Quantum calculations of highly excited vibrational spectrum of sulfur dioxide. I. Eigenenergies and assignments up to 15,000 cm(-1)

Citation
Gb. Ma et al., Quantum calculations of highly excited vibrational spectrum of sulfur dioxide. I. Eigenenergies and assignments up to 15,000 cm(-1), J CHEM PHYS, 110(17), 1999, pp. 8408-8416
Citations number
77
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
JOURNAL OF CHEMICAL PHYSICS
ISSN journal
00219606 → ACNP
Volume
110
Issue
17
Year of publication
1999
Pages
8408 - 8416
Database
ISI
SICI code
0021-9606(19990501)110:17<8408:QCOHEV>2.0.ZU;2-N
Abstract
The vibrational spectrum of SO2 up to 15 000 cm(-1) is calculated using a l ow-storage filter-diagonalization method based on the Chebyshev propagation . The Hamiltonian in the Radau coordinates is expressed on a direct product of one-dimensional discrete variable representation (DVR) grids. The exten ded symmetry-adapted discrete variable representation (ESADVR) is implement ed to accelerate the calculation of the action of kinetic energy operators, and multiple symmetry-adapted autocorrelation functions are obtained from the propagation of a single wave packet. Approximately 1000 vibrational ene rgy levels are identified and some of them are assigned according to the no dal structure of the eigenstates. Comparison with experimental data indicat es reasonably good agreement (<1%). The agreement, however, deteriorates wi th increasing energy, implicating imperfection in the potential energy surf ace used in the calculation. Statistical analyses indicate that the system is mostly regular in this energy range. There is some evidence of a normal- to-local mode transition at higher energies. (C) 1999 American Institute of Physics. [S0021-9606(99)00917-4].