铜的分子几何学和电子结构
Rina Bhowmick1, Sabyasachi Roy Chowdhury1, Bess Vlaisavljevich1
1Department of Chemistry, University of South Dakota, Vermillion, South Dakota 57069, United States.
铜表现出独特的多配置单个基态,平面三重态在能量上更高. 扩展的多参考扰动理论 (XMS-CASPT2) 准确地描述了这些电子结构和潜在能量表面.
科学领域:
- 计算化学的计算化学
- 量子化学 是一个量子化学.
- 材料科学 材料科学 材料科学
背景情况:
- 铜具有复杂的多配置电子结构.
- 密度函数理论 (DFT) 难以准确地确定旋转状态和能量,通常是由于Hartree-Fock交换.
- 了解这些电子特性对于它们的应用至关重要.
研究的目的:
- 为了研究未被替代和中三基铜的分子几何和电子结构.
- 使用先进的计算方法准确确定地面电子状态和能量.
- 在描述这些系统时评估不同密度函数理论 (DFT) 函数的性能.
主要方法:
- 在电子结构计算中使用扩展多参数平均二进制随机扰动理论 (XMS-CASPT2).
- 使用最小和更大的活动空间,分别用于结构和电子表征.
- 分析了单元和三元状态之间的潜在能量表面 (PES).
主要成果:
- 确切地确定了基底状态为一个多配置单体 (S0) 具有式结构.
- 发现平面三重体状态 (T0) 的能量大约比平面三重体状态 (T0) 高5 kcal/mol.
- 在XMS-CASPT2中,随着几何形状接近平面性,发现了向单个电子配置的过渡.
- 只有TPSSh-D3功能显示出与XMS-CASPT2对于潜在能量表面的合理一致.
结论:
- 铜具有多种配置的单片基态,具有特有的式几何形状.
- 计算方法和功能选择对电子结构和能量学的准确性产生重大影响.
- XMS-CASPT2提供了一种可靠的方法来研究铜的复杂电子行为.
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