精确的量子化学反应能量用于介导的电解质分解和密度函数近似值的评估
Sibali Debnath1, Verena A Neufeld1,2, Leif D Jacobson3
1Department of Chemistry, Columbia University, New York, New York 10027, United States.
The journal of physical chemistry. A
|October 25, 2023
概括
调查离子电池电解质分解对于性能至关重要. 这项研究对计算方法进行了基准测试,以准确预测固体电解质相间形成路径.
科学领域:
- 计算化学是一种计算化学.
- 材料科学是一种材料科学.
- 电化学 电化学 电化学
背景情况:
- 在阳极表面形成固体电解质间相 (SEI) 会影响离子电池的稳定性和性能.
- 电解质分解是SEI层发展的关键因素.
- 需要精确的计算建模来理解电解质的行为.
研究的目的:
- 评估乙烯碳酸盐和相关有机电解质分子的分解途径.
- 为了比较各种密度函数近似 (DFAs) 和相关波函数 (WF) 方法的准确性.
- 确定可靠的计算方法来研究SEI形成.
主要方法:
- 用密度函数近似 (DFAs) 来建模反应路径.
- 相关波函数 (WF) 方法,包括合集群理论 (CCSD) 和辅助场量子蒙特卡洛 (AFQMC),用于基准测试.
- 不同的DFA的表现与高级WF结果进行了评估.
主要成果:
- 对于电解质环开放的过渡状态障碍在不同的DFA之间有很大差异.
- 与CCSDT相比,M06-2X-D3,CAM-B3LYP-D3和B2GP-PLYP-D3 DFAs表现最好,平均误差在1.50-1.60 kcal/mol左右.
- 像DLPNO-CCSD(T) 和无相AFQMC这样的可扩展WF方法显示出很好的准确性,平均误差分别为1.38和1.74 kcal/mol.
结论:
- 与准确的波函数方法进行基准测试是必不可少的,因为DFA预测的差异很大.
- 特定的DFAs (M06-2X-D3,CAM-B3LYP-D3,B2GP-PLYP-D3) 和可扩展的WF方法为研究离子电池电解质分解和SEI形成提供了可靠的途径.
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