Simulation of Vibronic Spectra of Flexible Systems: Hybrid DVR-Harmonic Approaches.

ABSTRACT: Our general framework for the simulation of vibrational signatures in electronic spectra has been extended to treat one large-amplitude motion (LAM) at the anharmonic level, coupled to the other small-amplitude motions (SAM) treated as harmonic. The coupling between LAM and SAM is minimized thanks to the use of delocalized internal coordinates, which are built automatically from the molecular topology. General LAMs can be employed, ranging from intrinsic reaction coordinates to rigid or flexible paths based on the distinguished coordinate approach. The anharmonic model is based on a fully numerical method based on the discrete variable representation (DVR) theory, supporting different types of boundary conditions. The inclusion of this model in a general-purpose electronic structure code m

SUBMITTER: Baiardi A 

PROVIDER: S-EPMC5732573 | biostudies-literature | 2017 Jun

REPOSITORIES: biostudies-literature