Universal Steps in Quantum Dynamics with Time-Dependent Potential-Energy Surfaces: Beyond the Born-Oppenheimer Picture

Abstract

It was recently shown [G. Albareda, et al., Phys. Rev. Lett. 113, 083003 (2014)] that within the conditional decomposition approach to the coupled electron-nuclear dynamics, the electron-nuclear wave function can be exactly decomposed into an ensemble of nuclear wavepackets effectively governed by nuclear conditional time-dependent potential-energy surfaces (C-TDPESs). Employing a one-dimensional model system we show that for strong nonadiabatic couplings the nuclear C-TDPESs exhibit steps that bridge piecewise adiabatic Born-Oppenheimer PESs. The nature of these steps is identified as an effect of electron-nuclear correlation. Furthermore, a direct comparison with similar discontinuities recently reported in the context of the exact factorization framework allows us to draw conclusions about the universality of these discontinuities, viz. they are inherent to all nonadiabatic nuclear dynamics approaches based on (exact) time-dependent potential energy surfaces.

References in corpus (5)

• Efficient formalism for large scale ab initio molecular dynamics based on time-dependent density functional theory
• Applied Bohmian Mechanics
• The exact forces on classical nuclei in non-adiabatic charge transfer
• Correlated Electron-Nuclear Dynamics with Conditional Wave Functions
• Kinetic and potential components of the exact time-dependent correlation potential

Cited by in corpus (4)

• Simulating Vibronic Spectra without Born-Oppenheimer Surfaces
• Nonadiabatic \textit{ab initio} Quantum Dynamics without Potential Energy Surfaces
• Including arbitrary geometric correlations into one-dimensional time-dependent Schrödinger equations
• On the Measurement in Quantum Mechanics: the Consistent Measurement Apparatus