A revised formulation of the generalized subsystem vibrational analysis (GSVA)

Yunwen Tao; Wenli Zou; Sadisha Nanayakkara; Marek Freindorf; Elfi Kraka

doi:10.1007/s00214-021-02727-y

A revised formulation of the generalized subsystem vibrational analysis (GSVA)

Theor Chem Acc. 2021;140(3):31. doi: 10.1007/s00214-021-02727-y. Epub 2021 Mar 9.

Authors

Yunwen Tao¹, Wenli Zou², Sadisha Nanayakkara¹, Marek Freindorf¹, Elfi Kraka¹

Affiliations

¹ Department of Chemistry, Southern Methodist University, 3215 Daniel Ave, Dallas, TX 75275-0314 USA.
² Institute of Modern Physics, Northwest University, and Shaanxi Key Laboratory for Theoretical Physics Frontiers, Xi'an, 710127 Shaanxi People's Republic of China.

Abstract

In this work, a simplified formulation of our recently developed generalized subsystem vibrational analysis (GSVA) for obtaining intrinsic fragmental vibrations (J Chem Theory Comput 14:2558, 2018) is presented. In contrast to the earlier implementation, which requires the explicit definition of a non-redundant set of internal coordinate parameters to be constructed for the subsystem, the new implementation circumvents this process by employing massless Eckart conditions to the subsystem fragment paired with a Gram-Schmidt orthogonalization to span the same internal vibration space indirectly. This revised version of GSVA (rev-GSVA) can be applied to equilibrium structure as well as transition state structure, and it has been incorporated into the open-source package UniMoVib (https://github.com/zorkzou/UniMoVib).

Supplementary information: The online version contains supplementary material available at 10.1007/s00214-021-02727-y.

Keywords: GSVA; Harmonic approximation; Normal mode analysis; Subsystem; UniMoVib; Vibrational spectroscopy.