caa a22 4500 467919070 CHVBK 20180406152911.0 cr unu---uuuuu 170328e20060101xx s 000 0 eng 10.1007/s00706-005-0411-y doi (NATIONALLICENCE)springer-10.1007/s00706-005-0411-y The Role of Binary and Many-centre Molecular Interactions in Spin Crossover in the Solid State. Part I. Equation for Free Energy [Elektronische Daten] [Andrei B. Koudriavtsev, Wolfgang Linert] Summary.: A formalism has been developed that describes spin crossover equilibrium in the solid state by taking into account the effects of n nearest neighbours of a given molecule on its partition function. In this way binary and many-body interactions of the order n + 1 are included into the theoretical model and represented by non-ideality parameters connected with the splitting of free energy levels. Binary interactions are characterised by the main splittings whereas higher order interactions manifest themselves in asymmetries of splittings within multiplets. The contribution of molecular interactions can also be written in terms of formal excess free energies of the second, third, fourth and higher orders. Simple relationships between excess free energies and parameters of multiplets have been found for binary, ternary and quaternary interactions. This formalism is reduced to that of the model of binary interactions when effects of surroundings are additive leading to equidistant free energy multiplets. Higher order interactions may cause an abrupt spin crossover but in a limited range of compositions around the transition point. The regression of experimental transition curves of one-step spin crossover may yield estimates of excess energies up to the fifth order. Springer-Verlag/Wien, 2005 Keywords. Solid state nationallicence Thermodynamics nationallicence Molecular magnets nationallicence Spin crossover nationallicence Molecular interactions nationallicence Koudriavtsev Andrei B. Analytical Centre, D. Mendeleev University of Chemical Technology of Russia, 125047, Moscow, Russia aut Linert Wolfgang Vienna University of Technology, 1060, Wien, Österreich aut Monatshefte für Chemie / Chemical Monthly Springer-Verlag 137/1(2006-01-01), 15-33 0026-9247 137:1<15 2006 137 706 https://doi.org/10.1007/s00706-005-0411-y text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/s00706-005-0411-y text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Koudriavtsev Andrei B. Analytical Centre, D. Mendeleev University of Chemical Technology of Russia, 125047, Moscow, Russia aut NATIONALLICENCE 700 1- Linert Wolfgang Vienna University of Technology, 1060, Wien, Österreich aut NATIONALLICENCE 773 0- Monatshefte für Chemie / Chemical Monthly Springer-Verlag 137/1(2006-01-01), 15-33 0026-9247 137:1<15 2006 137 706 Metadata rights reserved Springer special CC-BY-NC licence nationallicence SWISSBIB 467919070 BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer