Cooperative pseudo-Jahn-Teller effect of the Fe(H2O)62+complexes in the sulfate heptahydrates

1983

Quadrupole splitting of Fe(II) spin crossover compounds study of temperature and pressure dependence and the implication for the interaction mechanism

1989

The temperature and pressure dependence of the quadrupole splitting ΔE Q of the 3/2→1/2 nuclear Mossbauer transition of57Fe in the spin crossover compounds [Fe x Zn1−x (2-pic)3]Cl2⋆EtOH and the deuterated analog [Fe x Zn1−x (2-pic-ND2)3] Cl2⋆EtOD (2-pic=2-picolylamine) have been studied. The change of ΔE Q can be linearly related to the defomation of the lattice as observed by X-ray measurements. The dependence of ΔE Q on temperatureT, pressurep, and the fraction γ of molecules in the electronic high spin state in the pure iron (x=1) compounds is therefore interpreted as a result of the change of the lattice contribution to the electric field gradient (EFG) at the nucleus only. The intrinsi…

Nature of the phase transition in spin crossover compounds

1990

Abstract Starting from the phenomenological free energy describing the spin equilibrium of continuous or gradual high spin (HS) ⇌ low spin (LS) transitions a reduced equation of state has been derived which is of the type known in mean field theories. The continuous HS ⇌ LS transitions of [Fe(2-pic-ND 2 ) 3 ]Cl 2 ·EtOD (2-pic = 2-picolylamine) at ambient pressure and p = 1200 bar and of [Fe(2-pic) 3 ]Cl 2 -MeOH can be classified as isobars above the critical point of the system. Around and below the critical point a complex behaviour is expected for thermodynamic reasons combined with the consequences of an elastic interaction mechanism between the HS and LS complex molecules in the crystal…

The effect of low pressure on a high-spin—low-spin transition

1983

Abstract The effect of low pressure ( p = 150 bar) on the high-spin (HS)—low-spin (LS) transition in [Fe x Zn 1− x (2-pic) 3 ]Cl 2 · EtOH ( x = 0.5, 1.0) was measured by Mossbauer spectroscopy and the results compared with theory. The linear dependence of the volume of the lattice on the HS fraction, which is the basic assumption of the theory, was proven by temperature dependent X-ray measurements.

Anomalous pressure dependence of the Lamb-Mössbauerf-factor in the spin crossover system [Fe(2-pic-ND2)3]Cl2·EtOD

1987

The pressure dependence of the Lamb-Mossbauer factor of the spin crossover compound [Fe(2-pic-ND2)3]Cl2·EtOD(2-pic-ND2=2-picolylamine, deuterated at the−NH2 group) has been measured at pressures up to 1500 bar and at three temperatures (115.7, 146.7, 185.6 K) around the transition temperatureT t=135 K. The temperature dependence of the unit cell volume has been determined by X-ray diffraction. In the transition region (T=146.7 K), the pressure dependence of thef-factor shows an anomalous increase as compared to the dependence below and above the transition. The behaviour off(p, T), its anomaly and absolute value, can be consistently explained within a theoretical model which treats the comp…