Prediction of the equilibrium structures and photomagnetic properties of the Prussian blue analogue RbMn[Fe(CN)6] by density functional theory

Javier Luzon, Miguel Castro, Esther J M Vertelman, Régis Y N Gengler, Petra J van Koningsbruggen, Olga Molodtsova, Martin Knupfer, Petra Rudolf, Paul H M van Loosdrecht, Ria Broer

Research output: Contribution to journalArticle

Abstract

A periodic density functional theory method using the B3LYP hybrid exchange-correlation potential is applied to the Prussian blue analogue RbMn[Fe(CN)6] to evaluate the suitability of the method for studying, and predicting, the photomagnetic behavior of Prussian blue analogues and related materials. The method allows correct description of the equilibrium structures of the different electronic configurations with regard to the cell parameters and bond distances. In agreement with the experimental data, the calculations have shown that the low-temperature phase (LT; Fe(2+)(t(6)2g, S = 0)-CN-Mn(3+)(t(3)2g e(1)g, S = 2)) is the stable phase at low temperature instead of the high-temperature phase (HT; Fe(3+)(t(5)2g, S = 1/2)-CN-Mn(2+)(t(3)2g e(2)g, S = 5/2)). Additionally, the method gives an estimation for the enthalpy difference (HT LT) with a value of 143 J mol(-1) K(-1). The comparison of our calculations with experimental data from the literature and from our calorimetric and X-ray photoelectron spectroscopy measurements on the Rb0.97Mn[Fe(CN)6]0.98 x 1.03 H2O compound is analyzed, and in general, a satisfactory agreement is obtained. The method also predicts the metastable nature of the electronic configuration of the high-temperature phase, a necessary condition to photoinduce that phase at low temperatures. It gives a photoactivation energy of 2.36 eV, which is in agreement with photoinduced demagnetization produced by a green laser.
Original languageEnglish
Pages (from-to)5742-5748
Number of pages7
JournalJournal of Physical Chemistry: Part A
Volume112
Issue number25
DOIs
Publication statusPublished - 31 May 2008

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Density functional theory
analogs
density functional theory
predictions
demagnetization
configurations
electronics
Temperature
Demagnetization
enthalpy
photoelectron spectroscopy
Enthalpy
cells
X ray photoelectron spectroscopy
lasers
ferric ferrocyanide
x rays
Lasers
energy

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Luzon, Javier ; Castro, Miguel ; Vertelman, Esther J M ; Gengler, Régis Y N ; van Koningsbruggen, Petra J ; Molodtsova, Olga ; Knupfer, Martin ; Rudolf, Petra ; van Loosdrecht, Paul H M ; Broer, Ria. / Prediction of the equilibrium structures and photomagnetic properties of the Prussian blue analogue RbMn[Fe(CN)6] by density functional theory. In: Journal of Physical Chemistry: Part A. 2008 ; Vol. 112, No. 25. pp. 5742-5748.
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title = "Prediction of the equilibrium structures and photomagnetic properties of the Prussian blue analogue RbMn[Fe(CN)6] by density functional theory",
abstract = "A periodic density functional theory method using the B3LYP hybrid exchange-correlation potential is applied to the Prussian blue analogue RbMn[Fe(CN)6] to evaluate the suitability of the method for studying, and predicting, the photomagnetic behavior of Prussian blue analogues and related materials. The method allows correct description of the equilibrium structures of the different electronic configurations with regard to the cell parameters and bond distances. In agreement with the experimental data, the calculations have shown that the low-temperature phase (LT; Fe(2+)(t(6)2g, S = 0)-CN-Mn(3+)(t(3)2g e(1)g, S = 2)) is the stable phase at low temperature instead of the high-temperature phase (HT; Fe(3+)(t(5)2g, S = 1/2)-CN-Mn(2+)(t(3)2g e(2)g, S = 5/2)). Additionally, the method gives an estimation for the enthalpy difference (HT LT) with a value of 143 J mol(-1) K(-1). The comparison of our calculations with experimental data from the literature and from our calorimetric and X-ray photoelectron spectroscopy measurements on the Rb0.97Mn[Fe(CN)6]0.98 x 1.03 H2O compound is analyzed, and in general, a satisfactory agreement is obtained. The method also predicts the metastable nature of the electronic configuration of the high-temperature phase, a necessary condition to photoinduce that phase at low temperatures. It gives a photoactivation energy of 2.36 eV, which is in agreement with photoinduced demagnetization produced by a green laser.",
author = "Javier Luzon and Miguel Castro and Vertelman, {Esther J M} and Gengler, {R{\'e}gis Y N} and {van Koningsbruggen}, {Petra J} and Olga Molodtsova and Martin Knupfer and Petra Rudolf and {van Loosdrecht}, {Paul H M} and Ria Broer",
year = "2008",
month = "5",
day = "31",
doi = "10.1021/jp800210j",
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Luzon, J, Castro, M, Vertelman, EJM, Gengler, RYN, van Koningsbruggen, PJ, Molodtsova, O, Knupfer, M, Rudolf, P, van Loosdrecht, PHM & Broer, R 2008, 'Prediction of the equilibrium structures and photomagnetic properties of the Prussian blue analogue RbMn[Fe(CN)6] by density functional theory', Journal of Physical Chemistry: Part A, vol. 112, no. 25, pp. 5742-5748. https://doi.org/10.1021/jp800210j

Prediction of the equilibrium structures and photomagnetic properties of the Prussian blue analogue RbMn[Fe(CN)6] by density functional theory. / Luzon, Javier; Castro, Miguel; Vertelman, Esther J M; Gengler, Régis Y N; van Koningsbruggen, Petra J; Molodtsova, Olga; Knupfer, Martin; Rudolf, Petra; van Loosdrecht, Paul H M; Broer, Ria.

In: Journal of Physical Chemistry: Part A, Vol. 112, No. 25, 31.05.2008, p. 5742-5748.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Prediction of the equilibrium structures and photomagnetic properties of the Prussian blue analogue RbMn[Fe(CN)6] by density functional theory

AU - Luzon, Javier

AU - Castro, Miguel

AU - Vertelman, Esther J M

AU - Gengler, Régis Y N

AU - van Koningsbruggen, Petra J

AU - Molodtsova, Olga

AU - Knupfer, Martin

AU - Rudolf, Petra

AU - van Loosdrecht, Paul H M

AU - Broer, Ria

PY - 2008/5/31

Y1 - 2008/5/31

N2 - A periodic density functional theory method using the B3LYP hybrid exchange-correlation potential is applied to the Prussian blue analogue RbMn[Fe(CN)6] to evaluate the suitability of the method for studying, and predicting, the photomagnetic behavior of Prussian blue analogues and related materials. The method allows correct description of the equilibrium structures of the different electronic configurations with regard to the cell parameters and bond distances. In agreement with the experimental data, the calculations have shown that the low-temperature phase (LT; Fe(2+)(t(6)2g, S = 0)-CN-Mn(3+)(t(3)2g e(1)g, S = 2)) is the stable phase at low temperature instead of the high-temperature phase (HT; Fe(3+)(t(5)2g, S = 1/2)-CN-Mn(2+)(t(3)2g e(2)g, S = 5/2)). Additionally, the method gives an estimation for the enthalpy difference (HT LT) with a value of 143 J mol(-1) K(-1). The comparison of our calculations with experimental data from the literature and from our calorimetric and X-ray photoelectron spectroscopy measurements on the Rb0.97Mn[Fe(CN)6]0.98 x 1.03 H2O compound is analyzed, and in general, a satisfactory agreement is obtained. The method also predicts the metastable nature of the electronic configuration of the high-temperature phase, a necessary condition to photoinduce that phase at low temperatures. It gives a photoactivation energy of 2.36 eV, which is in agreement with photoinduced demagnetization produced by a green laser.

AB - A periodic density functional theory method using the B3LYP hybrid exchange-correlation potential is applied to the Prussian blue analogue RbMn[Fe(CN)6] to evaluate the suitability of the method for studying, and predicting, the photomagnetic behavior of Prussian blue analogues and related materials. The method allows correct description of the equilibrium structures of the different electronic configurations with regard to the cell parameters and bond distances. In agreement with the experimental data, the calculations have shown that the low-temperature phase (LT; Fe(2+)(t(6)2g, S = 0)-CN-Mn(3+)(t(3)2g e(1)g, S = 2)) is the stable phase at low temperature instead of the high-temperature phase (HT; Fe(3+)(t(5)2g, S = 1/2)-CN-Mn(2+)(t(3)2g e(2)g, S = 5/2)). Additionally, the method gives an estimation for the enthalpy difference (HT LT) with a value of 143 J mol(-1) K(-1). The comparison of our calculations with experimental data from the literature and from our calorimetric and X-ray photoelectron spectroscopy measurements on the Rb0.97Mn[Fe(CN)6]0.98 x 1.03 H2O compound is analyzed, and in general, a satisfactory agreement is obtained. The method also predicts the metastable nature of the electronic configuration of the high-temperature phase, a necessary condition to photoinduce that phase at low temperatures. It gives a photoactivation energy of 2.36 eV, which is in agreement with photoinduced demagnetization produced by a green laser.

UR - http://www.scopus.com/inward/record.url?scp=52649139147&partnerID=8YFLogxK

UR - http://pubs.acs.org/doi/abs/10.1021/jp800210j

U2 - 10.1021/jp800210j

DO - 10.1021/jp800210j

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VL - 112

SP - 5742

EP - 5748

JO - Journal of Physical Chemistry: Part A

JF - Journal of Physical Chemistry: Part A

SN - 1089-5639

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ER -