Rovibrational states of Ar-HCN van der Waals complex: A localized representation calculation

M. Mladenović, Zlatko Bacic

Research output: Contribution to journalArticle

Abstract

All bound rovibrational states of Ar-HCN and Ar-DCN van der Waals complexes for J = 0-10 are calculated, assuming frozen HCN (DCN). The calculations are performed using the recently developed approach for accurate and efficient computation of highly excited rovibrational states of floppy triatomic molecules [M. Mladenovic and Z. Bacic, J. Chem. Phys. 93, 3039 (1990)]. Matrix representation of the Hamiltonian in body-fixed Jacobi coordinates is formed by combining the discrete variable representation of the angular coordinate and distributed Gaussian basis for the radial degree of freedom. The coupled low-frequency large amplitude vibrations are treated accurately, without any dynamical approximation. Model 2-D (R,θ) potential surface by Dykstra, having two minima at collinear Ar-HCN and Ar-NCH geometries, is employed. Besides energy levels and wave functions, for each state we calculate expectation values of Jacobi coordinates, 〈R〉 and 〈θ〉, degree of wave function delocalization, and effective rotational constants (for some states). Majority of states of Ar-H/DCN are delocalized over both potential minima. Comparison is made with available experimental data and possible refinements of the present potential surface are briefly discussed.

Original languageEnglish (US)
Pages (from-to)4988-5003
Number of pages16
JournalThe Journal of chemical physics
Volume94
Issue number7
StatePublished - 1991

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Wave functions
Hamiltonians
Excited states
wave functions
Electron energy levels
triatomic molecules
Molecules
Geometry
degrees of freedom
energy levels
low frequencies
vibration
matrices
geometry
approximation
excitation

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Rovibrational states of Ar-HCN van der Waals complex : A localized representation calculation. / Mladenović, M.; Bacic, Zlatko.

In: The Journal of chemical physics, Vol. 94, No. 7, 1991, p. 4988-5003.

Research output: Contribution to journalArticle

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