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Global potential energy surfaces for collisions
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10.1063/1.3475564
/content/aip/journal/jcp/133/16/10.1063/1.3475564
http://aip.metastore.ingenta.com/content/aip/journal/jcp/133/16/10.1063/1.3475564

Figures

Image of FIG. 1.
FIG. 1.

Energy level diagram of the three lowest triplet electronic states of the system. The fitted surfaces examined in this work are indicated to the left of the vertical dashed line. The geometries of the transition structures TS1 and TS5 are given in atomic units and radians.

Image of FIG. 2.
FIG. 2.

The RMSD given in is plotted vs energy bin for (a) the S1 surface, (b) the S2 surface, and (c) the S3 surface.

Image of FIG. 3.
FIG. 3.

Contour plots of the reaction. The S1, S2, and S3 state results for the calculations are given in (a), (b), and (c), respectively. The S1, S2, and S3 state results for the fitted PESs are given in (d), (e), and (f), respectively. The geometry is defined according to the TS1 transition state shown in Fig. 1. The (abscissa) and (ordinate) are varied to produce the energy contours. The energy zero corresponds to the equilibrium geometry of the separated reactants.

Image of FIG. 4.
FIG. 4.

Contour plots of the reaction. The S1, S2, and S3 state results for the calculations are given in (a), (b), and (c), respectively. The S1, S2, and S3 state results for the fitted PESs are given in (d), (e), and (f), respectively. The geometry is defined according to the TS5 transition state shown in Fig. 1. The (abscissa) and (ordinate) are varied to produce the energy contours. The energy zero corresponds to the equilibrium geometry of the separated reactants.

Image of FIG. 5.
FIG. 5.

The potential energy contours in Jacobi coordinates: (a) the S1, (b) the S2, and (c) the S3 electronic states of the PES of the current work; (d) the S1, (e) the S2, and (f) the S3 electronic states of Ref. 12. The triatom-atom Jacobi-like coordinate system of Ref. 26 is used as shown in the inset of (f), where is the distance from O atom to H, starts from the center of mass of , starts from the center of mass of , is the angle between and , and is the angle between and . All atoms are in the same plane, and the inset in (f) is not to scale. From the TS1 geometry given in Fig. 1, , , and are determined. With , , and fixed, the coordinates (abscissa) and (ordinate) are then varied to produce the contours.

Image of FIG. 6.
FIG. 6.

Potential energy contours of (a) the S1, (b) the S2, and (c) the S3 electronic states of the PES of the current work and those of (d) the S1, (e) the S2, and (f) the S3 electronic states of Ref. 12. The reactant is fixed at the corresponding geometry of TS5 shown in Fig. 1 with the location of the attacking oxygen varying in the plane of the . Lengths are given in atomic units.

Image of FIG. 7.
FIG. 7.

Rate constants in as a function of temperature in Kelvin. The hydrogen abstraction reaction is denoted with black lines and the elimination reaction is denoted with red lines. The filled circles are the current work, the filled triangles are the previous results from Ref. 12, the open squares are the experimental results of Ref. 29, the open diamonds are the experimental results of Ref. 28, and the open left triangles are derived from the computational results of Ref. 14. Note that the reaction rates of the elimination reaction are multiplied by 1000 for visualization purposes.

Image of FIG. 8.
FIG. 8.

(a) The total calculated cross sections as a function of collision energy in for the hydrogen abstraction reaction (black lines) and hydrogen elimination reaction (red lines). The filled circles are the current work, the filled triangles are the previous results from Ref. 12, the filled squares are the computational results of Ref. 7, and the open diamonds are the experimental results of Ref. 7. (b) The unweighted state resolved abstraction (black) and elimination (red) cross sections for the S1 state (solid lines), S2 state (dashed lines), and S3 state (dotted lines).

Image of FIG. 9.
FIG. 9.

(a) Opacity functions for the hydrogen abstraction (black) and elimination (red) reactions plotted vs impact parameter in atomic units. The S1 state is shown in solid lines, the S2 state is shown in dashed lines, and the S3 state is shown in dotted lines. (b) Opacity function for the hydrogen abstraction reaction for our previous simulation, Ref. 12, plotted vs impact parameter in atomic units. The S1 state is the solid line, the S2 state is the dashed line, and the S3 state is the dotted line.

Image of FIG. 10.
FIG. 10.

Velocity-flux contours , in units of . (a) The differential cross section of the OOH elimination product at collision energy of . (b)–(c) The differential cross section active OH product (formed from the attacking O-atom) at a collision energies of 49.6 and , respectively. (d)–(f) The differential cross sections of for nonreactive collisions at energies of 16.2, 49.6, and , or collision velocities of 4, 7, and , respectively. Note in (d)–(f) the contour scale is logarithmic.

Tables

Generic image for table
Table I.

Stationary point comparison between the fitted PES and the calculations for the reaction . All energies are given in relative to the reactant asymptote. The columns list energies of TS1 relative to the asymptote. The columns list energies of the product relative to the asymptote. Values in parentheses include zero-point correction. The geometry of the TS1 structure is given in Fig. 1 and is the same for each surface. Literature values are (a) Ref. 14 using from larger basis sets, (b) Ref. 7 using CCSD(T)/aug-cc-pVTZ, and (c) Ref. 5 which can be considered as benchmark.

Generic image for table
Table II.

Stationary point comparison between the fitted PES and the calculations for the reaction . All energies are given in relative to the reactant asymptote. The columns list energies of TS5 relative to the asymptote. The columns list energies of the product relative to the asymptote. Values in parentheses include zero-point correction. The geometry of the TS5 structure is given in Fig. 1 and is the same for the first two surfaces. Literature values are (a) Ref. 14 using from larger basis sets, (b) Ref. 7 using CCSD(T)/aug-cc-pVTZ, (c) Ref. 6 which can be considered as benchmark, and (d) Ref. 6 for S1 (Ref. 18).

Generic image for table
Table III.

Reaction rate constant parameters for the hydrogen abstraction and elimination reactions fit to the Arrhenius equation, for the computed reaction rates in the temperature range of 500–4000 K for products and 1500–4000 K for products.

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/content/aip/journal/jcp/133/16/10.1063/1.3475564
2010-10-27
2014-04-17
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Global potential energy surfaces for O(P3)+H2O(A11) collisions
http://aip.metastore.ingenta.com/content/aip/journal/jcp/133/16/10.1063/1.3475564
10.1063/1.3475564
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