Fully relativistic coupled cluster and DFT study of electric field gradients at Hg in 199Hg compounds

Vaida Arcisauskaité; Stefan Knecht; Stephan P. A. Sauer; Lars Bo Stegeager Hemmingsen

doi:10.1039/c2cp23080a

Fully relativistic coupled cluster and DFT study of electric field gradients at Hg in ¹⁹⁹Hg compounds

Vaida Arcisauskaité, Stefan Knecht, Stephan P. A. Sauer, Lars Bo Stegeager Hemmingsen

Department of Chemistry

23 Citations (Scopus)

Abstract

We investigate the magnitude and interplay of relativistic and electron correlation effects on the electric field gradient (EFG) at the position of Hg in linear and bent HgL₂ (L = CH₃, Cl, Br, I) and trigonal planar [HgCl₃]⁻ compounds using four-component relativistic Dirac-Coulomb (DC) and non-relativistic (NR) calculations at the Hartree-Fock (HF), DFT, MP2 and coupled cluster (CC) levels. The relativistic and electron correlation contributions to EFG have opposite signs and are not additive, demonstrating the importance of taking into account relativistic and electron correlation contributions on an equal footing. DC-MP2 overestimates the electron correlation correction by 0.48-0.56 a.u. for Hg-halides and by 0.8 a.u. for Hg(CH₃)₂, respectively, while DC-CCSD underestimates the correlation correction by 0.57-0.66 a.u. compared to the reference DC-CCSD-T data. EFGs obtained at the DC-DFT level vary considerably with the functional; DC-CAMB3LYP and DC-BH&H reproduce DC-CCSD-T results within 0.08-0.24 a.u. (1%-3%) for Hg(CH₃)₂ and Hg-halides, respectively. An updated value of the nuclear quadrupole moment of the I = 5/2 excited state of ¹⁹⁹Hg, Q(¹⁹⁹Hg) = 0.675(12) b is derived from the literature. This value compares well with that derived from our calculated EFG at the DC-CCSD-T level and the experimental data for Hg(CH₃)₂; Q(¹⁹⁹Hg) = 0.650 b.

Original language	English
Journal	Physical Chemistry Chemical Physics
Volume	14
Issue number	8
Pages (from-to)	2651-2657
ISSN	1463-9076
DOIs	https://doi.org/10.1039/c2cp23080a
Publication status	Published - 2012

Keywords

Faculty of Science
Quantum Chemistry
computational chemistry
spectroscopy
Former LIFE faculty

Access to Document

10.1039/c2cp23080a

Cite this

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title = "Fully relativistic coupled cluster and DFT study of electric field gradients at Hg in 199Hg compounds",

abstract = "We investigate the magnitude and interplay of relativistic and electron correlation effects on the electric field gradient (EFG) at the position of Hg in linear and bent HgL2 (L = CH3, Cl, Br, I) and trigonal planar [HgCl3]− compounds using four-component relativistic Dirac-Coulomb (DC) and non-relativistic (NR) calculations at the Hartree-Fock (HF), DFT, MP2 and coupled cluster (CC) levels. The relativistic and electron correlation contributions to EFG have opposite signs and are not additive, demonstrating the importance of taking into account relativistic and electron correlation contributions on an equal footing. DC-MP2 overestimates the electron correlation correction by 0.48-0.56 a.u. for Hg-halides and by 0.8 a.u. for Hg(CH3)2, respectively, while DC-CCSD underestimates the correlation correction by 0.57-0.66 a.u. compared to the reference DC-CCSD-T data. EFGs obtained at the DC-DFT level vary considerably with the functional; DC-CAMB3LYP and DC-BH&H reproduce DC-CCSD-T results within 0.08-0.24 a.u. (1%-3%) for Hg(CH3)2 and Hg-halides, respectively. An updated value of the nuclear quadrupole moment of the I = 5/2 excited state of 199Hg, Q(199Hg) = 0.675(12) b is derived from the literature. This value compares well with that derived from our calculated EFG at the DC-CCSD-T level and the experimental data for Hg(CH3)2; Q(199Hg) = 0.650 b.",

keywords = "Faculty of Science, Quantum Chemistry, computational chemistry, spectroscopy, Former LIFE faculty",

author = "Vaida Arcisauskait{\'e} and Stefan Knecht and Sauer, {Stephan P. A.} and Hemmingsen, {Lars Bo Stegeager}",

year = "2012",

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language = "English",

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journal = "Physical Chemistry Chemical Physics",

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T1 - Fully relativistic coupled cluster and DFT study of electric field gradients at Hg in 199Hg compounds

AU - Arcisauskaité, Vaida

AU - Knecht, Stefan

AU - Sauer, Stephan P. A.

AU - Hemmingsen, Lars Bo Stegeager

PY - 2012

Y1 - 2012

N2 - We investigate the magnitude and interplay of relativistic and electron correlation effects on the electric field gradient (EFG) at the position of Hg in linear and bent HgL2 (L = CH3, Cl, Br, I) and trigonal planar [HgCl3]− compounds using four-component relativistic Dirac-Coulomb (DC) and non-relativistic (NR) calculations at the Hartree-Fock (HF), DFT, MP2 and coupled cluster (CC) levels. The relativistic and electron correlation contributions to EFG have opposite signs and are not additive, demonstrating the importance of taking into account relativistic and electron correlation contributions on an equal footing. DC-MP2 overestimates the electron correlation correction by 0.48-0.56 a.u. for Hg-halides and by 0.8 a.u. for Hg(CH3)2, respectively, while DC-CCSD underestimates the correlation correction by 0.57-0.66 a.u. compared to the reference DC-CCSD-T data. EFGs obtained at the DC-DFT level vary considerably with the functional; DC-CAMB3LYP and DC-BH&H reproduce DC-CCSD-T results within 0.08-0.24 a.u. (1%-3%) for Hg(CH3)2 and Hg-halides, respectively. An updated value of the nuclear quadrupole moment of the I = 5/2 excited state of 199Hg, Q(199Hg) = 0.675(12) b is derived from the literature. This value compares well with that derived from our calculated EFG at the DC-CCSD-T level and the experimental data for Hg(CH3)2; Q(199Hg) = 0.650 b.

AB - We investigate the magnitude and interplay of relativistic and electron correlation effects on the electric field gradient (EFG) at the position of Hg in linear and bent HgL2 (L = CH3, Cl, Br, I) and trigonal planar [HgCl3]− compounds using four-component relativistic Dirac-Coulomb (DC) and non-relativistic (NR) calculations at the Hartree-Fock (HF), DFT, MP2 and coupled cluster (CC) levels. The relativistic and electron correlation contributions to EFG have opposite signs and are not additive, demonstrating the importance of taking into account relativistic and electron correlation contributions on an equal footing. DC-MP2 overestimates the electron correlation correction by 0.48-0.56 a.u. for Hg-halides and by 0.8 a.u. for Hg(CH3)2, respectively, while DC-CCSD underestimates the correlation correction by 0.57-0.66 a.u. compared to the reference DC-CCSD-T data. EFGs obtained at the DC-DFT level vary considerably with the functional; DC-CAMB3LYP and DC-BH&H reproduce DC-CCSD-T results within 0.08-0.24 a.u. (1%-3%) for Hg(CH3)2 and Hg-halides, respectively. An updated value of the nuclear quadrupole moment of the I = 5/2 excited state of 199Hg, Q(199Hg) = 0.675(12) b is derived from the literature. This value compares well with that derived from our calculated EFG at the DC-CCSD-T level and the experimental data for Hg(CH3)2; Q(199Hg) = 0.650 b.

KW - Faculty of Science

KW - Quantum Chemistry

KW - computational chemistry

KW - spectroscopy

KW - Former LIFE faculty

U2 - 10.1039/c2cp23080a

DO - 10.1039/c2cp23080a

M3 - Journal article

SN - 1463-9076

VL - 14

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JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

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