(a) From left to right, HOMO, HOMO-1, HOMO-2, HOMO-3 of the anion at .(b) From left to right, SOMOs of the ground state wave function at and for the first excited state wave function at , , and . Each state's point group symmetry, bond lengths and bond angles are given.
g and h vectors at (a) and (b) . Each vector has a top (left) and a side (right) view.
Calculated ab initio MRCI potential energy surfaces along the out-of-plane bending mode for the 2 A 2′, 2 E′, and 2 A 1″ electronic states. The origin is . The out-of-plane angle (θ) is in degrees. The 2 E′ surface (blue and green lines) depicts both the D3h and C3v conical intersections.
The vicinity of displaced along its g-direction. The magnitude of displacement is indicated by changes in the V-O(1) bond length. The conical intersection is at R(V-O(1)) = 1.628 Å. Displacements take the C3v point to Cs points.
The vicinity of displaced along its g-direction. The magnitude of displacement is indicated by changes in the V-O(1) bond length. The conical intersection is at R(V-O(1)) = 1.627 Å. Displacements take the D3h point to C2v points.
Linear interpolation path connecting the D3h conical intersection, , and a C2v ground state saddle point, , defined in Table II . Some geometry measurements (bond lengths and angles) are shown for the conical intersection and the ground state saddle point.
Comparison of expansion at the D3h ground state saddle point. The number of CSFs is given in Cs symmetry, and the total number of CSFs is the sum of A′ and A′′ CSFs. Relative energy is the energy difference between the ground state and the state of interest.
Anion minimum and critical points for the lowest three electronic states of neutral are reported. Bond lengths are in Å, and the bond angles are in degrees. Energy (cm−1) is relative to E 1( ). Energy of optimized state is in bold italic typeface. Here, is the minimum geometry of state J. The symmetry of the optimized state J is denoted below the symbol Q J . is a saddle point of state J, and is the geometry at the minimum energy crossing (mex) of states I and J. Results from Ref. 15 are in parenthesis.
Harmonic vibrational frequencies (cm−1) of VO3 and VO3 −. The D3h symmetry designations are applicable to and only.
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