Direct calculation of anharmonic vibrational states of polyatomic molecules using potential energy surfaces calculated from density functional theory

Abstract

Potential energy surface points computed from variants of density functional theory (DFT) are used to calculate directly the anharmonic vibrational frequencies of H2O, Cl−H2O, and (H2O)2. The method is an adaptation to DFT of a recent algorithm for direct calculations of anharmonic vibrational frequencies using ab initio electronic structure codes. The DFT calculations are performed using the BLYP and the B3LYP functionals and the results are compared with experiment, and also with those calculated directly from a potential energy surface obtained using ab initio Möller-Plesset second–order perturbation theory (MP2). The direct calculation of the vibrational states from the potential energy points is performed using the correlation-corrected vibrational self-consistent field (CC-VSCF) method. This method includes anharmonicity and correlations between different vibrational modes. The accuracy of this method is examined and it is shown that for the experimentally measured transitions the errors in the CC-VSCF calculations are much less than the errors due to the potential energy surface. By comparison with the experimentally measured frequencies the CC-VSCF method thus provides a test for the quality of the potential energy surfaces. The results obtained with the B3LYP functional, in contrast to those of the BLYP functional, are of comparable quality to those obtained with MP2. The B3LYP anharmonic frequencies are in good agreement with experiment, showing this DFT method describes well the anharmonic part of the potential energy surface. The BLYP results systematically underestimate both the harmonic and anharmonic frequencies and indicate that using this functional for the description of hydrogen-bonded systems may cause significant errors.