Velocity of the high-spin low-spin interface inside the thermal hysteresis loop of a spin-crossover crystal, via photothermal control of the interface motion

Phys Rev Lett. 2013 Feb 22;110(8):087208. doi: 10.1103/PhysRevLett.110.087208. Epub 2013 Feb 21.

Abstract

We investigated by optical microscopy the thermal transition of the spin-crossover dinuclear iron(II) compound [(Fe(NCSe)(py)(2))(2)(m-bpypz)]. In a high-quality crystal the high-spin (HS) low-spin (LS) thermal transition took place with a sizable hysteresis, at ~108 K and ~116 K on cooling and heating, respectively, through the growth of a single macroscopic domain with a straight LS and HS interface. The interface orientation was almost constant and its propagation velocity was close to ~6 and 26 μ m s(-1) for the on-cooling and on-heating processes, respectively. We found that the motion of the interface was sensitive to the intensity of the irradiation beam of the microscope, through a photothermal effect. By fine-tuning the intensity we could stop and even reverse the interface motion. This way we stabilized a biphasic state of the crystal, and we followed the spontaneous motion of the interface at different temperatures inside the thermal hysteresis loop. This experiment gives access for the first time to an accurate determination of the equilibrium temperature in the case of thermal hysteresis--which was not accessible by the usual quasistatic investigations. The temperature dependence of the propagation velocity inside the hysteretic interval was revealed to be highly nonlinear, and it was quantitatively reproduced by a dynamical mean-field theory, which made possible an estimate of the macroscopic energy barrier.

MeSH terms

  • Coordination Complexes / chemistry*
  • Ferrous Compounds / chemistry*
  • Hot Temperature
  • Models, Chemical*
  • Photochemical Processes
  • Pyrazoles / chemistry
  • Pyridines / chemistry
  • Surface Properties

Substances

  • Coordination Complexes
  • Ferrous Compounds
  • Pyrazoles
  • Pyridines