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Title: Communication: GAIMS—Generalized Ab Initio Multiple Spawning for both internal conversion and intersystem crossing processes

Abstract

Full multiple spawning is a formally exact method to describe the excited-state dynamics of molecular systems beyond the Born-Oppenheimer approximation. However, it has been limited until now to the description of radiationless transitions taking place between electronic states with the same spin multiplicity. This Communication presents a generalization of the full and ab initio multiple spawning methods to both internal conversion (mediated by nonadiabatic coupling terms) and intersystem crossing events (triggered by spin-orbit coupling matrix elements) based on a spin-diabatic representation. The results of two numerical applications, a model system and the deactivation of thioformaldehyde, validate the presented formalism and its implementation.

Authors:
;  [1];  [2]; ; ;  [3]
  1. Department of Chemistry and the PULSE Institute, Stanford University, Stanford, California 94305 (United States)
  2. (United States)
  3. Institute of Theoretical Chemistry, University of Vienna, Währinger Straße 17, 1090 Vienna (Austria)
Publication Date:
OSTI Identifier:
22660769
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 144; Journal Issue: 10; Other Information: (c) 2016 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
73 NUCLEAR PHYSICS AND RADIATION PHYSICS; BORN-OPPENHEIMER APPROXIMATION; EXCITED STATES; INTERNAL CONVERSION; L-S COUPLING; MATRIX ELEMENTS; MULTIPLICITY; RADIATIONLESS DECAY

Citation Formats

Curchod, Basile F. E., Martínez, Todd J., E-mail: toddjmartinez@gmail.com, SLAC National Accelerator Laboratory, Menlo Park, California 94025, Rauer, Clemens, Marquetand, Philipp, and González, Leticia. Communication: GAIMS—Generalized Ab Initio Multiple Spawning for both internal conversion and intersystem crossing processes. United States: N. p., 2016. Web. doi:10.1063/1.4943571.
Curchod, Basile F. E., Martínez, Todd J., E-mail: toddjmartinez@gmail.com, SLAC National Accelerator Laboratory, Menlo Park, California 94025, Rauer, Clemens, Marquetand, Philipp, & González, Leticia. Communication: GAIMS—Generalized Ab Initio Multiple Spawning for both internal conversion and intersystem crossing processes. United States. doi:10.1063/1.4943571.
Curchod, Basile F. E., Martínez, Todd J., E-mail: toddjmartinez@gmail.com, SLAC National Accelerator Laboratory, Menlo Park, California 94025, Rauer, Clemens, Marquetand, Philipp, and González, Leticia. Mon . "Communication: GAIMS—Generalized Ab Initio Multiple Spawning for both internal conversion and intersystem crossing processes". United States. doi:10.1063/1.4943571.
@article{osti_22660769,
title = {Communication: GAIMS—Generalized Ab Initio Multiple Spawning for both internal conversion and intersystem crossing processes},
author = {Curchod, Basile F. E. and Martínez, Todd J., E-mail: toddjmartinez@gmail.com and SLAC National Accelerator Laboratory, Menlo Park, California 94025 and Rauer, Clemens and Marquetand, Philipp and González, Leticia},
abstractNote = {Full multiple spawning is a formally exact method to describe the excited-state dynamics of molecular systems beyond the Born-Oppenheimer approximation. However, it has been limited until now to the description of radiationless transitions taking place between electronic states with the same spin multiplicity. This Communication presents a generalization of the full and ab initio multiple spawning methods to both internal conversion (mediated by nonadiabatic coupling terms) and intersystem crossing events (triggered by spin-orbit coupling matrix elements) based on a spin-diabatic representation. The results of two numerical applications, a model system and the deactivation of thioformaldehyde, validate the presented formalism and its implementation.},
doi = {10.1063/1.4943571},
journal = {Journal of Chemical Physics},
number = 10,
volume = 144,
place = {United States},
year = {Mon Mar 14 00:00:00 EDT 2016},
month = {Mon Mar 14 00:00:00 EDT 2016}
}