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Role of surface crossings in the photochemistry of nitromethane
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10.1063/1.1851977
/content/aip/journal/jcp/122/8/10.1063/1.1851977
http://aip.metastore.ingenta.com/content/aip/journal/jcp/122/8/10.1063/1.1851977

Figures

Image of FIG. 1.
FIG. 1.

Geometries of the critical points of nitromethane localized on the singlet surfaces at the CAS (14,11)/ANO-L level; conical intersections calculated at the CAS(14,10)/ level. The arrows in the lower structures correspond to imaginary modes (for stationary points) or nonadiabatic coupling (left) and gradient difference (right) vectors (for conical intersections). (a) , staggered minimum; (b) , eclipsed minimum; (c) , first-order saddle point; (d) , transition state for dissociation into ; (e) , minimum; (f) , transition state for dissociation into ; (g) , first-order saddle point; (h) , transition state for dissociation into ; (i) conical intersection; (j) conical intersection; (k) (Ci3) conical intersection; and (l) conical intersection. Structures represented with the MACMOLPLT program (Ref. 42).

Image of FIG. 2.
FIG. 2.

Singlet MS-CASPT2/ANO-L linear interpolations ( symmetry). The geometry of the initial point corresponds to the minimum of nitromethane, the geometry of the end point corresponds to (a) conical intersection; (b) conical intersection; (c) (Ci3) conical intersection. Two roots have been included in each symmetry block for the MS-CASPT2 calculations.

Image of FIG. 3.
FIG. 3.

Singlet MS-CASPT2/ANO-L linear interpolations ( symmetry): (a) from the Franck–Condon point to the conical intersection; (b) from the conical intersection to dissociation into . Four roots have been included in the MS-CASPT2 calculations.

Image of FIG. 4.
FIG. 4.

Geometries of the critical points of nitromethane localized on the triplet surfaces at the CAS(14,11)/ANO-L level; intersystem crossings calculated at the CAS(14,10)/ level. The arrows in the lower structures correspond to imaginary modes (for stationary points) or gradient difference vectors (for intersystem crossings). (a) , minimum; (b) , transition state for dissociation into ; (c) , first-order saddle point; (d) , transition state for dissociation into ; (e) , minimum; (f) , transition state for dissociation into ; (g) intersystem crossing; (h) intersystem crossing; (i) intersystem crossing; and (j) intersystem crossing. Structures represented with the MACMOLPLT program (Ref. 42).

Image of FIG. 5.
FIG. 5.

Singlet and triplet MS-CASPT2/ANO-L linear interpolations ( symmetry). The geometry of the initial point corresponds to the minimum of nitromethane, and the geometry of the end point corresponds to (a) intersystem crossing; (b) intersystem crossing; (c) intersystem crossing. Two roots have been included in each symmetry block for the MS-CASPT2 calculations, excepting the state which has been computed using one root. The lower graphics at the right of each principal figure represent the magnitude of the spin–orbit coupling constants along the respective interpolation curve.

Image of FIG. 6.
FIG. 6.

MS-CASPT2/ANO-L linear interpolations ( symmetry): (a) from the Franck–Condon point to the intersystem crossing; (b) from the intersystem crossing to dissociation into . Four roots have been included in the MS-CASPT2 calculations.

Image of FIG. 7.
FIG. 7.

Energy-level diagrams of all of the critical points involved in the photochemistry of nitromethane. (a) Single states. (b) Triplet states.

Tables

Generic image for table
Table I.

MS-CASPT2 energies of the critical points of nitromethane on the singlet surfaces. Zero point energy correction is included. Absolute reference energy, hartree.

Generic image for table
Table II.

MS-CASPT2 energies of the critical points of nitromethane on the triplet surfaces. Zero point energy correction is included. Absolute reference energy, hartree.

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/content/aip/journal/jcp/122/8/10.1063/1.1851977
2005-02-23
2014-04-18
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Role of surface crossings in the photochemistry of nitromethane
http://aip.metastore.ingenta.com/content/aip/journal/jcp/122/8/10.1063/1.1851977
10.1063/1.1851977
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