Theoretical calculation of absorption intensities of C₂H and C₂D

Abstract

The theory of dipole-allowed absorption intensities in triatomic molecules is presented for systems with three close-lying electronic states of doublet multiplicity. Its derivation is within the framework of a recently developed variational method [CARTER, S., HANDY, N. C., PUZZARINI, C., TARRONI, R., and PALMIERI, P., 2000, Molec. Phys., 98, 1967]. The method has been applied to the calculation of the infrared absorption spectrum of the C₂H radical and its deuterated isotopomer for energies up to 10 000 cm⁻¹ above the ground state, using highly accurate ab initio diabatic potential energy and dipole moment surfaces. The calculated spectra agree very well with those recorded experimentally in a neon matrix [FORNEY, D., JACOX, M. E., and THOMPSON, W. E., 1995, J. molec. Spectrosc., 170, 178] and assignments in the high energy region of the IR spectra are proposed for the first time.