Importance of Dispersion in the Molecular Geometries of Mn(III) Spin-Crossover Complexes

Sabyasachi Roy Chowdhury; Ngan Nguyen; Bess Vlaisavljevich

doi:10.1021/acs.jpca.2c08158

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Importance of Dispersion in the Molecular Geometries of Mn(III) Spin-Crossover Complexes

Journal article

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Importance of Dispersion in the Molecular Geometries of Mn(III) Spin-Crossover Complexes

Sabyasachi Roy Chowdhury, Ngan Nguyen and Bess Vlaisavljevich

The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, Vol.127(14), pp.3072-3081

04/13/2023

DOI: 10.1021/acs.jpca.2c08158

PMID: 37010904

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https://www.osti.gov/servlets/purl/1993575View

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Abstract

The computational investigation of the molecular geometries of a pair of manganese(III) spin-crossover complexes is reported. For the geometry of the quintet high-spin state, density functionals significantly overestimate Mn-Namine bond distances, although the geometry for the triplet intermediate-spin state is well described. Comparisons with several wave function-based methods demonstrate that this error is due to the limited ability of commonly used density functionals to recover dispersion beyond a certain extent. Among the methods employed for geometry optimization, restricted open-shell Moller-Plesset perturbation theory (MP2) appropriately describes the high-spin geometry but results in a slightly shorter Mn-O distance in both spin states. On the other hand, extended multistate complete active space second-order perturbation theory (XMS-CASPT2) provides a good description of the geometry for the intermediate-spin state but also sufficiently recovers dispersion, performing well for the high-spin state. Despite the fact that the electronic structure of both spin states is dominated by one-electron configuration, XMS-CASPT2 offers a balanced approach, leading to molecular geometries with much better agreement with experiment than MP2 and DFT. A scan along the Mn- Namine bond demonstrates that for these complexes coupled cluster methods (i.e., DLPNO-CCSD(T)) also yield bond distances in agreement with experiment while multiconfiguration pair density functional theory (MC-PDFT) is unable to recover dispersion well enough, analogous to single-reference DFT.

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Details

Title: Subtitle: Importance of Dispersion in the Molecular Geometries of Mn(III) Spin-Crossover Complexes
Creators: Sabyasachi Roy Chowdhury - University of South Dakota
Ngan Nguyen - University of South Dakota
Bess Vlaisavljevich - University of South Dakota
Resource Type: Journal article
Publication Details: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, Vol.127(14), pp.3072-3081
DOI: 10.1021/acs.jpca.2c08158
PMID: 37010904
NLM abbreviation: J Phys Chem A
ISSN: 1089-5639
eISSN: 1520-5215
Publisher: Amer Chemical Soc
Number of pages: 10
Grant note: OAC-1626516 / NSF; National Science Foundation (NSF) South Dakota Governors Office of Economic Development through the Center for Fluorinated Functional Materials DE-SC0019463 / U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Computational Chemical Sciences program; United States Department of Energy (DOE)
Language: English
Date published: 04/13/2023
Academic Unit: Chemistry
Record Identifier: 9984618526802771

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