Nonlinear stochastic relaxation dynamics in spin-crossover solid-state compounds

A study of dynamic of spin-crossover solid-state compound has been carried out. The investigated macroscopic phenomenological model for molecular spin-crossover complexes with optical control parameter has been extended to the case of noise action. The noise-driven phase transition was observed....

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Дата:2010
Автори: Gudyma, Iu.V., Maksymov, A.Iu.
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Опубліковано: Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України 2010
Назва видання:Semiconductor Physics Quantum Electronics & Optoelectronics
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Цитувати:Nonlinear stochastic relaxation dynamics in spin-crossover solid-state compounds / Iu.V. Gudyma, A.Iu. Maksymov // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2010. — Т. 13, № 4. — С. 357-362. — Бібліогр.: 20 назв. — англ.

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spelling nasplib_isofts_kiev_ua-123456789-1187402025-06-03T16:26:27Z Nonlinear stochastic relaxation dynamics in spin-crossover solid-state compounds Gudyma, Iu.V. Maksymov, A.Iu. A study of dynamic of spin-crossover solid-state compound has been carried out. The investigated macroscopic phenomenological model for molecular spin-crossover complexes with optical control parameter has been extended to the case of noise action. The noise-driven phase transition was observed. Also, ascertained was the role of additive noise as a main factor for suppressing the potential barrier height. 2010 Article Nonlinear stochastic relaxation dynamics in spin-crossover solid-state compounds / Iu.V. Gudyma, A.Iu. Maksymov // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2010. — Т. 13, № 4. — С. 357-362. — Бібліогр.: 20 назв. — англ. 1560-8034 PACS 05.45.-a, 42.65.Pc, 75.30.Wx https://nasplib.isofts.kiev.ua/handle/123456789/118740 en Semiconductor Physics Quantum Electronics & Optoelectronics application/pdf Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України
institution Digital Library of Periodicals of National Academy of Sciences of Ukraine
collection DSpace DC
language English
description A study of dynamic of spin-crossover solid-state compound has been carried out. The investigated macroscopic phenomenological model for molecular spin-crossover complexes with optical control parameter has been extended to the case of noise action. The noise-driven phase transition was observed. Also, ascertained was the role of additive noise as a main factor for suppressing the potential barrier height.
format Article
author Gudyma, Iu.V.
Maksymov, A.Iu.
spellingShingle Gudyma, Iu.V.
Maksymov, A.Iu.
Nonlinear stochastic relaxation dynamics in spin-crossover solid-state compounds
Semiconductor Physics Quantum Electronics & Optoelectronics
author_facet Gudyma, Iu.V.
Maksymov, A.Iu.
author_sort Gudyma, Iu.V.
title Nonlinear stochastic relaxation dynamics in spin-crossover solid-state compounds
title_short Nonlinear stochastic relaxation dynamics in spin-crossover solid-state compounds
title_full Nonlinear stochastic relaxation dynamics in spin-crossover solid-state compounds
title_fullStr Nonlinear stochastic relaxation dynamics in spin-crossover solid-state compounds
title_full_unstemmed Nonlinear stochastic relaxation dynamics in spin-crossover solid-state compounds
title_sort nonlinear stochastic relaxation dynamics in spin-crossover solid-state compounds
publisher Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України
publishDate 2010
url https://nasplib.isofts.kiev.ua/handle/123456789/118740
citation_txt Nonlinear stochastic relaxation dynamics in spin-crossover solid-state compounds / Iu.V. Gudyma, A.Iu. Maksymov // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2010. — Т. 13, № 4. — С. 357-362. — Бібліогр.: 20 назв. — англ.
series Semiconductor Physics Quantum Electronics & Optoelectronics
work_keys_str_mv AT gudymaiuv nonlinearstochasticrelaxationdynamicsinspincrossoversolidstatecompounds
AT maksymovaiu nonlinearstochasticrelaxationdynamicsinspincrossoversolidstatecompounds
first_indexed 2025-12-01T05:09:05Z
last_indexed 2025-12-01T05:09:05Z
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fulltext Semiconductor Physics, Quantum Electronics & Optoelectronics, 2010. V. 13, N 4. P. 357-362. PACS 05.45.-a, 42.65.Pc, 75.30.Wx Nonlinear stochastic relaxation dynamics in spin-crossover solid-state compounds Iu.V. Gudyma, A.Iu. Maksymov Chernivtsi National University, Department of General Physics, 58012 Chernivtsi, Ukraine, E-mail: yugudyma@gmail.com Abstract. A study of dynamic of spin-crossover solid-state compound has been carried out. The investigated macroscopic phenomenological model for molecular spin-crossover complexes with optical control parameter has been extended to the case of noise action. The noise-driven phase transition was observed. Also, ascertained was the role of additive noise as a main factor for suppressing the potential barrier height. Keywords: optical bistability, additive noise, multiplicative noise, noise-driven dynamics. Manuscript received 10.10.10; accepted for publication 02.12.10; published online 30.12.10. 1. Introduction With increasing needs in computing enormous volume of information, investigation of new molecular materials which may satisfy the requirements in the field of informational technology becomes actual. One of the most promising bistable materials is spin-crossover coordination complexes that possess two stable states: paramagnetic high-spin (HS) and diamagnetic low-spin (LS) states [1]. There is a class of inorganic complexes of chemical elements with electron configuration and central transition metal ion located in octahedral ligand field. Under the influence of environmental perturbation, namely: light irradiation, magnetic field, temperature, noise influence and others, there possible is the transition between the states of spin- crossover compounds. The transition provokes a drastic change in properties of spin-crossover complexes, in particular, magnetic properties due to spin rearrangement between sublevels of 3d-orbitals. Thus, there exist many experimental works where bistability in magnetic susceptibility is shown [2]. 74 dd − One of the most important developments in researches of spin crossover was that the equilibrium existing between high-spin and low-spin species could be perturbed by laser irradiation. A light irradiation of a spin-crossover system in the solid state at low temperature induces partial or complete conversion of a low-spin state to a high-spin metastable one with virtually infinitely long lifetime. This solid state effect became known as the LIESST effect (light induced excited spin state trapping) [3]. This effect is the basis of different light-induced bistability effects that provoke appearance of optical (light induced optical hysteresis, shortly LIOH) and thermal hysteresis (light induced thermal hysteresis, shortly LITH). A light-induced bistability in a spin transition solids leading to thermal and optical hysteresis has been well studied in [4, 5]. Until now, many experiments were performed to study the process and physics of the transition from one state to another, but there is still no clarity in this problem. Here, we propose to represent the model of spin-crossover complexes as a macroscopic phenomenological model written in terms of relaxation rate with light-induced phase transition. To fuller satisfy the condition of physical reality, we have taken into account environmental action on the system dynamics as additive and multiplicative Gaussian distributed noises. The environmental random noise influencing on spin-crossover solids can be represented as an interaction with a heat bath. This model may be described by macroscopic kinetic stochastic differential equation with a deterministic term possessing slow degree of freedom and random term with fast degree of freedom. Dynamics of a system being in contact with an environment playing a role of the heat bath is based on the concept of the Langevin equation. Such assumption is possible because the condition of heat bath does not depend on spin configuration. Detailed theoretical analysis of the states of spin-crossover compounds under cross-correlated noises was made in [6]. On the assumption of possible technological usage of these materials as data storage systems or display systems, it is important to know the lifetime of © 2010, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine 357 Semiconductor Physics, Quantum Electronics & Optoelectronics, 2010. V. 13, N 4. P. 357-362. metastable state or transition time from one state to another. Due to environmental perturbation and size limitation in any real system, the lifetime of a metastable state is not infinitely long. In this work, we also estimated the time of decay of the metastable state in a mean field approach by defining the mean first passage time (MFPT) for this metastable state. The estimation of MFPT was made in Kramers-like approximation by using a reflecting boundary condition at the minimum of the metastable state and absorption boundary condition at maximum of the potential barrier height that separates the stable and metastable states. A simple but very general approach to the classical MFPT problem was offered by Pontryagin et al. [7], which has been extended by us for investigation MFPT of spin-crossover solids. © 2010, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine 2. Model Here we regard the macroscopic phenomenological model of spin-crossover compounds in terms of a relaxation rate in the mean field approach. With this aim, it is necessary to admit one of the states of spin- crossover compound as a metastable state, and the other as a stable one. In our investigation, we did not focused on specific spin-crossover compound, but due to more widespread spin-crossover compounds with LS state as a ground one, we have considered that paramagnetic HS state is metastable. For the HS fractions , the static relaxation equation first investigated by Hauser with the Mainz group [8-10] is as follows: Hn ( ) ( ) ⎥ ⎦ ⎤ ⎢ ⎣ ⎡ −= ∞ Tk nEkTnk B Ha HHL exp, , (1) with ( ) ( ) ( ) HBaHa nTkTEnE α+= 0 , (2) where is the high-temperature asymptotic of the relaxation rates at the end of the process ( ); is the activation energy; is the Boltzmann constant; is the temperature, and is the self- acceleration factor of relaxation defined by the cooperative coefficient and depending linearly on the relative atomic concentration of the spin-crossover element and is proportional to the inverse temperature [11]. For simplicity, the activation energy has been equaled to zero, so the relaxation equation (1) takes the form: ∞k 0→Hn ( )0aE Bk T ( )Tα ( ) ( )[ HHHL nTkTnk α−= ∞ exp, ] . (3) The general form of macroscopic master equation in condition of light irradiation can be expressed in terms of photoexcitation and relaxation high-spin fraction flows from HS to LS state and vice versa [4]: relexc H dt dn Φ−Φ= . (4) The form of photoexcitation and relaxation excΦ relΦ -flows is as follows: Hn ( ) ( ,exp ,10 HHrel Hexc nkn nI α−=Φ −ω=Φ ∞ ) (5) where ω0I is the probability per time unit for a LS molecule to switch to the HS state, with the beam intensity and a proportionality factor that includes the absorption cross-section of the optically active element (here the bulk absorbance is neglected). By introducing a new variable and taking into account a denotation 0I ω ∞=τ kt ∞ω=β kI /0 , it is easy to obtain the final macroscopic master equation of the described model with non-dimensional quantities: ( ) ( HHH H nnn d nd α−−−β= τ exp1 ) . (6) From the stationary condition of the system when relexc Φ=Φ , which is realized at the spin-crossover point, one can estimate the possibility of existence of all theoretical realizable stable and unstable states. A comprehensive analysis of static and dynamical non- equilibrium kinetics of spin-crossover compounds was made by Gudyma in [12] and Varret in [13]. 3. Macroscopic stationary dynamics of spin-crossover compounds Any real system being in contact with environment may be modeled as a system that interacts with a heath bath. To more accurately describe our model, we must take into consideration an environmental noise influence. In other words, the control parameter from Eq. (6) is not constant, but fluctuates in time. Besides, it is necessary to take into account the direct action of heat bath on the system. Thus, it is need to assume that β ( ) ( )tt ξ+β=β in Eq. (6), which gives the following stochastic differential equation in Stratonovich interpretation: ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ),1 exp1ѓА τντξτντξ α τ ++=+−+ +−−−= HHH HHH H ngnfn nnn d dn (7) where the noise correlation functions are: ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ),2 ,2 ,2ѓМ 2 2 ττδχσετντξ ττδετντν ττδστξτ −′=′ −′=′ −′=′ (8) where σ and ε are the intensity of multiplicative noise and additive noise, respectively, which correspond to the influence of internal and external fluctuation on the system; χ is the correlation coefficient between additive and multiplicative noises. In a general case, external 358 Semiconductor Physics, Quantum Electronics & Optoelectronics, 2010. V. 13, N 4. P. 357-362. environmental fluctuations can influence on the internal fluctuations but, for simplicity, we did not take this effect into account. The analysis of states in spin- crossover solids under cross-correlated noises was made in the paper [6], which is based on the mathematical tools developed in [14]. The Eq. (7) can be reduced to the equivalent stochastic differential equation with one effective multiplicative noise [16]: ( ) ( ) (τΞ+= τ HH H nGnf d nd © 2010, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine ) (9) with the condition ( ) ( ) ( τ−τ′δ=τ′Ξτ 2Ξ ) . (10) The effective noise amplitude ( )HnG is determined as follows: ( ) ( ) ( ) 222 121σ ε+−χσε+−= HHH nnnG . (11) For nonlinear stochastic differential equations, one can obtain the Fokker-Planck equation corresponding to the Langevin equation in the following form [15]: ( ) ( ) ( ) ( ) ( )HH H HH H H nPnG n nPnf n nP 2 2 2 1, ∂ ∂ + ∂ ∂ = τ∂ τ∂ . (12) By solving the Fokker-Planck equation (12), we found the probability of system location at the phase space point. The stationary solution of this equation has the Gibbs-Boltzmann form: ( ) ( )effHst UNnP −= exp , (13) where is the normalization constant and N ( ) ( ) ( ) ( )[ ]∫ ∂ ∂ − −= Hn H H H HH eff nG nG n nGnf U 0 2 (14) represents the effective dynamical system potential. The extremes of this potential correspond to stationary fixed points of system dynamics. Bistable range of system with corresponding dynamic potentials at spinodal points obtained from Eq. (6) with stationary equilibrium condition and Eq. (14) are consequently shown in Fig. 1. The intersection point between the curves excΦ (photoexcited -flow marked as dotted curve in the plots) and (relaxed -flow marked as a dashed curve) from Fig. 1 represent the possible steady and unsteady states, thus we defined the range of bistability. The effective potential (marked as a solid curve on all plots from Fig. 1) at the spinodal points (the critical points of phase transition) between monostable-bistable range and bistable-monostable range are reflected in Fig. 1a and Fig. 1c, consequently. Shown in this figure is light-induced optical hysteresis (LIOH) where light irradiation in the first approach is the main control parameter. Analysis showed that noise acting also may lead to transition from one state to another. Non- stationary overall studies of noise action on the system are described in the following section. Hn relΦ Hn effU a b c Fig. 1. Light-induced bistable range with the effective dynamical potential : (a), (c) indicate the spinodal points of one state – two states transition; (b) is the realization of bistable state. effU 359 Semiconductor Physics, Quantum Electronics & Optoelectronics, 2010. V. 13, N 4. P. 357-362. 4. Noise driven dynamics of spin-crossover compounds It is generally known that the more suitable to find solution of numerically ordinary differential equations similar to Eq. (6) are the second-order Runge-Kutt type methods. One of the main requirements in this case is that the functions appearing in the equation are differentiable to some required order. But, unfortunately, if using the white-noise functions as in Eqs (7) and (8), even for a single realization of the white-noise term, these functions are highly irregular and non- differentiable. So, the only non-rigorous approach via a series of delta-functions spread all over the real axis can be realized. To solve the presented stochastic differential equation in the non-stationary case, we need to use more powerful computational methods. These methods may be developed from the second-order Runge-Kutt method with suitable modification based on application of integral algorithms described in [17]. It results in the Milshtein method: ( ) ( ) ( )( ) ( ) ( )( ) ( )( ) ( )( ){ } ( )( ) [ ], 2 1 2/3 2 2/1 hO unG n nGnfh unGhnn H H HH HHH + +⎥ ⎦ ⎤ ⎢ ⎣ ⎡ ∂ ∂ ++ ++=′ ττττ ττττ (15) where ; is the order of a time step in the system dynamics. ( ) ( )∫ ′ Ξ= τ τ τ dssuh 2/1 h We got the non-stationary solution of Eq. (7) from explicit two-stage second-order Runge-Kutt method well known as the Heun or explicit trapezoidal method [17, 18]: ( )( ) ( ) ( )( ) ( ) ( ) ( )( ) ( )( )[ ( ) © 2010, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine ] ( )( ) ( )( )[ .,, 2 ,, 2 ,,,τ 2/1 2/1 ynGnGuh ynfnfhnn nGuhnhfy HH HHHH HH +ττ′+ττ τ + ++ττ′+ττ+τ=τ′ τττ+τ= ] (16) The Eq. (16) is obtained from the Euler equation with stochastic process in its turn derived from the Milshtein method (15), if ( )( ){ } 0= ∂ ∂ τH H nG n (it corresponds to an additive noise case) [17]. The Euler equation resulting from (16) is as follows: ( ) ( ) ( )( ) ( )( ) ( ) [ ]2/32/1τ hOtuhnGnfhnn HHHH +τ+τ+τ=′ . (17) The derived Euler equation in midpoint quadratures has the following form: ( ) ( ) ( )( ) ( )( )[ ] ( ) ( )( ) ( )( )[ ].,, 2 ,, 2 2/1 τ′τ′+ττ τ + +τ′τ′+ττ+τ=τ′ HH HHHH nGnGuh nfnfhnn (18) By replacing ( )τ′Hn on the right-handside in the later equation by the predictor of the Euler method (17) again, we arrive to the Heun equation (16). Trajectories from Eq. (16) represent the solution of Eq. (9) with stochastic fluctuation in time of HS fractions. We carried out the simulation of HS fraction dynamic for 100 trajectories with 50000 time step and obtained the distribution of probability density functions (pdf) of HS fraction for a non-stationary case. Shown in Fig. 2 are the distributions of pdf in stationary and non- stationary cases under noise action. From the plots, we observe a qualitative difference in action of additive noise and that of multiplicative noise: while the increase in multiplicative noise intensity leads to the first-order phase transition, the increase in additive noise intensity only suppresses the potential barrier height, which makes HS and LS states to be unrecognized and is undesirable for sensor devices. Shown in Fig. 3 are the examples of stochastic trajectories for values of additive noise intensity 001.0=σ and 18.0=σ . The later value corresponds to spinodal point between bistable-monostable regions. The stochastic trajectories in Fig. 3 are only illustration of the processes that take place in a noise-driven system. In practice, it is impossible to determine the one isolated trajectory, due to time-scale of occurred processes. So, one can only detect the average value of stochastic fluctuations, which is important to know for designing stable spin-crossover sensor devices. 5. Lifetime of the metastable state in the mean field approach As we have seen above, the dynamic of the HS fraction in spin-crossover compounds under environmental noise action is modeled as fluctuation in time of Brownian particle. After the pioneering contribution by Kramers, well described in [19], the escape problem of Brownian particle became an important subject of studies in nonlinear stochastic systems. The most common analysis of metastable state decay is based on the MFPT technique in a Kramer-like approximation described in general aspects by Pontryagin in [7]. The escape time from a metastable state in the stationary case was studied in [12, 20]. The general expression for MFPT is as follows: ( ) ( ) ( ) ( )[ ]∫ ∫ ψ ψ =→ b n x a eff rand H H xG x x dxnaT 2 , (19) where ( ) ( ) ( )[ ] ⎥ ⎦ ⎤ ⎢ ⎣ ⎡ ′ ′ ′ =ψ ∫ z a eff rand zd zG zfz 2 det2exp . (20) Here, we supplemented theoretically obtained MFPT by computing simulation. The results are shown 360 Semiconductor Physics, Quantum Electronics & Optoelectronics, 2010. V. 13, N 4. P. 357-362. in Fig. 4. Shown in the figure is estimation of MFPT between stationary and non-stationary cases (see the normalized time values), so the intersection of time curves is not necessary to take into consideration. a b c d Fig. 2. Additive (a), (b), (c) and multiplicative (d) noise actions on the probability density function distribution. Simulation was carried out for 100 trajectories and 50000 time steps for each trajectory. a b Fig. 3. The examples of stochastic trajectories for multiplicative noise 001.0=σ (a) and (b). The values of additive noise in both cases have the same magnitude 18.0=σ 1.0=ε . Fig. 4. Normalized MFPT for given values of the additive noise intensity. The value of multiplicative noise is constant ( 1.0=σ ). © 2010, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine MFPT in Fig. 4 is corresponded by the bistable potential in Fig. 1c with a reflecting boundary condition at the point 16.0=a , and absorption boundary condition at the point 4.0=b . These points indicate the range of metastable state. Given in Table 1 are the values of MFPT for the stationary case. From the type of change 361 Semiconductor Physics, Quantum Electronics & Optoelectronics, 2010. V. 13, N 4. P. 357-362. in values in Table 1, we can conclude that the increase in the additive noise intensity decreases the lifetime of metastable states. This fact is not favorable for manufacturing data storage systems. Table 1. Computed stationary values of . ( )HnaT → Hn T (a → nH) for ε = 0.01 T (a → nH) for ε = 0.3 0.16 690.85 39.47 0.2 671.03 38.02 0.3 501.91 27.1 0.4 109.95 5.58 © 2010, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine 6. Concluding remarks Using the Fokker-Planck equation and its solutions, we studied the noise-dependence properties of the critical behavior of the spin-crossover compound based on extended phenomenological model for spin-crossover compound kinetics in the noise case action. The investigated bistable range may be induced by light irradiation that leads to occurrence of light-induced optical hysteresis. Non-equilibrium dynamical investigation in terms of heat bath firstly developed in [12] has been extended here to the case of two noises action. Dynamical study of the presented noisy model has been made in the frame of Heun algorithm also known as explicit trapezoidal method. The probability density function distribution for stationary and non- stationary dynamics has been obtained. Also, we have shown that the multiplicative noise influence may lead to transition from the metastable to stable state. Action of additive noise is reduced to suppression of the potential barrier height. 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