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Avoided crossings, conical intersections, and low-lying excited states with a single reference method: The restricted active space spin-flip configuration interaction approach
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10.1063/1.4747341
/content/aip/journal/jcp/137/8/10.1063/1.4747341
http://aip.metastore.ingenta.com/content/aip/journal/jcp/137/8/10.1063/1.4747341

Figures

Image of FIG. 1.
FIG. 1.

Representation of the RASCI-SF wavefunction up to the inclusion of configurations with one hole in RAS1 and one electron in RAS3.

Image of FIG. 2.
FIG. 2.

Adiabatic (empty and full circles) and diabatic (thin gray lines) ionic and neutral potential energy profiles of LiF computed at the RAS(6,6)-SF/6-311+G* level.

Image of FIG. 3.
FIG. 3.

Dipole moments (left) and frontier natural orbital occupancies (right) of ground (full circles) and excited (empty circles) 1Σ+ states of LiF along the molecular dissociation. Dashed grey lines in the dipole moment plot indicate zero (bottom) and the punctual charges dipole limit (top), respectively.

Image of FIG. 4.
FIG. 4.

CC double bond torsion (or twist) and pyramidalization distortion in ethene.

Image of FIG. 5.
FIG. 5.

Torsion (top) and piramidalization at 90° torsion (bottom) of ethylene energy curves of ground (empty circles) and lowest excited (full circles) states at the RAS(8,5)-SF/6-311G** computational level. All energies are referenced with respect to the S0 state energy for the D2h geometry.

Image of FIG. 6.
FIG. 6.

RAS(8,5)-SF energy surfaces for the two lowest singlet states of ethene along the torsion and piramidalization distortions.

Image of FIG. 7.
FIG. 7.

Contribution (in %) of the full occupation of the π-space (solid grey) and different degrees of π* populations (diagonal stripes) of the ground state wavefunction for the C2n H2n+2 linear polyenes computed by the RAS-nSF(0) truncation.

Image of FIG. 8.
FIG. 8.

Difference of the particle contribution (in %) between the and RAS-nSF(h,p) wavefunctions (vertical bars) and RAS-nSF(h,p) vs. RAS-nSF(0) excitation energies (full triangles) of the state.

Image of FIG. 9.
FIG. 9.

Ground to , , and transition energies of linear polyenes, C2n H2n+2, computed at the RAS(2n,2n)-nSF/6-31+G** level with hole and particle configurations (empty markers), and their fittings to Eq. (9) (solid lines).

Tables

Generic image for table
Table I.

Crossing distance R c (Å) and the asymptotic energy difference ΔE (eV).

Generic image for table
Table II.

Vertical excitation energies (in eV) to the , , , and states for the studied all-trans polyenes, i.e., C2n H2n+2 with 2 ⩽ n ⩽ 7. RAS-nSF transition energies are computed with (RAS-nSF(h,p)) and without (RAS-nSF(0)) hole and particle configurations. Results are compared to CIS,70 CASSCF,37 CASPT2,37,62 and experimental data.

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/content/aip/journal/jcp/137/8/10.1063/1.4747341
2012-08-24
2014-04-19
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Avoided crossings, conical intersections, and low-lying excited states with a single reference method: The restricted active space spin-flip configuration interaction approach
http://aip.metastore.ingenta.com/content/aip/journal/jcp/137/8/10.1063/1.4747341
10.1063/1.4747341
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