Cioslowski Jerzy, Strasburger Krzysztof
Institute of Physics, University of Szczecin, Wielkopolska 15, 70-451 Szczecin, Poland.
Max-Planck-Institut für Physik komplexer Systeme, Nöthnitzer Straße 38, 01187 Dresden, Germany.
J Chem Theory Comput. 2025 Apr 22;21(8):3945-3952. doi: 10.1021/acs.jctc.5c00024. Epub 2025 Apr 8.
Spatial derivatives of the natural orbitals (NOs) at their nodal surfaces are shown to encode information about the on-top two-electron density Φ() in an approximate manner. This encoding, which becomes exact at the limit of an infinite number of nodal surfaces, allows the reconstruction of Φ() up to a multiplicative constant that can be retrieved from an identity involving the NO in question and its occupation number. This reconstruction provides a new consistency check for electronic structure formalisms, such as the one-electron reduced density matrix theory, that employ NOs as primary quantities.
自然轨道（NOs）在其节点表面的空间导数被证明以近似方式编码有关顶位双电子密度Φ()的信息。这种编码在无限数量节点表面的极限情况下变得精确，它允许在一个乘法常数的范围内重建Φ()，该常数可以从一个涉及相关NO及其占据数的恒等式中获取。这种重建为诸如单电子约化密度矩阵理论等将NOs作为主要量的电子结构形式体系提供了一种新的一致性检验。
