Time-Dependent Quantum Wave Packet Study of the Si + OH arrow right SiO + H Reaction: Cross Sections and Rate Constants

The dynamics of the Si( super(3)P) + OH(X super(2) capital pi ) arrow right SiO(X super(1) capital sigma super(+)) + H( super(2)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. ( J. C...

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Bibliographic Details
Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2017-03, Vol.121 (8), p.1675-1685
Main Authors: Santamaria, Alejandro Rivero, Dayou, Fabrice, Rubayo-Soneira, Jesus, Monnerville, Maurice
Format: Article
Language:English
Subjects:
Collision dynamics
Cross sections
Mathematical analysis
Rate constants
Silicon dioxide
Temperature dependence
Time dependence
Wave packets
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Summary:The dynamics of the Si( super(3)P) + OH(X super(2) capital pi ) arrow right SiO(X super(1) capital sigma super(+)) + H( super(2)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. ( J. Chem. Phys. 2013, 139, 204305) for the ground X super(2)A' electronic state. Total reaction probabilities have been calculated for the first 15 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. ( Chem. Phys. Lett. 2014, 610-611, 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.
ISSN:1089-5639
1520-5215
DOI:10.1021/acs.jpca.7b00174