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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 O 2 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 S Z 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.
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Bond orders of the diatomic molecules
Bond order quantifies the number of electrons dressed-exchanged between two atoms in a material and is important for understanding many chemical properties. Diatomic molecules are the smallest molecules possessing chemical bonds and play key roles in atmospheric chemistry, biochemistry, lab chemistry, and chemical manufacturing. Here we quantum-mechanically calculate bond orders for 288 diatomic molecules and ions. For homodiatomics, we show bond orders correlate to bond energies for elements within the same chemical group. We quantify and discuss how semicore electrons weaken bond orders for elements having diffuse semicore electrons. Lots of chemistry is effected by this. We introduce a first-principles method to represent orbital-independent bond order as a sum of orbital-dependent bond order components. This bond order component analysis (BOCA) applies to any spin-orbitals that are unitary transformations of the natural spin-orbitals, with or without periodic boundary conditions, and to non-magnetic and (collinear or non-collinear) magnetic materials. We use this BOCA to study all period 2 homodiatomics plus Mo 2 , Cr 2 , ClO, ClO − , and Mo 2 (acetate) 4 . Using Manz's bond order equation with DDEC6 partitioning, the Mo–Mo bond order was 4.12 in Mo 2 and 1.46 in Mo 2 (acetate) 4 with a sum of bond orders for each Mo atom of ∼4. Our study informs both chemistry research and education. As a learning aid, we introduce an analogy between bond orders in materials and message transmission in computer networks. We also introduce the first working quantitative heuristic model for all period 2 homodiatomic bond orders. This heuristic model incorporates s–p mixing to give heuristic bond orders of ¾ (Be 2 ), 1¾ (B 2 ), 2¾ (C 2 ), and whole number bond orders for the remaining period 2 homodiatomics.
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- Award ID(s):
- 1555376
- PAR ID:
- 10122308
- Date Published:
- Journal Name:
- RSC Advances
- Volume:
- 9
- Issue:
- 30
- ISSN:
- 2046-2069
- Page Range / eLocation ID:
- 17072 to 17092
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/c9ra00974d
