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Instantons, semi-classical trajectories of quantum tunneling in imaginary time, have long been used to study thermodynamic and transport properties in a myriad of condensed matter and high energy systems. A recent experiment in…

The accuracy of rate constants calculated using transition state theory depends crucially on the correct identification of a recrossing--free dividing surface. We show here that it is possible to define such optimal dividing surface in…

Microcanonical instanton theory offers the promise of providing rate constants for chemical reactions including quantum tunneling of atoms over the whole temperature range. We discuss different rate expressions, which require the…

Chemical Physics · Physics 2020-09-09 Sean R. McConnell , Andreas Löhle , Johannes Kästner

For the system with one-dimensional spatially periodic potential we demonstrate that small periodic in time perturbation results in appearance of chaotic instanton solutions. We estimate parameter of local instability, width of stochastic…

Chaotic Dynamics · Physics 2009-11-10 V. I. Kuvshinov , A. V. Kuzmin , R. G. Shulyakovsky

Chaotic instanton approach allows to describe analytically the influence of the polychromatic perturbation on quantum properties of nonlinear systems. Double well system with single, multiple and polychromatic kicked perturbation is…

Chaotic Dynamics · Physics 2011-01-04 V. I. Kuvshinov , A. V. Kuzmin , V. A. Piatrou

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

Semi-classical analysis is used to investigate synchronous quantum tunneling in a multidimensional potential energy surface (PES) characterized by four degenerate minima, serving as a foundational model for coupled vibrational modes. The…

Quantum Physics · Physics 2026-05-19 Pervez Hoodbhoy , M. Haashir Ismail , M. Mufassir

Adaptive perturbation is a new method for perturbatively computing the eigenvalues and eigenstates of quantum mechanical Hamiltonians that heretofore were not believed to be obtainable by such methods. The novel feature of adaptive…

High Energy Physics - Theory · Physics 2007-05-23 Marvin Weinstein

A trivial flaw in the utilization of artificial neural networks in interpolating chemical potential energy surfaces (PES) whose descriptors are Cartesian coordinates is their dependence on simple translations and rotations of the molecule…

Chemical Physics · Physics 2020-09-15 Sean R. McConnell , Johannes Kästner

Equilibrium rate theories play a crucial role in understanding rare, reactive events. However, they are inapplicable to a range of irreversible processes in systems driven far from thermodynamic equilibrium like active and biological…

Statistical Mechanics · Physics 2025-10-21 Eric R. Heller , David T. Limmer

Fermi's golden rule defines the transition rate between weakly coupled states and can thus be used to describe a multitude of molecular processes including electron-transfer reactions and light-matter interaction. However, it can only be…

Chemical Physics · Physics 2020-03-03 Eric R. Heller , Jeremy O. Richardson

Path integral molecular dynamics simulations, combined with an ab initio evaluation of interactions using electronic structure theory, incorporate the quantum mechanical nature of both the electrons and nuclei, which are essential to…

Chemical Physics · Physics 2016-02-15 Ondrej Marsalek , Thomas E. Markland

The interplay of quantum and classical fluctuations in the vicinity of a quantum critical point (QCP) gives rise to various regimes or phases with distinct quantum character. In this work, we show that the R\'enyi entropy is a precious tool…

Statistical Mechanics · Physics 2023-12-29 Miha Srdinšek , Michele Casula , Rodolphe Vuilleumier

The use of ring polymer molecular dynamics (RPMD) for the direct simulation of electron transfer (ET) reaction dynamics is analyzed in the context of Marcus theory, semiclassical instanton theory, and exact quantum dynamics approaches. For…

Statistical Mechanics · Physics 2011-08-19 Artur R. Menzeleev , Nandini Ananth , Thomas F. Miller

We investigate how to reliably remove unwanted global phase windings in gain-based optical oscillator networks, thereby ensuring convergence to the true synchronized configuration corresponding to the XY Hamiltonian's global minimum.…

Optics · Physics 2025-05-08 Richard Zhipeng Wang , Natalia G. Berloff

The strong enhancement of tunneling couplings typically observed in tunneling splittings in the quantum map is investigated. We show that the transition from instanton to noninstanton tunneling, which is known to occur in tunneling…

Mesoscale and Nanoscale Physics · Physics 2024-02-20 Yasutaka Hanada , Kensuke S. Ikeda , Akira Shudo

Adaptive perturbation is a new method for perturbatively computing the eigenvalues and eigenstates of quantum mechanical Hamiltonians that are widely believed not to be solvable by such methods. The novel feature of adaptive perturbation…

High Energy Physics - Theory · Physics 2008-11-26 Marvin Weinstein

We revisit the path integral description of quantum tunneling and lay the groundwork for its generalization to excites states through real-time path integral techniques. For clarity, we focus on the simple toy model of a point particle in a…

High Energy Physics - Theory · Physics 2025-07-30 Thomas Steingasser , David I. Kaiser

The ring-polymer instanton approach is applied to compute the ground-state tunnelling splitting of four isotopomers of the formic acid dimer using the accurate PES of Qu and Bowman [Phys. Chem. Chem. Phys., 2016, 18, 24835]. As well as…

Chemical Physics · Physics 2017-08-23 Jeremy O. Richardson

We show how to do semiclassical nonperturbative computations within the worldline approach to quantum field theory using ``worldline instantons''. These worldline instantons are classical solutions to the Euclidean worldline loop equations…

High Energy Physics - Theory · Physics 2009-11-11 Gerald V. Dunne , Christian Schubert