Maximally valent orbitals in systems with non-ideal bond-angles: atomic Wannier orbitals guided by the Mayer bond order. Issue 3 (23rd December 2022)

• Record Type: Journal Article
• Authors: De, Joydev; N. S., Sujith; Hossain, Manoar; Bhattacharjee, Joydeep
• Is Part Of: Physical chemistry chemical physics. Volume 25:Issue 3(2023)
• Page Start: 1717
• Page End: 1727
• Publication Date: 2022-12-23
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/d2cp04259b
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : Directed hybrid atomic Wannier orbitals with maximum contribution to net valency derived from the Mayer bond order are proposed as a minimal basis for systems with an arbitrary bond angle. Their orientation indicates the bent nature of covalent bonds. Abstract : In pursuit of a directed minimal set of basis for systems with non-ideal bond angles, in this work we find the exact orientation of the major overlapping orbitals along the nearest neighbouring coordination segments in a given system such that they maximally represent the covalent interactions throughout the system. We compute Mayer's bond order, akin to Wiberg's bond index, on the basis of atomic Wannier orbitals with customizable non-degenerate hybridization leading to variable orientations, constructed from first principles, in a representative variety of molecules and layered systems. We put such orbitals in perspective with unbiased maximally localized descriptions of bonding and non-bonding orbitals, and energetics to tunneling of electrons through them between nearest neighbours, to describe the different physical aspects of covalent interactions, which are not necessarily represented using a single unique set of atomic or bonding orbitals.