Using neural networks, optimized coordinates, and high-dimensional model representations to obtain a vinyl bromide potential surface.
We demonstrate that it is possible to obtain good potentials using high-dimensional model representations (HDMRs) fitted with neural networks (NNs) from data in 12 dimensions and 15 dimensions. The HDMR represents the potential as a sum of lower-dimensional functions and our NN-based approach makes it possible to obtain all of these functions from one set of fitting points. To reduce the number of terms in the HDMR, we use optimized redundant coordinates. By using exponential neurons, one obtains a potential in sum-of-products form, which greatly facilitates quantum dynamics calculations. A 12-dimensional (reference) potential surface for vinyl bromide is first refitted to show that it can be represented as a sum of two-dimensional functions. To fit 3d functions of the original coordinates, to improve the potential, a huge amount of data would be required. Redundant coordinates avoid this problem. They enable us to bypass the combinatorial explosion of the number of terms which plagues all HDMR and multimode-type methods. We also fit to a set of approximately 70,000 ab initio points for vinyl bromide in 15 dimensions [M. Malshe et al., J. Chem. Phys. 127, 134105 (2007)] and show that it is possible to obtain a surface in sum-of-products form of quality similar to the quality of the full-dimensional fit. Although we obtain a full-dimensional surface, we limit the cost of the fitting by building it from fits of six-dimensional functions, each of which requires only a small NN.
Manzhos
Sergei
S
Département de chimie, Université de Montréal, Case postale 6128, succursale Centre-ville Montréal, (Québec) H3C 3J7 Canada. sergei.manzhos@gmail.com
Carrington
Tucker
T