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Quantum dynamics study of fulvene double bond photoisomerization: The role of intramolecular vibrational energy redistribution and excitation energy
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10.1063/1.3643767
/content/aip/journal/jcp/135/13/10.1063/1.3643767
http://aip.metastore.ingenta.com/content/aip/journal/jcp/135/13/10.1063/1.3643767

Figures

Image of FIG. 1.
FIG. 1.

Potential energy surface sketch for the S1 and S0 states of fulvene along the torsional and symmetric bond alternation coordinates, displaying the paths for photostability (1) and photoisomerization (2).

Image of FIG. 2.
FIG. 2.

(a) Potential energy profile for the initial excited state relaxation coordinate along planar structures (energies in eV with respect to S1 energy at FC structure; ab initio data in blue and model data in red). (b) Bond lengths in Å for optimized structures along the relaxation coordinate.

Image of FIG. 3.
FIG. 3.

(a)–(h) Relevant conical intersection structures for fulvene, showing the mass-weighted displacements corresponding to the gd and ic vectors. (i) and (j) Torsion and pyramidalization coordinates.

Image of FIG. 4.
FIG. 4.

Electronic wave function analysis along the torsional coordinate. (a) Correlating orbitals involved in the excitations. (b) Electronic states and dominant configurations.

Image of FIG. 5.
FIG. 5.

Plot of the model surfaces in the (,φ) plane (cuts for (,θ) = (0,0)). Dark surface: W11; light surface: W22.

Image of FIG. 6.
FIG. 6.

Seam energy and locus of the seam in the (,φ) plane (a and b, respectively; cuts for (,θ) = (0,0)), comparing the model (continuous line) with the ab initio data (full diamonds).

Image of FIG. 7.
FIG. 7.

(a) Reactant and product populations for the two adiabatic states after instantaneous vertical excitation. (dotted line); (short hashed line); (long hashed line); (continuous line). (b) Detailed plot of and . (c) Same as (a) for the diabatic states.

Image of FIG. 8.
FIG. 8.

(a) Reactant and product adiabatic populations for the two states after excitation with a pulse of 25 fs and 3.0 eV (see Eq. (9)). (dotted line); (short hashed line); (long hashed line); (continuous line). (b) Detailed plot of and .

Image of FIG. 9.
FIG. 9.

(a) Reactant and product adiabatic populations for the two states after excitation with a pulse of 25 fs and 2.0 eV (see Eq. (9)). (dotted line); (short hashed line); (long hashed line); (continuous line). (b) Detailed plot of and .

Tables

Generic image for table
Table I.

Energies of the optimized critical points relative to CI plan at the ab initio level (CASSCF and CASPT2) compared to the four-dimensional model Hamiltonian W.

Generic image for table
Table II.

Summary of propagation results.

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/content/aip/journal/jcp/135/13/10.1063/1.3643767
2011-10-03
2014-04-20
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Quantum dynamics study of fulvene double bond photoisomerization: The role of intramolecular vibrational energy redistribution and excitation energy
http://aip.metastore.ingenta.com/content/aip/journal/jcp/135/13/10.1063/1.3643767
10.1063/1.3643767
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