Gaussian process model for extrapolation of scattering observables for complex molecules: From benzene to benzonitrile

Cui, Jie; Krems, Roman V.; Li, Zhiying

doi:10.1063/1.4933137

Title: Gaussian process model for extrapolation of scattering observables for complex molecules: From benzene to benzonitrile

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Abstract

We consider a problem of extrapolating the collision properties of a large polyatomic molecule A–H to make predictions of the dynamical properties for another molecule related to A–H by the substitution of the H atom with a small molecular group X, without explicitly computing the potential energy surface for A–X. We assume that the effect of the −H →−X substitution is embodied in a multidimensional function with unknown parameters characterizing the change of the potential energy surface. We propose to apply the Gaussian Process model to determine the dependence of the dynamical observables on the unknown parameters. This can be used to produce an interval of the observable values which corresponds to physical variations of the potential parameters. We show that the Gaussian Process model combined with classical trajectory calculations can be used to obtain the dependence of the cross sections for collisions of C{sub 6}H{sub 5}CN with He on the unknown parameters describing the interaction of the He atom with the CN fragment of the molecule. The unknown parameters are then varied within physically reasonable ranges to produce a prediction uncertainty of the cross sections. The results are normalized to the cross sections for He — C{sub 6}H{sub 6}more »« less

Authors:

Cui, Jie; Krems, Roman V. ^[1]; Li, Zhiying ^[2]

Department of Chemistry, University of British Columbia, Vancouver, British Columbia V6T 1Z1 (Canada)
Department of Earth and Ocean Sciences, University of British Columbia, Vancouver, British Columbia V6T 1Z1 (Canada)

Publication Date:: Wed Oct 21 00:00:00 EDT 2015

OSTI Identifier:: 22493118

Resource Type:: Journal Article

Journal Name:: Journal of Chemical Physics

Additional Journal Information:: Journal Volume: 143; Journal Issue: 15; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BENZENE; COLLISIONS; CROSS SECTIONS; EXTRAPOLATION; GAUSSIAN PROCESSES; HELIUM; HYDROGEN; INTERACTIONS; MOLECULES; POTENTIAL ENERGY; SCATTERING

Citation Formats


                    Cui, Jie, Krems, Roman V., and Li, Zhiying. Gaussian process model for extrapolation of scattering observables for complex molecules: From benzene to benzonitrile.  United States: N. p., 2015. 
        Web.  doi:10.1063/1.4933137.

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                    Cui, Jie, Krems, Roman V., & Li, Zhiying. Gaussian process model for extrapolation of scattering observables for complex molecules: From benzene to benzonitrile.  United States.  https://doi.org/10.1063/1.4933137

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                    Cui, Jie, Krems, Roman V., and Li, Zhiying. 2015.  
        "Gaussian process model for extrapolation of scattering observables for complex molecules: From benzene to benzonitrile".  United States.  https://doi.org/10.1063/1.4933137.

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@article{osti_22493118,

  title        = {Gaussian process model for extrapolation of scattering observables for complex molecules: From benzene to benzonitrile},

  author       = {Cui, Jie and Krems, Roman V. and Li, Zhiying},

  abstractNote = {We consider a problem of extrapolating the collision properties of a large polyatomic molecule A–H to make predictions of the dynamical properties for another molecule related to A–H by the substitution of the H atom with a small molecular group X, without explicitly computing the potential energy surface for A–X. We assume that the effect of the −H →−X substitution is embodied in a multidimensional function with unknown parameters characterizing the change of the potential energy surface. We propose to apply the Gaussian Process model to determine the dependence of the dynamical observables on the unknown parameters. This can be used to produce an interval of the observable values which corresponds to physical variations of the potential parameters. We show that the Gaussian Process model combined with classical trajectory calculations can be used to obtain the dependence of the cross sections for collisions of C{sub 6}H{sub 5}CN with He on the unknown parameters describing the interaction of the He atom with the CN fragment of the molecule. The unknown parameters are then varied within physically reasonable ranges to produce a prediction uncertainty of the cross sections. The results are normalized to the cross sections for He — C{sub 6}H{sub 6} collisions obtained from quantum scattering calculations in order to provide a prediction interval of the thermally averaged cross sections for collisions of C{sub 6}H{sub 5}CN with He.},

  doi          = {10.1063/1.4933137},

  url          = {https://www.osti.gov/biblio/22493118},
  journal      = {Journal of Chemical Physics},

  issn         = {0021-9606},

  number       = 15,

  volume       = 143,

  place        = {United States},

  year         = {Wed Oct 21 00:00:00 EDT 2015},

  month        = {Wed Oct 21 00:00:00 EDT 2015}

}

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