Direct grid-based quantum dynamics on propagated diabatic potential energy surfaces

[Display omitted] •A new direct scheme for quantum dynamics simulations of photoexcited states.•Automatic generation of potential energy surfaces with machine learning.•Propagation of diabatic states enables direct grid-based quantum dynamics.•Requires fewer electronic structure evaluations than gen...

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Bibliographic Details
Published in:Chemical physics letters 2017-09, Vol.683, p.228-233
Main Authors: Richings, Gareth W., Habershon, Scott
Format: Article
Language:English
Subjects:
Butatriene
Diabatisation
Direct-dynamics
Grid-based quantum dynamics
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Summary:[Display omitted] •A new direct scheme for quantum dynamics simulations of photoexcited states.•Automatic generation of potential energy surfaces with machine learning.•Propagation of diabatic states enables direct grid-based quantum dynamics.•Requires fewer electronic structure evaluations than generation of fitted diabatic surfaces. We present a method for performing non-adiabatic, grid-based nuclear quantum dynamics calculations using diabatic potential energy surfaces (PESs) generated “on-the-fly”. Gaussian process regression is used to interpolate PESs by using electronic structure energies, calculated at points in configuration space determined by the nuclear dynamics, and diabatising the results using the propagation diabatisation method reported recently (Richings and Worth, 2015). Our new method is successfully demonstrated using a grid-based approach to model the non-adiabatic dynamics of the butatriene cation. Overall, our scheme offers a route towards accurate quantum dynamics on diabatic PESs learnt on-the-fly.
ISSN:0009-2614
1873-4448
DOI:10.1016/j.cplett.2017.01.063