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Prediction of the Equilibrium Structures and Photomagnetic Properties of the Prussian Blue Analogue RbMn[Fe(CN)6] by Density Functional Theory
- Source :
- The Journal of Physical Chemistry. A: Molecules, Spectroscopy, Kinetics, Environment, & General Theory, 112(25), 5742-5748. AMER CHEMICAL SOC
- Publication Year :
- 2008
- Publisher :
- American Chemical Society (ACS), 2008.
-
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; Fe2+(t(2g)(6), S = 0)-CN-Mn-3+(t(2g)(3)e(g)(1), S = 2)) is the stable phase at low temperature instead of the high-temperature phase (HT; Fe3+(t(2g)(5), S = 1/2)-CN-Mn2+(t(2g)(3)e(2)g, S = 5/2)). Additionally, the method gives an estimation for the enthalpy difference (HT double left right arrow 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)center dot 1.03H(2)O 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.
- Subjects :
- Prussian blue
Phase transition
Enthalpy
RUBIDIUM MANGANESE HEXACYANOFERRATE
NITROPRUSSIDE
SPIN-CROSSOVER SYSTEM
Photochemistry
PHOTOINDUCED MAGNETIZATION
chemistry.chemical_compound
LIGHT
CHARGE-TRANSFER
chemistry
X-ray photoelectron spectroscopy
Metastability
Phase (matter)
VALENCE TAUTOMERIC TRANSITION
PHASE-TRANSITION
Physical chemistry
ELECTRON-TRANSFER
METAL-COMPLEXES
Density functional theory
Electron configuration
Physical and Theoretical Chemistry
Subjects
Details
- ISSN :
- 15205215 and 10895639
- Volume :
- 112
- Database :
- OpenAIRE
- Journal :
- The Journal of Physical Chemistry A
- Accession number :
- edsair.doi.dedup.....c808f3abf5dea8bb909c8dc3fe9bfb6b