Accurate potential energy surface and calculated spectroscopic properties for CdH2 isotopomers.
Ab initio calculations employing the coupled cluster method CCSD(T), in conjunction with a small-core pseudopotential for the cadmium atom, have been employed to construct a near-equilibrium potential energy function (PEF) and an electric dipole moment function (EDMF) for CdH(2). The significance of the spin-orbit interaction was checked and found to be of minor importance. Making use of two pieces of experimental information for the most abundant isotopomer (114)CdH(2), we obtained a refined PEF, which, within variational calculations of rovibrational states and wave functions, reproduces all available experimental data (S. Yu, A.Shayesteh, and P. F. Bernath, J. Chem. Phys. 2005, 122, 194301) very well. In addition, numerous predictions are made. In particular, the nu(2) band origins for (114)CdH(2) and (114)CdD(2) are predicted at 605.9 and 436.9 cm(-1), respectively, and the state perturbing the e parity levels of the (0,0(0),1) state of (114)CdH(2) at J = 12-17 is identified as the (0,3(3),0) state. Assignments for further perturbations found in the emission spectra are given as well.
Sebald
Peter
P
Institut für Physikalische Chemie, Universität Göttingen, Tammannstrasse 6, D-37077 Göttingen, Germany.
Oswald
Rainer
R
Botschwina
Peter
P
Stoll
Hermann
H
Figgen
Detlev
D