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
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].