Ab initio potential energy surface and infrared spectra of H-2-CO and D-2-CO vanderWaals complexes

摘要

A new four-dimensional intermolecular potential energy surface for the H-2-CO complex with fixed intramolecular distances of H-2 and CO is presented. The symmetry-adapted perturbation theory has been used to calculate the interaction energy. A large basis set of spdfg type has been used including bond functions. An analytical fit of the ab initio potential energy surface has the global minimum of -109.272 cm(-1) at the intermolecular separation of 7.76 bohr for the linear geometry with the C atom pointing toward the H-2 molecule. This potential has been used to calculate rovibrational energy levels of CO-para-H-2 and CO-ortho-D-2 complexes. The resulting dissociation energies are 23.709 cm(-1) and 30.756 cm(-1), respectively. The computed levels have been used to generate the infrared spectrum accompanying the fundamental vibrational excitation of CO. The transition energies predicted agree well with those observed by McKellar [Chem. Phys. Lett. 186, 58 (1991)]. (C) 1998 American Institute of Physics. [S0021-9606(98)02409-X]. [References: 57]