Representation of the RASCI-SF wavefunction up to the inclusion of configurations with one hole in RAS1 and one electron in RAS3.
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.
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.
CC double bond torsion (or twist) and pyramidalization distortion in ethene.
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.
RAS(8,5)-SF energy surfaces for the two lowest singlet states of ethene along the torsion and piramidalization distortions.
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.
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.
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).
Crossing distance R c (Å) and the asymptotic energy difference ΔE ∞ (eV).
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.
Article metrics loading...
Full text loading...