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AsH3 ultraviolet photochemistry: An ab initio view
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10.1063/1.4727851
/content/aip/journal/jcp/136/22/10.1063/1.4727851
http://aip.metastore.ingenta.com/content/aip/journal/jcp/136/22/10.1063/1.4727851

Figures

Image of FIG. 1.
FIG. 1.

Bending PESs for the low-lying states of AsH3 computed at R = 2.850 a 0 = without including SO coupling. The A 1 states are shown in black, the E states in red, the singlet states with solid lines and closed circles, the triplet states with dashed lines and open circles. The vertical dashed line indicates the equilibrium angle (θ = 123.9°) for the ground state.

Image of FIG. 2.
FIG. 2.

Minimal-energy-path PESs for the low-lying states of AsH3 computed in C 3v symmetry (R 1 = R 2 = R 3) without including SO coupling. Notation is the same as in Fig. 1.

Image of FIG. 3.
FIG. 3.

PES along the H2As–H recoil coordinate for the low-lying states of AsH3 computed without including SO coupling for R 1 = R 2 = 2.850 a 0 and θ = 123.9°. The 1 A states are shown in black, 1 A in red, 3 A in blue, 3 A in green.

Image of FIG. 4.
FIG. 4.

PES along the H2As–H recoil coordinate for the low-lying states of AsH3 computed without including SO coupling for R 1 = R 2 = 2.850 a 0 and θ = 90° (planar geometry). The 1 A states are shown in black, 1 A in red, 3 A in blue, 3 A in green.

Image of FIG. 5.
FIG. 5.

Calculated 2D PESs for the and states of AsH3 as functions of one As–H distance and the θ angle. The other two As–H distances are fixed at the ground state equilibrium value of 2.850 a 0.

Image of FIG. 6.
FIG. 6.

Calculated transition moments (red) and (blue) obtained as functions of the θ angle in the C 3v group for R 1 = R 2 = R 3 = 2.850 a 0 (see text).

Image of FIG. 7.
FIG. 7.

Calculated transition moments for Cartesian components of the and transitions obtained as functions of the H2As–H recoil coordinate for R 1 = R 2 = 2.850 a 0 and θ = 123.9°.

Tables

Generic image for table
Table I.

Equilibrium H–X–H angles α and bending angles θ, and inversion barriers E inv for the and states of the XH3 molecules. θ = 90° corresponds to planar geometry.

Generic image for table
Table II.

Technical details of the MRD–CI calculations of AsH3 in C s symmetry at T = 0.1 μE h . N ref and N root refer to the number of reference configurations and roots treated, respectively. SAFTOT designates the total number of generated spin-adapted functions (SAF), and SAFSEL the number of selected SAFs at R e = 2.850 a 0 and θ e = 123.9°.

Generic image for table
Table III.

MRD–CI geometries, vertical excitation energies E vert and energies E for selected features in the bending potentials of AsH3. Notation min and max used in the third column corresponds to the global and local extrema in the Λ − S bending PESs.

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/content/aip/journal/jcp/136/22/10.1063/1.4727851
2012-06-13
2014-04-23
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: AsH3 ultraviolet photochemistry: An ab initio view
http://aip.metastore.ingenta.com/content/aip/journal/jcp/136/22/10.1063/1.4727851
10.1063/1.4727851
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