Panadés-Barrueta Ramón L, Peláez Daniel
Laboratoire de Physique des Lasers, Atomes et Molécules (PhLAM), Université Lille 1, Villeneuve d'Ascq Cedex, France.
Institut des Sciences Moléculaires d'Orsay (ISMO) - UMR 8214, Bât. 520, Université Paris-Saclay, 91405 Orsay Cedex, France.
J Chem Phys. 2020 Dec 21;153(23):234110. doi: 10.1063/5.0027143.
The sum-of-products finite-basis-representation (SOP-FBR) approach for the automated multidimensional fit of potential energy surfaces (PESs) is presented. In its current implementation, the method yields a PES in the so-called Tucker sum-of-products form, but it is not restricted to this specific ansatz. The novelty of our algorithm lies in the fact that the fit is performed in terms of a direct product of a Schmidt basis, also known as natural potentials. These encode in a non-trivial way all the physics of the problem and, hence, circumvent the usual extra ad hoc and a posteriori adjustments (e.g., damping functions) of the fitted PES. Moreover, we avoid the intermediate refitting stage common to other tensor-decomposition methods, typically used in the context of nuclear quantum dynamics. The resulting SOP-FBR PES is analytical and differentiable ad infinitum. Our ansatz is fully general and can be used in combination with most (molecular) dynamics codes. In particular, it has been interfaced and extensively tested with the Heidelberg implementation of the multiconfiguration time-dependent Hartree quantum dynamical software package.
