Document Detail

Kinetically constrained ring-polymer molecular dynamics for non-adiabatic chemical reactions.
MedLine Citation:
PMID:  24527896     Owner:  NLM     Status:  In-Data-Review    
We extend ring-polymer molecular dynamics (RPMD) to allow for the direct simulation of general, electronically non-adiabatic chemical processes. The kinetically constrained (KC) RPMD method uses the imaginary-time path-integral representation in the set of nuclear coordinates and electronic states to provide continuous equations of motion that describe the quantized, electronically non-adiabatic dynamics of the system. KC-RPMD preserves the favorable properties of the usual RPMD formulation in the position representation, including rigorous detailed balance, time-reversal symmetry, and invariance of reaction rate calculations to the choice of dividing surface. However, the new method overcomes significant shortcomings of position-representation RPMD by enabling the description of non-adiabatic transitions between states associated with general, many-electron wavefunctions and by accurately describing deep-tunneling processes across asymmetric barriers. We demonstrate that KC-RPMD yields excellent numerical results for a range of model systems, including a simple avoided-crossing reaction and condensed-phase electron-transfer reactions across multiple regimes for the electronic coupling and thermodynamic driving force.
Artur R Menzeleev; Franziska Bell; Thomas F Miller
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Publication Detail:
Type:  Journal Article    
Journal Detail:
Title:  The Journal of chemical physics     Volume:  140     ISSN:  1089-7690     ISO Abbreviation:  J Chem Phys     Publication Date:  2014 Feb 
Date Detail:
Created Date:  2014-02-17     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  0375360     Medline TA:  J Chem Phys     Country:  United States    
Other Details:
Languages:  eng     Pagination:  064103     Citation Subset:  IM    
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