Summary.
Parameters of the formalism [1–6] describing spin crossover in the solid state have been defined via molecular potentials in model systems of neutral and ionic complexes. In the first instance Lennard-Jones and electric dipole–dipole potentials have been used whereas in ionic systems Lennard-Jones and electric point-charge potentials have been used. Electric dipole–dipole interaction of neutral complexes brings about a positive excess energy controlled by the difference of electric dipole moments of HS and LS molecules. Differences of the order of Δμ = 1–2 D cause an abrupt spin crossover in systems with T1/2 = 100–150 K. Magnetic coupling contributes both to the excess energy and excess entropy, however the overall effect is equivalent to a modest positive excess energy. Ionic systems in the absence of specific interactions are characterised by very small excess energies corresponding to practically linear van’t Hoff plots. Detectable positive and negative excess energies in these systems may arise from interactions of ligands belonging to neighbouring complexes. The HOMO–LUMO overlap in HS–LS pairs can bring about a nontrivial variation of the shape of transition curves. Examples of regression analysis of experimental transition curves in terms of molecular potentials are given.
Similar content being viewed by others
References
AB Koudriavtsev (1999) Chem Phys 241 109 Occurrence Handle10.1016/S0301-0104(98)00405-4 Occurrence Handle1:CAS:528:DyaK1MXlvValtQ%3D%3D
Koudriavtsev AB, Jameson RF, Linert W (2001) The Law of Mass Action. Springer, Berlin Heidelberg
AB Koudriavtsev AF Stassen JG Haasnoot M Gruner P Weinberge W Liner (2003) Phys Chem Chem Phys 5 3666 Occurrence Handle1:CAS:528:DC%2BD3sXmsVShu74%3D
AB Koudriavtsev AF Stassen JG Haasnoot M Gruner P Weinberge W Liner (2003) Phys Chem Chem Phys 5 3676 Occurrence Handle1:CAS:528:DC%2BD3sXmsVShu7w%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
Koudriavtsev AB, Linert W (2005) Monatsh Chem (Part I)
R Boc W Liner (2003) Monatsh Chem 134 199
Spiering H (2004) Elastic Interaction in Spin-Crossover Compounds. In: Gütlich P, Goodwin H (eds) Top Curr Chem, vol 235. Springer, Berlin Heidelberg, p 171
Jensen L (1965) Many-centre Forces and Stability of Crystals. In: Sinanoglu O (Ed) Modern Quantum Chemistry. Academic Press, New York, p 231
H Spierin T Kohlhaa H Romsted A Hause C Bruns-Yilma P Gütlic (1999) Coord Chem Rev 190–192 629
Letard JF, Guionneau P, Rabardel L, Howard JAK, Goeta AE, Chasseau D, Kahn O (1998) Inorg Chem 17: 4432; Guionneau P, Letard JF, Yufit DS, Chasseau D, Bravic G, Goeta AE, Howard JAK, Kahn O (1999) J Mater Chem 9: 985
Moelwyn-Hughes EA (1970) Physikalische Chemie. Georg Thieme Verlag, Stuttgart
Kalinnikov VT, Rakitin YuV (1980) Vvedenie v magnetokhimiyu. Nauka, Moskva
Carlin RL (1986) Magnetochemistry. Springer, Berlin Heidelberg
V Ksenofontov H Spiering S Reiman Y Garcia AB Gaspar N Moliner JA Real P Gutlich (2001) Chem Phys Lett 348 381 Occurrence Handle10.1016/S0009-2614(01)01114-9 Occurrence Handle1:CAS:528:DC%2BD3MXos1Cgsbo%3D
JF Letard JA Real N Moliner AB Gaspar L Capes O Cador O Kahn (1999) J Am Chem Soc 121 10630 Occurrence Handle10.1021/ja991476p Occurrence Handle1:CAS:528:DyaK1MXmvFCktLY%3D
G Chastanet AB Gaspar JA Real JF Letard (2001) J Chem Soc Chem Comm 2001 819
AB Gaspar V Ksenofontov JA Real P Gütlich (2003) Chem Phys Lett 373 385 Occurrence Handle10.1016/S0009-2614(03)00560-8 Occurrence Handle1:CAS:528:DC%2BD3sXjs1Cltrg%3D
S Brooker DJ de Geest RJ Kelly PG Plieger B Moubaraki KS Murray GB Jameson (2002) J Chem Soc, Dalton Trans 2002 2080
Dova E, Stassen AF, Driessen RAJ, Sonneveld E, Goubitz K, Peschar R, Haasnoot JG, Reedijk J, Schenk H (2001) Acta Cryst B 57: 531; Dova E, Peschar R, Sakata M, Kato K, Stassen AF, Schenk H, Haasnoot JG (2004) Acta Cryst B 60: 528
AF Stassen M Grunert E Dova M Mueller P Weinberger G Wiesinger H Schenk W Linert JG Haasnoot J Reedijk (2003) Eur J Inorg Chem 12 2273
M Sorai J Ensling KM Hasselbach P Gütlich (1977) Chem Phys 20 197 Occurrence Handle10.1016/0301-0104(77)85023-4 Occurrence Handle1:CAS:528:DyaE2sXhs1ehsbg%3D
N Moliner L Salmon L Capes MC Munoz JF Letard A Bousseksou JP Tuchagues JJ McGarvey AC Dennis M Castro R Burriel JA Real (2002) J Phys Chem B 106 4276 Occurrence Handle10.1021/jp013872b Occurrence Handle1:CAS:528:DC%2BD38XisVelt70%3D
JA Real MC Munoz J Faus X Solans (1997) Inorg Chem 36 3008 Occurrence Handle1:CAS:528:DyaK2sXjslOkur0%3D
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
BM Axilrod E Teller (1943) J Chem Phys 11 299 Occurrence Handle10.1063/1.1723844 Occurrence Handle1:CAS:528:DyaH3sXjtlShsA%3D%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 II. Non-ideality Parameters Defined via Binary Molecular Potentials. Monatsh. Chem. 137, 35–53 (2006). https://doi.org/10.1007/s00706-005-0412-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00706-005-0412-x