当前位置: X-MOL 学术J. Phys. Chem. A › 论文详情
Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)
Temperature-Dependent Approach to Electronic Charge Transfer.
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2020-06-05 , DOI: 10.1021/acs.jpca.0c02496
Marco Franco-Pérez 1 , José L Gázquez 2 , Paul W Ayers 3 , Alberto Vela 4
Affiliation  

A charge transfer model is developed within the framework of the grand canonical ensemble through the analysis of the behavior of the fractional charge as a function of the chemical potential of the bath when the temperature and the external chemical potential are kept fixed. Departing from the fact that, before the interaction between two species, each one has a zero fractional charge, one can identify two situations after the interaction occurs where the fractional charge of at least one of the species is different from zero, indicating that there has been charge transference. One of them corresponds to the case when one of the species is immersed in a bath conformed by the other one, while the other is related to the case in which both species are present in equal amounts (stoichiometric proportion). Correlations between the fractional charges and average energies, thus obtained with experimental equilibrium constants, kinetic rate constants, hydration constants, and bond enthalpies, indicate that, although at the experimental temperatures, they are very small quantities, they have chemically meaningful information. Additionally, in the stoichiometric case, one also finds a rather good correlation between the equalized chemical potential and the one obtained from experimental information for a test set of diatomic and triatomic molecules.

中文翻译:

电子电荷转移的温度相关方法。

在温度和外部化学势保持固定的情况下,通过分析分数电荷随浴液化学势的变化,在大典范系综框架内建立了电荷转移模型。与以下事实不同:在两个物种之间的相互作用之前,每个物种的分数电荷为零,在相互作用发生后,至少一种物种的分数电荷不同于零的情况可以识别两种情况,表明存在被电荷转移。其中一种对应于一种物质浸入另一种浸没的浴槽中的情况,而另一种涉及其中两种物质以相等的量(化学计量比)存在的情况。因此,通过实验平衡常数,动力学速率常数,水合常数和键焓得到的分数电荷与平均能量之间的相关性表明,尽管在实验温度下,它们的数量非常小,但它们具有化学上有意义的信息。另外,在化学计量的情况下,人们还发现,在均衡的化学势与从双原子和三原子分子测试集的实验信息获得的化学势之间存在相当好的相关性。
更新日期:2020-07-02
down
wechat
bug