Transition state spectroscopy of the excited electronic states of LiHF

Abstract

The A, B, B ′←X absorption spectrum of LiHF has been simulated and compared to recent experimental data by Polanyi and co-workers [J. Chem. Phys. 113 (2000) 9897]. Global potential energy surfaces were fitted for the four electronic states involved, based on about 3000 ab initio adiabatic energies calculated at MRDCI level. A single rotational transition J=0← J=1 was simulated using a wavepacket method for several vibrational states of the LiHF(X) complex. The rotational and vibrational temperature were fitted to reproduce the experimental results. The attribution of some peaks of the spectrum differs from that made in the experimental work.