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The ultraviolet spectrum of OCS from first principles: Electronic transitions, vibrational structure and temperature dependence
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10.1063/1.4739756
/content/aip/journal/jcp/137/5/10.1063/1.4739756
http://aip.metastore.ingenta.com/content/aip/journal/jcp/137/5/10.1063/1.4739756

Figures

Image of FIG. 1.
FIG. 1.

Upper panel: Potential energy surfaces for the 1–2 1 A states (black), the 3–5 1 A states (blue), and the first two 3 A states (red) along the dissociation coordinate R for r = 2.2 a 0 and γ = 5°. Lower panel: The same as in the upper panel but for states of A symmetry.

Image of FIG. 2.
FIG. 2.

Same as in Fig. 1 but along the bending coordinate γ for R = 4.2 a 0 and r = 2.2 a 0.

Image of FIG. 3.
FIG. 3.

Two-dimensional contour representations of the local PES of the X state (1 1 A ) with γ = 0° (a) and r = 2.2 a 0 (b). The spacing between the contours is 0.25 eV and the red contours represent 0.25 eV which is approximately the vibrational zero point energy.

Image of FIG. 4.
FIG. 4.

Two-dimensional contour representations of the potential energy surface of the A state (2 1 A ) with γ = 25° (a) and r = 2.2 a 0 (b). The spacing between the contours is 0.5 eV and the red contours represent 6.0 eV which is approximately the total energy, E ph + E 0, following excitation at λ = 223 nm. The blue dots mark the A state FC point: R = 4.23 a 0, r = 2.18 a 0, and γ = 8.4°. The FC point for the A state is defined as the expectation value of R, r, and γ for the ground state vibrational wave function times the A state TDM, i.e., Ψ(0, 0, 0) μA.

Image of FIG. 5.
FIG. 5.

Two-dimensional contour representations of the potential energy surface of the B state (1 1 A ) with γ = 25° (a) and r = 2.2 a 0 (b). Details are the same as in Fig. 4. The blue dots mark the B state FC point: R = 4.23 a 0, r = 2.16 a 0, and γ = 7.0°.

Image of FIG. 6.
FIG. 6.

Two-dimensional contour representations of the potential energy surface of the C state (2 1 A ) with γ = 25° (a) and r = 2.2 a 0 (b). Details are the same as in Fig. 4. The blue dots mark the C state FC point: R = 4.24 a 0, r = 2.19 a 0, and γ = 6.3°.

Image of FIG. 7.
FIG. 7.

Two-dimensional contour representation of the potential energy surface of the c state (2 3 A ) with γ = 25° (a) and r = 2.2 a 0 (b). Details are the same as in Fig. 4. The blue dots mark the c state FC point: R = 4.22 a 0, r = 2.20 a 0 and γ = 6.0°.

Image of FIG. 8.
FIG. 8.

Cuts along γ of the TDMs between the electronic ground state and the different excited states. Panel (a): A symmetry; panel (b): A symmetry. The singlet and triplet states are shown in black and red, respectively. The cut is at R = 4.3 a 0 and r = 2.2 a 0. The magnitudes of the transition dipole vectors are shown.

Image of FIG. 9.
FIG. 9.

Two-dimensional contour representations of |μA| for r = 2.2  a 0 The spacing between the contours is 0.05 au and the red contour represents 0.5 au. The blue dots marks the A state FC point (R = 4.23 a 0 and γ = 8.4°).

Image of FIG. 10.
FIG. 10.

Modulus of the autocorrelation functions (multiplied by 100) for photodissociation via the A state of OCS (black line) and N2O (red line). The initial vibrational state is (0, 0, 0).

Image of FIG. 11.
FIG. 11.

(a) Cross sections for excitation of the different singlet states A, B, and C; the initial vibrational state is (0, 0, 0). (b) The same as in (a) but for the triplet states a, b, c, and d.

Image of FIG. 12.
FIG. 12.

(a) The A state cross section for various initial vibrational states. (b) A state cross sections for various initial states multiplied by the Boltzmann weighting factor w i = Q −1(1 + v 2)exp ( − E i /(k B T)) with T = 300 K and Q being the partition function.

Image of FIG. 13.
FIG. 13.

The total cross section (scaled by a factor of 1.3) compared with the experimental cross section of Wu et al. 17 (shifted upward by 0.25 for clarity of the presentation). The temperature in the calculation and the measurement is 170 K.

Image of FIG. 14.
FIG. 14.

Temperature dependence of the total absorption cross section for four excitation energies. Calculations: solid lines (scaled by 1.3); measured cross sections:17 open squares.

Image of FIG. 15.
FIG. 15.

(a) Comparison of the calculated total cross section (multiplied by 1.3) and the measured cross section of Molina et al. 12 in the low-energy tail for two temperatures. (b) The contributions of the individual excited states as indicated for 295 K. (c) A state cross sections for initial vibrational states (0, v 2, 0). No extra scaling was applied in (b) and (c); none of the cross sections in (a), (b), and (c) was shifted on the energy scale.

Tables

Generic image for table
Table I.

Characteristics of the PESs of the excited singlet states A, B, and C and the triplet state c. The values V FC and |μFC| were calculated at an approximate FC point (R = 4.2 a 0, r = 2.2 a 0, and γ = 5°). Numbers in parentheses indicate powers of 10.

Generic image for table
Table II.

Characteristics of the local ground state PES. Bond lengths are given in a 0, dissociation energy D 0 in eV, and vibrational energies in cm−1.

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/content/aip/journal/jcp/137/5/10.1063/1.4739756
2012-08-06
2014-04-20
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: The ultraviolet spectrum of OCS from first principles: Electronic transitions, vibrational structure and temperature dependence
http://aip.metastore.ingenta.com/content/aip/journal/jcp/137/5/10.1063/1.4739756
10.1063/1.4739756
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