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Reduced dimensionality spin-orbit dynamics of CH3 + HCl CH4 + Cl on ab initio surfaces
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10.1063/1.3592732
/content/aip/journal/jcp/134/20/10.1063/1.3592732
http://aip.metastore.ingenta.com/content/aip/journal/jcp/134/20/10.1063/1.3592732

Figures

Image of FIG. 1.
FIG. 1.

Diagram of the three HCl + CH3 Cl + CH4 potential energy surfaces as a function of reaction coordinate. The two excited states in the diabatic representation break degeneracy due to spin-orbit coupling in the adiabatic representation, leading to a four fold degenerate ground state and a two fold degenerate excited state split by 882 cm−1.

Image of FIG. 2.
FIG. 2.

HCl + CH3 Cl + CH4 stationary point geometries and Jacobi coordinate definition. Bond lengths given in Å.

Image of FIG. 3.
FIG. 3.

Contour diagram of ground A1 (gray) and excited E (color) diabatic states for reaction HCl + CH3 Cl + CH4, computed from the basis set extrapolated surface model. Large δ corresponds to the Cl + CH4 reactant channel; small δ the HCl + CH3 channel. The surfaces are asymptotically degenerate but diverge in the interaction region, where the highest E contour lies 0.35 eV above the corresponding A1 contour.

Image of FIG. 4.
FIG. 4.

Minimum energy path for the diabatic and adiabatic basis set extrapolated surfaces in Cl + CH4 channel. Spin orbit splitting for the adiabatic surfaces (−1/3, +2/3) shown for the asymptotic region in the inset. Diabatic surfaces: (black, dashed); adiabatic surfaces: (black, solid), (green), (red).

Image of FIG. 5.
FIG. 5.

J-shifted thermal rate constants on the adiabatic ground state surfaces . (a) Forward reaction, for the IB surface. (b) Reverse reaction, for IB and Q//T surfaces. TST computed from IB ab initio energies.

Image of FIG. 6.
FIG. 6.

The eight lowest hyperspherical adiabats for the HCl + CH3 Cl + CH4 reaction. Quantum states s = (i, ν) are asymptotically grouped in terms of vibrational quantum number ν. Asymptotic electronic states are A1: Cl (2P3/2) + CH4 (solid black), E: Cl (2P3/2) + CH4 (green), HCl + CH3 (blue, R) and E: Cl* (2P1/2) + CH4 (red). Potential ridge and minimum energy path along Cl + CH4 channel are given as black dashed lines; TS location indicated by red triangle.

Image of FIG. 7.
FIG. 7.

(a) J = 0 reaction probabilities for the CH3 + HCl → CH4 + Cl(2P) reaction. CRP (red), nonadiabatic pathways (black, dashed). (b) Time delay analysis for identification of resonances (black). J = 0 CRP (red).

Image of FIG. 8.
FIG. 8.

Initial state selected integral cross sections as a function of collision energy for reaction HCl(ν) + CH3 → Cl + CH4.

Image of FIG. 9.
FIG. 9.

Initial state selected nonadiabatic branching ratio for HCl(ν) + CH3 → Cl(2P1/2) + CH4.

Image of FIG. 10.
FIG. 10.

Ground state nonadiabatic cross section ratio for Cl* + CH4 → HCl + CH3.

Image of FIG. 11.
FIG. 11.

Nonreactive inelastic probability for the Cl + CH4 (ν = 0) → Cl* + CH4 transition.

Tables

Generic image for table
Table I.

Basis set tests for reaction HCl + CH3 Cl + CH4. CCSD(T) relative energies in kcal mol−1; vibrationally corrected barrier heights shown in parentheses.

Generic image for table
Table II.

TS geometric parameters at MP2/cc-pV(T+d)Z-dk level of theory. Stationary point moments of inertia in amu× bohr2.

Generic image for table
Table III.

Harmonic frequencies for stationary points at the MP2/cc-pV(T+d)Z-dk level, in cm−1. Transition state frequencies are given prior to (pre) and following (post) curvilinear projection of explicitly treated vibrational modes.

Generic image for table
Table IV.

PES parameters for the IB and the Q//T surfaces. The number of ab initio grid points (#) and the sum of squared residuals (SSR/a.u.2) are given for each surface. The total number of grid points including evaluated data is shown in parenthesis.

Generic image for table
Table V.

SOC surface parameters. Powers of 10 in parentheses. The number of ab initio grid points (#) and the sum of squared residuals (SSR/a.u.2) are given for each surface.

Generic image for table
Table VI.

Energetic properties of ground state diabatic and adiabatic IB surfaces for reaction HCl + CH3 Cl + CH4. Energies given in kcal mol−1.

Generic image for table
Table VII.

Scattering numerical parameters.a

Generic image for table
Table VIII.

Theoretical thermal rate constants for CH3 + HCl CH4 + Cl (2P3/2) on (IB). Rates given in cm3 molecule−1 s−1; powers of ten shown in parentheses.

Generic image for table
Table IX.

Approximate location of nonadiabatic transition for the HCl + CH3 → Cl* + CH4 reaction.

Generic image for table
Table X.

Branching ratio model for nonadiabatic production of Cl*. Energies in cm−1, branching ratio at 1.3 eV.

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/content/aip/journal/jcp/134/20/10.1063/1.3592732
2011-05-26
2014-04-18
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Reduced dimensionality spin-orbit dynamics of CH3 + HCl ⇌ CH4 + Cl on ab initio surfaces
http://aip.metastore.ingenta.com/content/aip/journal/jcp/134/20/10.1063/1.3592732
10.1063/1.3592732
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