Title

Anharmonic Vibrational Analysis of the Gas-Phase Infrared Spectrum of 1,1-Difluoroethylene Using the Operator Van Vleck Canonical Perturbation Theory

Abstract

Anharmonic vibration frequencies of 1,1-difluoroethylene (11DFE) in the gas phase are predicted by means of the numerical-analytic operator version of the canonical van Vleck perturbation theory in the second and fourth orders (CVPT2 and CVPT4). The full quartic and “semi-diagonal” sextic rectilinear normal coordinate potential energy surfaces, needed for CVPT2 and CVPT4, respectively, were obtained with the MP2/cc-pVTZ quantum-mechanical model. CVPT2 is superior to the traditional second-order vibrational perturbation theory approach (VPT2) because of the uniform general treatment of the Fermi and second-order Darling–Dennison resonances. The fourth-order version, CVPT4, provides a more refined solution and proves convergence of the perturbative treatment. Labeling of the basis functions by polyad numbers breaks down the infinite Hamiltonian matrix into a block-diagonal form. The polyad expression for 11DFE has been determined as P = 14(ν1 + ν7) + 8ν2 + 6(ν3 + ν8) + 4(ν4 + ν9) + 3(ν6 + ν11 + ν12) + 2(ν5 + ν10), where the νi are quantum numbers. The theoretical prediction of anharmonic infrared absorption intensities corroborated an assignment of the majority of observed gas-phase bands up to 3500 cm–1. The solution was refined by iteratively fitting harmonic frequencies, until predicted fundamental anharmonic frequencies matched the observed values. The average error for about 90 observed frequencies after fitting only fundamental frequencies is ∼1.05 cm–1. The fitted “semi-experimental” harmonic frequencies agree very well the quantum-mechanical predictions based on the CCSD(T)/cc-pVTZ and CCSD(T)/cc-pVQZ models.

Publisher

American Chemical Society

Publication Date

1-1-2013

Publication Title

Journal of Physical Chemistry A

Department

Chemistry and Biochemistry

Document Type

Article

DOI

10.1021/jp311398z

Keywords

Quartic force-field, Higher-derivative methods, Ab initio calculations, Polyatomic molecules

Language

English

Format

text

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