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Coupled-surface investigation of the photodissociation of : Effect of exciting the symmetric and antisymmetric stretching modes
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10.1063/1.3132222
/content/aip/journal/jcp/130/23/10.1063/1.3132222
http://aip.metastore.ingenta.com/content/aip/journal/jcp/130/23/10.1063/1.3132222

Figures

Image of FIG. 1.
FIG. 1.

Energy as a function of the longest N–H bond distance for the two lowest adiabatic states of based on fitted adiabatic surfaces from Ref. 55. The three N–H distances are denoted as . The minimum of the electronic state is planar with ( symmetry). The saddle point is planar with and ( symmetry), and the lowest-energy conical intersection is also planar. The minimum of the state is tetrahedral with . The zero of energy is the minimum of the ground electronic state. Reactant (i.e., ) as well as product (i.e., ) ZPEs are indicated. The vibrationally adiabatic curves for four sets of vibrational quantum numbers (see Fig. 2 for labeled curves) are represented above the segment of the reaction path comprised between the minimum of the electronic state and its saddle point. The energies of all the remaining vibrational levels studied in the present work are also indicated. Note that the diagram is only schematic (not to scale) between 1 and 5 eV and beyond 2 Å to make relevant quantities more discernible.

Image of FIG. 2.
FIG. 2.

Blowup of a key portion of Fig. 1 showing vibrationally adiabatic potential curves for the (0000), (1000), (0010), and (0600) states and energy levels for the remaining states studied in the present work. Vibrational quanta for and are indicated in bold to avoid confusion. The zero of energy is the minimum of the ground electronic state.

Image of FIG. 3.
FIG. 3.

H kinetic energy distributions at the end of FSTU/SD and simulations compared to experimental results of Hause et al. (Ref. 14) for . The maximum of the experimental distribution is normalized to 1, and the maxima of the theoretical distributions to 0.75 for ease of comparison.

Image of FIG. 4.
FIG. 4.

H kinetic energy distributions at the end of FSTU/SD and simulations compared to experimental results of Hause et al. (Ref. 14) for . The maximum of the experimental distribution is normalized to 1, and the maxima of the theoretical distributions to 0.75 for ease of comparison.

Image of FIG. 5.
FIG. 5.

Probability of producing excited-state products as a function of total energy for and (squares); and (rhombi); and (triangles); and , ; , ; , ; , ; and , (circles); and , ; , ; , ; , ; and , (crosses).

Image of FIG. 6.
FIG. 6.

Effective quantum number from single-surface calculations with , , and , (b) 0.01, (c) 0.1, and (d) 1/6.

Image of FIG. 7.
FIG. 7.

Effective quantum number from single-surface calculations with , , and , (b) 0.01, (c) 0.1, and (d) 1/6.

Image of FIG. 8.
FIG. 8.

Generalized-normal-mode vibrational frequencies in the adiabatic electronically excited state along the reaction path connecting the well to the saddle point . The frequencies were computed with the reaction coordinate (taken as the MEP in isoinertial coordinates downhill from the saddle point to the excited-state minimum) projected out. The curves reflect an adiabatic correlation of the vibrational modes.

Image of FIG. 9.
FIG. 9.

Vibrational frequencies in the adiabatic electronically excited state along the reaction path connecting the well to the saddle point . These frequencies were computed without projecting out the reaction coordinate; when a frequency becomes imaginary it is plotted as a negative number. The curves reflect an approximate diabatic correlation of the vibrational modes.

Tables

Generic image for table
Table I.

Excited-state populations as a function of initial vibrational state. For each method, results are ordered by increasing total energy.

Generic image for table
Table II.

Excited-state populations obtained with the FSTU method as a function of initial vibrational state. Results are ordered by increasing total energy.

Generic image for table
Table III.

Percentage of trajectories that dissociate after hops for , , and for different values of the diabatic coupling. [All calculations in this table employ a Wigner distribution for the modes with . The umbrella mode frequency is ; .]

Generic image for table
Table IV.

Average time of the first downward hop, percentage of trajectories that dissociate on the ground electronic state without attempting any upward hop, average fraction of attempted upward hops that are allowed, and average final probability for the excited electronic state, when or for different values of the diabatic coupling. [All calculations in this table employ a Wigner distribution for the modes with . The umbrella mode frequency is ; .]

Generic image for table
Table V.

Average time , average adiabatic energy gap , average maximum N–H distance , and average nonplanarity angle at the last downward hop. [All calculations in this table employ a Wigner distribution for the modes with . The umbrella mode frequency is ; .]

Generic image for table
Table VI.

Excited-state FSTU populations as a function of initial vibrational state for trajectories initiated at the state saddle point. Results are ordered by increasing total energy. [All calculations in this table employ a QC distribution for the modes with . The umbrella mode frequency is , and the initial conditions are EU (i.e., is unrestricted).]

Generic image for table
Table VII.

Classification of trajectories by their number of outer turning points and the potential surface to which they dissociate, for three pairs of initial vibrational states. [The (0010), (1000) calculations in this table are FSTU/SD calculations that employ a Wigner distribution for the modes with . The (0120) and (2100) calculations employ FSTU and a QC distribution. The (0340) and (4300) calculations employ FSTU and a Wigner distribution. The umbrella mode frequency is always , and the initial conditions correspond to .]

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2009-06-16
2014-04-16
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Coupled-surface investigation of the photodissociation of NH3(Ã): Effect of exciting the symmetric and antisymmetric stretching modes
http://aip.metastore.ingenta.com/content/aip/journal/jcp/130/23/10.1063/1.3132222
10.1063/1.3132222
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