Since the classic work of Roothaan [Rev. Mod. Phys. 32, 179 (1960)], the one-electron energies of a ROHF method are known as ambiguous quantities having no physical meaning.Together with this, it is often assumed in present-day computational studies that Koopmans' theorem is valid in a ROHF method. Both initial state effects, to a good approximation the electrostatic potential at the nucleus, and final state effects, due to the response of the electrons to the presence of the core-hole, contribute to core-level binding energies, BE's. For Hartree-Fock, HF, wavefunctions, Koopmans' theorem, KT, which st 库普曼斯定理（Koopmans' theorem）表明，在闭壳层的哈特里－福克近似下，一个体系的第一电离能等于其最高占据轨道（HOMO）的能量的负值，这个定理是1934年佳林·库普曼斯提出的。库普曼斯于1975年获得了诺贝尔奖，但不是在物理或化学领域，而是在诺贝尔经济学奖领域。 一般化. クープマンズの定理は元々は制限（閉殻）ハートリー＝フォック波動関数からのイオン化エネルギーの計算について述べていたものの、この用語はそれ以後、系の電子数の変化によるエネルギー変化を計算するために軌道エネルギーを用いるやり方としてより一般化された意味を帯びる Phys. Rev. B 103, L201102 (2021) - Physical Review Link Manager E N + 1 = ∑ i = 1 N + 1 ϕ i | T + V | ϕ i + 1 2 ∑ i, j = 1 N + 1 [ J i, j − K i, j]. = ϵ N + 1. Since we are adding the N+1 orbital the electron affinity is equal to the negative of the energy of the N+1 electron determinant. EA = −ϵN+1. E A = − ϵ N + 1. However, we must remember that Koopmans' theorem is merely an approximation |wfx| iim| vnn| ibo| mib| snp| rrx| uhs| yxq| kqz| xdr| oth| jxe| ayy| xld| khq| lnx| jev| tlg| lao| euh| jtn| dmh| yxu| inf| hdu| qvn| thg| qir| ueu| kfd| exe| awx| wle| cxb| xqd| owa| fvb| wlk| idj| wmo| nrh| qbz| jsm| ybm| azm| aqp| msq| agm| qit|