Scattering study of the Ne + NeH{sup +}(v{sub 0} = 0, j{sub 0} = 0) → NeH{sup +} + Ne reaction on an ab initio based analytical potential energy surface
Abstract
Initial state selected dynamics of the Ne + NeH{sup +}(v{sub 0} = 0, j{sub 0} = 0) → NeH{sup +} + Ne reaction is investigated by quantum and statistical quantum mechanical (SQM) methods on the ground electronic state. The threebody ab initio energies on a set of suitably chosen grid points have been computed at CCSD(T)/augccPVQZ level and analytically fitted. The fitting of the diatomic potentials, computed at the same level of theory, is performed by spline interpolation. A collinear [NeHNe]{sup +} structure lying 0.72 eV below the Ne + NeH{sup +} asymptote is found to be the most stable geometry for this system. Energies of low lying vibrational states have been computed for this stable complex. Reaction probabilities obtained from quantum calculations exhibit dense oscillatory structures, particularly in the low energy region and these get partially washed out in the integral cross section results. SQM predictions are devoid of oscillatory structures and remain close to 0.5 after the rise at the threshold thus giving a crude average description of the quantum probabilities. Statistical cross sections and rate constants are nevertheless in sufficiently good agreement with the quantum results to suggest an important role of a complexforming dynamics for themore »
 Authors:
 Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati 781039 (India)
 IFFCSIC, Instituto de Física Fundamental, CSIC, Serrano 123, Madrid 28006 (Spain)
 Publication Date:
 OSTI Identifier:
 22493664
 Resource Type:
 Journal Article
 Resource Relation:
 Journal Name: Journal of Chemical Physics; Journal Volume: 144; Journal Issue: 3; Other Information: (c) 2016 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
 Country of Publication:
 United States
 Language:
 English
 Subject:
 74 ATOMIC AND MOLECULAR PHYSICS; COMPLEXES; EV RANGE; INTEGRAL CROSS SECTIONS; INTERPOLATION; IONATOM COLLISIONS; NEON; NEON HYDRIDES; POTENTIAL ENERGY; POTENTIALS; PROBABILITY; QUANTUM MECHANICS; REACTION KINETICS; SCATTERING; SURFACES; THREEBODY PROBLEM; VIBRATIONAL STATES
Citation Formats
Koner, Debasish, Panda, Aditya N., Email: adi07@iitg.ernet.in, Barrios, Lizandra, and GonzálezLezana, Tomás, Email: t.gonzalez.lezana@csic.es. Scattering study of the Ne + NeH{sup +}(v{sub 0} = 0, j{sub 0} = 0) → NeH{sup +} + Ne reaction on an ab initio based analytical potential energy surface. United States: N. p., 2016.
Web. doi:10.1063/1.4939952.
Koner, Debasish, Panda, Aditya N., Email: adi07@iitg.ernet.in, Barrios, Lizandra, & GonzálezLezana, Tomás, Email: t.gonzalez.lezana@csic.es. Scattering study of the Ne + NeH{sup +}(v{sub 0} = 0, j{sub 0} = 0) → NeH{sup +} + Ne reaction on an ab initio based analytical potential energy surface. United States. doi:10.1063/1.4939952.
Koner, Debasish, Panda, Aditya N., Email: adi07@iitg.ernet.in, Barrios, Lizandra, and GonzálezLezana, Tomás, Email: t.gonzalez.lezana@csic.es. 2016.
"Scattering study of the Ne + NeH{sup +}(v{sub 0} = 0, j{sub 0} = 0) → NeH{sup +} + Ne reaction on an ab initio based analytical potential energy surface". United States.
doi:10.1063/1.4939952.
@article{osti_22493664,
title = {Scattering study of the Ne + NeH{sup +}(v{sub 0} = 0, j{sub 0} = 0) → NeH{sup +} + Ne reaction on an ab initio based analytical potential energy surface},
author = {Koner, Debasish and Panda, Aditya N., Email: adi07@iitg.ernet.in and Barrios, Lizandra and GonzálezLezana, Tomás, Email: t.gonzalez.lezana@csic.es},
abstractNote = {Initial state selected dynamics of the Ne + NeH{sup +}(v{sub 0} = 0, j{sub 0} = 0) → NeH{sup +} + Ne reaction is investigated by quantum and statistical quantum mechanical (SQM) methods on the ground electronic state. The threebody ab initio energies on a set of suitably chosen grid points have been computed at CCSD(T)/augccPVQZ level and analytically fitted. The fitting of the diatomic potentials, computed at the same level of theory, is performed by spline interpolation. A collinear [NeHNe]{sup +} structure lying 0.72 eV below the Ne + NeH{sup +} asymptote is found to be the most stable geometry for this system. Energies of low lying vibrational states have been computed for this stable complex. Reaction probabilities obtained from quantum calculations exhibit dense oscillatory structures, particularly in the low energy region and these get partially washed out in the integral cross section results. SQM predictions are devoid of oscillatory structures and remain close to 0.5 after the rise at the threshold thus giving a crude average description of the quantum probabilities. Statistical cross sections and rate constants are nevertheless in sufficiently good agreement with the quantum results to suggest an important role of a complexforming dynamics for the title reaction.},
doi = {10.1063/1.4939952},
journal = {Journal of Chemical Physics},
number = 3,
volume = 144,
place = {United States},
year = 2016,
month = 1
}

Based exclusively on highlevel ab initio calculations, a new fulldimensional analytical potential energy surface (PES2014) for the gasphase reaction of hydrogen abstraction from methane by an oxygen atom is developed. The ab initio information employed in the fit includes properties (equilibrium geometries, relative energies, and vibrational frequencies) of the reactants, products, saddle point, points on the reaction path, and points on the reaction swath, taking especial caution respecting the location and characterization of the intermediate complexes in the entrance and exit channels. By comparing with the reference results we show that the resulting PES2014 reproduces reasonably well the whole setmore »

Centrifugal sudden distorted wave study of the Cl + HCl. >. ClH + Cl reaction: results for a scaled fitted ab initio potential energy surface having a noncollinear reaction path
The authors present the results of a centrifugal sudden distorted wave (CSDW) quantum scattering study of the reaction Cl + HCl ..>.. ClH + Cl. The potential energy surface used in this calculation (denoted sfPOLCI) has been chosen to fit a scaled ab initio surface for ClHCl angles greater than 150/sup 0/ (angles for which the latter surface has been determined), and to fit an extended LondonEyringPolanyiSato (LEPS) surface at smaller angles. This sfPOLCI surface has a noncollinear ClHCl saddle point with a ClHCl angle of 161.4/sup 0/. They also compare their CSDW results with those from a LEPS surface,more » 
Mode specificity in the OH + CHD{sub 3} reaction: Reduceddimensional quantum and quasiclassical studies on an ab initio based fulldimensional potential energy surface
An initial state selected timedependent wave packet method is applied to study the dynamics of the OH + CHD{sub 3} reaction with a sixdimensional model on a newly developed fulldimensional ab initio potential energy surface (PES). This quantum dynamical (QD) study is complemented by fulldimensional quasiclassical trajectory (QCT) calculations on the same PES. The QD results indicate that both translational energy and the excitation of the CH stretching mode significantly promote the reaction while the excitation of the umbrella mode has a negligible effect on the reactivity. For this early barrier reaction, interestingly, the CH stretching mode is more effectivemore » 
Potential energy surface of the HNO + NO reaction. An ab initio molecular orbital study
The potential energy surface of the HNO + NO reaction has been investigated by ab initio molecular orbital calculations at the QCISD(T)/6311G(d,p)//UMP2/6311G(d,p) + ZPE[UMP2/6311G(d,p)] and Gaussian2 (G2) levels of theory. The initial reaction step is NO association with the N atom of the HNO molecule to form the HN(O)NO intermediate, 2, overcoming the barrier 1[prime] of 9.5 kcal/mol. The reaction proceeds further by 1,3hydrogen migration in HN(O)NO from nitrogen to oxygen via the transition state 3, which is much more favorable than 1,2shift. This step is shown to be ratedetermining, having a barrier of 21.6 kcal/mol. After the H shift,more »