Time-Dependent Quantum Wave Packet Study ...
Document type :
Article dans une revue scientifique: Article original
DOI :
Title :
Time-Dependent Quantum Wave Packet Study of the Si + OH → SiO + H Reaction: Cross Sections and Rate Constants
Author(s) :
Rivero Santamaria, Alejandro [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Dayou, Fabrice [Auteur]
Laboratoire d'Etude du Rayonnement et de la Matière en Astrophysique [LERMA]
Rubayo-Soneira, Jesus [Auteur]
Instituto Superior de Tecnologias y Ciencias Aplicadas - InSTEC (CUBA)
Monnerville, Maurice [Auteur correspondant]
Physico-Chimie Moléculaire Théorique [PCMT]
Physico-Chimie Moléculaire Théorique [PCMT]
Dayou, Fabrice [Auteur]
Laboratoire d'Etude du Rayonnement et de la Matière en Astrophysique [LERMA]
Rubayo-Soneira, Jesus [Auteur]
Instituto Superior de Tecnologias y Ciencias Aplicadas - InSTEC (CUBA)
Monnerville, Maurice [Auteur correspondant]

Physico-Chimie Moléculaire Théorique [PCMT]
Journal title :
Journal of Physical Chemistry A
Pages :
1675-1685
Publisher :
American Chemical Society
Publication date :
2017-02-07
ISSN :
1089-5639
HAL domain(s) :
Physique [physics]/Physique [physics]/Chimie-Physique [physics.chem-ph]
English abstract : [en]
The dynamics of the Si(<sup>3</sup>P)+OH(X<sup>2</sup>Π) → SiO(X<sup>1</sup>Σ<sup>+</sup>)+H(<sup>2</sup>S) reaction is investigated by means of the time-dependent wave packet (TDWP) approach using an ab initio ...
Show more >The dynamics of the Si(<sup>3</sup>P)+OH(X<sup>2</sup>Π) → SiO(X<sup>1</sup>Σ<sup>+</sup>)+H(<sup>2</sup>S) reaction is investigated by means of the time-dependent wave packet (TDWP) approach using an ab initio potential energy surface recently developed by Dayou et al. (<i>J. Chem. Phys.</i> <b>2013</b> ,<i>139</i>, 204305) for the ground X<sup>2</sup>A' electronic state. Total reaction probabilities have been calculated for the first fifteen rotational states j = 0-14 of OH(v = 0, j) at a total angular momentum J = 0 up to a collision energy of 1 eV. Integral cross-sections and state-selected rate constants for the temperature range 10-500 K were obtained within the J-shifting approximation. The reaction probabilities display highly oscillatory structures indicating the contribution of long-lived quasibound states supported by the deep SiOH/HSiO wells. The cross sections behave with collision energies as expected for a barrierless reaction and are slightly sensitive to the initial rotational excitation of OH. The thermal rate constants show a marked temperature dependence below 200 K with a maximum value around 15 K. The TDWP results globally agree with the results of earlier quasi-classical trajectory (QCT) calculations carried out by Rivero-Santamaria et al. (<i>Chem. Phys. Lett.</i> <b>2014</b>, <i>610-611</i>, 335-340) with the same potential energy surface. In particular, the thermal rate constants display a similar temperature dependence, with TDWP values smaller than the QCT ones over the whole temperature range.Show less >
Show more >The dynamics of the Si(<sup>3</sup>P)+OH(X<sup>2</sup>Π) → SiO(X<sup>1</sup>Σ<sup>+</sup>)+H(<sup>2</sup>S) reaction is investigated by means of the time-dependent wave packet (TDWP) approach using an ab initio potential energy surface recently developed by Dayou et al. (<i>J. Chem. Phys.</i> <b>2013</b> ,<i>139</i>, 204305) for the ground X<sup>2</sup>A' electronic state. Total reaction probabilities have been calculated for the first fifteen rotational states j = 0-14 of OH(v = 0, j) at a total angular momentum J = 0 up to a collision energy of 1 eV. Integral cross-sections and state-selected rate constants for the temperature range 10-500 K were obtained within the J-shifting approximation. The reaction probabilities display highly oscillatory structures indicating the contribution of long-lived quasibound states supported by the deep SiOH/HSiO wells. The cross sections behave with collision energies as expected for a barrierless reaction and are slightly sensitive to the initial rotational excitation of OH. The thermal rate constants show a marked temperature dependence below 200 K with a maximum value around 15 K. The TDWP results globally agree with the results of earlier quasi-classical trajectory (QCT) calculations carried out by Rivero-Santamaria et al. (<i>Chem. Phys. Lett.</i> <b>2014</b>, <i>610-611</i>, 335-340) with the same potential energy surface. In particular, the thermal rate constants display a similar temperature dependence, with TDWP values smaller than the QCT ones over the whole temperature range.Show less >
Language :
Anglais
Peer reviewed article :
Oui
Audience :
Internationale
Popular science :
Non
Comment :
10 pages
Source :