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Photoexcited conversion of gauche-1,3-butadiene to bicyclobutane via a conical intersection: Energies and reduced density matrices from the anti-Hermitian contracted Schrödinger equation
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10.1063/1.3606466
/content/aip/journal/jcp/135/2/10.1063/1.3606466
http://aip.metastore.ingenta.com/content/aip/journal/jcp/135/2/10.1063/1.3606466

Figures

Image of FIG. 1.
FIG. 1.

The MCSCF (top), MRPT2 (middle), and ACSE (bottom) potential energy curves for a reaction pathway from photoexcited gauche-1,3-butadiene to bicyclobutane are plotted as a function of path distance from the disrotatory transition state. The critical points GBUT, the CI, the TSD, and BIBUT are all labeled. The conical intersection was given an arbitrary path distance based upon its geometric similarity to the TSD. Details of the selected reaction pathway are given in the text.

Image of FIG. 2.
FIG. 2.

Critical points on the potential energy surface for the photoexcited conversion of gauche-1,3-butadiene to bicyclobutane as computed by the ACSE in the 6-31G* basis set. The solid lines represent a path for the conversion of excited-state reactants to ground-state products, and the dashed lines represent a potential reverse reaction. Further details of the selected reaction pathway are provided in the text. Energies relative to gauche-1,3-butadiene are computed in kcal/mol.

Tables

Generic image for table
Table I.

Total energies (H) and relative energies (kcal/mol) are reported for the ground and first excited states of gauche-1,3-butadiene (GBUT), the conical intersection (CI), the disrotatory transition state (TSD), the conrotatory transition state (TSC), and bicyclobutane (BIBUT) in the 6-31G* basis set.

Generic image for table
Table II.

Excitation energies (mH) are reported for gauche-1,3-butadiene (GBUT), the conical intersection (CI), the disrotatory transition state (TSD), the conrotatory transition state (TSC), and bicyclobutane (BIBUT) in the 6-31G* basis set.

Generic image for table
Table III.

Energies relative to the MCSCF (mH) are reported for the ground and first excited states of gauche-1,3-butadiene (GBUT), the conical intersection (CI), the disrotatory transition state (TSD), the conrotatory transition state (TSC), and bicyclobutane (BIBUT) in the 6-31G* basis set.

Generic image for table
Table IV.

Natural occupation numbers are reported for the ground and first excited states of the disrotatory transition state (TSD) and the conical intersection (CI) in the 6-31G* basis set from the MCSCF and ACSE methods.

Generic image for table
Table V.

Natural occupation numbers are reported for the ground and first excited states of gauche-1,3-butadiene (GBUT) and bicyclobutane (BIBUT) in the 6-31G* basis set from the MCSCF and the ACSE methods.

Generic image for table
Table VI.

The lowest 2 D, 2 Q, and 2 G eigenvalues are reported for the ground and first excited states of gauche-1,3-butadiene (GBUT), the conical intersection (CI), the disrotatory transition state (TSD), the conrotatory transition state (TSC), and bicyclobutane (BIBUT) in the 6-31G* basis set.

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/content/aip/journal/jcp/135/2/10.1063/1.3606466
2011-07-12
2014-04-19
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Photoexcited conversion of gauche-1,3-butadiene to bicyclobutane via a conical intersection: Energies and reduced density matrices from the anti-Hermitian contracted Schrödinger equation
http://aip.metastore.ingenta.com/content/aip/journal/jcp/135/2/10.1063/1.3606466
10.1063/1.3606466
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