The Electronic Structure Signature of the Spin Cross-Over Transition of [Co(dpzca)2]

Xin Zhang, Sai Mu, Yang Liu, Jian Luo, Jian Zhang, Alpha T. N'Diaye, Axel Enders, Peter A. Dowben

Research output: Contribution to journalArticle

Abstract

The unoccupied electronic structure of the spin crossover molecule cobalt (II) N-(2-pyrazylcarbonyl)-2-pyrazinecarboxamide, [Co(dpzca)2] was investigated, using X-ray absorption spectroscopy (XAS) and compared with magnetometry (SQUID) measurements. The temperature dependence of the XAS and molecular magnetic susceptibility χmT are in general agreement for [Co(dpzca)2], and consistent with density functional theory (DFT). This agreement of magnetic susceptibility and X-ray absorption spectroscopy provides strong evidence that the changes in magnetic moment can be ascribed to changes in electronic structure. Calculations show the choice of Coulomb correlation energy U has a profound effect on the electronic structure of the low spin state, but has little influence on the electronic structure of the high spin state. In the temperature dependence of the XAS, there is also evidence of an X-ray induced excited state trapping for [Co(dpzca)2] at 15 K.

Original languageEnglish (US)
Pages (from-to)445-458
Number of pages14
JournalZeitschrift fur Physikalische Chemie
Volume232
Issue number4
DOIs
StatePublished - May 24 2018

Fingerprint

X ray absorption spectroscopy
Electron transitions
Electronic structure
signatures
electronic structure
absorption spectroscopy
Magnetic susceptibility
x rays
Pyrazinamide
SQUIDs
magnetic permeability
Cobalt
Magnetic moments
temperature dependence
Excited states
Density functional theory
magnetic measurement
crossovers
X rays
cobalt

Keywords

  • cobalt (II) N-(2-pyrazylcarbonyl)-2-pyrazinecarboxamide
  • density functional theory
  • spin crossover transition
  • X-ray induced excited state trapping

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

The Electronic Structure Signature of the Spin Cross-Over Transition of [Co(dpzca)2]. / Zhang, Xin; Mu, Sai; Liu, Yang; Luo, Jian; Zhang, Jian; N'Diaye, Alpha T.; Enders, Axel; Dowben, Peter A.

In: Zeitschrift fur Physikalische Chemie, Vol. 232, No. 4, 24.05.2018, p. 445-458.

Research output: Contribution to journalArticle

Zhang, Xin ; Mu, Sai ; Liu, Yang ; Luo, Jian ; Zhang, Jian ; N'Diaye, Alpha T. ; Enders, Axel ; Dowben, Peter A. / The Electronic Structure Signature of the Spin Cross-Over Transition of [Co(dpzca)2]. In: Zeitschrift fur Physikalische Chemie. 2018 ; Vol. 232, No. 4. pp. 445-458.
@article{8e26b36a592f4f07a793fe9b6320bf55,
title = "The Electronic Structure Signature of the Spin Cross-Over Transition of [Co(dpzca)2]",
abstract = "The unoccupied electronic structure of the spin crossover molecule cobalt (II) N-(2-pyrazylcarbonyl)-2-pyrazinecarboxamide, [Co(dpzca)2] was investigated, using X-ray absorption spectroscopy (XAS) and compared with magnetometry (SQUID) measurements. The temperature dependence of the XAS and molecular magnetic susceptibility χmT are in general agreement for [Co(dpzca)2], and consistent with density functional theory (DFT). This agreement of magnetic susceptibility and X-ray absorption spectroscopy provides strong evidence that the changes in magnetic moment can be ascribed to changes in electronic structure. Calculations show the choice of Coulomb correlation energy U has a profound effect on the electronic structure of the low spin state, but has little influence on the electronic structure of the high spin state. In the temperature dependence of the XAS, there is also evidence of an X-ray induced excited state trapping for [Co(dpzca)2] at 15 K.",
keywords = "cobalt (II) N-(2-pyrazylcarbonyl)-2-pyrazinecarboxamide, density functional theory, spin crossover transition, X-ray induced excited state trapping",
author = "Xin Zhang and Sai Mu and Yang Liu and Jian Luo and Jian Zhang and N'Diaye, {Alpha T.} and Axel Enders and Dowben, {Peter A.}",
year = "2018",
month = "5",
day = "24",
doi = "10.1515/zpch-2017-0932",
language = "English (US)",
volume = "232",
pages = "445--458",
journal = "Zeitschrift fur Physikalische Chemie",
issn = "0942-9352",
publisher = "Oldenbourg Wissenschaftsverlag GmbH",
number = "4",

}

TY - JOUR

T1 - The Electronic Structure Signature of the Spin Cross-Over Transition of [Co(dpzca)2]

AU - Zhang, Xin

AU - Mu, Sai

AU - Liu, Yang

AU - Luo, Jian

AU - Zhang, Jian

AU - N'Diaye, Alpha T.

AU - Enders, Axel

AU - Dowben, Peter A.

PY - 2018/5/24

Y1 - 2018/5/24

N2 - The unoccupied electronic structure of the spin crossover molecule cobalt (II) N-(2-pyrazylcarbonyl)-2-pyrazinecarboxamide, [Co(dpzca)2] was investigated, using X-ray absorption spectroscopy (XAS) and compared with magnetometry (SQUID) measurements. The temperature dependence of the XAS and molecular magnetic susceptibility χmT are in general agreement for [Co(dpzca)2], and consistent with density functional theory (DFT). This agreement of magnetic susceptibility and X-ray absorption spectroscopy provides strong evidence that the changes in magnetic moment can be ascribed to changes in electronic structure. Calculations show the choice of Coulomb correlation energy U has a profound effect on the electronic structure of the low spin state, but has little influence on the electronic structure of the high spin state. In the temperature dependence of the XAS, there is also evidence of an X-ray induced excited state trapping for [Co(dpzca)2] at 15 K.

AB - The unoccupied electronic structure of the spin crossover molecule cobalt (II) N-(2-pyrazylcarbonyl)-2-pyrazinecarboxamide, [Co(dpzca)2] was investigated, using X-ray absorption spectroscopy (XAS) and compared with magnetometry (SQUID) measurements. The temperature dependence of the XAS and molecular magnetic susceptibility χmT are in general agreement for [Co(dpzca)2], and consistent with density functional theory (DFT). This agreement of magnetic susceptibility and X-ray absorption spectroscopy provides strong evidence that the changes in magnetic moment can be ascribed to changes in electronic structure. Calculations show the choice of Coulomb correlation energy U has a profound effect on the electronic structure of the low spin state, but has little influence on the electronic structure of the high spin state. In the temperature dependence of the XAS, there is also evidence of an X-ray induced excited state trapping for [Co(dpzca)2] at 15 K.

KW - cobalt (II) N-(2-pyrazylcarbonyl)-2-pyrazinecarboxamide

KW - density functional theory

KW - spin crossover transition

KW - X-ray induced excited state trapping

UR - http://www.scopus.com/inward/record.url?scp=85041032527&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85041032527&partnerID=8YFLogxK

U2 - 10.1515/zpch-2017-0932

DO - 10.1515/zpch-2017-0932

M3 - Article

VL - 232

SP - 445

EP - 458

JO - Zeitschrift fur Physikalische Chemie

JF - Zeitschrift fur Physikalische Chemie

SN - 0942-9352

IS - 4

ER -