Experimental and theoretical study of the electronic structure of methyl chloroformate and methyl cyanoformate

The HeI photoelectron spectra of methyl chloroformate (CH 3OC(O)Cl) and methyl cyanoformate (CH 3OC(O)CN) in the gas phase have been obtained for the first time. A complete theoretical study involving the calculation of the ionization energies using outer valence Green’s functional (OVGF) was perfor...

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Bibliographic Details
Published in:Journal of molecular structure 2006-12, Vol.800 (1), p.62-68
Main Authors: Zeng, Xiao-Qing, Ge, Mao-Fa, Du, Lin, Sun, Zheng, Wang, Dian-Xun
Format: Article
Language:English
Subjects:
Ab initio calculation
HeI photoelectron spectroscopy
Ionization energy
Methyl chloroformate
Methyl cyanoformate
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Summary:The HeI photoelectron spectra of methyl chloroformate (CH 3OC(O)Cl) and methyl cyanoformate (CH 3OC(O)CN) in the gas phase have been obtained for the first time. A complete theoretical study involving the calculation of the ionization energies using outer valence Green’s functional (OVGF) was performed, based on the calculated and previously reported energetically favorable cis-conformer (the carbonyl group eclipses the methyl group). Calculations of cationic-radical forms were carried out in order to interpret the main characters of the first six highest occupied molecular orbitals (HOMOs). The first vertical ionization potentials are 11.36 eV for CH 3OC(O)Cl and 11.65 eV for CH 3OC(O)CN, each attributed to {19a′(n O(C O) , n Cl)} −1 and {18a′(n O(C O) )} −1, respectively.
ISSN:0022-2860
1872-8014
DOI:10.1016/j.molstruc.2006.03.080