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Title: Microscopic theory of cooperative spin crossover: Interaction of molecular modes with phonons

In this article, we present a new microscopic theoretical approach to the description of spin crossover in molecular crystals. The spin crossover crystals under consideration are composed of molecular fragments formed by the spin-crossover metal ion and its nearest ligand surrounding and exhibiting well defined localized (molecular) vibrations. As distinguished from the previous models of this phenomenon, the developed approach takes into account the interaction of spin-crossover ions not only with the phonons but also a strong coupling of the electronic shells with molecular modes. This leads to an effective coupling of the local modes with phonons which is shown to be responsible for the cooperative spin transition accompanied by the structural reorganization. The transition is characterized by the two order parameters representing the mean values of the products of electronic diagonal matrices and the coordinates of the local modes for the high- and low-spin states of the spin crossover complex. Finally, we demonstrate that the approach provides a reasonable explanation of the observed spin transition in the [Fe(ptz){sub 6}](BF{sub 4}){sub 2} crystal. The theory well reproduces the observed abrupt low-spin → high-spin transition and the temperature dependence of the high-spin fraction in a wide temperature range as well asmore » the pronounced hysteresis loop. At the same time within the limiting approximations adopted in the developed model, the evaluated high-spin fraction vs. T shows that the cooperative spin-lattice transition proves to be incomplete in the sense that the high-spin fraction does not reach its maximum value at high temperature.« less
Authors:
; ; ;  [1] ;  [2] ; ;  [3]
  1. Institute of Applied Physics, Academy of Sciences of Moldova, Academy Str. 5, MD-2028 Kishinev (Moldova, Republic of)
  2. Department of Chemistry, Ben-Gurion University of the Negev, P.O. Box 653, Beer-Sheva 84105 (Israel)
  3. Departement für Chemie und Biochemie, Universität Bern, Freiestrasse 3, CH-3012 Bern (Switzerland)
Publication Date:
OSTI Identifier:
22493582
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 143; Journal Issue: 8; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BORON FLUORIDES; COUPLING; ELECTRONIC STRUCTURE; HYSTERESIS; IONS; IRON COMPOUNDS; LIGANDS; MATRICES; MOLECULAR CRYSTALS; ORDER PARAMETERS; PHONONS; SPIN; TEMPERATURE DEPENDENCE