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Modeling the absorption spectrum of the permanganate ion in vacuum and in aqueous solution

Olsen, Jógvan Magnus Haugaard and Hedegård, Erik Donovan LU (2017) In Physical Chemistry Chemical Physics 19(24). p.15870-15875
Abstract

The absorption spectrum of the MnO4 - ion has been a test-bed for quantum-chemical methods over the last decades. Its correct description requires highly-correlated multiconfigurational methods, which are incompatible with the inclusion of finite-temperature and solvent effects due to their high computational demands. Therefore, implicit solvent models are usually employed. Here we show that implicit solvent models are not sufficiently accurate to model the solvent shift of MnO4 -, and we analyze the origins of their failure. We obtain the correct solvent shift for MnO4 - in aqueous solution by employing the polarizable embedding (PE) model combined with a range-separated... (More)

The absorption spectrum of the MnO4 - ion has been a test-bed for quantum-chemical methods over the last decades. Its correct description requires highly-correlated multiconfigurational methods, which are incompatible with the inclusion of finite-temperature and solvent effects due to their high computational demands. Therefore, implicit solvent models are usually employed. Here we show that implicit solvent models are not sufficiently accurate to model the solvent shift of MnO4 -, and we analyze the origins of their failure. We obtain the correct solvent shift for MnO4 - in aqueous solution by employing the polarizable embedding (PE) model combined with a range-separated complete active space short-range density functional theory method (CAS-srDFT). Finite-temperature effects are taken into account by averaging over structures obtained from ab initio molecular dynamics simulations. The explicit treatment of finite-temperature and solvent effects facilitates the interpretation of the bands in the low-energy region of the MnO4 - absorption spectrum, whose assignment has been elusive.

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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Physical Chemistry Chemical Physics
volume
19
issue
24
pages
6 pages
publisher
The Royal Society of Chemistry
external identifiers
  • scopus:85024120930
  • wos:000403965500028
ISSN
1463-9076
DOI
10.1039/c7cp01194f
language
English
LU publication?
yes
id
03676e36-7f98-40c3-900b-e012ff2f248a
date added to LUP
2017-07-27 14:27:27
date last changed
2017-09-18 11:40:08
@article{03676e36-7f98-40c3-900b-e012ff2f248a,
  abstract     = {<p>The absorption spectrum of the MnO<sub>4</sub> <sup>-</sup> ion has been a test-bed for quantum-chemical methods over the last decades. Its correct description requires highly-correlated multiconfigurational methods, which are incompatible with the inclusion of finite-temperature and solvent effects due to their high computational demands. Therefore, implicit solvent models are usually employed. Here we show that implicit solvent models are not sufficiently accurate to model the solvent shift of MnO<sub>4</sub> <sup>-</sup>, and we analyze the origins of their failure. We obtain the correct solvent shift for MnO<sub>4</sub> <sup>-</sup> in aqueous solution by employing the polarizable embedding (PE) model combined with a range-separated complete active space short-range density functional theory method (CAS-srDFT). Finite-temperature effects are taken into account by averaging over structures obtained from ab initio molecular dynamics simulations. The explicit treatment of finite-temperature and solvent effects facilitates the interpretation of the bands in the low-energy region of the MnO<sub>4</sub> <sup>-</sup> absorption spectrum, whose assignment has been elusive.</p>},
  author       = {Olsen, Jógvan Magnus Haugaard and Hedegård, Erik Donovan},
  issn         = {1463-9076},
  language     = {eng},
  number       = {24},
  pages        = {15870--15875},
  publisher    = {The Royal Society of Chemistry},
  series       = {Physical Chemistry Chemical Physics},
  title        = {Modeling the absorption spectrum of the permanganate ion in vacuum and in aqueous solution},
  url          = {http://dx.doi.org/10.1039/c7cp01194f},
  volume       = {19},
  year         = {2017},
}