Accurate quantum calculation of the bound and resonant rovibrational states of Li-(H2).
In a recent paper [B. Poirier, Chem. Phys. 308, 305 (2005)] a full-dimensional quantum method for computing the rovibrational dynamics of triatomic systems was presented, incorporating three key features: (1) exact analytical treatment of Coriolis coupling, (2) three-body "effective potential," and (3) a single bend angle basis for all rotational states. In this paper, these ideas are applied to the Li-(H2) electrostatic complex, to compute all of the rovibrational bound state energies, and a number of resonance energies and widths, to very high accuracy (thousandths of a wave number). This application is very challenging, owing to the long-range nature of the interaction and to narrow level spacings near dissociation. Nevertheless, by combining the present method with a G4 symmetry-adapted phase-space-optimized representation, only modest basis sizes are required for which the matrices are amenable to direct diagonalization. Several new bound levels are reported, as compared with a previous calculation [D. T. Chang, G. Surratt, G. Ristroff, and G. I. Gellene, J. Chem. Phys. 116, 9188 (2002)]. The resonances exhibit a clear-cut separation into shape and Feshbach varieties, with the latter characterized by extremely long lifetimes (microseconds or longer).
Xiao
Yingsheng
Y
Department of Chemistry and Biochemistry, Texas Tech University, Box 41061, Lubbock, Texas 79409-1061, USA.
Poirier
Bill
B