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We propose a new quantum transition-state theory for calculating Fermi's golden-rule rates in complex multidimensional systems. This method is able to account for the nuclear quantum effects of delocalization, zero-point energy and…

Chemical Physics · Physics 2019-03-27 Manish J. Thapa , Wei Fang , Jeremy O. Richardson

We present semiclassical approximations to Green's functions of multidimensional systems, extending Gutzwiller's work to the classically forbidden region. Based on steepest-descent integrals over these functions, we derive an instanton…

Chemical Physics · Physics 2015-10-08 Jeremy O. Richardson , Rainer Bauer , Michael Thoss

We present a consistent theory of energy balance and conversion in a single-molecule junction with strong interactions between electrons on the molecular linker (dot) and phonons in the nuclear environment where the Marcus-type electron…

Mesoscale and Nanoscale Physics · Physics 2020-01-22 Natalya A. Zimbovskaya , Abraham Nitzan

An elementary excitation in an aggregate of coupled particles generates a collective excited state. We show that the dynamics of these excitations can be controlled by applying a transient external potential which modifies the phase of the…

Quantum Physics · Physics 2013-06-14 Ping Xiang , Marina Litinskaya , Evgeny A. Shapiro , Roman V. Krems

The effect of solvation on the electron transfer (ET) rate processes is investigated on the basis of the exact theory constructed in J. Phys. Chem. B Vol. 110, (2006); quant-ph/0604071. The nature of solvation is studied in a close relation…

Chemical Physics · Physics 2007-05-23 Ping Han , Rui-Xue Xu , Ping Cui , Yan Mo , Guozhong He , YiJing Yan

Thermoelectric energy conversion is perhaps the most promising of the potential applications of molecular electronics. Ultimately, it is desirable for this technology to operate at around room temperature, and it is therefore important to…

Mesoscale and Nanoscale Physics · Physics 2020-06-30 Jakub K. Sowa , Jan A. Mol. Erik M. Gauger

Based on a true phase space probability distribution function and an ensemble averaging procedure we have recently developed [Phys. Rev. E 65, 021109 (2002)] a non-Markovian quantum Kramers' equation to derive the quantum rate coefficient…

Statistical Mechanics · Physics 2009-11-07 Dhruba Banerjee , Suman Kumar Banik , Bidhan Chandra Bag , Deb Shankar Ray

The interaction between molecular (atomic) electron(s) and the vacuum field of a reflective cavity generates a significant interest thanks to the rapid developments in nanophotonics. Such interaction which lies within the realm of cavity…

Chemical Physics · Physics 2019-05-22 Alexander Semenov , Abraham Nitzan

The complex amplitudes of the electronic wavefunctions on different sites are used as Kramers variables for describing Electron Transfer. The strong coupling of the electronic charge to the many nuclei, ions, dipoles, etc, of the…

Condensed Matter · Physics 2009-11-07 S. Aubry , G. Kopidakis

Although Marcus theory is widely used to describe charge transfer in molecular systems, in its usual form it is restricted to transfer from one molecule to another. If a charge is delocalised across multiple donor molecules, this approach…

Chemical Physics · Physics 2019-11-28 Natasha B. Taylor , Ivan Kassal

We examine the impact of the intrinsic molecular reorganization energy on switching in two-state quantum-dot cellular automata (QCA) cells. Switching a bit involves an electron transferring between charge centers within the molecule. This…

Quantum Physics · Physics 2022-03-31 Subhash S. Pidaparthi , Craig S. Lent

Electron transfer processes in Debye solvents are studied using a spectral analysis method recently proposed. Spectral structure of a nonadiabatic two-state diffusion equation is investigated to reveal various kinetic regimes characterized…

Statistical Mechanics · Physics 2009-11-07 YounJoon Jung , Jianshu Cao

Utilization of electron transfer methods for description of quantum transport is popular due to simplicity of the formulation and its ability to account for basic physics of electron exchange between system and baths. At the same time,…

Mesoscale and Nanoscale Physics · Physics 2019-09-05 Nicolas Bergmann , Michael Galperin

We present a state-space-based path integral method to calculate the rate of electron transfer (ET) in multi-state, multi-electron condensed-phase processes. We employ an exact path integral in discrete electronic states and continuous…

Chemical Physics · Physics 2016-06-07 Jessica Ryan Duke , Nandini Ananth

We present a novel {\em ab initio} approach for computing intramolecular charge and energy transfer rates based upon a projection operator scheme that parses out specific internal nuclear motions that accompany the electronic transition.…

Materials Science · Physics 2016-12-22 Xummo Yang , Eric R. Bittner

The crossover from nonadiabatic to adiabatic electron transfer has been theoretically studied under a spin-boson model (dissipative two-state system) description. We present numerically exact data for the thermal transfer rate and the…

Condensed Matter · Physics 2009-11-07 L. Muehlbacher , R. Egger

We study nonadiabatic electron transfer within the biased spin-boson model. We calculate the incoherent transfer rate in analytic form at all temperatures for a power law form of the spectral density of the solvent coupling. In the Ohmic…

Statistical Mechanics · Physics 2009-10-31 G. Lang , E. Paladino , U. Weiss

Marcus--Hush theory explains electron transfer in terms of reorganization energies, driving forces, electronic couplings, and reduced free-energy or energy-gap descriptions. These descriptions do not by themselves determine when the…

Chemical Physics · Physics 2026-05-19 Stephen Wiggins

Energy transfer during molecular collisions on metal surfaces plays a pivotal role in a host of critical interfacial processes. Despite significant efforts, our understanding of relevant energy transfer mechanisms, even in an…

Chemical Physics · Physics 2025-03-24 Gang Meng , Bin Jiang

Quantum rate theory encompasses the electron-transfer rate constant concept of electrochemical reactions as a particular setting, besides demonstrating that the electrodynamics of these reactions obey relativistic quantum mechanical rules.…