Related papers: Generalized energy gap law: An open system dynamic…
We present an approach for carrying out non-adiabatic molecular dynamics simulations of systems in which non-adiabatic transitions arise from the coupling between the classical atomic motions and a quasi-continuum of electronic quantum…
A generalized formalism of the so-called non-adiabatic quantum molecular dynamics is presented, which applies for atomic many-body systems in external laser fields. The theory treats the nuclear dynamics and electronic transitions…
For more than 50 years, an elegant energy gap (EG) law developed by Englman and Jortner [Mol. Phys. {\bf 18}, 145 (1970)] has served as a key theory to understand and model nearly exponential dependence of nonradiative transition rates on…
With recent developments in simulating nonadiabatic systems to high accuracy, it has become possible to determine how much energy is attributed to nuclear quantum effects beyond zero-point energy. In this work we calculate the…
Describing the dynamics of nuclei in molecules requires a potential energy surface, which is traditionally provided by the Born-Oppenheimer or adiabatic approximation. However, we also need to assign masses to the nuclei. There, the…
We present generalized adiabatic theorems for closed and open quantum systems that can be applied to slow modulations of rapidly varying fields, such as oscillatory fields that occur in optical experiments and light induced processes. The…
The nonadiabatic photodissociation dynamics of alkali halide molecules excited by a femtosecond laser pulse in the gas phase are investigated theoretically, and it is shown that the population of the photoexcited molecules exhibits…
The most important law of radioactivity is that of the exponential decay. In the realm of quantum mechanics, however, this decay law is neither rigorous nor fundamental. The deviations from the exponential decay have been observed…
An approach to non-adiabatic dynamics of atoms in molecular and condensed matter systems under general non-equilibrium conditions is proposed. In this method interaction between nuclei and electrons is considered explicitly up to the second…
We prove the adiabatic theorem for quantum evolution without the traditional gap condition. All that this adiabatic theorem needs is a (piecewise) twice differentiable finite dimensional spectral projection. The result implies that the…
A general quantum adiabatic theorem with and without the time-dependent orthogonalization is proven, which can be applied to understand the origin of activation energies in chemical reactions. Further proofs are also developed for the…
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…
On-the-fly quantum nonadiabatic dynamics for large systems greatly benefits from the adiabatic representation readily available from the electronic structure programs. However, frequently occurring in this representation conical…
Adiabatic quantum computation, based on the adiabatic theorem, is a promising alternative to conventional quantum computation. The validity of an adiabatic algorithm depends on the existence of a nonzero energy gap between the ground and…
The spontaneous decay of an excited atom by photon emission is one of the most common and elementary physical process present in nature and in laboratories. The decay is random in time with constant probability density, as it can be…
The Born-Oppenheimer approximation leads to the counterintuitive result of a vanishing electronic flux density upon vibrational dynamics in the electronic ground state. To circumvent this long known issue, we propose using pairwise…
Thermodynamic principles are often deceptively simple and yet surprisingly powerful. We show how a simple rule, such as the net flow of energy in and out of a moving atom under nonequilibrium steady state condition, can expose the…
This report presents a new approach for treating the coupling of electrons and nuclei in quantum mechanical calculations for molecules and condensed matter. It includes the standard "Born-Oppenheimer approximation" as a special case but…
Extended Lagrangian Born-Oppenheimer molecular dynamics based on Kohn-Sham density functional theory is generalized in the limit of vanishing self-consistent field optimization prior to the force evaluations. The equations of motion are…
We present a means of studying rare reactive pathways in open quantum systems using Transition Path Theory and ensembles of quantum jump trajectories. This approach allows for elucidation of reactive paths for dissipative, nonadiabatic…