A μSR study of the spin-crossover

The spin-crossover phenomenon is a cooperative low-spin to high-spin transition which can be initiated using temperature or light-irradiation. We have used muon-spin relaxation (μSR) to study this effect in Fe(PM-PEA)₂(NCS)₂ and Fe(PMAzA)₂(NCS)₂. We find Gaussian or exponential muon relaxation in the high-spin phase for the two compounds, reflecting differences in their intermolecular interactions. For both compounds, the low-spin phase gives rise to root-exponential relaxation which we associate with a dilute distribution of fluctuating moments resulting from incomplete spin crossover.     

Two-variable macroscopic model for spin-crossover solids: Static and dynamic effects of the correlations

In order to investigate the role of nearest neighbors correlations in the relaxation of the High Spin fraction in spin crossover compounds, we have developed a two macro-variable dynamical model based on Kubo's treatement of the master equation. This is compared to the local equilibrium approach, where short-range correlations are assumed to follow adiabatically the long range-order parameter. The sigmoidal shape of the relaxation, previously associated with the effects of interactions, and the so-called “tail effect”, i.e. the extra-slowing down at long times due to the correlations are obtained. The accurate comparison to experimental relaxation data confirms the coexistence of short-range and long-range interactions in spin-crossover solids. Received 20 April 2000     

Fascinating electronic games in iron complexes

Summary Coordination compounds of transition metal ions with open-shell electron configurations may exhibit dynamic electronic-structure phenomena, depending on the nature of the coordinating ligand sphere. The change of spin state with temperature (?thermal spin-crossover?), light-induced electron transfer processes leading to long-lived metastable charge and spin states (e.g., ?LIESST? effect), are some of the fascinating electronic games encountered in transition metal compounds, which are presently under extensive study by chemists and physicists. M?ssbauer spectroscopy plays a dominant role in the investigation of such phenomena in iron compounds, as will be demonstrated in this paper. This work will focus on selected examples of ?thermal spin-crossover? in iron(II) complexes and switching between different spin states by irradiation with light of different wavelength (LIESST effect), demonstrating that M?ssbauer spectroscopy besides other physical techniques proves to be a highly elegant tool for following the spin state conversion and the concomitant changes of molecular and crystal structure properties. Finally, M?ssbauer emission spectroscopy, both time integral and time differential, has been employed to generate and identify long-lived excited spin states by making use of the nuclear disintegration of⁵⁷Co as an intrinsic molecular light source (NIESST=nuclear decay-induced excited-spin-state trapping). Lifetime measurements by optical techniques on LIESST states and by time-differential M?ssbauer coincidence spectroscopy on NIESST states prove that the relaxation pathways in the mechanisms for LIESST and NIESST are identical. Dedicated to Prof. Harry B. Gray on the occasion of his 60th birthday. Paper presented at ICAME-95, Rimini, 10–16 September 1995.     

Noise-induced optical bistability and state transitions in spin-crossover solids with delayed feedback

Considering the time-delayed feedback and environmental perturbations in spin-crossover system, we construct a stochastic delayed differential equation to study the state transitions from the low spin (LS) state to the high spin (HS) state in spin-crossover solids. It is shown that the delayed feedback and noise can induce optical bistability and state transitions. The mean first-passage time (MFPT) of the transition from the LS state to the HS state as the function of the noise intensity exhibits a maximum, and the noise-enhanced stability is observed. However the MFPT decreases with increase of the delayed feedback intensity, thus the delayed feedback accelerates the conversion from the LS state to the HS state.     

Non-linear Relaxation of the Photo-induced High Spin State in Spin-Crossover Solids: Effect of Correlations

We investigate a microscopic model based on the pair approximation, for the dynamical properties of the photo-induced high-spin state in spin-crossover solids at low temperature. The model uses the Ising-like hamiltonian and combines long- and short-range interactions. The stochastic treatment of the latter provides a set of two coupled differential equations for the macroscopic short- and long-range order parameters, which reproduce successfully the main features of the experimental relaxation curves.     

Light-induced bistability in spin transition solids leading to thermal and optical hysteresis

We investigate the behaviour of photo-excitable, bistable systems, under permanent light irradiation, in presence of relaxation towards the non-excited state. Cooperativity causes bistability of the steady state, leading to light-induced thermal and optical hysteresis (LITH and LIOH). The light-induced instability is expected to induce demixtion, i.e. the coexistence of domains of the two stable steady states. Such effects are evidenced by magnetic and reflectivity measurements on the spin-crossover solid solution: , with x= 0.3, 0.5, 0.85. Experimental data are in quantitative agreement with a simple macroscopic model which includes a non-linear relaxation term in the master equation. Received: 5 June 1997 / Accepted: 17 July 1998     

Reentrant behavior of magnetic ordered phase in spin-crossover solids with quenched disordered ligand field

The Ising-like model of spin-crossover solid compounds with quenched random ligand field has been investigated by the mean-field (infinite-range) approximation. An exact solution for the problem is found within the replica formalism. The magnetic diagrams are obtained; the relations between the intermolecular coupling and the temperature as well as the reentrant phenomena of the magnetic ordered phase are discussed.     

Spin-crossover behavior in a new series of iron (II) compounds based on the ligand 5-(2-pyridyl)-1,2,4-triazole

The title ligand (hereafter LL), is found to form an exciting new series of pseudo-octahedral Fe(II) compounds with formula Fe(LL)₃X₂. N Solvent, which exhibit conveniently studied spin-crossover transformations between nominal⁵T and¹A states of Fe(II). Mössbauer spectra indicate that the spin-crossover transformations for these new systems are probably of the continuous type. There is considerable variation in the degree of conversion to low spin with decreasing temperature depending on gegen ion, solvation and/or location of methyl substituent on the triazole - ligand. The Mössbauer spectra for particular complexes in this group show an absence of both noticeable hysteresis and mechanical grinding effects.     

Intersystem crossing in Fe(II) coordination compounds

Fe(II) spin-crossover systems can be quantitatively converted from the low-spin (LS) to the high-spin (HS) state well below the thermal transition temperature by irradiating either into the metal-ligand charge transfer or d-d absorption bands, and even in low-spin systems a transient population of the HS state can be achieved. This fact can be made use of to determine HS LS relaxation rate constants for a wide variety of Fe(II) spin-crossover and low-spin systems. The HS LS relaxation shows strong deviations from an Arrhenius behaviour, with nearly temperature-independent tunnelling below 70 K and a thermally activated process above 100 K. The range of more than 12 orders of magnitude in the low temperature tunnelling rate constant can be understood in terms of a non-adiabatic multiphonon process, where in the strong vibronic coupling limit an inverse energy gap law holds.     

Positive muons in spin-crossover complex [Fe(NCS)2(phen)2]

Diamagnetic muon species in a spin-crossover complex diisothiocyanatobisphenanthrolineiron(II) were investigated: two species with different spin relaxation functions and rates were observed over the range from 21 to 293 K. The sum of their yields changed at about the spin transition temperature of the complex, where the spin state of the complex changes from paramagnetic to diamagnetic when it is cooled down across the temperature. The results suggest that paramagnetic muon species could exhibit diamagnetic muon-like SR signals in paramagnetic environment.     

Photo-Induced Transformations: Three States Model

Here, we propose an extension of the diabatic approach to photo-induced phase transitions and suggest three states model, which mimics a system with three local diabatic states or equivalently two states where one of them is unstable against a nonsymmetric distortion. The model allows to discuss symmetry breaking transformations and is intended to describe photo-induced transformations in molecular systems, where a path of structural relaxation involves two coordinates. The three states are mapped into a minimum version of Ising spin-1 model, which exhibits metastability. Conditions for switching between stable and metastable phases are discussed in terms of a competition between crystal field, changed by illumination, and dipolar coupling. Examples are neutral (N) to ionic (I) transformation in mixed-stack charge-transfer system and low-temperature photo-induced spin-crossover transformation in metal complexes.     

Special features of the EPR spectroscopy of a system of centers with different relaxation times

We found that the interaction of paramagnetic centers that have different relaxation times differs fundamentally from the interaction of centers having close relaxation times. Simulation showed that in this case there is an anomalous redistribution of the spectral-line intensity from the center to the wings with a virtually preserved distance between extremal points (super-Lorentzian shape of the line), which leads to underestimation of the total intensity recorded. The results obtained make it possible to explain a number of aspects of the radiospectroscopy of carbon materials of practical importance such as the nature of the generally accepted maximum on the curve for the dependence of the total intensity of an EPR signal on the temperature of the heat treatment of organic compounds and the degree of metamorphism of natural coals, the specific features of the effect of oxygen molecules and paramagnetic ions of metals on the EPR spectra of carbon materials, etc. Belarusian State University, 4, F. Skorina Ave., Minsk, 220080 Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 2, pp. 224–229, March–April, 1998.     

Effect of optical pumping on the momentum relaxation time of graphene in the terahertz range

The momentum relaxation time of a photoexcited graphene in the THz frequency range has been studied by using terabertz time domain spectroscopy under optical pumping at room temperature. It is found that the momentum relaxation time of the graphene as a function of the optical pumping intensity exhibits a threshold behavior. The features of the momentum relaxation time as a function of the optical pumping intensity are also investigated. The results are useful for understanding the basic underlying physics of graphene scattering as well as finding the possible applications in carbon- based electronics.     

有部分峰重叠时NOESY谱的全弛豫矩阵分析

采取用理论计算的NOESY峰强度代替NOESY谱中重叠的对角峰或交叉峰强度,用理论计算值和实验数据相结合的方法解决峰强度矩阵的完整化问题,用全弛豫矩阵分析法定量分析了谱中有部分峰重叠的天然有机化合物冬凌草乙素的相敏NOESY谱,计算出冬凌草乙素分子中各质子间的交叉弛豫速率,根据1/r_ij⁶∝σ_ij计算出相应的质子间距离,结果表明:用全弛豫矩阵分析法计算出的质子间距与分子力学计算得到的质子间距离完全一致。该方法能够用于谱中有部分峰重叠的天然有机化合物的NOESY谱的定量处理,可以为核磁共振方法确定分子在溶液中的三维空间结构提供可靠的结构参数     

Picosecond buildup and relaxation of intense stimulated emission in GaAs

In support of the idea developed previously based on circumstantial evidence, we have found that stimulated emission emerges in GaAs and its intensity increases with a picosecond delay relative to the front of powerful picosecond optical pumping that produced a dense electron-hole plasma. The emission intensity relaxes with decreasing pumping with a characteristic time of ～10 ps. We have derived the dependences of the delay time, the relaxation time, and the duration of the picosecond emission pulse on its photon energy. The estimates based on the fact that the relaxation of emission is determined by electron-hole plasma cooling correspond to the measured relaxation time.     

Associated relaxation time and intensity correlation function of a bistable system driven by cross-correlation additive and multiplicative coloured noise sources

The associated relaxation time and the intensity correlation function of a bistable system driven by an additive and a multiplicative coloured noise with coloured cross-correlation are investigated. Using the Novikov theorem and the projection operator method, the analytic expressions of the stationary probability distribution P_st(x), the relaxation time T_c, and the normalized correlation function C(s) of the system are obtained. The effects of the noise intensity, the cross-correlation strength λ and the cross-correlation time τ are discussed. By numerical computation, it is found that the cross-correlation strength |λ| and the quantum noise intensity D decrease the relaxation of the system from unstable points. The cross-correlation time τ delays relaxation of the system from unstable points. The cross-correlation strength λ and the cross-correlation time τ can alter the effects of the pump noise intensity Q. Thus, the relaxation time T_c is a stochastic resonant phenomenon, and distribution curves exhibit a single-maximum structure.     

简并四波混频信号的饱和效应

本文由光学Bloch方程和密度矩阵方程出发,研究了二能级系统共振型简并四波混频(DFWM)的饱和效应,给出了DFWM信号强度与泵浦光强度的函数关系.饱和泵浦光强的大小取决于纵向弛豫时间T1和横向弛豫时T2.对理论结果与相应实验进行了比较,表明二者符合得很好.     

Pressure and temperature induced high spin–low spin phase transition: Macroscopic and microscopic consideration

The behavior under pressure of the high spin–low spin phase transition in the coordination compounds containing 3d ions is analyzed using thermodynamic and microscopic approaches. For thermodynamic approach the mean field model with interactions between spin-crossover molecules is considered. Microscopic model takes into account the interaction of d electrons of the transition metal ions with full symmetric distortions of the ligands. The relationship of the thermodynamic interaction parameters with microscopic ones is installed and shown how the quantum–mechanical interactions form the cooperativity of the system. Within the microscopic model the temperature and pressure dependences of the high spin fraction in 2-D compounds {Fe(3-Fpy)₂[M(CN)₄]} (M=Pd, Pt) are simulated and microscopic parameters are evaluated. It is concluded that different experimental behaviors of the temperature and pressure induced spin transitions are determined by different variations of the inelastic and elastic energies under pressure, and vibrational component of the free energy drives the ST equally with electronic part.     

Temperature dependence of the spin state of a Co3+ Ion in RCoO3 (R = La,Gd) cobaltites

Changes in the spin state of Co³⁺ ions in LaCoO₃ and GdCoO₃ compounds are studied through the use of the temperature dependence of the magnetic susceptibility and the modified crystal field theory. It is shown that the spin subsystem of Co³⁺ ions in LaCoO₃ and GdCoO₃ undergoes the spin-crossover type transition between the high-spin (S = 2) and low-spin (S = 0) states without any contribution of the intermediate-spin state (S = 1).     

用MOCVD方法制备的n型GaN薄膜紫外光电导

报道了用MOCVD方法制备的非掺杂的和Mg弱掺杂的n型GaN薄膜的紫外光电导特性.结果表明这些n型样品具有显著的紫外光响应,而且光响应弛豫时间也较短.在弱光范围,光响应随光强的变小呈线性减弱,且光响应的弛豫时间变长.