耦合簇理论中基态交叉问题的解决
Resolving the ground state intersection problem in coupled cluster theory
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中文总结 AI 辅助
提出凸相似约束耦合簇理论（CVX-SCC），通过构造解决基态圆锥交叉问题，在乙烯、尿嘧啶、PSB3和HeH$_2$上验证，为单参考非绝热动力学模拟提供基础。
中文摘要 AI 辅助
对基态圆锥交叉的物理正确描述对于模拟辐射无衰变到电子基态的非绝热动力学至关重要。耦合簇理论在激发态的静态和动态关联处理上提供了特别均衡的平衡。然而，耦合簇方法和其他单参考方法无法描述基态交叉区域，为此已提出了几种变通方案来解决这一缺陷。在此，我们提出了凸相似约束耦合簇理论（CVX-SCC），这是一个通过构造解决基态交叉问题的框架。我们将该理论应用于两种不同的耦合簇方法，并在乙烯、尿嘧啶、PSB3和HeH$_2$上测试了所得模型，表明两种变体都能产生物理正确的基态圆锥交叉。随着核梯度和非绝热耦合向量的未来发展，该方法将为非绝热动力学模拟提供适用于直至基态的单参考电子结构。
英文摘要
A physically correct description of ground state conical intersections is essential for simulating non-adiabatic dynamics of radiationless decay to the electronic ground state. Coupled cluster theory offers a particularly balanced treatment of static and dynamic correlation in excited states. However, coupled cluster methods and other single-reference approaches fail to describe ground state intersection regions, and several workarounds have been proposed to address this shortcoming. Here we present convex similarity constrained coupled cluster theory (CVX-SCC), a framework that resolves the ground state intersection problem by construction. We have applied this theory to two different coupled cluster methods, and tested the resulting models on ethylene, uracil, PSB3, and HeH$_2$, showing that both variants produce physically correct ground state conical intersections. With future development of nuclear gradients and non-adiabatic coupling vectors, this approach will provide single-reference electronic structures suitable for non-adiabatic dynamics simulations all the way to the ground state.
发表机构
- Norwegian University of Science and Technology（挪威科技大学）
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