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Relativistic Polarizable Embedding.
Hedegård, Erik Donovan; Bast, Radovan; Kongsted, Jacob; Olsen, Jógvan Magnus Haugaard; Jensen, Hans Jørgen Aagaard.
Afiliação
  • Hedegård ED; Department of Theoretical Chemistry, Lund University , Lund 221 00, Sweden.
  • Bast R; High Performance Computing Group, UiT The Arctic University of Norway , Tromsø 9037, Norway.
  • Kongsted J; Department of Physics, Chemistry and Pharmacy, University of Southern Denmark , DK-5230 Odense M, Denmark.
  • Olsen JMH; Department of Physics, Chemistry and Pharmacy, University of Southern Denmark , DK-5230 Odense M, Denmark.
  • Jensen HJA; Department of Physics, Chemistry and Pharmacy, University of Southern Denmark , DK-5230 Odense M, Denmark.
J Chem Theory Comput ; 13(6): 2870-2880, 2017 Jun 13.
Article em En | MEDLINE | ID: mdl-28493714
ABSTRACT
Most chemistry, including chemistry where relativistic effects are important, occurs in an environment, and in many cases, this environment has a significant effect on the chemistry. In nonrelativistic quantum chemistry, a lot of progress has been achieved with respect to including environments such as a solvent or protein in the calculations, and now is the time to extend the possibilities for also doing this in relativistic quantum chemistry. The polarizable embedding (PE) model efficiently incorporates electrostatic effects of the environment by describing it as a collection of localized electric multipoles and polarizabilities obtained through quantum chemical calculations. In this article, we present the theory and implementation of four- and exact two-component Hamiltonians within a PE framework. We denote the methods the PE-4c-DFT and PE-X2C-DFT models. The models include a linear response formalism to calculate time-dependent (TD) properties PE-TD-4c-DFT and PE-TD-X2C-DFT. With this first implementation, we calculate the PE-TD-4c-PBE0 excitation energies of the TcO4- and ReO4- ions in an explicit water solvent. This initial investigation focuses on the relative size of relativistic and solvent contributions to the excitation energies. The solvent effect is divided into an indirect solvent effect due to the structural perturbation of the XO4- ion and a direct electrostatic effect. The relativistic effects as well as both types of solvent effects are found to contribute to a shift in the excitation energies, but they do so to different extents depending on the ion and the electronic transition in question.

Texto completo: 1 Base de dados: MEDLINE Idioma: En Ano de publicação: 2017 Tipo de documento: Article País de afiliação: Suécia

Texto completo: 1 Base de dados: MEDLINE Idioma: En Ano de publicação: 2017 Tipo de documento: Article País de afiliação: Suécia