skip to main content

DOE PAGESDOE PAGES

Title: Communication: GAIMS—generalized ab initio multiple spawning for both internal conversion and intersystem crossing processes

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. Lastly, the results of two numerical applications, a model system and the deactivation of thioformaldehyde, validate the presented formalism and its implementation.
Authors:
 [1] ;  [2] ; ORCiD logo [2] ; ORCiD logo [2] ; ORCiD logo [1]
  1. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  2. Univ. of Vienna, Vienna (Austria)
Publication Date:
Grant/Contract Number:
AC02-76SF00515
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 10; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 74 ATOMIC AND MOLECULAR PHYSICS; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; non adiabatic dynamics; intersystem crossing; ab initio molecular dynamics; self organized systems; non adiabatic reactions; non adiabatic couplings; wave functions
OSTI Identifier:
1257515
Alternate Identifier(s):
OSTI ID: 1241425

Curchod, Basile F. E., Rauer, Clemens, Marquetand, Philipp, Gonzalez, Leticia, and Martinez, Todd J.. Communication: GAIMS—generalized ab initio multiple spawning for both internal conversion and intersystem crossing processes. United States: N. p., Web. doi:10.1063/1.4943571.
Curchod, Basile F. E., Rauer, Clemens, Marquetand, Philipp, Gonzalez, Leticia, & Martinez, Todd J.. 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., Rauer, Clemens, Marquetand, Philipp, Gonzalez, Leticia, and Martinez, Todd J.. 2016. "Communication: GAIMS—generalized ab initio multiple spawning for both internal conversion and intersystem crossing processes". United States. doi:10.1063/1.4943571. https://www.osti.gov/servlets/purl/1257515.
@article{osti_1257515,
title = {Communication: GAIMS—generalized ab initio multiple spawning for both internal conversion and intersystem crossing processes},
author = {Curchod, Basile F. E. and Rauer, Clemens and Marquetand, Philipp and Gonzalez, Leticia and Martinez, Todd J.},
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. Lastly, 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 = {2016},
month = {3}
}