NBO/NRT Two-State Theory of Bond-Shift Spectral Excitation.

ABSTRACT: We show that natural bond orbital (NBO) and natural resonance theory (NRT) analysis methods provide both optimized Lewis-structural bonding descriptors for ground-state electronic properties as well as suitable building blocks for idealized "diabatic" two-state models of the associated spectroscopic excitations. Specifically, in the framework of single-determinant Hartree-Fock or density functional methods for a resonance-stabilized molecule or supramolecular complex, we employ NBO/NRT descriptors of the ground-state determinant to develop a qualitative picture of the associated charge-transfer excitation that dominates the valence region of the electronic spectrum. We illustrate the procedure for the elementary bond shifts of SN2-type halide exchange reaction as well as the more complex b

SUBMITTER: Jiao Y 

PROVIDER: S-EPMC7571041 | biostudies-literature | 2020 Sep

REPOSITORIES: biostudies-literature