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Relativistic Polarizable Embedding

Hedegård, Erik Donovan LU ; Bast, Radovan; Kongsted, Jacob LU ; Olsen, Jógvan Magnus Haugaard and Jensen, Hans Jørgen Aagaard (2017) In Journal of Chemical Theory and Computation 13(6). p.2870-2880
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... (More)

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.

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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Chemical Theory and Computation
volume
13
issue
6
pages
11 pages
publisher
The American Chemical Society
external identifiers
  • scopus:85020697557
  • wos:000403530100046
ISSN
1549-9618
DOI
10.1021/acs.jctc.7b00162
language
English
LU publication?
yes
id
283c3a85-15db-4510-8db7-fa234d92f912
date added to LUP
2017-07-04 09:35:07
date last changed
2017-09-18 11:37:37
@article{283c3a85-15db-4510-8db7-fa234d92f912,
  abstract     = {<p>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 TcO<sub>4</sub> <sup>-</sup> and ReO<sub>4</sub> <sup>-</sup> 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 XO<sub>4</sub> <sup>-</sup> 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.</p>},
  author       = {Hedegård, Erik Donovan and Bast, Radovan and Kongsted, Jacob and Olsen, Jógvan Magnus Haugaard and Jensen, Hans Jørgen Aagaard},
  issn         = {1549-9618},
  language     = {eng},
  month        = {06},
  number       = {6},
  pages        = {2870--2880},
  publisher    = {The American Chemical Society},
  series       = {Journal of Chemical Theory and Computation},
  title        = {Relativistic Polarizable Embedding},
  url          = {http://dx.doi.org/10.1021/acs.jctc.7b00162},
  volume       = {13},
  year         = {2017},
}