Abstract
A new global potential energy surface for the ground electronic state (12 A′) of the Ar+H2 +→ArH++H reaction has been constructed by multi-reference configuration interaction method with Davidson correction and a basis set of aug-cc-pVQZ. Using 6080 ab initio single-point energies of all the regions for the dynamics, a many-body expansion function form has been used to fit these points. The quantum reactive scattering dynamics calculations taking into account the Coriolis coupling (CC) were carried out on the new potential energy surface over a range of collision energies (0.03–1.0 eV). The reaction probabilities and integral cross sections for the title reaction were calculated. The significance of including the CC quantum scattering calculation has been revealed by the comparison between the CC and the centrifugal sudden approximation calculation. The calculated cross section is in agreement with the experimental result at collision energy 1.0 eV.
This research was supported by the National Nature Science Foundation of China (NNSFC) (Grant Nos. 11274205 and 11274206).
I. INTRODUCTION
II. POTENTIAL ENERGY SURFACE OF THE Ar+H_{2} ^{+}→ArH^{+}+H REACTION
A. Details of the ab initio calculations
B. Fitting
III. TIME-DEPENDENT QUANTUM WAVE PACKET DYNAMICS
IV. CONCLUSIONS
Key Topics
- Hydrogen reactions
- 23.0
- Non adiabatic reactions
- 21.0
- Ab initio calculations
- 20.0
- Chemical reaction cross sections
- 16.0
- Ion molecule reactions
- 13.0
Figures
The ab initio energy at different active orbitals for three different Ar–H–H angles. Black line represents 16 active orbitals (14 a′+ 2 a″), red line represents 17 active orbitals (14 a′+ 3 a″), blue line represents 18 active orbitals (14 a′+ 4 a″).
The ab initio energy at different active orbitals for three different Ar–H–H angles. Black line represents 16 active orbitals (14 a′+ 2 a″), red line represents 17 active orbitals (14 a′+ 3 a″), blue line represents 18 active orbitals (14 a′+ 4 a″).
Contour plots of the new PES for four different Ar–H–H angles in internal coordinates (energies are given in kcal/mol).
Contour plots of the new PES for four different Ar–H–H angles in internal coordinates (energies are given in kcal/mol).
The comparison of the asymptotic region between the LLZ and present PES through the contour map corresponding to 45° (energies are given in kcal/mol).
The comparison of the asymptotic region between the LLZ and present PES through the contour map corresponding to 45° (energies are given in kcal/mol).
The comparison of the interaction region between the LLZ and present PESs through the contour map corresponding to 45° (energies are given in kcal/mol).
The comparison of the interaction region between the LLZ and present PESs through the contour map corresponding to 45° (energies are given in kcal/mol).
N K -dependent reaction probabilities of the Ar + H2 + (v i = 0, j i = 0) → ArH+ + H reaction on the new surface at J = 90 and 100. (—) represents N K = 8; (----) represents N K = 9; and (-•-•) represents N K = 10.
N K -dependent reaction probabilities of the Ar + H2 + (v i = 0, j i = 0) → ArH+ + H reaction on the new surface at J = 90 and 100. (—) represents N K = 8; (----) represents N K = 9; and (-•-•) represents N K = 10.
Dependence of the reaction probabilities on the collision energy of the Ar + H2 + (v i = 0, j i = 0) → ArH+ + H reaction on the new surface at J = 10, 20, 30, 40, 50, 60, 70, 80, 90, and 100. (—) represents CC and (----) represents CS.
Dependence of the reaction probabilities on the collision energy of the Ar + H2 + (v i = 0, j i = 0) → ArH+ + H reaction on the new surface at J = 10, 20, 30, 40, 50, 60, 70, 80, 90, and 100. (—) represents CC and (----) represents CS.
Weighed partial wave contributions to the integral cross sections of Ar + H2 + (v i = 0, j i = 0) → ArH+ + H reaction as a function of total angular momentum J at four collision energies 0.1, 0.4, 0.7, and 1.0 eV. (—) represents CC and (----) represents CS.
Weighed partial wave contributions to the integral cross sections of Ar + H2 + (v i = 0, j i = 0) → ArH+ + H reaction as a function of total angular momentum J at four collision energies 0.1, 0.4, 0.7, and 1.0 eV. (—) represents CC and (----) represents CS.
Dependence of the integral reaction cross sections on the collision energy of the Ar + H2 + (v i = 0, j i = 0) → ArH+ + H reaction on the new surface. (—) represents CC, (----) represents CS, and (•) experimental measurement (Ref. 8 ).
Dependence of the integral reaction cross sections on the collision energy of the Ar + H2 + (v i = 0, j i = 0) → ArH+ + H reaction on the new surface. (—) represents CC, (----) represents CS, and (•) experimental measurement (Ref. 8 ).
Tables
The ab initio energy of the stationary points geometries of two larger basis sets. (Energies and interatomic distances are given in atomic units.)
The ab initio energy of the stationary points geometries of two larger basis sets. (Energies and interatomic distances are given in atomic units.)
Dissociation energies and equilibrium distances of the two-body terms. (Energies are given in eV, interatomic distances in bohr.)
Dissociation energies and equilibrium distances of the two-body terms. (Energies are given in eV, interatomic distances in bohr.)
Parameters of the three-body terms for M = 10. β AB = 0.8500203052, β BC = 0.05.
Parameters of the three-body terms for M = 10. β AB = 0.8500203052, β BC = 0.05.
Equilibrium distances of ArH2 + complex and the well depth. (Energies are given in kcal/mol, interatomic distances in bohr.)
Equilibrium distances of ArH2 + complex and the well depth. (Energies are given in kcal/mol, interatomic distances in bohr.)
Parameters for the quantum calculations (all quantities are given in a.u., unless otherwise indicated).
Parameters for the quantum calculations (all quantities are given in a.u., unless otherwise indicated).
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