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Issue 35, 2008
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Calculation of local excitations in large systems by embedding wave-function theory in density-functional theory

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Abstract

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 ffspectrum 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.

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

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Publication details

The article was received on 04 Apr 2008, accepted on 21 May 2008 and first published on 04 Jul 2008


Article type: Paper
DOI: 10.1039/B805739G
Phys. Chem. Chem. Phys., 2008,10, 5353-5362

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

    A. S. P. Gomes, C. R. Jacob and L. Visscher, Phys. Chem. Chem. Phys., 2008, 10, 5353
    DOI: 10.1039/B805739G

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