Dynamical Steps that Bridge Piecewise Adiabatic Shapes in the Exact Time-Dependent Potential Energy Surface

Gross

2016

Self Cite

The full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-pro t purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. Nonadiabatic quantum interferences emerge whenever nuclear wavefunctions in different electronic states meet and interact in a nonadiabatic region.In this work, we analyze how nonadiabatic quantum interferences translate in the context of the exact factorization of the molecular wavefunction. In particular, we focus our attention on the shape of the time-dependent potential energy surface-the exact surface on which the nuclear dynamics takes place. We use a one-dimensional exactly solvable model to reproduce different conditions for quantum interferences, whose characteristic features already appear in one-dimension. The time-dependent potential energy surface develops complex features when strong interferences are present, in clear contrast to the observed behavior in simple nonadiabatic crossing cases. Nevertheless, independent classical trajectories propagated on the exact time-dependent potential energy surface reasonably conserve a distribution in configuration space that mimics one of the exact nuclear probability densities. Published by AIP Publishing.[http://dx

Section: Appendix: a Simple Model Of Nonadiabatic Quantum Interferencsupporting

confidence: 66%

Section: Fig 8 Contributions To the Full Tdpess Represented Inmentioning

confidence: 75%

Section: Introductionmentioning

confidence: 98%

See 1 more Smart Citation

An exact factorization perspective on quantum interferences in nonadiabatic dynamics

Curchod

Gross

2016

Self Cite

“…A detailed analysis of the shape of the GD component was given here, while earlier work had focussed on the GI component. 57,58 In particular, we explained why the shape is a sigmoid, and why the step in the GD component largely cancels that in the GI component. The effect of the GD part of the TDPES was analyzed also under a different perspective, by pointing out the qualitative connection with the momentum adjustment in the TSH procedure.…”

Section: Discussionmentioning

confidence: 94%

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

Abedi

Suzuki

et al. 2015

Self Cite

110

195

Non-adiabatic processes in the charge transfer reaction of O2 molecules with potassium surfaces without dissociation J. Chem. Phys. 141, 074711 (2014) The exact forces on classical nuclei in non-adiabatic charge transfer The decomposition of electronic and nuclear motion presented in Abedi et al. [Phys. Rev. Lett. 105, 123002 (2010)] yields a time-dependent potential that drives the nuclear motion and fully accounts for the coupling to the electronic subsystem. Here, we show 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. We point out the importance of step and bump features in the exact potential that are critical in obtaining the correct splitting of the quasiclassical nuclear wave packet in space after it passes through an avoided crossing between two Born-Oppenheimer surfaces and analyze their structure. Finally, an analysis of the exact potentials in the context of trajectory surface hopping is presented, including preliminary investigations of velocity-adjustment and the force-induced decoherence effect. C 2015 AIP Publishing LLC.[http://dx

“…The TDPES of the theory based on the exact factorization remains unaffected if compared to the BO case, up to within the first-order perturbation, as shown in Eq. (33). The vector potential, that is identically zero in the adiabatic treatment, becomes…”

Section: Nuclear Velocity Perturbation Theorymentioning

confidence: 99%

Nuclear velocity perturbation theory for vibrational circular dichroism: An approach based on the exact factorization of the electron-nuclear wave function

Scherrer

Sebastiani

et al. 2015

Self Cite

The nuclear velocity perturbation theory (NVPT) for vibrational circular dichroism (VCD) is derived from the exact factorization of the electron-nuclear wave function. This new formalism offers an exact starting point to include correction terms to the Born-Oppenheimer (BO) form of the molecular wave function, similarly to the complete-adiabatic approximation. The corrections depend on a small parameter that, in a classical treatment of the nuclei, is identified as the nuclear velocity. Apart from proposing a rigorous basis for the NVPT, we show that the rotational strengths, related to the intensity of the VCD signal, contain a new contribution beyond-BO that can be evaluated with the NVPT and that only arises when the exact factorization approach is employed. Numerical results are presented for chiral and non-chiral systems to test the validity of the approach.