Modeling the absorption spectrum of the permanganate ion in vacuum and in aqueous solution
(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
- Olsen, Jógvan Magnus Haugaard and Hedegård, Erik Donovan LU
- organization
- publishing date
- 2017
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Physical Chemistry Chemical Physics
- volume
- 19
- issue
- 24
- pages
- 6 pages
- publisher
- Royal Society of Chemistry
- external identifiers
-
- scopus:85024120930
- pmid:28589192
- 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
- 2024-04-14 15:01:42
@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 = {{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}},
doi = {{10.1039/c7cp01194f}},
volume = {{19}},
year = {{2017}},
}