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 wave packets 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 potential-energy surfaces. 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.
Highlights
The description of the correlated electron-nuclear dynamics remains a formidable challenge in condensed-matter physics and theoretical chemistry [1,2,3,4,5,6]
Within the exact factorization and conditional decomposition frameworks the same physics can be successfully described by a single effective time-dependent potential that drives the nuclear dynamics along adiabatic segments of Born-Oppenheimer potential-energy surfaces (BOPESs) connected by sudden transitions or jumps
Within the conditional decomposition (CD) framework, an ensemble of C-TDPESs governs the dynamics of the conditional nuclear wave functions and provides us with an alternative approach for the study of nonadiabatic processes
Summary
The description of the correlated electron-nuclear dynamics remains a formidable challenge in condensed-matter physics and theoretical chemistry [1,2,3,4,5,6]. Towards an alternative description of the coupled electronnuclear dynamics beyond the Born-Oppenheimer (BO) picture (i.e., the Born-Huang expansion of the molecular wave function), two different formally exact frameworks, viz., the exact factorization (EF) [24] and the conditional decomposition (CD) [25], have been recently proposed. These two alternative approaches are to be added to the already existing frameworks that avoid the BO picture of nonadiabatic dynamics [26,27,28].
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
