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Photoracemization and excited state relaxation through non-adiabatic pathways in chromium (III) oxalate ions
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10.1063/1.4736561
/content/aip/journal/jcp/137/3/10.1063/1.4736561
http://aip.metastore.ingenta.com/content/aip/journal/jcp/137/3/10.1063/1.4736561

Figures

Image of FIG. 1.
FIG. 1.

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.

Image of FIG. 2.
FIG. 2.

Structure of single Cr(C2O4) unit.

Image of FIG. 3.
FIG. 3.

Left (a) and right (b) (L-, R-) optical isomers of [Cr(C2O4)3]3− system.

Image of FIG. 4.
FIG. 4.

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).

Image of FIG. 5.
FIG. 5.

The structure of the [Cr(C2O4)3]3− complex (R-isomer) (a) at the ground state, (b) at the minimum energy CI point.

Image of FIG. 6.
FIG. 6.

Change in orbital configuration when distorting from Oh symmetry of given metal centre (4T2g state) to D3 symmetry (4(A 1E) state) in [Cr(C2O4)3]3−.

Tables

Generic image for table
Table I.

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.

Generic image for table
Table II.

Comparison of calculated IR vibrations (B3LYP - PCM, with water as a solvent and cc-pVTZ basis set) in cm−1 to experiment.29,31

Generic image for table
Table III.

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

Generic image for table
Table IV.

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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/content/aip/journal/jcp/137/3/10.1063/1.4736561
2012-07-18
2014-04-17
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Photoracemization and excited state relaxation through non-adiabatic pathways in chromium (III) oxalate ions
http://aip.metastore.ingenta.com/content/aip/journal/jcp/137/3/10.1063/1.4736561
10.1063/1.4736561
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