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Exploration of H2 binding to the [NiFe]-hydrogenase active site with multiconfigurational density functional theory

Dong, Geng LU ; Ryde, Ulf LU ; Aa Jensen, Hans Jørgen and Hedegård, Erik D. LU (2018) In Physical Chemistry Chemical Physics 20(2). p.794-801
Abstract

The combination of density functional theory (DFT) with a multiconfigurational wave function is an efficient way to include dynamical correlation in calculations with multiconfiguration self-consistent field wave functions. These methods can potentially be employed to elucidate reaction mechanisms in bio-inorganic chemistry, where many other methods become either too computationally expensive or too inaccurate. In this paper, a complete active space (CAS) short-range DFT (CAS-srDFT) hybrid was employed to investigate a bio-inorganic system, namely H2 binding to the active site of [NiFe] hydrogenase. This system was previously investigated with coupled-cluster (CC) and multiconfigurational methods in the form of... (More)

The combination of density functional theory (DFT) with a multiconfigurational wave function is an efficient way to include dynamical correlation in calculations with multiconfiguration self-consistent field wave functions. These methods can potentially be employed to elucidate reaction mechanisms in bio-inorganic chemistry, where many other methods become either too computationally expensive or too inaccurate. In this paper, a complete active space (CAS) short-range DFT (CAS-srDFT) hybrid was employed to investigate a bio-inorganic system, namely H2 binding to the active site of [NiFe] hydrogenase. This system was previously investigated with coupled-cluster (CC) and multiconfigurational methods in the form of cumulant-approximated second-order perturbation theory, based on the density matrix renormalization group (DMRG). We find that it is more favorable for H2 to bind to Ni than to Fe, in agreement with previous CC and DMRG calculations. The accuracy of CAS-srDFT is comparable to both CC and DMRG, despite much smaller active spaces were employed than in the corresponding DMRG calculations. This enhanced efficiency at the smaller active spaces shows that CAS-srDFT can become a useful method for bio-inorganic chemistry.

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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Physical Chemistry Chemical Physics
volume
20
issue
2
pages
8 pages
publisher
Royal Society of Chemistry
external identifiers
  • scopus:85040195867
ISSN
1463-9076
DOI
10.1039/c7cp06767d
language
English
LU publication?
yes
id
a2f807c6-1458-45f4-8209-040d0ee398d3
date added to LUP
2018-01-15 08:50:23
date last changed
2018-01-16 03:00:02
@article{a2f807c6-1458-45f4-8209-040d0ee398d3,
  abstract     = {<p>The combination of density functional theory (DFT) with a multiconfigurational wave function is an efficient way to include dynamical correlation in calculations with multiconfiguration self-consistent field wave functions. These methods can potentially be employed to elucidate reaction mechanisms in bio-inorganic chemistry, where many other methods become either too computationally expensive or too inaccurate. In this paper, a complete active space (CAS) short-range DFT (CAS-srDFT) hybrid was employed to investigate a bio-inorganic system, namely H<sub>2</sub> binding to the active site of [NiFe] hydrogenase. This system was previously investigated with coupled-cluster (CC) and multiconfigurational methods in the form of cumulant-approximated second-order perturbation theory, based on the density matrix renormalization group (DMRG). We find that it is more favorable for H<sub>2</sub> to bind to Ni than to Fe, in agreement with previous CC and DMRG calculations. The accuracy of CAS-srDFT is comparable to both CC and DMRG, despite much smaller active spaces were employed than in the corresponding DMRG calculations. This enhanced efficiency at the smaller active spaces shows that CAS-srDFT can become a useful method for bio-inorganic chemistry.</p>},
  author       = {Dong, Geng and Ryde, Ulf and Aa Jensen, Hans Jørgen and Hedegård, Erik D.},
  issn         = {1463-9076},
  language     = {eng},
  number       = {2},
  pages        = {794--801},
  publisher    = {Royal Society of Chemistry},
  series       = {Physical Chemistry Chemical Physics},
  title        = {Exploration of H<sub>2</sub> binding to the [NiFe]-hydrogenase active site with multiconfigurational density functional theory},
  url          = {http://dx.doi.org/10.1039/c7cp06767d},
  volume       = {20},
  year         = {2018},
}