Infrared study of spin crossover Fe-picolylamine complex

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.Comment: 6 pages (text) and 6 figures,submitted to J. Phys. Soc. Jp

Phase Transition in a One-Dimensional Extended Peierls-Hubbard Model with a Pulse of Oscillating Electric Field: I. Threshold Behavior in Ionic-to-Neutral Transition

Photoinduced dynamics of charge density and lattice displacements is calculated by solving the time-dependent Schr\"odinger equation for a one-dimensional extended Peierls-Hubbard model with alternating potentials for the mixed-stack organic charge-transfer complex, TTF-CA. A pulse of oscillating electric field is incorporated into the Peierls phase of the transfer integral. The frequency, the amplitude, and the duration of the pulse are varied to study the nonlinear and cooperative character of the photoinduced transition. When the dimerized ionic phase is photoexcited, the threshold behavior is clearly observed by plotting the final ionicity as a function of the increment of the total energy. Above the threshold photoexcitation, the electronic state reaches the neutral one with equidistant molecules after the electric field is turned off. The transition is initiated by nucleation of a metastable neutral domain, for which an electric field with frequency below the linear absorption peak is more effective than that at the peak. When the pulse is strong and short, the charge transfer takes place on the same time scale with the disappearance of dimerization. As the pulse becomes weak and long, the dimerization-induced polarization is disordered to restore the inversion symmetry on average before the charge transfer takes place to bring the system neutral. Thus, a paraelectric ionic phase is transiently realized by a weak electric field. It is shown that infrared light also induces the ionic-to-neutral transition, which is characterized by the threshold behavior.Comment: 24 pages, 11 figure

Transient Analysis of Luminescent Coupling Effects in Multi-junction Solar Cells

We investigate the luminescent coupling (LC) effects in a four-junction GaInP/GaAs//GaInAsP/GaInAs concentrator solar cell based on transient open-circuit voltage (Voc) measurements under monochromatic illumination. Photocurrent generation in the non-absorbing GaInAs bottom subcell due to LC from upper subcells shows superlinear behavior with increasing light intensity. Along with this, a Voc enhancement is observed and quantified for illumination intensities that span almost six orders of magnitude. The Voc increase is explained and studied using a series-connected diode model including subcell shunt resistances, capacitances, and LC effects. The impact of unilluminated subcells on the subcell Voc determination is discussed for multi-junction solar cells. Finally, in the analysis of the LC generated photocurrent, namely, the coupling factor from the GaInAsP to the non-absorbing GaInAs subcell, a characteristic dependency on bias voltage is shown and explained by a result of competing photo- and electroluminescence mechanisms