Quantum calculation of highly excited vibrational energy levels of CS2(X) on a new empirical potential energy surface and semiclassical analysis of 1:2 Fermi resonance.
We report a refined potential energy function for the ground electronic state of CS2 based on a least-squares fitting to several low-lying experimental vibrational frequencies. Energy levels up to 20,000 cm(-1) have been obtained on this empirical potential using the Lanczos algorithm and potential optimized discrete variable representation. Among them, 329 levels below 10,000 cm(-1) are assigned with approximate normal mode quantum numbers (n1, n(0)2, n3), based on expectation values of one-dimensional (1D) reference Hamiltonians. An effective Hamiltonian is extracted from these assigned levels. The agreement with experimental data, including those of several isotopically substituted species, is excellent. In addition, some Fermi and anharmonic resonances are analyzed. The nearest neighbor level spacing and delta3 distributions indicated that the vibrational spectrum of CS2 is largely regular in the energy range up to 20,000 cm(-1). Semiclassical phase space analysis, including bifurcation analysis of the spectroscopic Hamiltonian, is used to interpret subtle anomalies signaled by expectation values used in normal mode assignments. The meaning of Fermi resonance is clarified by contrasting the semiclassical analysis of CS2 and CO2.
Zhou
Cheng
C
Department of Chemistry, University of New Mexico, Albuquerque 87111, USA.
Xie
Daiqian
D
Chen
Rongqing
R
Yan
Guosen
G
Guo
Hua
H
Tyng
Vivian
V
Kellman
Michael E
ME
D002246:Carbon Disulfide / Q000032:analysis / Q000737:chemistry*; D002627:Chemistry, Physical / Q000379:methods; D007700:Kinetics; D008962:Models, Theoretical; D011789:Quantum Theory; D013055:Spectrophotometry, Infrared / Q000379:methods*; D014732:Vibration
D002246:Carbon Disulfide