Lazarenko Maksym M, Zabashta Yuriy F, Alekseev Oleksandr M, Alekseev Sergei A, Yablochkova Kateryna S, Vergun Liena Yu, Andrusenko Dmytro A, Cherevko Konstantin V, Shevchenko Victoria B, Dinzhos Roman V, Bulavin Leonid A
Taras Shevchenko National University of Kyiv 64, Volodymyrska Street Kyiv UA 01601 Ukraine
Petro Mohyla Black Sea National University Mykolayiv Ukraine.
RSC Adv. 2024 Dec 11;14(53):39242-39252. doi: 10.1039/d4ra06983h. eCollection 2024 Dec 10.
In the present manuscript, we highlight the contradictions in the thermally activated processes theory which treats a system's activated state as a state of the phonon subsystem. We offer an alternative model, in which the activated state is treated as an electron subsystem state. The mechanism of the activated state formation is as follows: thermal fluctuations excite electrons of some particles within the activation zone. This excitation is then shared with other particles in the ground state. This creates a locally-equilibrium activated state. We estimate the lifetime of such a state and derive expressions for the activation energy and entropy, necessary to calculate the number of excited particles in the activation zone and the energy of the particle's excitation. We validate the model experimentally, by examining the behavior of nanocrystals of undecylenic acid in pores of silica gels using dielectric spectroscopy and the analysis of the complex dielectric permittivity behavior at different temperatures and with different frequencies of the external field. The estimated number of excited particles in the activation zone of the nanocrystals and the particle excitation energy for the dielectric relaxation process observed in undecylenic acid confirm that the results of the experiment align well with the proposed model.
在本手稿中，我们强调了热激活过程理论中的矛盾之处，该理论将系统的激活态视为声子子系统的一种状态。我们提出了一种替代模型，其中激活态被视为电子子系统状态。激活态形成的机制如下：热涨落激发激活区内某些粒子的电子。然后这种激发与处于基态的其他粒子共享。这就产生了局部平衡的激活态。我们估计了这种状态的寿命，并推导了激活能和熵的表达式，这些对于计算激活区内激发粒子的数量和粒子激发能是必要的。我们通过使用介电谱研究硅胶孔中十一烯酸纳米晶体的行为，并分析不同温度和不同外场频率下复介电常数的行为，对该模型进行了实验验证。在十一烯酸中观察到的纳米晶体激活区中激发粒子的估计数量和介电弛豫过程的粒子激发能证实，实验结果与所提出的模型吻合良好。
