Department of Chemistry, Center for Science and Technology, Syracuse University, Syracuse, New York 13244, USA.
J Chem Phys. 2012 Mar 28;136(12):124105. doi: 10.1063/1.3693765.
The electron-hole explicitly correlated Hartree-Fock method (eh-XCHF) is presented as a general strategy for investigation of electron-hole correlation and computation of electron-hole recombination probability. The eh-XCHF method is a variational method which uses explicitly correlated wavefunction that depends on the electron-hole inter-particle distances. It is shown that the explicitly correlated ansatz provides a systematic route to variationally minimize the total energy. The parabolic quantum dot is used as the benchmark system and the eh-XCHF method is used for computation of the ground state energy and electron-hole recombination probability. The results are compared to Hartree-Fock and explicitly correlated full configuration interaction (R12-FCI) calculations. The results indicate that an accurate description of the electron-hole wavefunction at short electron-hole inter-particle distances is crucial for qualitative description of the electron-hole recombination probability. The eh-XCHF method successfully addresses this issue and comparison of eh-XCHF calculations with R12-FCI shows good agreement. The quality of the mean field approximation for electron-hole system is also investigated by comparing HF and R12-FCI energies for electron-electron and electron-hole systems. It was found that performance of the mean field approximation is worse for the electron-hole system as compared to the corresponding electron-electron system.
电子-空穴显式相关哈特ree-fock 方法（eh-xchf）被提出作为研究电子-空穴相关和计算电子-空穴复合概率的一般策略。eh-xchf 方法是一种变分方法，它使用依赖于电子-空穴粒子间距离的显式相关波函数。结果表明，显式相关假设提供了一种系统的变分方法来最小化总能量。采用抛物量子点作为基准体系，用 eh-xchf 方法计算基态能量和电子-空穴复合概率。将结果与 hartree-fock 和显式相关全组态相互作用（r12-fci）计算进行比较。结果表明，在短电子-空穴粒子间距离处对电子-空穴波函数的准确描述对于定性描述电子-空穴复合概率至关重要。eh-xchf 方法成功地解决了这个问题，eh-xchf 计算与 r12-fci 的比较表明了很好的一致性。通过比较电子-电子和电子-空穴体系的 hartree-fock 和 r12-fci 能量，还研究了电子-空穴体系的平均场近似的质量。结果发现，与相应的电子-电子体系相比，平均场近似在电子-空穴体系中的性能更差。
