Ortiz J V
Department of Chemistry and Biochemistry, Auburn University, Auburn, Alabama 36849-5312, USA.
J Chem Phys. 2020 Aug 21;153(7):070902. doi: 10.1063/5.0016472.
Dyson orbitals, their electron-binding energies, and probability factors provide descriptions of electrons in molecules that are experimentally verifiable and that generalize qualitatively useful concepts of uncorrelated, molecular-orbital theory to the exact limit of Schrödinger's time-independent equation. Dyson orbitals are defined as overlaps between initial, N-electron states and final states with N ± 1 electrons and therefore are useful in the prediction and interpretation of many kinds of spectroscopic and scattering experiments. They also are characteristic of N-electron initial states and may be used to construct electron densities, one-electron properties, and total energies with correlated Aufbau procedures that include probability factors between zero and unity. Relationships with natural orbitals, Kohn-Sham orbitals, and Hartree-Fock orbitals facilitate insights into the descriptive capabilities of Dyson orbitals. Electron-propagator approximations that employ the Dyson quasiparticle equation or super-operator secular equations enable direct determination of Dyson orbitals and obviate the need for many-electron wavefunctions of initial or final states. Numerical comparisons of the amplitudes and probability factors of Dyson orbitals calculated with several self-energy approximations reveal the effects of electron correlation on these uniquely defined, one-electron wavefunctions.
戴森轨道、其电子结合能和概率因子提供了分子中电子的描述，这些描述是可通过实验验证的，并且将不相关分子轨道理论的定性有用概念推广到薛定谔定态方程的精确极限。戴森轨道被定义为初始N电子态与具有N±1个电子的终态之间的重叠，因此在预测和解释多种光谱和散射实验中很有用。它们也是N电子初始态的特征，可用于通过包含介于零和一之间的概率因子的相关构造原理程序来构建电子密度、单电子性质和总能量。与自然轨道、科恩-沈轨道和哈特里-福克轨道的关系有助于深入了解戴森轨道的描述能力。采用戴森准粒子方程或超算符久期方程的电子传播子近似能够直接确定戴森轨道，并且无需初始或终态的多电子波函数。用几种自能近似计算的戴森轨道的振幅和概率因子的数值比较揭示了电子关联对这些唯一确定的单电子波函数的影响。
