JM ;
ELLISON, GB .
TETRAHEDRON, 1986, 42 (22) :6263-6267
[43]  
OMONT A, 1994, LECT NOTE PHYS, P134
[44]  
OSCHENFELD C, 1997, J CHEM PHYS, V106, P4141
[45]   IS INTERSTELLAR DETECTION OF HIGHER MEMBERS OF THE LINEAR RADICALS CNCH AND CNN FEASIBLE [J].
PAUZAT, F ;
ELLINGER, Y ;
MCLEAN, AD .
ASTROPHYSICAL JOURNAL, 1991, 369 (01) :L13-L16
[46]   Some interstellar reactions involving electrons and neutral species: Attachment and isomerization [J].
Petrie, S ;
Herbst, E .
ASTROPHYSICAL JOURNAL, 1997, 491 (01) :210-215
[47]   ELECTRON CORRELATION THEORIES AND THEIR APPLICATION TO STUDY OF SIMPLE REACTION POTENTIAL SURFACES [J].
POPLE, JA ;
KRISHNAN, R ;
SCHLEGEL, HB ;
BINKLEY, JS .
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, 1978, 14 (05) :545-560
[48]   MOLECULAR-ORBITAL THEORY OF THE ELECTRONIC-STRUCTURE OF ORGANIC-MOLECULES .40. STRUCTURES AND ENERGIES OF C-1-C-3 CARBOCATIONS, INCLUDING EFFECTS OF ELECTRON CORRELATION [J].
RAGHAVACHARI, K ;
WHITESIDE, RA ;
POPLE, JA ;
SCHLEYER, PV .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1981, 103 (19) :5649-5657
[49]   LABORATORY MILLIMETER AND SUBMILLIMETER SPECTRUM OF CCH [J].
SASTRY, KVLN ;
HELMINGER, P ;
CHARO, A ;
HERBST, E ;
DELUCIA, FC .
ASTROPHYSICAL JOURNAL, 1981, 251 (02) :L119-L120
[50]   Mass spectrometry as a tool to probe the gas-phase reactivity of neutral molecules [J].
Schalley, CA ;
Hornung, G ;
Schroder, D ;
Schwarz, H .
INTERNATIONAL JOURNAL OF MASS SPECTROMETRY, 1998, 172 (03) :181-208