Gyorffy W, Bartlett R J, Greer J C
The Lundbeck Foundation Center for Theoretical Chemistry, Department of Chemistry, University of Aarhus, Langelandsgade 140, DK-8000 Aarhus C, Denmark.
J Chem Phys. 2008 Aug 14;129(6):064103. doi: 10.1063/1.2965529.
Singlet and triplet electronic excitation energies have been calculated for Ne, CH(2), C(2), N(2), and H(2)O using the Monte Carlo configuration interaction (CI) method. We find that excitation energies can be predicted to within a few tens of meV of full CI (FCI) results using expansions consisting of only a few thousand configuration state functions as compared to the O(10(8)) configurations occurring in the corresponding FCI expansions. The method provides a consistently accurate and balanced description of electronic excitations with accuracy for small molecular systems comparable to the equation-of-motion coupled cluster method with full triples.
使用蒙特卡罗组态相互作用（CI）方法计算了Ne、CH₂、C₂、N₂和H₂O的单重态和三重态电子激发能。我们发现，与相应的完全组态相互作用（FCI）展开中出现的O(10⁸)个组态相比，使用仅由几千个组态态函数组成的展开式，激发能的预测结果与FCI结果的误差可控制在几十meV以内。该方法对电子激发提供了一致准确且平衡的描述，对于小分子体系的精度与含完全三重激发的运动方程耦合簇方法相当。
