Novel mechanism of photoinduced reversible phase transitions in molecule-based magnets

A novel microscopic mechanism of bi-directional structural changes is proposed for the photo-induced magnetic phase transition in Co-Fe Prussian blue analogues on the basis of ab initio quantum chemical cluster calculations. It is shown that the local potential energies of various spin states of Co are sensitive to the number of nearest neighbor Fe vacancies. As a result, the forward and backward structural changes are most readily initiated by excitation of different local regions by different photons. This mechanism suggests an effective strategy to realize photoinduced reversible phase transitions in a general system consisting of two local components.Comment: 4 pages, LaTex, 3 figures, to appear in Phys. Rev. Let

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

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

Dynamics of charge density and lattice displacements after the neutral phase is photoexcited is studied by solving the time-dependent Schr\"odinger equation for a one-dimensional extended Peierls-Hubbard model with alternating potentials. In contrast to the ionic-to-neutral transition studied previously, the neutral-to-ionic transition proceeds in an uncooperative manner as far as the one-dimensional system is concerned. The final ionicity is a linear function of the increment of the total energy. After the electric field is turned off, the electronic state does not significantly change, roughly keeping the ionicity, even if the transition is not completed, because the ionic domains never proliferate. As a consequence, an electric field with frequency just at the linear absorption peak causes the neutral-to-ionic transition the most efficiently. These findings are consistent with the recent experiments on the mixed-stack organic charge-transfer complex, TTF-CA. We artificially modify or remove the electron-lattice coupling to discuss the origin of such differences between the two transitions.Comment: 17 pages, 9 figure

Charge-Transfer Excitations in One-Dimensional Dimerized Mott Insulators

We investigate the optical properties of one-dimensional (1D) dimerized Mott insulators using the 1D dimerized extended Hubbard model. Numerical calculations and a perturbative analysis from the decoupled-dimer limit clarify that there are three relevant classes of charge-transfer (CT) states generated by photoexcitation: interdimer CT unbound states, interdimer CT exciton states, and intradimer CT exciton states. This classification is applied to understanding the optical properties of an organic molecular material, 1,3,5-trithia-2,4,6-triazapentalenyl (TTTA), which is known for its photoinduced transition from the dimerized spin-singlet phase to the regular paramagnetic phase. We conclude that the lowest photoexcited state of TTTA is the interdimer CT exciton state and the second lowest state is the intradimer CT exciton state.Comment: 6 pages, 6 figures, to be published in J. Phys. Soc. Jp

Electronic and Lattice Dynamics in The Photoinduced Ionic-to-Neutral Phase Transition in a One-Dimensional Extended Peierls-Hubbard Model

Real-time dynamics of charge density and lattice displacements is studied during photoinduced ionic-to-neutral phase transitions by using a one-dimensional extended Peierls-Hubbard model with alternating potentials for the one-dimensional mixed-stack charge-transfer complex, TTF-CA. The time-dependent Schr\"odinger equation and the classical equation of motion are solved for the electronic and lattice parts, respectively. We show how neutral domains grow in the ionic background. As the photoexcitation becomes intense, more neutral domains are created. Above threshold intensity, the neutral phase is finally achieved. After the photoexcitation, ionic domains with wrong polarization also appear. They quickly reduce the averaged staggered lattice displacement, compared with the averaged ionicity. As the degree of initial lattice disorder increases, more solitons appear between these ionic domains with different polarizations, which obstruct the growth of neutral domains and slow down the transition.Comment: 9 pages, 10 figures, submitted to J. Phys. Soc. Jp

Effects of Lattice and Molecular Phonons on Photoinduced Neutral-to-Ionic Transition Dynamics in Tetrathiafulvalene-pp-Chloranil

For electronic states and photoinduced charge dynamics near the neutral-ionic transition in the mixed-stack charge-transfer complex tetrathiafulvalene-$p$-chloranil (TTF-CA), we review the effects of Peierls coupling to lattice phonons modulating transfer integrals and Holstein couplings to molecular vibrations modulating site energies. The former stabilizes the ionic phase and reduces discontinuities in the phase transition, while the latter stabilizes the neutral phase and enhances the discontinuities. To reproduce the experimentally observed ionicity, optical conductivity and photoinduced charge dynamics, both couplings are quantitatively important. In particular, strong Holstein couplings to form the highly-stabilized neutral phase are necessary for the ionic phase to be a Mott insulator with large ionicity. A comparison with the observed photoinduced charge dynamics indicates the presence of strings of lattice dimerization in the neutral phase above the transition temperature.Comment: 9 pages, 7 figures, accepted for publication in J. Phys. Soc. Jp

Photoinduced metallic properties of one-dimensional strongly correlated electron systems

We study photoinduced optical responses of one-dimensional strongly correlated electron systems. The optical conductivity spectra are calculated for the ground state and a photoexcited state in the one-dimensional Hubbard model at half filling by using the exact diagonalization method. It is found that, in the Mott insulator phase, the photoexcited state has large spectral weights including the Drude weight below the optical gap. As a consequence, the spectral weight above the optical gap is largely reduced. These results imply that a metallic state is induced by photoexcitation. Comparison between the photoexcited and hole-doped states shows that the photoexcitation is similar to chemical doping.Comment: 4 pages, 4 figures, submitted to J. Phys. Soc. Jp

Direct evidence of electronic ferroelectricity in YbFe2O4 using neutron diffraction and nonlinear spectroscopy

We report the first observation of room temperature spontaneous electric polarization in an electronic ferroelectric material, a YbFe2O4 single crystal. The observation was based on second harmonic generation (SHG), a nonlinear optical process. Tensor analysis of the SHG signal revealed that this material has a polar charge superstructure with Cm symmetry. This result settles the long-term discussion on the uncertainty about electronic ferroelectric properties, including the charge order structure. We present a complete picture of the polar charge ordering of this material via consistent results from two different characterization methods. The SHG signal shows the same temperature dependence as the superlattice signal observed in neutron diffraction experiments. These results prove ferroelectric coupling to electron ordering in YbFe2O4, which results in electronic ferroelectricity which is enabled by the real space ordering of iron cations with different valences. The existence of electronic ferroelectricity holds promise for future electronics technologies where devices run a thousand times faster than frequency of the present CPU (a few gigahertz) embedded in smartphones, etc

100 ps time-resolved solution scattering utilizing a wide-bandwidth X-ray beam from multilayer optics

A new method of time-resolved solution scattering utilizing X-ray multilayer optics is presented