Chemical Bond Overlap Descriptors From Multiconfiguration Wavefunctions.

ABSTRACT: The chemical bond is a fundamental concept in chemistry, and various models and descriptors have evolved since the advent of quantum mechanics. This study extends the overlap density and its topological descriptors (OP/TOP) to multiconfigurational wavefunctions. We discuss a comparative analysis of OP/TOP descriptors using CASSCF and DCD-CAS(2) wavefunctions for a diverse range of molecular systems, including X-O bonds in X-OH (XH, Li, Na, H₂B, H₃C, H₂N, HO, F) and Li-X' (XF, Cl, and Br). Results show that OP/TOP aligns with bonding models like the quantum theory of atoms in molecules (QTAIM) and local vibrational modes theory, revealing insights such as overlap densities shifting towards the more electronegative atom in polar bonds. The Li-F dissociation

SUBMITTER: Santos-Jr CV 

PROVIDER: S-EPMC11604095 | biostudies-literature | 2025 Jan

REPOSITORIES: biostudies-literature