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research article

Polarizable embedding with a multiconfiguration short-range density functional theory linear response method

Hedegard, Erik Donovan
•
Olsen, Jogvan Magnus Haugaard
•
Knecht, Stefan
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2015
Journal Of Chemical Physics

We present here the coupling of a polarizable embedding (PE) model to the recently developed multiconfiguration short-range density functional theory method (MC-srDFT), which can treat multiconfigurational systems with a simultaneous account for dynamical and static correlation effects. PE-MC-srDFT is designed to combine efficient treatment of complicated electronic structures with inclusion of effects from the surrounding environment. The environmental effects encompass classical electrostatic interactions as well as polarization of both the quantum region and the environment. Using response theory, molecular properties such as excitation energies and oscillator strengths can be obtained. The PE-MC-srDFT method and the additional terms required for linear response have been implemented in a development version of DALTON. To benchmark the PE-MC-srDFT approach against the literature data, we have investigated the low-lying electronic excitations of acetone and uracil, both immersed in water solution. The PE-MC-srDFT results are consistent and accurate, both in terms of the calculated solvent shift and, unlike regular PE-MCSCF, also with respect to the individual absolute excitation energies. To demonstrate the capabilities of PE-MC-srDFT, we also investigated the retinylidene Schiff base chromophore embedded in the channelrhodopsin protein. While using a much more compact reference wave function in terms of active space, our PE-MC-srDFT approach yields excitation energies comparable in quality to CASSCF/CASPT2 benchmarks. (C) 2015 AIP Publishing LLC.

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Type
research article
DOI
10.1063/1.4914922
Web of Science ID

WOS:000351530100013

Author(s)
Hedegard, Erik Donovan
•
Olsen, Jogvan Magnus Haugaard
•
Knecht, Stefan
•
Kongsted, Jacob
•
Jensen, Hans Jorgen Aagaard
Date Issued

2015

Publisher

Amer Inst Physics

Published in
Journal Of Chemical Physics
Volume

142

Issue

11

Article Number

114113

Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
ISIC  
Available on Infoscience
May 29, 2015
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/114413
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