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.
Similar content being viewed by others
References
JA Real AB Gaspar V Niel MC Munoz (2003) Coord Chem Revs 236 121 Occurrence Handle10.1016/S0010-8545(02)00220-5 Occurrence Handle1:CAS:528:DC%2BD3sXkvVyqsA%3D%3D
P Gütlich A Hauser H Spiering (1994) Angew Chem Int Ed 33 2024
JG Haasnoot (2000) Coord Chem Rev 200 131 Occurrence Handle10.1016/S0010-8545(00)00266-6
M Sorai (2001) Bull Chem Soc Jap 74 2223 Occurrence Handle1:CAS:528:DC%2BD38XjtlGjug%3D%3D
R Boca W Linert (2003) Monatsh Chem 134 199 Occurrence Handle1:CAS:528:DC%2BD3sXnt1KnsA%3D%3D
Linert W, Grunert M, Koudriavtsev AB (2004) Isoequilibrium and Isokinetic Relationships in Spin Crossover. In: Gütlich P, Goodwin H (eds) Top Curr Chem, vol 235. Springer, Berlin Heidelberg, p 105
J Wajnflasz R Pick (1970) J Phys Status Solidi 40 537 Occurrence Handle1:CAS:528:DyaE3cXkvFWnt7Y%3D
R Bari J Sivardiere (1972) Phys Rev B 5 4466
VV Zelentsov GL Lapushkin SS Sobolev VI Shipilov (1986) Dokl AN SSSR, Ser Khim 289 393
A Bousseksou J Nasser J Linares K Boukheddaden F Varret (1992) J Phys I France 2 1381 Occurrence Handle10.1051/jp1:1992217 Occurrence Handle1:CAS:528:DyaK38Xlt1eis7o%3D
CP Slichter HG Drickamer (1972) J Chem Phys 56 2142 Occurrence Handle10.1063/1.1677511 Occurrence Handle1:CAS:528:DyaE38XptVWktg%3D%3D
M Sorai S Seki (1974) J Phys Chem Solids 35 555 Occurrence Handle1:CAS:528:DyaE2cXktVKrtL0%3D
S Ohnishi S Sugano (1981) J Phys C 14 39 Occurrence Handle1:CAS:528:DyaL3MXhsVOlt7k%3D
H Spiering E Meissner H Köppen EW Müller P Gütlich (1982) Chem Phys 68 65 Occurrence Handle10.1016/0301-0104(82)85080-5 Occurrence Handle1:CAS:528:DyaL38XksVygtL8%3D
H Köppen EW Müller CP Köhler H Spiering E Meissner P Gütlich (1982) Chem Phys Lett 91 348
R Jakobi H Spiering P Gütlich (1992) J Phys Chem Solids 53 267 Occurrence Handle1:CAS:528:DyaK38Xhs1Sitb8%3D Occurrence Handle10.1016/0022-3697(92)90055-I
H Romstedt A Hauser H Spiering (1998) J Phys Chem Solids 59 265 Occurrence Handle1:CAS:528:DyaK1cXltlGhug%3D%3D
H Spiering T Kohlhaas H Romstedt A Hauser C Bruns-Yilmaz P Gütlich (1999) Coord Chem Rev 190–192 629
Alder BJ, Hoover WG (1968) Computational Methods in Statistical Mechanics. In: Temperley HNV, Rowlinson JS, Rushbrooke GS (eds) Physics of Simple Liquids. North Holland, Amsterdam, p 103
G Baranovic (2003) Chem Phys Lett 369 668 Occurrence Handle10.1016/S0009-2614(03)00028-9 Occurrence Handle1:CAS:528:DC%2BD3sXhtVOmu7w%3D
G Baranovic D Babi (2004) Spectrochim Acta A 60 1013
DA Scherlis DA Estrin (2002) Int J Quant Chem 87 158 Occurrence Handle10.1002/qua.10043 Occurrence Handle1:CAS:528:DC%2BD38XitF2ksro%3D
H Paulsen AX Trautwein (2004) J Phys Chem Solids 65 793 Occurrence Handle1:CAS:528:DC%2BD2cXht1yjtLw%3D Occurrence Handle10.1016/j.jpcs.2003.11.017
Bousseksou A, Constan-Machado H, Varret F (1995) J Phys I France 5: 747; Tuchagues JP, Bousseksou A, Molnár G, McGarvey JJ, Varret F (2004) The Role of Molecular Vibrations in the Spin Crossover Phenomenon. In: Gütlich P, Goodwin H (eds) Top Curr Chem, vol 235. Springer, Berlin Heidelberg, p 84
AB Koudriavtsev (1999) Chem Phys 241 109 Occurrence Handle10.1016/S0301-0104(98)00405-4 Occurrence Handle1:CAS:528:DyaK1MXlvValtQ%3D%3D
AB Koudriavtsev AF Stassen JG Haasnoot M Grunert P Weinberger W Linert (2003) Phys Chem Chem Phys 5 3666 Occurrence Handle1:CAS:528:DC%2BD3sXmsVShu74%3D
AB Koudriavtsev AF Stassen JG Haasnoot M Grunert P Weinberger W Linert (2003) Phys Chem Chem Phys 5 3676 Occurrence Handle1:CAS:528:DC%2BD3sXmsVShu7w%3D
Koudriavtsev AB, Jameson RF, Linert W (2001) The Law of Mass Action. Springer, Berlin Heidelberg
O Roubeau JG Haasnoot E Codjovi F Varret J Reedijk (2002) Chem Mater 14 2559 Occurrence Handle10.1021/cm0116626 Occurrence Handle1:CAS:528:DC%2BD38XjsFOrtbk%3D
Kudryavtsev A, Linert W (1996) Physico-Chemical Applications of NMR. WSPC, Singapore
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Koudriavtsev, A., Linert, W. The Role of Binary and Many-centre Molecular Interactions in Spin Crossover in the Solid State. Part I. Equation for Free Energy. Monatsh. Chem. 137, 15–33 (2006). https://doi.org/10.1007/s00706-005-0411-y
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00706-005-0411-y