Local Bond-Stretch Coordinates for Anharmonic Vibrational Computations.

Abstract

The local bond-stretch (LBS) method is presented as a means of obtaining a set of localized, rectilinear vibrational modes. Three variants of the LBS method are considered: pure LBS, projected LBS (pLBS), and orthogonal, projected LBS (opLBS). These variants feature different degrees of localization and different coupling terms in the kinetic energy operator, such that the most localized method (LBS) has the largest number and magnitude of coupling terms, and the least localized (opLBS) has the least coupling terms. The different LBS variants are exemplified in computations on overtone vibrational spectra of water, nitroxyl (chemical formula HNO), formaldehyde, and 1,3-butadiene computed with a vibrational coupled cluster band Lanczos approach. These spectra are calculated using potential energy surfaces (PESs) obtained with the adaptive density-guided approach (ADGA). We observe faster convergence with respect to the coupling level in the PES when using the LBS variants compared to normal coordinates. Among the LBS variants, pLBS and opLBS appear most promising.