Vibrational quasi-degenerate perturbation theory: applications to fermi resonance in CO2, H2CO, and C6H6

• Published in: Physical chemistry chemical physics : PCCP Vol. 10; no. 13; pp. 1781 - 1788
• Main Authors: Yagi, Kiyoshi, Hirata, So, Hirao, Kimihiko
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 01.01.2008
• Subjects: Absorption; Benzene - analysis; Carbon Dioxide - analysis; Chemistry; Chemistry, Physical - methods; Computer Simulation; Exact sciences and technology; Formaldehyde - analysis; General and physical chemistry; Models, Statistical; Molecular Structure; Spectrophotometry - methods; Perturbation theory; Vibrational interaction; Correlation; Mode coupling; Reference; Wave function; Infrared absorption; Theoretical study; Configuration interaction; Algorithm; Perturbation method; Dynamics; Frequency; Resonance; SCF calculations
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/b719093j

A quasi-degenerate perturbation method with vibrational self-consistent field (VSCF) reference wavefunction is developed. It simultaneously accounts for strong anharmonic mode-mode coupling among a few states (static correlation) by a configuration interaction theory and for weak coupling with a vast number of the other states (dynamic correlation) by a perturbation theory. A general formula is derived based on the van Vleck perturbation theory. An algorithm that selects a compact set of the most important VSCF configurations which contribute to the static correlation is proposed and a scheme to limit the number of configurations considered for dynamic correlation is also implemented. This method reproduces the vibrational frequencies of CO2 and H2CO that are subject to the strongest anharmonic mode-mode coupling within 10 cm(-1) of vibrational configuration interaction results in a computational expense reduced by a factor of one to two orders of magnitude. The method also reproduces the infrared absorption of C6H6 in the CH stretching (nu12) frequency region, in which combination tones nu13nu16 and nu2nu13nu18 appear on account of an intensity borrowing from nu12via the anharmonic coupling.