铁素/铁,甲/甲和甲/甲:从气相电离能到溶介质中的一个电子还原潜力
Hongyan Zhao1, Yi Pan1, Kai-Chung Lau1
1Department of Chemistry, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong. kaichung@cityu.edu.hk.
Physical chemistry chemical physics : PCCP
|June 16, 2023
概括
我们开发了一种可靠的理论方法,准确地预测铁,和金属氧化还原对的还原潜力. 这种方法结合了精确的电离能计算和溶解自由能校正,以获得精确的结果.
科学领域:
- 计算化学计算化学
- 电化学 电化学 电化学
- 量子化学 是一个量子化学.
背景情况:
- 金属复合物 (Cp2M) 在催化和材料科学中至关重要.
- 准确预测它们的氧化还原潜力对于理解和设计新应用是必不可少的.
- 现有的理论方法往往难以实现这些系统的高精度.
研究的目的:
- 建立一个强大的理论协议,准确地确定金属氧化还原对 (Cp2M+/Cp2M) 的还原潜力.
- 评估不同溶解模型在预测吉布斯自由能量溶解中的性能.
- 为Cp2Fe+/Cp2Fe,Cp2Co+/Cp2Co和Cp2Ni+/Cp2Ni提供可靠的理论预测.
主要方法:
- 使用明确相关的CCSD (T) -F12方法计算气相电离能.
- 包括零点能量,核心价值相关性和相对论效应.
- 使用波恩-哈伯热化学循环与基布斯自由能量溶解 (ΔGsolv) 来自PCM,SMD和uESE模型.
- 使用密度函数理论 (DFT) 进行溶解能量计算.
主要成果:
- 结合高水平IE计算的SMD溶解模型,准确地预测中性和阴性金属之间的溶解能量的差异.
- 开发的理论协议为Fe,Co和Ni金属对产生了可靠的降解潜力.
- 预测值与实验数据非常一致,最大绝对偏差约为120mV.
结论:
- 提出的理论程序提供了一种可靠和准确的方法来预测金属的还原潜力.
- 这种方法在准确性方面优于现有的理论方法.
- 这些发现适用于水性和非水性介质,扩大了其实用性.
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