Nonadiabatic quantum dynamics without potential energy surfaces

@article{Albareda2019NonadiabaticQD,
  title={Nonadiabatic quantum dynamics without potential energy surfaces},
  author={Guillermo Albareda and Aaron Kelly and {\'A}ngel Rubio},
  journal={Physical Review Materials},
  year={2019}
}
We present an efficient \textit{ab initio} algorithm for quantum dynamics simulations of interacting systems that is based on the conditional decomposition of the many-body wavefunction [Phys. Rev. Lett. 113, 083003 (2014)]. Starting with this formally exact approach, we develop a stochastic wavefunction ansatz using a set of interacting conditional wavefunctions as a basis. We show that this technique achieves quantitative accuracy for a photo-excited proton-coupled electron transfer problem… 

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References

SHOWING 1-10 OF 90 REFERENCES

Surface Hopping Dynamics beyond Nonadiabatic Couplings for Quantum Coherence.

Numerical simulations with two-state models and a multidimensional multistate realistic molecule show that the electron-nuclear coupling beyond the nonadiabatic coupling terms can describe the quantum coherence properly.

Conditional Born-Oppenheimer Dynamics: Quantum Dynamics Simulations for the Model Porphine.

A new theoretical approach to solve adiabatic quantum molecular dynamics halfway between wave function and trajectory-based methods and can be exploited to circumvent the calculation and storage of many-body quantities whose size scales exponentially with the number of nuclear degrees of freedom.

Coupled-Trajectory Quantum-Classical Approach to Electronic Decoherence in Nonadiabatic Processes.

We present a novel quantum-classical approach to nonadiabatic dynamics, deduced from the coupled electronic and nuclear equations in the framework of the exact factorization of the electron-nuclear

A novel algorithm for non-adiabatic direct dynamics using variational Gaussian wavepackets.

This work presents the first direct dynamics calculations using a novel algorithm, based on the powerful multi-configuration time-dependent Hartree (MCTDH) wavepacket propagation method, that provides a feasible direct dynamics algorithm for the description of this non-adiabatic process.

Trajectory-based solution of the nonadiabatic quantum dynamics equations: an on-the-fly approach for molecular dynamics simulations.

An on-the-fly trajectory-based nonadiabatic molecular dynamics algorithm is derived, which is able to capture nuclear quantum effects that are missing in the traditional trajectory surface hopping approach based on the independent trajectory approximation.

The exact forces on classical nuclei in non-adiabatic charge transfer.

It is shown that propagation of an ensemble of independent classical nuclear trajectories on this exact potential yields dynamics that are essentially indistinguishable from the exact quantum dynamics for a model non-adiabatic charge transfer problem.

Electronically nonadiabatic dynamics via semiclassical initial value methods.

  • W. Miller
  • Physics
    The journal of physical chemistry. A
  • 2009
Of special interest is the fact that, though the classical trajectories generated by the MMST Hamiltonian are "Ehrenfest trajectories", when they are used within the SC-IVR framework, the nuclear motion emerges from regions of nonadiabaticity on one potential energy surface (PES) or another, and not on an average PES as in the traditional Ehrenfest model.

Universal steps in quantum dynamics with time-dependent potential-energy surfaces: Beyond the Born-Oppenheimer picture

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

Correlated electron-nuclear dynamics with conditional wave functions.

The molecular Schrödinger equation is rewritten in terms of nonunitary equations of motion for the nuclei that depend parametrically on the configuration of an ensemble of generally defined electronic trajectories to circumvent the calculation of the computationally demanding Born-Oppenheimer potential-energy surfaces and nonadiabatic coupling elements.
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