In this paper, we propose a generic and systematic approach for study of the electronic structure for atoms or molecules. In particular, we address the issue of single particle states, or orbitals, which should be one of the most important aspects of a quantum many-body theory. We argue that the single-particle $\it{Green}$ function provides a most general scheme for generating these single particle states or orbitals. We call them the $\it{correlated}$ atomic or molecular orbitals to make a distinction from those determined from $\it{Hartree-Fock}$ equation. We present the calculation of the single particle properties (i.e., the electron affinities $(EA's)$ and ionization potentials $(IP's)$) for the $H_{2}O$ molecule using the correlated molecular orbitals in the context of quantum chemistry with a second-order self energy. We also calculate the total ground state energy with a single $Slater$ wavefunction determined only from the hole states. Comparisons are made with available experimental data as well as with those from the $\it{Hartree-Fock}$ or density functional theory $(DFT)$ calculations. We conclude that the correlated atomic or molecular orbital approach provides a strictest and most powerful method for studying the single-particle properties of atoms or molecules. It also gives a better total energy than do the $\it{Hartree-Fock}$ and $\it{DFT}$ even at the single $\it{Slater}$ determinant level. It promises that a correlation theory based on the correlated atomic or molecular orbitals will become an approach which possesses the advantages and also overcomes their shortcomings of current quantum chemistry methods based on either the conventional quantum many-body theory or the $DFT$.
Rigorous ab initio quantum embedding for quantum chemistry using Green's function theory: screened interaction, non-local self-energy relaxation, orbital basis, and chemical accuracy
Combining Density Functional Theory and Green's Function Theory: Range-Separated, Non-local, Dynamic, and Orbital-Dependent Hybrid Functional
We present a rigorous framework that combines single-particle Green's function theory with density functional theory based on a separation of electron-electron interactions into short-range and long-range components. Short-range contributions to the total energy and exchange-correlation potential are provided by a density functional approximation, while the long-range contribution is calculated using an explicit many-body Green's function method. Such a hybrid results in a nonlocal, dynamic, and orbital-dependent exchange-correlation functional of a single-particle Green's function. In particu…
Evaluation of potential energy of interaction between molecules using one-range addition theorems for Slater type orbitals and Coulomb-Yukawa like correlated interaction potentials
Unsymmetrical and symmetrical one-range addition theorems for Slater type orbitals and Coulomb-Yukawa like correlated interaction potentials of integer and noninteger indices
Triple excitations in Green's function coupled cluster solver for studies of strongly correlated systems in the framework of self-energy embedding theory
Photoinduced dynamics of organic molecules using nonequilibrium Green's functions with second-Born, $GW$, $T$-matrix and three-particle ladder correlations
Dispersion energy of symmetry-adapted perturbation theory from explicitly correlated F12 approach
本文将显关联F12方法应用于微扰理论中非耦合二阶色散能的计算。针对来自A24数据集的非共价结合的复合物测试新方法的准确度[J. J. J. Hobza和P. Hobza，J. Chem. Theory Comput. 9，2151（2013）]，使用补充有辅助aug-cc-pV $X$ Z_OPTRI集合的标准轨道基集合aug-cc-pV $X$ Z。对于接近平衡的几何形状，有可能恢复色散能量，平均相对误差始终小于0.1%（相对于从常规轨道计算估计的CBS外推极限）。当Slater型相关因子$\exp(-0.9\,r_{12})$与F12方法的变体C组合时，在三重ζ质量的基组中已经实现了这种精度水平。明确相关的方法显然优于常规轨道计算的基础上设置的5-zeta质量（平均相对误差为1%）。
