Jablonski diagram for Oh Cr (III) complexes – full black lines with arrows represent absorption or emission processes, black wavy lines with arrows represent radiationless deactivation processes. Adapted from Ref. 3.
Structure of single Cr(C2O4) unit.
Left (a) and right (b) (L-, R-) optical isomers of [Cr(C2O4)3]3− system.
General picture of potential energy surfaces (PES) for ground and non-adibatically coupled excited states of the [Cr(C2O4)3]3− complex (dc–derivative coupling vector, gd–gradient difference vector, ISC–intersystem crossing, CI–conical intersection, TBP–trigonal bipyramid).
The structure of the [Cr(C2O4)3]3− complex (R-isomer) (a) at the ground state, (b) at the minimum energy CI point.
Change in orbital configuration when distorting from Oh symmetry of given metal centre (4T2g state) to D3 symmetry (4(A 1 ⊕ E) state) in [Cr(C2O4)3]3−.
Main structural parameters of Cr (III) oxalato systems. DFT calculations performed using B3LYP functional. CASSCF calculations performed using SDD basis set for Cr atom and 6-31g(d,p) for O and C atoms.
Comparison of calculated IR vibrations (B3LYP - PCM, with water as a solvent and cc-pVTZ basis set) in cm−1 to experiment.29,31
Main absorption spectral bands of [Cr(C2O4)3]3− (in nm (eV)) with oscillator strengths f and their symmetries using D3 irreducible representationsa: TD-DFT using the cc-pVTZ basis set on all the atoms; and previous experimental findings.31
Ordering of electronically excited states in [Cr(C2O4)3]3− (CASSCF: SDD for Cr and 6-31g(d,p) basis set for C and O atoms). Vertical energies taken from a CASSCF calculation (using a Slater determinant (SD) many-electron MS = +1/2 basis) with orbitals state averaged over 12 states.
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