Stretch-bend combination polyads in the Ã1Au [A tilde superscript 1 A subscript u] state of acetylene, C2H2 [C subscript 2 H subscript 2]

Abstract

Rotational analyses are reported for a number of newly-discovered vibrational levels of the S1-trans [S subscriopt 1 -trans](Ã1Au) [A tilde superscript 1 A subscript u] state of C2H2 [C subscript 2 H subscript 2]. These levels are combinations where the Franck–Condon active v2' [v subscript 2 prime] and v3' [v subscript 3 prime] vibrational modes are excited together with the low-lying bending vibrations, v4' [v subscript 4 prime] and v6' [v subscript 6 prime]. The structures of the bands are complicated by strong a- and b-axis Coriolis coupling, as well as Darling–Dennison resonance for those bands that involve overtones of the bending vibrations. The most interesting result is the strong anharmonicity in the combinations of v3' [v subscript 3 prime] (trans bend, ag [a subscript g]) and v6' [v subscript 6 prime] (in-plane cis bend, bu [b subscript u]). This anharmonicity presumably represents the approach of the molecule to the trans–cis isomerization barrier, where ab initio results have predicted the transition state to be half-linear, corresponding to simultaneous excitation of v3' [v subscript 3 prime] and v6' [v subscript 6 prime]. The anharmonicity also causes difficulty in the least squares fitting of some of the polyads, because the simple model of Coriolis coupling and Darling–Dennison resonance starts to break down. The effective Darling–Dennison parameter, K4466 [K subscript 4466], is found to increase rapidly with excitation of v3' [v subscript 3 prime], while many small centrifugal distortion terms have had to be included in the least squares fits in order to reproduce the rotational structure correctly. Fermi resonances become important where the K-structures of different polyads overlap, as happens with the 2131B1 [2 superscript 1 3 superscript 1 B superscript 1] and 31B3 [3 superscript 1 B superscript 3] polyads (B = 4 or 6). The aim of this work is to establish the detailed vibrational level structure of the S1-trans [S subscript 1 -trans] state in order to search for possible S1-cis [S subscript 1 -cis] (1A2) [(superscript 1 A subscript 2)] levels. This work, along with results from other workers, identifies at least one K sub-level of every single vibrational level expected up to a vibrational energy of 3500 cm−1 [cm superscript -1].