  Infrared (IR) absorption spectroscopy has been used to probe the evolution of
microscopic vibrational states upon the temperature- and photo-induced spin
crossovers in [Fe(2-picolylamine)3]Cl2EtOH (Fe-pic). To overcome the small
sizes and the strong IR absorption of the crystal samples used, an IR
synchrotron radiation source and an IR microscope have been used. The obtained
IR spectra of Fe-pic show large changes between high-spin and low-spin states
for both the temperature- and the photo- induced spin crossovers. Although the
spectra in the temperature- and photo-induced high-spin states are relatively
similar to each other, they show distinct differences below 750 cm-1. This
demonstrates that the photo-induced high-spin state involves microscopically
different characters from those of the temperature-induced high-spin state. The
results are discussed in terms of local pressure and structural deformations
within the picolylamine ligands, and in terms of their possible relevance to
the development of macroscopic photo-induced phase in Fe-pic.
