Local Bond-Stretch Coordinates for Anharmonic Vibrational Computations.

IF 2.7 2区化学 Q3 CHEMISTRY, PHYSICAL

The Journal of Physical Chemistry A Pub Date : 2025-04-02 DOI:10.1021/acs.jpca.4c07704

Sebastian Riis Thomsen, Nicolai Machholdt Høyer, Mads Greisen Højlund, Ove Christiansen

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引用次数: 0

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.

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来源期刊

The Journal of Physical Chemistry A 化学-物理：原子、分子和化学物理

CiteScore

5.20

自引率

10.30%

发文量

922

审稿时长

1.3 months

期刊介绍： The Journal of Physical Chemistry A is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.