Nonequilibrium reaction rate theory: Formulation and implementation within the hierarchical equations of motion approach

Abstract

The study of chemical reactions in environments under nonequilibrium conditions has been of interest recently in a variety of contexts, including current-induced reactions in molecular junctions and scanning tunneling microscopy experiments. In this work, we outline a fully quantum mechanical, numerically exact approach to describe chemical reaction rates in such nonequilibrium situations. The approach is based on an extension of the flux correlation function formalism to nonequilibrium conditions and uses a mixed real and imaginary time hierarchical equations of motion approach for the calculation of rate constants. As a specific example, we investigate current-induced intramolecular proton transfer reactions in a molecular junction for different applied bias voltages and molecule-lead coupling strengths.

References in corpus (16)

• Perspective: Numerically "exact" approach to open quantum dynamics: The hierarchical equations of motion (HEOM)
• Reduced hierarchical equations of motion in real and imaginary time: Correlated initial states and thermodynamic quantities
• High-performance solution of hierarchical equations of motions for studying energy-transfer in light-harvesting complexes
• Hierarchical Quantum Master Equation Approach to Electronic-Vibrational Coupling in Nonequilibrium Transport through Nanosystems
• Current-induced nonequilibrium vibrations in single-molecule devices
• Current-induced atomic dynamics, instabilities, and Raman signals: Quasi-classical Langevin equation approach
• Theoretical investigation of the dynamic electronic response of a quantum dot driven by time-dependent voltage
• Hierarchical equations of motion approach to hybrid fermionic and bosonic environments: Matrix product state formulation in twin space
• Out-of-equilibrium catalysis of chemical reactions by electronic tunnel currents
• Hierarchical quantum master equation approach to current fluctuations in nonequilibrium charge transport through nanosystems
• Non-oscillatory flux correlation functions for efficient nonadiabatic rate theory
• Unraveling current-induced dissociation mechanisms in single-molecule junctions
• Proton Tunneling in a Two-Dimensional Potential Energy Surface with a Non-linear System-Bath Interaction: Thermal Suppression of Reaction Rate
• First-passage time theory of activated rate chemical processes in electronic molecular junctions
• Nonequilibrium density matrix for simultaneous heat and charge steady-state transport in quantum open systems
• Controlling the conductance of molecular junctions using proton transfer reactions: A theoretical model study

Cited by in corpus (6)

• Quantum Dynamics of Vibrational Polariton Chemistry
• Efficient low temperature simulations for fermionic reservoirs with the hierarchical equations of motion method: Application to the Anderson impurity model
• Investigating the Collective Nature of Cavity Modified Chemical Kinetics under Vibrational Strong Coupling
• Current-induced bond rupture in single-molecule junctions: Effects of multiple electronic states and vibrational modes
• Current-induced forces in nanosystems: A hierarchical equations of motion approach
• Twin-Space Representation of Classical Mapping Model in the Constraint Phase Space Representation: Numerically Exact Approach to Open Quantum Systems