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Wave packet calculations on nonadiabatic effects for the O(3 P)+HF(1Σ+) reaction under hyperthermal conditions
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10.1063/1.4753811
/content/aip/journal/jcp/137/11/10.1063/1.4753811
http://aip.metastore.ingenta.com/content/aip/journal/jcp/137/11/10.1063/1.4753811

Figures

Image of FIG. 1.
FIG. 1.

(Top) Minimum energy path for the O(3 P)+HF reaction (in eV) for the two first energy roots; (left) for the adiabatic 13 A and 23 A states, denoted E and E +, respectively, resulting from the regularized diabatic states of Ref. 26; (right) for the diabatic 3Σ and 3Π states (denoted E 0 and E1) at a collinear geometry. (Bottom) Contour plots (in eV) of the two diabatic (left) 3Σ and (right) 3Π state at OHF collinear geometry, indicating with a line in black the conical intersection seams.

Image of FIG. 2.
FIG. 2.

Total reaction probabilities as a function of collision energy for the O(3 P)+HF(v = 0, j = 0) reaction at total angular momentum J = 0. Top panel: sum over initial electronic states in the diabatic and adiabatic representations. Middle panel: comparison between the adiabatic 23A probability and that obtained in the 2×2 diabatic representation starting in the 3Π state. Bottom panel: The same but for the ground adiabatic 13A state and for the initial diabatic 3Σ state for each of the two diabatic electronic states (considering the 2×2 electronic diabatic Hamiltonian).

Image of FIG. 3.
FIG. 3.

Total reaction probabilities as a function of the collision energy calculated for the O(3 P)+HF(v = 0, j = 0) reaction on the 13 A (left panels) and 23 A (right panels) initial adiabatic electronic states at several values of the total angular momentum J using the CS approximation in reactant (red) and product (black) Jacobi coordinates and the CC methodology (blue).

Image of FIG. 4.
FIG. 4.

Electronically and vibrationally state-resolved reaction probabilities as a function of collision energy for the O(3 P)+HF(α,v = 0, j = 0)→OH(α,v′ = 0–2)+F reaction at J = 0. Bottom panels: ending in the same diabatic electronic state of the initial wave packet (α = α = 3Σ or 3Π). Middle panels: with different initial and final electronic state (α ≠ α). Top panels: obtained in the adiabatic representation for the 13 A (left) and 23 A (right) states.

Image of FIG. 5.
FIG. 5.

Electronically and rotationally state-resolved reaction probabilities as a function of collision energy for the O(3 P)+HF(α,v = 0, j = 0)→OH(α,v′ = 0, j = 0–3)+F reaction at J = 0. Bottom panels: ending in the same diabatic electronic state of the initial wave packet (α = α = 3Σ or 3Π). Middle panels: with different initial and final electronic state (α ≠ α). Top panels: obtained in the adiabatic representation for the 13 A (left) and 23 A (right) states.

Image of FIG. 6.
FIG. 6.

Rotationally state-resolved reaction probabilities as a function of collision energy for the O(3 P)+HF(v = 0, j = 0)→OH(v′ = 0, j = 0–5)+F reaction at J = 0 calculated in the adiabatic (red) and diabatic (blue) representations.

Image of FIG. 7.
FIG. 7.

Total integral cross sections as a function of collision energy for the O(3 P) + HF(v = 0, j = 0)→OH+F reaction in the adiabatic and diabatic representations. Bottom panel: obtained for the adiabatic 13 A and 23 A and diabatic 3Σ and 3Π states. Middle panel: total diabatic versus total adiabatic. Top panel: diagonal and nondiagonal cross sections obtained in the diabatic representation for the two initial and final electronic states.

Image of FIG. 8.
FIG. 8.

Vibrationally state-resolved integral cross section as a function of collision energy for the O(3 P)+HF(v = 0, j = 0)→OH(v′)+F reaction obtained for the 13 A and 23 A adiabatic states and for the 3Σ and 3Π coupled diabatic states as indicated. In the diabatic cases, the cross sections for the two possible final electronic states have been added.

Image of FIG. 9.
FIG. 9.

Product rotational distributions for the O(3 P)+HF(v = 0, j = 0)→OH(v′, j )+F reaction at selected collision energies: 1.8 eV (black squares), 2.0 eV (open circles), 2.2 eV (black circles), and 2.4 eV (open triangles), for the adiabatic 13 A and 23 A states and for the diabatic 3Σ and 3Π coupled states as indicated. In the diabatic states, the cross sections for the two possible final electronic states have been added.

Image of FIG. 10.
FIG. 10.

Total integral cross section as a function of the total energy for the O(3 P)+HF(v = 0,1,2, j = 0) reaction. Exact CC calculations for v = 0 (red). J-shifting calculations for v = 0 (blue), v = 1 (green), and v = 2 (grey). Notice the very good agreement between the exact CC and J-shifting calculations for v = 0.

Tables

Generic image for table
Table I.

Parameters used in the wave packet calculations in product Jacobi coordinates. Distances are in Å, and energies in eV.

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/content/aip/journal/jcp/137/11/10.1063/1.4753811
2012-09-21
2014-04-19
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Wave packet calculations on nonadiabatic effects for the O(3P)+HF(1Σ+) reaction under hyperthermal conditions
http://aip.metastore.ingenta.com/content/aip/journal/jcp/137/11/10.1063/1.4753811
10.1063/1.4753811
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