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A novel and readily understandable derivation of the Golden Rule of time dependent perturbation theory is presented. The derivation is based on adiabatic turning on of the perturbation as used, for instance, in some formal developments of…

Quantum Physics · Physics 2020-06-24 M G Burt

The energy evolution of a quantum chaotic system under the perturbation that harmonically depends on time is studied for the case of large perturbation, in which the rate of transition calculated from the Fermi golden rule (FGR) is about or…

Chaotic Dynamics · Physics 2007-05-23 P. V. Elyutin , A. N. Rubtsov

A model is proposed for studying the reaction dynamics in complex quantum systems in which the complete mixing of states is hindered by an internal barrier. Such systems are often treated by the transition-state theory, also known in…

Quantum Physics · Physics 2021-11-03 G. F. Bertsch , K. Hagino

The quantum instanton approximation is a type of quantum transition state theory that calculates the chemical reaction rate using the reactive flux correlation function and its low order derivatives at time zero. Here we present several…

Chemical Physics · Physics 2009-11-11 Sandy Yang , Takeshi Yamamoto , William H. Miller

A sampling procedure to compute exactly the rate of activated processes arising in systems at equilibrium or nonequilibrium steady state is presented. The procedure is a generalization of the method in [A. Warmflash, P. Bhimalapuram, and A.…

Computational Physics · Physics 2009-04-27 Eric Vanden-Eijnden , Maddalena Venturoli

The Wolynes theory of electronically nonadiabatic reaction rates [P. G. Wolynes, J. Chem. Phys. 87, 6559 (1987)] is based on a saddle point approximation to the time integral of a reactive flux autocorrelation function in the nonadiabatic…

Chemical Physics · Physics 2017-10-31 Joseph E. Lawrence , David E. Manolopoulos

We apply the functional renormalization group (FRG) method to calculate the conductance of a quantum dot in the Kondo regime. Starting from the exact FRG equations in Keldysh formulation for the Kondo exchange Hamiltonian in pseudo-fermion…

Strongly Correlated Electrons · Physics 2015-10-28 Holger Schmidt , Peter Woelfle

We develop a Gaussian process regression enhanced line integral string method to accelerate ring polymer instanton calculations of tunneling rates and tunneling splittings in molecular proton transfer reactions. By exploiting uncertainty…

Chemical Physics · Physics 2026-02-20 Chenghao Zhang , Amke Nimmrich , Axel Gomez , Munira Khalil , Niranjan Govind

Marcus-Levich-Jortner (MLJ) theory is one of the most commonly used methods for including nuclear quantum effects into the calculation of electron-transfer rates and for interpreting experimental data. It divides the molecular problem into…

Chemical Physics · Physics 2020-10-29 Eric R. Heller , Jeremy O. Richardson

We present a Gedankenexperiment that leads to a violation of detailed balance if quantum mechanical transition probabilities are treated in the usual way by applying Fermi's "golden rule". This Gedankenexperiment introduces a collection of…

Quantum Physics · Physics 2020-09-21 Daniel Braak , Jochen Mannhart

We present a new method for calculating quantum tunneling rates using lattice Monte Carlo simulations in imaginary time. This method is designed with the goal of studying false vacuum decay non-perturbatively on the lattice. We derive a new…

High Energy Physics - Lattice · Physics 2026-03-03 Luchang Jin , Joshua Swaim

It was shown recently that there exists a true quantum transition-state theory (QTST) corresponding to the t->0+ limit of a (new form of) quantum flux-side time-correlation function. Remarkably, this QTST is identical to ring-polymer…

Chemical Physics · Physics 2013-09-05 Timothy J. H. Hele , Stuart C. Althorpe

Fermi's golden rule applies to a situation in which a single quantum state $|\psi\rangle$ is coupled to a near-continuum. This "quasi-continuum coupling" structure results in a rate equation for the population of $|\psi\rangle$. Here we…

Quantum Physics · Physics 2017-11-30 Siddhartha Santra , Benjamin Cruikshank , Radhakrishnan Balu , Kurt Jacobs

In this work, we use path integral techniques to predict the switching rate in a single-mode bistable open quantum system. While analytical expressions are well-known to be accessible for systems subject to Gaussian noise obeying classical…

Many-body states described by a Schr\"{o}dinger equation include states of overlapping waves of non-vanishing interaction energies. These peculiar states formed in many-body transitions remain in asymptotic regions, and lead a new component…

High Energy Physics - Phenomenology · Physics 2020-06-24 Kenzo Ishikawa , Yutaka Tobita

We present a new method for the numerical calculation of canonical reaction rate constants in complex molecular systems, which is based on a path integral formulation of the flux-flux correlation function. Central is the partitioning of the…

Chemical Physics · Physics 2011-11-15 Yonggang Yang , Oliver Kühn

It is well known that the electron transfer (ET) reaction in donor-bridge-acceptor systems is much influenced by the bridge conformational changes. However, the importance of the dynamical contribution to the ET rate is still under debate.…

Chemical Physics · Physics 2009-03-31 Kazuhiro Tsusaka

A simple quantum mechanical model consisting of a discrete level resonantly coupled to a continuum of finite width, where the coupling can be varied from perturbative to strong (Fano-Anderson model), is considered. The particle is initially…

Quantum Physics · Physics 2019-02-19 E. Kogan

We introduce a new Forward-Flux Sampling in Time (FFST) algorithm to efficiently measure transition times in rare-event processes in non-equilibrium systems, and apply it to study the first-order (discontinuous) kinetic transition in the…

Statistical Mechanics · Physics 2015-05-19 David A. Adams , Robert M. Ziff , Leonard M. Sander

The Gr\"uneisen ratio $\Gamma$, i.e., the singular part of the ratio of thermal expansion to the specific heat, has been broadly employed to explore both finite-$T$ and quantum critical points (QCPs). For a genuine quantum phase transition…