Comparing the accuracy of perturbative and variational calculations for predicting fundamental vibrational frequencies of dihalomethanes

The Journal of Chemical Physics
Sergey V KrasnoshchekovDeborah L Crittenden

Abstract

Three dihalogenated methane derivatives (CH2F2, CH2FCl, and CH2Cl2) were used as model systems to compare and assess the accuracy of two different approaches for predicting observed fundamental frequencies: canonical operator Van Vleck vibrational perturbation theory (CVPT) and vibrational configuration interaction (VCI). For convenience and consistency, both methods employ the Watson Hamiltonian in rectilinear normal coordinates, expanding the potential energy surface (PES) as a Taylor series about equilibrium and constructing the wavefunction from a harmonic oscillator product basis. At the highest levels of theory considered here, fourth-order CVPT and VCI in a harmonic oscillator basis with up to 10 quanta of vibrational excitation in conjunction with a 4-mode representation sextic force field (SFF-4MR) computed at MP2/cc-pVTZ with replacement CCSD(T)/aug-cc-pVQZ harmonic force constants, the agreement between computed fundamentals is closer to 0.3 cm-1 on average, with a maximum difference of 1.7 cm-1. The major remaining accuracy-limiting factors are the accuracy of the underlying electronic structure model, followed by the incompleteness of the PES expansion. Nonetheless, computed and experimental fundamentals agree to w...Continue Reading

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Citations

Jul 2, 2018·The Journal of Chemical Physics·Alexei A Kananenka, J L Skinner
Sep 24, 2020·Physical Chemistry Chemical Physics : PCCP·Arman Nejad, Deborah L Crittenden

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