Current-induced dissociation in molecular junctions beyond the paradigm of vibrational heating: The role of anti-bonding electronic states

Abstract

The interaction between electronic and nuclear degrees of freedom in single-molecule junctions is an essential mechanism, which may result in the current-induced rupture of chemical bonds. As such, it is fundamental for the stability of molecular junctions and for the applicability of molecular electronic devices. In this publication, we study current-induced bond rupture in molecular junctions using a numerically exact scheme, which is based on the hierarchical quantum master equation (HQME) method in combination with a discrete variable representation for the nuclear degrees of freedom. Employing generic models for molecular junctions with dissociative nuclear potentials, we identify distinct mechanisms leading to dissociation, namely the electronic population of anti-bonding electronic states and the current-induced heating of vibrational modes. Our results reveal that the latter plays a negligible role whenever the electronic population of anti-bonding states is energetically possible. Consequently, the significance of current-induced heating as a source for dissociation in molecular junctions involving an active anti-bonding state is restricted to the non-resonant transport regime, which reframes the predominant paradigm in the field of molecular electronics.

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• Hierarchical equations of motion approach to hybrid fermionic and bosonic environments: Matrix product state formulation in twin space
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• Unraveling current-induced dissociation mechanisms in single-molecule junctions
• Assessing mixed quantum-classical molecular dynamics methods for nonadiabatic dynamics of molecules on metal surfaces
• Nonequilibrium reaction rate theory: Formulation and implementation within the hierarchical equations of motion approach
• Efficient implementation and performance analysis of the independent electron surface hopping method for dynamics at metal surfaces
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• Nonadiabatic H-Atom Scattering Channels on Ge(111) Elucidated by the Hierarchical Equations of Motion
• Spin-Dependent Transport Through a Colloidal Quantum Dot: The Role of Exchange Interactions