Ring-polymer instanton theory of electron transfer in the nonadiabatic limit
arXiv:1508.05195 · doi:10.1063/1.4932362
Abstract
We take the golden-rule instanton method derived in the previous paper [arXiv:1509.04919] and reformulate it using a ring-polymer approach. This gives equations which can be used to compute the rates of electron-transfer reactions in the nonadiabatic (golden-rule) limit numerically within a semiclassical approximation. The multidimensional ring-polymer instanton trajectories are obtained efficiently by minimization of the action. In this form, comparison with Wolynes' quantum instanton method [P. G. Wolynes, J. Chem. Phys. 87, 6559 (1987)] is possible and we show that our semiclassical approach is the steepest-descent limit of this method. We discuss advantages and disadvantages of both methods and give examples of where the new approach is more accurate.
Submitted to the Journal of Chemical Physics. 10 pages, 1 figure
References in corpus (2)
Cited by in corpus (21)
- Derivation of instanton rate theory from first principles
- An analysis of nonadiabatic ring-polymer molecular dynamics and its application to vibronic spectra
- Spin-selective electron transfer reactions of radical pairs: beyond the Haberkorn master equation
- Analytic continuation of Wolynes theory into the Marcus inverted regime
- On the calculation of quantum mechanical electron transfer rates
- Partition-free approach to open quantum systems in harmonic environments: an exact stochastic Liouville equation
- Effects of tunnelling and asymmetry for system-bath models of electron transfer
- Nonadiabatic instanton rate theory beyond the golden-rule limit
- An analysis of isomorphic RPMD in the golden rule limit
- Nonadiabatic quantum transition-state theory in the golden-rule limit. I. Theory and application to model systems
- Nonadiabatic quantum transition-state theory in the golden-rule limit. II. Overcoming the pitfalls of the saddle-point and semiclassical approximations
- Calculation of Reaction Rate Constants in the Canonical and Microcanonical Ensemble
- Revisiting nuclear tunnelling in the aqueous ferrous-ferric electron transfer
- An improved path-integral method for golden-rule rates
- Multistate ring polymer instantons and nonadiabatic reaction rates
- A general non-adiabatic quantum instanton approximation
- Semiclassical instanton theory for reaction rates at any temperature: How a rigorous real-time derivation solves the crossover temperature problem
- Divide-and-Conquer Method for Instanton Rate Theory
- Evaluation of transition rates from nonequilibrium instantons
- Extending non-adiabatic rate theory to strong electronic couplings in the Marcus inverted regime
- Instanton Theory for Nonadiabatic Tunneling through Near-Barrier Crossings