TY - JOUR
T1 - Accurate quantum calculation of the bound and resonant rovibrational states of Li- (H2)
AU - Xiao, Yingsheng
AU - Poirier, Bill
N1 - Funding Information:
This work was largely supported by the Office of Advanced Scientific Computing Research, Mathematical, Information, and Computational Sciences Division of the U.S. Department of Energy, under Contract No. DE-FG03-02ER25534. Acknowledgment is also made to The Welch Foundation (Grant No. D-1523), to Research Corporation, and to the donors of The Petroleum Research Fund, administered by the American Chemical Society. The authors also wish to express gratitude to Joel Bowman, Tucker Carrington, Jr., Gregory Gellene, William Hase, Michael Minkoff, Edward Quitevis, Pierre-Nicholas Roy, and Albert Wagner for many stimulating discussions.
PY - 2005/3/22
Y1 - 2005/3/22
N2 - 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).
AB - 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).
UR - http://www.scopus.com/inward/record.url?scp=17444415663&partnerID=8YFLogxK
U2 - 10.1063/1.1875116
DO - 10.1063/1.1875116
M3 - Article
AN - SCOPUS:17444415663
SN - 0021-9606
VL - 122
JO - The Journal of Chemical Physics
JF - The Journal of Chemical Physics
IS - 12
M1 - 124318
ER -