Photophysical properties of metal complexes

Ward, Michael D.

doi:10.1039/b514853g

Cited by 6 publications

(2 citation statements)

References 291 publications

(300 reference statements)

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“…44,45 Another problematic area for the application of TDDFT concerns excitations for heavy open-shell systems where inclusion of spin-orbit (SO) coupling is necessary already for a qualitative description of the system. Given the increasing interest in the organometallic and inorganic chemistry of molecules containing lanthanides, actinides and heavy transition elements, 46,47 it is desirable to have alternative methods available that can handle such difficult cases.…”

Section: Introductionmentioning

confidence: 99%

Calculation of local excitations in large systems by embedding wave-function theory in density-functional theory

Gomes

Jacob

Visscher

2008

Phys. Chem. Chem. Phys.

160

247

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We present a simple and efficient embedding scheme for the wave-function based calculation of the energies of local excitations in large systems. By introducing an embedding potential obtained from density-functional theory (DFT) it is possible to describe the effect of an environment on local excitations of an embedded system in wave-function theory (WFT) calculations of the excitation energies. We outline the implementation of such a WFT-in-DFT embedding procedure employing the ADF, Dalton and DIRAC codes, where the embedded subsystem is treated with coupled cluster methods. We then evaluate this procedure in the calculation of the solvatochromic shift of acetone in water and of the f-f spectrum of NpO22+ embedded in a Cs2UO2Cl4 crystal and find that our scheme does effectively incorporate the environment effect in both cases. A particularly interesting finding is that with our embedding scheme we can model the equatorial Cl- ligands in NpO2Cl42- quite accurately, compared to a fully wavefunction-based calculation, and this opens up the possibility of modeling the interaction of different ligands to actinyl species with relatively high accuracy but at a much reduced computational cost.

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