When a mixture of ClCN or BrCN with a large excess of neon is codeposited at 4.3 K with a beam of neon atoms that have been excited in a microwave discharge, the infrared spectrum of the resulting solid includes prominent absorptions of the uncharged isocyanide, ClNC or BrNC, and of the corresponding cation, ClCN+ or BrCN+. The NC-stretching fundamentals of the isocyanides trapped in solid neon lie close to the positions for their previously reported argon-matrix counterparts. The CN-stretching absorptions of ClCN+ and BrCN+ and the CCl-stretching absorption of ClCN+ appear very close to the gas-phase band centers. Absorptions of two overtones and one combination band of ClCN+ are identified. Reversible photoisomerization of ClCN+ to ClNC+ occurs. The two stretching vibrational fundamentals and several infrared and near infrared absorptions associated with electronic transitions of ClNC+ are observed. Minor infrared peaks are attributed to the vibrational fundamental absorptions of the CX and CX+ species (X = Cl, Br).
Citation: Journal of Chemical Physics
Pub Type: Journals
BrCN+, CBr, CBr+, CINC+, infrared spectrum, neon matrix, photoisomerization