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

Physical Review A 94, 062511 (2016)

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

Guillermo Albareda, Ali Abedi, Ivano Tavernelli, Angel Rubio

In the conditional approach to molecular dynamics the electron-nuclear wavefunction is exactly decomposed into an ensemble of nuclear wavepackets governed by conditional time-dependent potential-energy surfaces (ℂ-TDPESs) [G. Albareda, et al., Phys. Rev. Lett. 105, 123002 (2014)]. Employing a one-dimensional model system we show that for strong nonadiabatic couplings the ℂ-TDPESs exhibit steps that bridge between piecewise adiabatic shapes. By a detailed analysis of the steps, we discuss the ultimate nature of electron-nuclear correlations and by comparing them with the discontinuities of the exact time-dependent potential-energy surface of the exact factorization approach we elaborate on the universality of this feature when a single time-dependent potential-energy surface governs the nonadiabatic nuclear dynamics.

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http://dx.doi.org/10.1103/PhysRevA.94.062511
arxiv
http://arxiv.org/abs/arXiv:1512.08531

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