精确的理论评估的MLCT过渡在[M(Terpy) 2+ (M = Fe, Ru, Os) 复合体中
Aleksandr A Chamkin1, Elena S Chamkina1
1A.N.Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences, Moscow, Russia.
Journal of computational chemistry
|September 11, 2025
概括
本研究评估了[M(terpy) ]2+复合体中金属到配体电荷转移 (MLCT) 的计算方法. 多参照理论准确地预测MLCT能量,为电色材料提供成本效益的解决方案.
科学领域:
- 计算化学的计算化学
- 材料科学 材料科学 材料科学
- 频谱学是一种光谱学.
背景情况:
- 金属到联体电荷转移 (MLCT) 过渡对于电色应用至关重要.
- 精确的理论预测MLCT能量在[M(terpy) ]2+复合体 (M=Fe,Ru,Os) 中具有挑战性,但很重要.
研究的目的:
- 为[M(terpy) 2+复合体中MLCT过渡指导可靠和成本有效的计算方法.
- 评估各种计算方法,包括多引用理论和时间依赖密度函数理论 (TD-DFT).
主要方法:
- 评估了多参考扰动理论 (NEVPT2,CASPT2),DLPNO-STEOM-CCSD,ADC(2),以及44个TD-DFT函数.
- 为[M(terpy) ]2+复合体计算的垂直MLCT激发能量.
- 将理论结果与实验吸收最大值进行比较.
主要成果:
- 多参考方法显示了与实验数据最一致的一致性.
- X2C NEVPT ((14, 13) /x2c-QZVPPall级别为MLCT能量提供了最好的理论估计.
- 由于其多引用性质,DLPNO-STEOM-CCSD对铁复合体没有成功.
- 像r2SCAN这样的本地元GGA在TD-DFT中提供了准确性和计算成本的良好平衡.
结论:
- 在这些系统中计算MLCT过渡时,多引用理论是可靠的.
- 建议使用X2C NEVPT ((14,13) /x2c-QZVPPall方法来准确地预测MLCT的能量.
- 与本地元GGA结合的TD-DFT为类似计算提供了具有成本效益的替代方案.
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