The He I and He II photoelectron (PE) spectra of methyl pseudohalides (MeNCO, MeNCS, MeNCSe, MeSCN, and MeSeCN) have been recorded. Assignments are based on ab initio quantum chemical calculations, and their comparison with high‐resolution He I spectra and He I/He II band intensity ratios. Contradictions found in previous works are largely resolved. The strikingly different spectra of the isomeric forms are interpreted using a consistent model for a methyl‐distorted NCX substructure. The effects of the heavy atoms are also discussed. © 1992 John Wiley & Sons, Inc.
ASJC Scopus subject areas
- Atomic and Molecular Physics, and Optics
- Condensed Matter Physics
- Physical and Theoretical Chemistry