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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.
 [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:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 10; Journal ID: ISSN 0021-9606
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
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:
Alternate Identifier(s):
OSTI ID: 1241425