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Title: A global ab initio potential energy surface for the X{sup  2}A{sup ′} ground state of the Si + OH → SiO + H reaction

Abstract

We report the first global potential energy surface (PES) for the X{sup  2}A{sup ′} ground electronic state of the Si({sup 3}P) + OH(X{sup 2}Π) → SiO(X{sup 1}Σ{sub g}{sup +}) + H({sup 2}S) reaction. The PES is based on a large number of ab initio energies obtained from multireference configuration interaction calculations plus Davidson correction (MRCI+Q) using basis sets of quadruple zeta quality. Corrections were applied to the ab initio energies in the reactant channel allowing a proper description of long-range interactions between Si({sup 3}P) and OH(X{sup 2}Π). An analytical representation of the global PES has been developed by means of the reproducing kernel Hilbert space method. The reaction is found barrierless. Two minima, corresponding to the SiOH and HSiO isomers, and six saddle points, among which the isomerization transition state, have been characterized on the PES. The vibrational spectra of the SiOH/HSiO radicals have been computed from second-order perturbation theory and quantum dynamics methods. The structural, energetic, and spectroscopic properties of the two isomers are in good agreement with experimental data and previous high quality calculations.

Authors:
 [1]; ; ;  [2]
  1. Laboratoire d'Etude du Rayonnement et de la Matière en Astrophysique (UMR 8112 du CNRS), Observatoire de Paris-Meudon, Université Pierre et Marie Curie, 92195 Meudon Cedex (France)
  2. Laboratoire de Physique des Lasers, Atomes et Molécules (UMR 8523 du CNRS), Université Lille I Sciences et Technologies, 59655 Villeneuve d'Ascq Cedex (France)
Publication Date:
OSTI Identifier:
22251356
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 139; Journal Issue: 20; Other Information: (c) 2013 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; CONFIGURATION INTERACTION; GROUND STATES; HILBERT SPACE; INTERACTION RANGE; ISOMERIZATION; ISOMERS; PERTURBATION THEORY; POTENTIAL ENERGY; SILICON OXIDES; SPECTRA; SURFACES

Citation Formats

Dayou, Fabrice, Duflot, Denis, Rivero-Santamaría, Alejandro, and Monnerville, Maurice. A global ab initio potential energy surface for the X{sup  2}A{sup ′} ground state of the Si + OH → SiO + H reaction. United States: N. p., 2013. Web. doi:10.1063/1.4832324.
Dayou, Fabrice, Duflot, Denis, Rivero-Santamaría, Alejandro, & Monnerville, Maurice. A global ab initio potential energy surface for the X{sup  2}A{sup ′} ground state of the Si + OH → SiO + H reaction. United States. doi:10.1063/1.4832324.
Dayou, Fabrice, Duflot, Denis, Rivero-Santamaría, Alejandro, and Monnerville, Maurice. Thu . "A global ab initio potential energy surface for the X{sup  2}A{sup ′} ground state of the Si + OH → SiO + H reaction". United States. doi:10.1063/1.4832324.
@article{osti_22251356,
title = {A global ab initio potential energy surface for the X{sup  2}A{sup ′} ground state of the Si + OH → SiO + H reaction},
author = {Dayou, Fabrice and Duflot, Denis and Rivero-Santamaría, Alejandro and Monnerville, Maurice},
abstractNote = {We report the first global potential energy surface (PES) for the X{sup  2}A{sup ′} ground electronic state of the Si({sup 3}P) + OH(X{sup 2}Π) → SiO(X{sup 1}Σ{sub g}{sup +}) + H({sup 2}S) reaction. The PES is based on a large number of ab initio energies obtained from multireference configuration interaction calculations plus Davidson correction (MRCI+Q) using basis sets of quadruple zeta quality. Corrections were applied to the ab initio energies in the reactant channel allowing a proper description of long-range interactions between Si({sup 3}P) and OH(X{sup 2}Π). An analytical representation of the global PES has been developed by means of the reproducing kernel Hilbert space method. The reaction is found barrierless. Two minima, corresponding to the SiOH and HSiO isomers, and six saddle points, among which the isomerization transition state, have been characterized on the PES. The vibrational spectra of the SiOH/HSiO radicals have been computed from second-order perturbation theory and quantum dynamics methods. The structural, energetic, and spectroscopic properties of the two isomers are in good agreement with experimental data and previous high quality calculations.},
doi = {10.1063/1.4832324},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 20,
volume = 139,
place = {United States},
year = {2013},
month = {11}
}