Photoelectron spectra of nitrosomethane, t-nitrosobutane and some perhalogenonitrosomethanes

Nikolaus P. Ernsting, Josef Pfab, Jennifer C. Green, Joachim Römelt

Research output: Contribution to journalArticle

Abstract

The He(I) photoelectron spectrum of nitrosomethane has been re-examined and re-assigned on the basis of ab initio SCF-CI calculations for the molecule and the three lowest doublet ion states and a comparison with isoelectronic molecules. He(I) and in most cases He(II) photoelectron spectra and assignments are presented for t-nitrosobutane(2-methyl-2-nitrosopropane), trifluoro-, trichloro- and tribromonitrosomethane, as well as for the mixed substituted chlorofluoro- and chloro-bromonitrosomethanes. The ionisation sequence n - < n+ < p(NO) implying a breakdown of Koopmans' approximation has been established for these compounds and n+/n - lone-pair splittings varying from 2.8 to 6.0 eV have been determined for the nitroso group. The characteristic ionisation energies associated with this group correlate well with the substituent electronegativities. For the trihalogenonitrosomethanes the halogen lone-pair ionisations have also been assigned by comparison with related molecules.

Original languageEnglish
Pages (from-to)844-859
Number of pages16
JournalJournal of the Chemical Society, Faraday Transactions 2: Molecular and Chemical Physics
Volume76
DOIs
Publication statusPublished - 1980

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