Representing global reactive potential energy surfaces using Gaussian processes

B Kolb, P Marshall, B Zhao, B Jiang… - The Journal of Physical …, 2017 - ACS Publications
The Journal of Physical Chemistry A, 2017ACS Publications
Representation of multidimensional global potential energy surfaces suitable for spectral
and dynamical calculations from high-level ab initio calculations remains a challenge. Here,
we present a detailed study on constructing potential energy surfaces using a machine
learning method, namely, Gaussian process regression. Tests for the 3A ″state of SH2,
which facilitates the SH+ H↔ S (3P)+ H2 abstraction reaction and the SH+ H′↔ SH′+ H
exchange reaction, suggest that the Gaussian process is capable of providing a reasonable …
Representation of multidimensional global potential energy surfaces suitable for spectral and dynamical calculations from high-level ab initio calculations remains a challenge. Here, we present a detailed study on constructing potential energy surfaces using a machine learning method, namely, Gaussian process regression. Tests for the 3A″ state of SH2, which facilitates the SH + H ↔ S(3P) + H2 abstraction reaction and the SH + H′ ↔ SH′ + H exchange reaction, suggest that the Gaussian process is capable of providing a reasonable potential energy surface with a small number (∼1 × 102) of ab initio points, but it needs substantially more points (∼1 × 103) to converge reaction probabilities. The implications of these observations for construction of potential energy surfaces are discussed.
ACS Publications
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