CASSCF study of the relation between the Fe charge and the Mossbauer isomer shift

Aymeric Sadoc; Ria Broer; Coen de Graaf

doi:10.1016/j.cplett.2008.02.034

CASSCF study of the relation between the Fe charge and the Mossbauer isomer shift

Aymeric Sadoc, Ria Broer, Coen de Graaf^*

^*Corresponding author for this work

Theoretical Chemistry

Research output: Contribution to journal › Article › Academic › peer-review

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Abstract

Multiconfigurational wave functions are calculated for a series of Fe complexes. We find a linear correlation between the experimental Fe-57 Mossbauer isomer shift and the calculated electron density at the Fe nucleus. However, the analysis of the wave function in valence bond terms shows that there is no straightforward relation between the density at the nucleus and the Fe charge. The analysis of the CASSCF wave function expressed in localized orbitals shows that the isomer shift is very sensitive to the weight of charge transfer configurations and hence to the covalency, rather than to the absolute charge. (c) 2008 Elsevier B. V. All rights reserved.

Original language	English
Pages (from-to)	196-200
Number of pages	5
Journal	Chemical Physics Letters
Volume	454
Issue number	4-6
DOIs	https://doi.org/10.1016/j.cplett.2008.02.034
Publication status	Published - 20-Mar-2008

Keywords

MOLECULAR WAVE-FUNCTIONS
TRANSITION-METAL ATOMS
ANO BASIS-SETS
AB-INITIO
FE-57
SPECTRA
STATES
DFT
SPECTROSCOPY
CALIBRATION

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title = "CASSCF study of the relation between the Fe charge and the Mossbauer isomer shift",

abstract = "Multiconfigurational wave functions are calculated for a series of Fe complexes. We find a linear correlation between the experimental Fe-57 Mossbauer isomer shift and the calculated electron density at the Fe nucleus. However, the analysis of the wave function in valence bond terms shows that there is no straightforward relation between the density at the nucleus and the Fe charge. The analysis of the CASSCF wave function expressed in localized orbitals shows that the isomer shift is very sensitive to the weight of charge transfer configurations and hence to the covalency, rather than to the absolute charge. (c) 2008 Elsevier B. V. All rights reserved.",

keywords = "MOLECULAR WAVE-FUNCTIONS, TRANSITION-METAL ATOMS, ANO BASIS-SETS, AB-INITIO, FE-57, SPECTRA, STATES, DFT, SPECTROSCOPY, CALIBRATION",

author = "Aymeric Sadoc and Ria Broer and {de Graaf}, Coen",

year = "2008",

month = mar,

day = "20",

doi = "10.1016/j.cplett.2008.02.034",

language = "English",

volume = "454",

pages = "196--200",

journal = "Chemical Physics Letters",

issn = "1873-4448",

publisher = "ELSEVIER SCIENCE BV",

number = "4-6",

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TY - JOUR

T1 - CASSCF study of the relation between the Fe charge and the Mossbauer isomer shift

AU - Sadoc, Aymeric

AU - Broer, Ria

AU - de Graaf, Coen

PY - 2008/3/20

Y1 - 2008/3/20

N2 - Multiconfigurational wave functions are calculated for a series of Fe complexes. We find a linear correlation between the experimental Fe-57 Mossbauer isomer shift and the calculated electron density at the Fe nucleus. However, the analysis of the wave function in valence bond terms shows that there is no straightforward relation between the density at the nucleus and the Fe charge. The analysis of the CASSCF wave function expressed in localized orbitals shows that the isomer shift is very sensitive to the weight of charge transfer configurations and hence to the covalency, rather than to the absolute charge. (c) 2008 Elsevier B. V. All rights reserved.

AB - Multiconfigurational wave functions are calculated for a series of Fe complexes. We find a linear correlation between the experimental Fe-57 Mossbauer isomer shift and the calculated electron density at the Fe nucleus. However, the analysis of the wave function in valence bond terms shows that there is no straightforward relation between the density at the nucleus and the Fe charge. The analysis of the CASSCF wave function expressed in localized orbitals shows that the isomer shift is very sensitive to the weight of charge transfer configurations and hence to the covalency, rather than to the absolute charge. (c) 2008 Elsevier B. V. All rights reserved.

KW - MOLECULAR WAVE-FUNCTIONS

KW - TRANSITION-METAL ATOMS

KW - ANO BASIS-SETS

KW - AB-INITIO

KW - FE-57

KW - SPECTRA

KW - STATES

KW - DFT

KW - SPECTROSCOPY

KW - CALIBRATION

U2 - 10.1016/j.cplett.2008.02.034

DO - 10.1016/j.cplett.2008.02.034

M3 - Article

SN - 1873-4448

VL - 454

SP - 196

EP - 200

JO - Chemical Physics Letters

JF - Chemical Physics Letters

IS - 4-6

ER -