Critical evaluation of anharmonic corrections to the equilibrium isotope effect for methyl cation transfer from vacuum to dielectric continuum

Abstract

Harmonic and anharmonic vibrational frequencies are computed for isotopologues of methyl cation in vacuum and in apolarised continuum model (PCM) dielectric continuum (ϵ = 80) within Gaussian09. Comparison of results in vacuum for two methods (B3LYP and second-order Møller–Plesset perturbation theory) and three basis sets (6-31+G(d), cc-aug-PVDZ, cc-aug-PVQZ) with published anharmonic frequencies obtained from an accurate vibrational configuration interaction (VCI) method shows the smallest root mean square error in the frequencies from B3LYP/6-31+G(d) with anharmonic corrections. Using this method to calculate isotopic partition function ratios (IPFRs) for all six pairs of CH3+, CH2D+, CHD2+ and CD3+ gives better results for anharmonic frequencies than for unscaled harmonic frequencies, but scaled harmonic frequencies give even better results for less cost. The scaling factor is simply the ratio of the sum of the anharmonic VCI frequencies to the sum of the harmonic B3LYP/6-31+G(d) frequencies, which corresponds to the dominance of zero-point energy changes in determining the IPFRs. Both the scaled and unscaled harmonic frequencies provide reasonable estimates for the equilibrium isotope effects (EIEs) upon transfer of methyl cation from vacuum to PCM ‘water’, but the anharmonic PCM calculations give erratic results. The use of scaled B3LYP/6-31+G(d) harmonic frequencies is recommended for the estimations of EIEs rather than expensive anharmonic corrections.