An analysis of model proton-coupled electron transfer reactions via the mixed quantum-classical Liouville approach

Journal Article · Mon Jul 28 04:00:00 EDT 2014 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4890915· OSTI ID:22419924

Shakib, Farnaz A.; Hanna, Gabriel ^[1]

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1. Department of Chemistry, University of Alberta, Edmonton, Alberta AB T6G 2G2 (Canada)

The nonadiabatic dynamics of model proton-coupled electron transfer (PCET) reactions is investigated for the first time using a surface-hopping algorithm based on the solution of the mixed quantum-classical Liouville equation (QCLE). This method provides a rigorous treatment of quantum coherence/decoherence effects in the dynamics of mixed quantum-classical systems, which is lacking in the molecular dynamics with quantum transitions surface-hopping approach commonly used for simulating PCET reactions. Within this approach, the protonic and electronic coordinates are treated quantum mechanically and the solvent coordinate evolves classically on both single adiabatic surfaces and on coherently coupled pairs of adiabatic surfaces. Both concerted and sequential PCET reactions are studied in detail under various subsystem-bath coupling conditions and insights into the dynamical principles underlying PCET reactions are gained. Notably, an examination of the trajectories reveals that the system spends the majority of its time on the average of two coherently coupled adiabatic surfaces, during which a phase enters into the calculation of an observable. In general, the results of this paper demonstrate the applicability of QCLE-based surface-hopping dynamics to the study of PCET and emphasize the importance of mean surface evolution and decoherence effects in the calculation of PCET rate constants.

• OSTI ID: 22419924
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 4 Vol. 141; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
BOLTZMANN-VLASOV EQUATION
COUPLING
ELECTRON TRANSFER
MOLECULAR DYNAMICS METHOD
PROTONS
REACTION KINETICS
SOLUTIONS
SOLVENTS
SURFACES