Out-of-equilibrium catalysis of chemical reactions by electronic tunnel currents

Abstract

We present an escape rate theory for current-induced chemical reactions. We use Keldysh nonequilibrium Green's functions to derive a Langevin equation for the reaction coordinate. Due to the out of equilibrium electronic degrees of freedom, the friction, noise, and effective temperature in the Langevin equation depend locally on the reaction coordinate. As an example, we consider the dissociation of diatomic molecules induced by the electronic current from a scanning tunnelling microscope tip. In the resonant tunnelling regime, the molecular dissociation involves two processes which are intricately interconnected: a modification of the potential energy barrier and heating of the molecule. The decrease of the molecular barrier (i.e. the current induced catalytic reduction of the barrier) accompanied by the appearance of the effective, reaction-coordinate-dependent temperature is an alternative mechanism for current-induced chemical reactions, which is distinctly different from the usual paradigm of pumping vibrational degrees of freedom.

arXiv commentAccepted by JCP. Minor revision according to referees, one new figure

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Cited by in corpus (24)

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• Selectivity in single-molecule reactions by tip-induced redox chemistry
• Current-induced bond rupture in single-molecule junctions
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• Hierarchical quantum master equation approach to vibronic reaction dynamics at metal surfaces
• Current-induced dissociation in molecular junctions beyond the paradigm of vibrational heating: The role of anti-bonding electronic states
• Current-induced atomic motion, structural instabilities, and negative temperatures on molecule-electrode interfaces in electronic junctions
• Unraveling current-induced dissociation mechanisms in single-molecule junctions
• High voltage assisted mechanical stabilization of single-molecule junctions
• Nonequilibrium reaction rate theory: Formulation and implementation within the hierarchical equations of motion approach
• Non-renewal statistics for electron transport in a molecular junction with electron-vibration interaction
• First-passage time theory of activated rate chemical processes in electronic molecular junctions
• Timescale separation solution of Kadanoff-Baym equations for quantum transport in time-dependent fields
• Vibrationally dependent electron-electron interactions in resonant electron transport through single-molecule junctions
• Nonequilibrium Green's function theory for nonadiabatic effects in quantum electron transport
• Non-Adiabatic Effects of Nuclear Motion in Quantum Transport of Electrons: A Self-Consistent Keldysh-Langevin Study
• Cooling molecular electronic junctions by AC current
• Non-equilibrium Green's function theory for non-adiabatic effects in quantum transport: inclusion of electron-electron interactions
• Current-induced bond rupture in single-molecule junctions: Effects of multiple electronic states and vibrational modes
• Controlling the conductance of molecular junctions using proton transfer reactions: A theoretical model study
• Waiting time between charging and discharging processes in molecular junctions
• Nonadiabatic corrections to electric current in molecular junction due to nuclear motion at the molecule-electrode interfaces
• Current-induced forces in nanosystems: A hierarchical equations of motion approach
• Emergence of negative viscosities and colored noise under current-driven Ehrenfest molecular dynamics