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Title: Full-dimensional global potential energy surfaces describing abstraction and exchange for the H + H{sub 2}S reaction

Abstract

For the H + H{sub 2}S system, ∼34 000 data points are sampled over a large configuration space including both abstraction and exchange channels, and calculated at the level of explicitly correlated unrestricted coupled cluster method with singles, doubles, and perturbative triples excitations with the augmented correlation-consistent polarized triple zeta basis set (UCCSD(T)-F12a/aug-cc-pVTZ). The data set was fit using the newly proposed permutation invariant polynomial-neural network (PIP-NN) method with three different vectors as the input: two redundant sets of PIPs, one with the maximum order four (PES-I) and one with the maximum order three (PES-II), and nine non-redundant PIPs (PES-III). All these PESs show small fitting errors and essentially the same performance in representing the title system. Various kinetics and dynamical properties are calculated using the tunneling corrected transition state theory and quasi-classical trajectory, and compared with available experimental results. At a collision energy of 10 kcal/mol, both the H{sub 2} and SH products are found to be internally cold, with ∼20% of H{sub 2} at its first vibrational excited state, while SH is essentially a spectator. The angular distributions of the products are mainly in backward with considerable contributions from sideway direction. In addition, analytical partial derivatives of any PIP-NNmore » PES with respect to the coordinates of atoms are derived by making use of the monomial symmetrization algorithm [Z. Xie and J. M. Bowman, J. Chem. Theory Comput. 6, 26–34 (2010)]. It can not only accelerate the evaluation of the derivatives, but also improve the energy convergence significantly.« less

Authors:
;  [1]
  1. School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 401331 (China)
Publication Date:
OSTI Identifier:
22675990
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 145; Journal Issue: 1; Other Information: (c) 2016 Author(s); Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANGULAR DISTRIBUTION; EXPERIMENTAL DATA; HYDROGEN SULFIDES; POTENTIAL ENERGY; TUNNEL EFFECT

Citation Formats

Lu, Dandan, and Li, Jun, E-mail: jli15@cqu.edu.edu. Full-dimensional global potential energy surfaces describing abstraction and exchange for the H + H{sub 2}S reaction. United States: N. p., 2016. Web. doi:10.1063/1.4954765.
Lu, Dandan, & Li, Jun, E-mail: jli15@cqu.edu.edu. Full-dimensional global potential energy surfaces describing abstraction and exchange for the H + H{sub 2}S reaction. United States. doi:10.1063/1.4954765.
Lu, Dandan, and Li, Jun, E-mail: jli15@cqu.edu.edu. Thu . "Full-dimensional global potential energy surfaces describing abstraction and exchange for the H + H{sub 2}S reaction". United States. doi:10.1063/1.4954765.
@article{osti_22675990,
title = {Full-dimensional global potential energy surfaces describing abstraction and exchange for the H + H{sub 2}S reaction},
author = {Lu, Dandan and Li, Jun, E-mail: jli15@cqu.edu.edu},
abstractNote = {For the H + H{sub 2}S system, ∼34 000 data points are sampled over a large configuration space including both abstraction and exchange channels, and calculated at the level of explicitly correlated unrestricted coupled cluster method with singles, doubles, and perturbative triples excitations with the augmented correlation-consistent polarized triple zeta basis set (UCCSD(T)-F12a/aug-cc-pVTZ). The data set was fit using the newly proposed permutation invariant polynomial-neural network (PIP-NN) method with three different vectors as the input: two redundant sets of PIPs, one with the maximum order four (PES-I) and one with the maximum order three (PES-II), and nine non-redundant PIPs (PES-III). All these PESs show small fitting errors and essentially the same performance in representing the title system. Various kinetics and dynamical properties are calculated using the tunneling corrected transition state theory and quasi-classical trajectory, and compared with available experimental results. At a collision energy of 10 kcal/mol, both the H{sub 2} and SH products are found to be internally cold, with ∼20% of H{sub 2} at its first vibrational excited state, while SH is essentially a spectator. The angular distributions of the products are mainly in backward with considerable contributions from sideway direction. In addition, analytical partial derivatives of any PIP-NN PES with respect to the coordinates of atoms are derived by making use of the monomial symmetrization algorithm [Z. Xie and J. M. Bowman, J. Chem. Theory Comput. 6, 26–34 (2010)]. It can not only accelerate the evaluation of the derivatives, but also improve the energy convergence significantly.},
doi = {10.1063/1.4954765},
journal = {Journal of Chemical Physics},
number = 1,
volume = 145,
place = {United States},
year = {Thu Jul 07 00:00:00 EDT 2016},
month = {Thu Jul 07 00:00:00 EDT 2016}
}