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1.
J Chem Phys ; 157(19): 194105, 2022 Nov 21.
Artigo em Inglês | MEDLINE | ID: mdl-36414452

RESUMO

Physical kinetic roughening processes are well-known to exhibit universal scaling of observables that fluctuate in space and time. Are there analogous dynamic scaling laws that are unique to the chemical reaction mechanisms available synthetically and occurring naturally? Here, we formulate an approach to the dynamic scaling of stochastic fluctuations in thermodynamic observables at and away from equilibrium. Both analytical expressions and numerical simulations confirm our dynamic scaling ansatz with associated scaling exponents, function, and law. A survey of common chemical mechanisms reveals classes that organize according to the molecularity of the reactions involved, the nature of the reaction vessel and external reservoirs, (non)equilibrium conditions, and the extent of autocatalysis in the reaction network. Varying experimental parameters, such as temperature, can cause coupled reactions capable of chemical feedback to transition between these classes. While path observables, such as the dynamical activity, have scaling exponents that are time-independent, the variance in the entropy production and flow can have time-dependent scaling exponents and self-averaging properties as a result of temporal correlations that emerge during thermodynamically irreversible processes. Altogether, these results establish dynamic universality classes in the nonequilibrium fluctuations of thermodynamic observables for well-mixed chemical reactions.


Assuntos
Termodinâmica , Entropia , Temperatura , Cinética
2.
J Chem Phys ; 147(16): 164102, 2017 Oct 28.
Artigo em Inglês | MEDLINE | ID: mdl-29096482

RESUMO

In the present study, we have proposed the Fokker-Planck equation in a simple way for a Langevin equation of motion having ordinary derivative (OD), the Gaussian random force and a generalized frictional memory kernel. The equation may be associated with or without conservative force field from harmonic potential. We extend this method for a charged Brownian particle in the presence of a magnetic field. Thus, the present method is applicable for a Langevin equation of motion with OD, the Gaussian colored thermal noise and any kind of linear force field that may be conservative or not. It is also simple to apply this method for the colored Gaussian noise that is not related to the damping strength.

3.
J Chem Phys ; 141(22): 224101, 2014 Dec 14.
Artigo em Inglês | MEDLINE | ID: mdl-25494726

RESUMO

In this paper, we have studied the properties of a Brownian particle at stationary state in the presence of a fluctuating magnetic field. Time dependence of the field makes the system thermodynamically open. As a signature of that the steady state distribution function becomes function of damping strength, intensity of fluctuations and constant parts of the applied magnetic field. It also depends on the correlation time of the fluctuating magnetic field. Our another observation is that the random magnetic field can induce the resonant activation phenomenon. Here correlation time is increased under the fixed variance of the fluctuating field. But if the correlation time (τ) increases under the fixed field strength then the mean first passage time rapidly grows at low τ and it almost converges at other limit. This is sharp contrast to the usual colored noise driven open system case where the mean first passage time diverges exponentially. We have also observed that a giant enhancement of barrier crossing rate occurs particularly at large strength of constant parts of the applied magnetic field even for very weak fluctuating magnetic field. Finally, break down of the Arrhenius result and disappearance of the Kramers' turn over phenomenon may occur in the presence of a fluctuating magnetic field.

4.
Phys Rev E ; 98(1-1): 012120, 2018 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-30110736

RESUMO

A one-dimensional linear autonomous system coupled to a generic stationary nonequilibrium fluctuating bath can exhibit resonant response when its damped oscillation period matches some characteristic bath's relaxation time. This condition justifies invoking the stochastic resonance paradigm, even if it can be achieved more easily by tuning the system to the bath and not vice versa, as is usually the case. The simple nature of the mechanism numerically investigated here suggests a number of interesting applications for instance in the context of (1) energy harvesting from random ambient vibrations, (2) activated barrier crossing through a saddle point, or (3) an unstable limit cycle.

5.
Artigo em Inglês | MEDLINE | ID: mdl-25974476

RESUMO

In this paper we present properties of an external colored cross-correlated noise-driven Brownian system which is coupled to a thermal bath. Multiplicative cross-correlated noises can stabilize the transition state. Thus by monitoring the interference between the noises one can understand the mechanism of a chemical reaction. At the same time, we have investigated how the interference affects the barrier-crossing dynamics. In its presence breakdown of the Arrhenius result occurs. The breakdown becomes prominent if the multiplicative noises become additive in nature. We have also investigated how the power law behavior of the rate constant as a function of damping strength is affected by the properties of external colored noises. Furthermore, we have observed that multiplicative colored cross-correlated noises can induce the resonant activation phenomenon.


Assuntos
Modelos Teóricos , Movimento (Física) , Processos Estocásticos , Temperatura
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