Quantum calculations of highly excited vibrational spectrum of sulfur dioxide. II. Normal to local mode transition and quantum stochasticity

Authors
Citation
Gb. Ma et H. Guo, Quantum calculations of highly excited vibrational spectrum of sulfur dioxide. II. Normal to local mode transition and quantum stochasticity, J CHEM PHYS, 111(9), 1999, pp. 4032-4040
Citations number
63
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
JOURNAL OF CHEMICAL PHYSICS
ISSN journal
00219606 → ACNP
Volume
111
Issue
9
Year of publication
1999
Pages
4032 - 4040
Database
ISI
SICI code
0021-9606(19990901)111:9<4032:QCOHEV>2.0.ZU;2-T
Abstract
We report a quantum mechanical calculation of highly excited vibrational sp ectrum of SO2 up to 25 000 cm(-1), using a filter-diagonalization method ba sed on the Chebyshev propagation. Our results indicate a graduate transitio n from a normal mode regime at low energies to a local mode regime near 25 000 cm(-1), which is marked by a decreasing energy gap between the (n(1),0, 0) and (n(1)-1,0,1) states and bifurcation of the corresponding wave functi ons. Approximately 4700 vibrational levels are found below 25 000 cm(-1) an d statistical analysis reveals that the SO2 vibration in this energy range is largely regular although the existence of chaos cannot be excluded. (C) 1999 American Institute of Physics. [S0021-9606(99)02133-9].