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Photodissociation of carbon dioxide in singlet valence electronic states. I. Six multiply intersecting ab initio potential energy surfaces
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10.1063/1.4808369
/content/aip/journal/jcp/138/22/10.1063/1.4808369
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/22/10.1063/1.4808369

Figures

Image of FIG. 1.
FIG. 1.

Cuts through the PESs of the states 1, 2, 3 ′ (a, c, e) and 1, 2, 3 ″ (b, d, f) along one CO bond distance . The fixed bond angle is indicated in each panel. The second CO bond is fixed at 2.2  in (a-d). In (e) and (f), the OO bond is kept fixed at 2.3  . Dots are the adiabatic energies. Solid lines are states diabatized at bent CIs as described in Sec. IV A . For ″ states, the ground electronic state , shown with gray dots, sets the vertical energy scale.

Image of FIG. 2.
FIG. 2.

Cuts through the PESs of the states 1, 2, 3 ′ (a, c) and 1, 2, 3 ″ (b, d) along bond angle α. The two CO bonds are fixed at 2.2  (a, b) and at 2.5  (c, d). Dots are the adiabatic energies. Solid lines are states diabatized at bent CIs as described in Sec. IV A .

Image of FIG. 3.
FIG. 3.

Contour maps of the ground electronic state : ( , ) plane, with α fixed at 179° (a) and 70° (b), and ( , α) plane with fixed at 2.2  (c) and 2.6  (d). Energy of the dotted contour in (a), (c), and (d) is 2.1 eV, in (b) it is 8.4 eV. Contour spacing is 0.35 eV.

Image of FIG. 4.
FIG. 4.

Contour maps in the ( , ) plane of the adiabatic states 2 ′ (a) and 3 ′ (b) for α = 179°. The states are components of 1Π and 1Δ, respectively. Black solid line in each panel indicates the closed CI seam for ′ (a) and ″ (b) symmetry states. Energy of the dotted contour is 7.5 eV, and the contour spacing is 0.25 eV.

Image of FIG. 5.
FIG. 5.

Contour maps in the ( , α) plane of the adiabatic states 2 ′ (a), 3 ′ (b), 1 ″ (c), and 3 ″ (d). The second CO bond is fixed at 2.2  . Energy of the dotted contour is 7.6 eV, and the contour spacing is 0.20 eV.

Image of FIG. 6.
FIG. 6.

Contour maps in the ( , ) plane of the adiabatic states 2 ′ (a), 3 ′ (b), 1 ″ (c), and 3 ″ (d). The angle α is fixed at 160°. Energy of the dotted contour is 8.0 eV, and the contour spacing is 0.25 eV.

Image of FIG. 7.
FIG. 7.

CASSCF energies of the electronic states 1—5 ′ (a, c) and 1—5 ″ (b, d) along one CO bond distance . The second CO bond is fixed at 2.4  : the fixed bond angle is indicated in each panel. In all panels, dots and solid lines denote adiabatic energies. In panels (a) and (b), lines are color coded according to the values as explained in text. Following a particular color, one follows a diabatic state. Diabatic assignments using spectroscopic symbols are given. Arrows in panel (b) indicate the Δ/Π CIs discussed in Sec. III C . For ″ states, the ground electronic state , shown with gray dotted line, sets the vertical energy scale.

Image of FIG. 8.
FIG. 8.

Adiabatic CASSCF energies of states 1—5 ′ (a) and 1—5 ″ (b) along the bond angle. Fixed CO bond distances are 2.4  and 2.5  . The two uppermost states in each symmetry block are drawn gray. Arrow indicates direction towards the carbene-like OCO minimum in the given state. Correlation with the diabatic states at linearity is marked to the right of each panel.

Image of FIG. 9.
FIG. 9.

Diabatic potentials (diagonal matrix elements) for the Σ (green), Π (blue), and Δ (red) states and the off-diagonal couplings (black solid line) as functions of one CO bond distance. ′ and ″ states are shown in (a) and (b), respectively. The second CO bond is fixed at 2.2  and the bond angle is fixed at 175°. Black dashed line is the ground electronic state.

Image of FIG. 10.
FIG. 10.

The diabatic potentials (a), (c), (b), and (d), and the off-diagonal coupling elements (e) and (f) in the ( , α) plane with the CO bond fixed at 2.2 . Energy of the dotted contour in (a)–(d) is 8.6 eV, and the contour spacing is 0.20 eV. In (e) and (f), the respective numbers are −1.20 eV and 0.20 eV.

Tables

Generic image for table
Table I.

Properties of the adiabatic ground electronic state : The OCO bond angle (α, in °), CO, and OO bond distances (in ), and the energy Δ relative to the global minimum (in eV, including the vibrational ZPE corrections), calculated for three equilibrium geometries and the two arrangement channels.

Generic image for table
Table II.

Energies (in cm) of the low lying vibrational states in the ground electronic state , measured relative to the ground level (0, 0, 0). The states calculated with the original potential (“PES1”) and with the potential rescaled along the symmetric stretch and the bend (“PES2”) are compared with the best theoretical estimates of Refs. and with the experimental values of Ref. (denoted “Expt.”). The energy difference (in cm) is shown in parenthesis. The quantum numbers are defined in text.

Generic image for table
Table III.

Properties of the PESs of the first five excited singlet states of CO: Vertical excitation energy (in eV); band origin (in eV), which includes ZPEs of the ground and the excited electronic states; equilibrium CO bond lengths and (in ); equilibrium OCO bond angle α (in °); quantum mechanical vibrational frequencies ω, ω, and ω near equilibrium (in cm); quantum mechanical dissociation thresholds (O/CO) and (C/O2) in the O + CO and C + O arrangement channels, respectively (in eV).

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/content/aip/journal/jcp/138/22/10.1063/1.4808369
2013-06-12
2014-04-18
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Photodissociation of carbon dioxide in singlet valence electronic states. I. Six multiply intersecting ab initio potential energy surfaces
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/22/10.1063/1.4808369
10.1063/1.4808369
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