Rapid anharmonic vibrational corrections derived from partial Hessian analysis

Abstract

Vibrational analysis within a partial Hessian framework can successfully describe the vibrational properties of a variety of systems where the vibrational modes of interest are localized within a specific region of the system. We have developed a new approach to calculating anharmonic frequencies based on vibrational frequencies and normal modes obtained from a partial Hessian analysis using second-order vibrational perturbation theory and the transition optimized shifted Hermite method. This allows anharmonic frequencies for vibrational modes that are spatially localized to be determined at a significantly reduced computational cost. Several molecular systems are examined in order to demonstrate the effectiveness of this method including organic molecules adsorbed on the Si(100)-2×1 surface, model peptides in solution, and the C-H stretching region of polycyclic aromatic hydrocarbons. Overall, for a range of systems, anharmonic frequencies calculated using the partial Hessian approach are found to be in close agreement with the results obtained using full anharmonic calculations while providing a significant reduction in computational cost.