First-principles calculations on anharmonic vibrational frequencies of polyethylene and polyacetylene in the approximation

The frequencies of the infrared- and/or Raman-active (k=0) vibrations of polyethylene and polyacetylene are computed by taking account of the anharmonicity in the potential energy surfaces (PESs) and the resulting phonon-phonon couplings explicitly. The electronic part of the calculations is based on Gaussian-basis-set crystalline orbital theory at the Hartree-Fock and second-order Møller-Plesset (MP2) perturbation levels, providing one-, two-, and/or three-dimensional slices of the PES (namely, using the so-called n -mode coupling approximation with n=3), which are in turn expanded in the fourth-order Taylor series with respect to the normal coordinates. The vibrational part uses the vibrational self-consistent field, vibrational MP2, and vibrational truncated configuration-interaction (VCI) methods within the approximation, which amounts to including only k=0 phonons. It is shown that accounting for both electron correlation and anharmonicity is essential in achieving good agreement (the mean and maximum absolute deviations less than 50 and 90 cm-1, respectively, for polyethylene and polyacetylene) between computed and observed frequencies. The corresponding values for the calculations including only one of such effects are in excess of 120 and 300 cm-1, respectively. The VCI calculations also reproduce semiquantitatively the frequency separation and intensity ratio of the Fermi doublet involving the V₂ (0) fundamental and V₈ (π ) first overtone in polyethylene.