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Issue 47, 2016
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Ring-polymer molecular dynamical calculations for the F + HCl → HF + Cl reaction on the ground 12A′ potential energy surface

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Abstract

The reaction kinetics of the heavy-light-heavy abstraction reaction F + HCl → HF + Cl on the ground electronic state potential energy surface (PES) is investigated theoretically by a recently developed ring polymer molecular dynamics (RPMD) approach. First, a new PES is developed by the permutation invariant polynomial neural network (PIP-NN) approach based on 30 620 points sampled over a large configuration space from the latest and most accurate Deskevich−Hayes−Takahashi−Skodje−Nesbitt (DHTSN) PES (J. Chem. Phys., 2006, 124, 224303). Excellent fitting performance was achieved with only 521 parameters. The PIP-NN PES is 11 times faster than the DHTSN PES. Besides, the first analytical derivatives with respect to the coordinates of the atoms have been obtained for the PIP-NN PES. The RPMD rate coefficients on the PIP-NN PES are calculated and compared with available theoretical and experimental results. It is found that the experimental rate coefficients are significantly larger than the theoretical results on the DHTSN PES, due to its overestimated reaction barrier. We conclude that a reliable PES for this important heavy-light-heavy reaction is highly desirable.

Graphical abstract: Ring-polymer molecular dynamical calculations for the F + HCl → HF + Cl reaction on the ground 12A′ potential energy surface

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Publication details

The article was received on 16 May 2016, accepted on 27 Jun 2016 and first published on 28 Jun 2016


Article type: Paper
DOI: 10.1039/C6CP03306G
Citation: Phys. Chem. Chem. Phys., 2016,18, 32031-32041
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    Ring-polymer molecular dynamical calculations for the F + HCl → HF + Cl reaction on the ground 12A′ potential energy surface

    M. Bai, D. Lu, Y. Li and J. Li, Phys. Chem. Chem. Phys., 2016, 18, 32031
    DOI: 10.1039/C6CP03306G

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