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 makes available to the user a large panel of quantum chemistry models, for both isolated and condensed phases. The flexibility and reliability of the new framework are illustrated by some case studies, covering various types of LAMs, ranging from a small test case, the photoelectron spectrum of ammonia, to larger systems, such as phenylanthracene and cyclobutanone.

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

Baiardi, Alberto;Bloino, Julien;Barone, Vincenzo
2017

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 makes available to the user a large panel of quantum chemistry models, for both isolated and condensed phases. The flexibility and reliability of the new framework are illustrated by some case studies, covering various types of LAMs, ranging from a small test case, the photoelectron spectrum of ammonia, to larger systems, such as phenylanthracene and cyclobutanone.
2017
Computer Science Applications1707 Computer Vision and Pattern Recognition; Physical and Theoretical Chemistry
File in questo prodotto:
Non ci sono file associati a questo prodotto.

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11384/75950
 Attenzione

Attenzione! I dati visualizzati non sono stati sottoposti a validazione da parte dell'ateneo

Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 37
  • ???jsp.display-item.citation.isi??? 36
social impact