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Ab Initio studies of the interaction potential for the Xe–NO(X2Π) van der Waals complex: Bound states and fully quantum and quasi-classical scattering
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10.1063/1.4731286
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Affiliations:
1 Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742-2021, USA
3 Department of Chemistry, Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Road, Oxford, OX1 3QZ, United Kingdom
a) Electronic mail: jklos@umd.edu.
b) Electronic mail: aoiz@quim.ucm.es.
c) Electronic mail: mark.brouard@chem.ox.ac.uk.
J. Chem. Phys. 137, 014312 (2012)
/content/aip/journal/jcp/137/1/10.1063/1.4731286
http://aip.metastore.ingenta.com/content/aip/journal/jcp/137/1/10.1063/1.4731286

## Figures

FIG. 1.

Radial V lm (R) expansion coefficients of the (a) V sum and (b) V diff diabats, respectively.

FIG. 2.

Contour plots of the adiabatic surfaces, (a) A and (b) A ′′. Energy in cm−1. γ = 0° corresponds to the linear Xe–N–O configuration. The contour corresponding to 508 cm−1 represents that of the collision energy of 63 meV. Negative energy contours, dashed (blue) line; positive energy contours, solid (red) line.

FIG. 3.

Contour plots of the diabatic surfaces, (a) V sum and (b) V diff. Energy in cm−1. γ = 0° corresponds to the linear Xe–N–O configuration. The contour corresponding to 508 cm−1 represents the collision energy of 63 meV. Contours as in Fig. 2.

FIG. 4.

Integral cross sections at E col = 63 meV for rotational transitions from the initial j = 0.5 and Ω = 1/2 NO rotational state. Open squares and solid (blue) line, o–s QM data; open circles and dotted-dashed (black) line, c–s QM data; filled circles and dashed (red) line, QCT results. The o–s QM results are summed over final Λ-doublet and Ω states and averaged over initial Λ-doublet levels.

FIG. 5.

Open-shell QM integral cross sections at E col = 63 meV from j = 0.5, Ω = 1/2, and ε = +1 (e) initial state into the Ω = 1/2, F 1 (upper panel) and Ω = 3/2, F 2 (lower panel) manifolds. Open (blue) circles ee transitions; filled (red) circles ef transitions.

FIG. 6.

Integral cross sections for collision energy E col = 63 meV from the initial rotational states: (a) j = 2.5, (b) j = 5.5, (c) j = 8.5, and (d) j = 14.5 (j = 0, 2, 8, and 14, respectively, for c–s calculations). The QM o–s results are summed over final Λ-doublet and Ω states and averaged over initial Λ-doublet levels. Lines and symbols as in Fig. 4.

FIG. 7.

Top panel: Total opacity functions, P(J; j = 0.5), from QCT (dashed, red line), open-shell QM (solid, blue line) and closed-shell QM (dotted-dashed, black line) calculations for E col = 63 meV for initial rotational state Ω=1/2, j = 0.5 (j = 0 for c–s calculations). Bottom panel: Total (summed over final rotational states) opacity functions from the o–s QM calculations resolved for the final spin–orbit manifold with Ω = 1/2 (F1) and Ω = 3/2 (F2), respectively. They sum up to form a red dashed line representing the total o–s QM P(J). The upper x axes show the corresponding values of the impact parameter, b = [ℓ(ℓ + 1)]1/2/k, where k = (2μE coll)1/2/ℏ.

FIG. 8.

Rotationally state resolved opacity functions, P(J; j = 0 → j ), from closed-shell QM calculations for E col = 63 meV for various odd Δj transitions. The arrows in each panel indicate the J value of the glory associated to the L-type rainbow; all of them correspond to a value of J = 123. As can be seen, for Δj > 5 the bulge associated with the rainbow scattering is absent.

FIG. 9.

Total opacity functions from the closed-shell QM calculations at collision energy E col = 63 meV for the initial rotational state j = 0 for the series of Rg–NO(X) systems.

FIG. 10.

Total opacity P(J; j) functions from the QCT (top panel), o–s QM, (middle panel) and c–s QM (bottom panel) calculations for E col = 63 meV as a function of initial rotational state j. The o–s results are averaged and summed over the two initial and final, respectively, lambda doublet components transitions and summed over F 1F 1 and F 1F 2 transitions.

FIG. 11.

Panel (a): Classical deflection function (scattering angle vs. impact parameter) for rotationally inelastic scattering of NO in its ground state (j = 0) with Xe at 63 meV collision energy. Deflection angles above the glory impact parameter (≈4.2 Å) are negative, corresponding to far-side collisions. The top x axis shows the values of the orbital angular momentum. Panel (b): Total differential cross sections from the QCT, o–s QM, and c–s QM calculations at E col = 63 meV for initial rotational state j = 0.5 (j = 0 for c–s calculations). The o–s QM DCS is summed over all final states and averaged over initial fine states.

FIG. 12.

State-to-state angular distributions, 2πsin θdσ/dω, for selected transitions out of the initial j = 0.5 rotational level from the QCT and o–s QM calculations at E col = 63 meV. The o–s QM DCSs are summed over Ω = 1/2, 3/2 and e and f final states and averaged over initial e and f states. Solid (blue) line, o–s QM data; dashed (red) line, QCT data.

FIG. 13.

Same as Fig. 12 but out of the initial j = 14.5 rotational level at a collision energy of E col = 63 meV.

FIG. 14.

o–s QM DCS for selected transitions out of the initial j = 0.5 rotational level and selected Λ-doublet components at E col = 63 meV. The left and right columns display the parity breaking and parity conserving transitions, respectively.

## Tables

Table I.

Dispersion coefficients, C n, l , of the V sum diabat of the Xe–NO(X 2Π) complex in units of .

Table II.

The interaction energies at the stationary points of adiabatic A and A ′′ surfaces, and the diabatic V sum surface.

Table III.

Selected bound states (up to an energy of −68 cm−1) of Xe–NO(X 2Π) complex for up to . Energies are in cm−1 relative to the energy of the separated monomers. n s and n b specify the number of nodes in the van der Waals stretching and bending modes of the complex, respectively. The P quantum number denotes the projection of the total angular momentum J on the z axis of the molecular frame. The + and − signs denote the total parity p.

Table IV.

Integral cross sections obtained from the o–s QM, c–s QM, and QCT scattering calculations for Ecol = 63 meV with respect to the initial state with j = 1/2, Ω = 1/2, ε = +1 (e), or ε = −1 (f) (j = 0 in case of the closed-shell and QCT approach). The SO-conserving (F1 →F1) and SO-changing (F1 →F2) o–s QM cross sections are given resolved for initial and final Λ-doublets and also summed over final and averaged over initial Λ-doublet and summed over final Ω (ΔΩ = 0 + ΔΩ = 1 column). Cross sections are in units of Å2.

/content/aip/journal/jcp/137/1/10.1063/1.4731286
2012-07-06
2014-04-18

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