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Polarizable Embedding Complex Polarization Propagator in Four- and Two-Component Frameworks

Creutzberg, Joel LU and Hedegård, Erik D. LU (2022) In Journal of Chemical Theory and Computation 18(6). p.3671-3686
Abstract

Explicit embedding methods combined with the complex polarization propagator (CPP) enable the modeling of spectroscopy for increasingly complex systems with a high density of states. We present the first derivation and implementation of the CPP in four- and exact-two-component (X2C) polarizable embedding (PE) frameworks. We denote the developed methods PE-4c-CPP and PE-X2C-CPP, respectively. We illustrate the methods by estimating the solvent effect on ultraviolet-visible (UV-vis) and X-ray atomic absorption (XAS) spectra of [Rh(H2O)6]3+ and [Ir(H2O)6]3+ immersed in aqueous solution. We moreover estimate solvent effects on UV-vis spectra of a platinum complex that can be photochemically activated (in water) to kill cancer cells. Our... (More)

Explicit embedding methods combined with the complex polarization propagator (CPP) enable the modeling of spectroscopy for increasingly complex systems with a high density of states. We present the first derivation and implementation of the CPP in four- and exact-two-component (X2C) polarizable embedding (PE) frameworks. We denote the developed methods PE-4c-CPP and PE-X2C-CPP, respectively. We illustrate the methods by estimating the solvent effect on ultraviolet-visible (UV-vis) and X-ray atomic absorption (XAS) spectra of [Rh(H2O)6]3+ and [Ir(H2O)6]3+ immersed in aqueous solution. We moreover estimate solvent effects on UV-vis spectra of a platinum complex that can be photochemically activated (in water) to kill cancer cells. Our results clearly show that the inclusion of the environment is required: UV-vis and (to a lesser degree) XAS spectra can become qualitatively different from vacuum calculations. Comparison of PE-4c-CPP and PE-X2C-CPP methods shows that X2C essentially reproduces the solvent effect obtained with the 4c methods.

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organization
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type
Contribution to journal
publication status
published
subject
in
Journal of Chemical Theory and Computation
volume
18
issue
6
pages
16 pages
publisher
The American Chemical Society (ACS)
external identifiers
  • scopus:85131192192
  • pmid:35549262
ISSN
1549-9618
DOI
10.1021/acs.jctc.1c01249
language
English
LU publication?
yes
id
4750af05-3b9c-42ae-a6f2-24d3d787392d
date added to LUP
2022-08-18 13:55:43
date last changed
2024-06-26 05:56:58
@article{4750af05-3b9c-42ae-a6f2-24d3d787392d,
  abstract     = {{<p>Explicit embedding methods combined with the complex polarization propagator (CPP) enable the modeling of spectroscopy for increasingly complex systems with a high density of states. We present the first derivation and implementation of the CPP in four- and exact-two-component (X2C) polarizable embedding (PE) frameworks. We denote the developed methods PE-4c-CPP and PE-X2C-CPP, respectively. We illustrate the methods by estimating the solvent effect on ultraviolet-visible (UV-vis) and X-ray atomic absorption (XAS) spectra of [Rh(H2O)6]3+ and [Ir(H2O)6]3+ immersed in aqueous solution. We moreover estimate solvent effects on UV-vis spectra of a platinum complex that can be photochemically activated (in water) to kill cancer cells. Our results clearly show that the inclusion of the environment is required: UV-vis and (to a lesser degree) XAS spectra can become qualitatively different from vacuum calculations. Comparison of PE-4c-CPP and PE-X2C-CPP methods shows that X2C essentially reproduces the solvent effect obtained with the 4c methods. </p>}},
  author       = {{Creutzberg, Joel and Hedegård, Erik D.}},
  issn         = {{1549-9618}},
  language     = {{eng}},
  month        = {{06}},
  number       = {{6}},
  pages        = {{3671--3686}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{Journal of Chemical Theory and Computation}},
  title        = {{Polarizable Embedding Complex Polarization Propagator in Four- and Two-Component Frameworks}},
  url          = {{http://dx.doi.org/10.1021/acs.jctc.1c01249}},
  doi          = {{10.1021/acs.jctc.1c01249}},
  volume       = {{18}},
  year         = {{2022}},
}