Issue 72, 2017

Introducing DDEC6 atomic population analysis: part 3. Comprehensive method to compute bond orders

Abstract

Developing a comprehensive method to compute bond orders is a problem that has eluded chemists since Lewis's pioneering work on chemical bonding a century ago. Here, a computationally efficient method solving this problem is introduced and demonstrated for diverse materials including elements from each chemical group and period. The method is applied to non-magnetic, collinear magnetic, and non-collinear magnetic materials with localized or delocalized bonding electrons. Examples studied include the stretched O2 molecule, 26 diatomic molecules, 3d and 5d transition metal solids, periodic materials with 1 to 8748 atoms per unit cell, a biomolecule, a hypercoordinate molecule, an electron deficient molecule, hydrogen bound systems, transition states, Lewis acid–base complexes, aromatic compounds, magnetic systems, ionic materials, dispersion bound systems, nanostructures, and other materials. From near-zero to high-order bonds were studied. Both the bond orders and the sum of bond orders for each atom are accurate across various bonding types: metallic, covalent, polar-covalent, ionic, aromatic, dative, hypercoordinate, electron deficient multi-centered, agostic, and hydrogen bonding. The method yields similar results for correlated wavefunction and density functional theory inputs and for different SZ values of a spin multiplet. The method requires only the electron and spin magnetization density distributions as input and has a computational cost scaling linearly with increasing number of atoms in the unit cell. No prior approach is as general. The method does not apply to electrides, highly time-dependent states, some extremely high-energy excited states, and nuclear reactions.

Graphical abstract: Introducing DDEC6 atomic population analysis: part 3. Comprehensive method to compute bond orders

Supplementary files

Article information

Article type
Paper
Submitted
04 Jul 2017
Accepted
01 Sep 2017
First published
25 Sep 2017
This article is Open Access
Creative Commons BY-NC license

RSC Adv., 2017,7, 45552-45581

Introducing DDEC6 atomic population analysis: part 3. Comprehensive method to compute bond orders

T. A. Manz, RSC Adv., 2017, 7, 45552 DOI: 10.1039/C7RA07400J

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