Reduced dimension rovibrational variational calculations of the S(1) state of C2H2. II. The S(1) rovibrational manifold and the effects of isomerization.
Reduced dimension variational calculations have been performed for the rovibrational level structure of the S1 state of acetylene. The state exhibits an unusually complicated level structure, for various reasons. First, the potential energy surface has two accessible conformers, trans and cis. The cis conformer lies about 2700 cm(-1) above the trans, and the barrier to cis-trans isomerization lies about 5000 cm(-1) above the trans minimum. The trans vibrations ν4 (torsion) and ν6 (asym. bend) interact very strongly by Darling-Dennison and Coriolis resonances, such that their combination levels and overtones form polyads with unexpected structures. Both conformers exhibit very large x36 cross-anharmonicity since the pathway to isomerization is a combination of ν6 and ν3 (sym. bend). Near the isomerization barrier, the vibrational levels show an even-odd K-staggering of their rotational levels as a result of quantum mechanical tunneling through the barrier. The present calculations address all of these complications, and reproduce the observed K-structures of the bending and C-C stretching levels with good qualitative accuracy. It is expected that they will assist with the assignment of the irregular patterns near the isomerization barrier.
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
P Bryan
PB
Changala
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
Joshua H
JH
Baraban
Department of Chemistry and Biochemistry, Institute for Theoretical Chemistry, The University of Texas at Austin, Austin, Texas 78712, USA.
John F
JF
Stanton
Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan and Department of Chemistry, University of British Columbia, Vancouver, British Columbia V6T 1Z1, Canada.
Anthony J
AJ
Merer
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
Robert W
RW
Field