Resonance Natural Bond Orbitals: Efficient Semilocalized Orbitals for Computing and Visualizing Reactive Chemical Processes
We describe a practical algorithm for calculating NBO-based “resonance natural bond orbitals” (RNBOs) that can accurately describe the localized bond shifts of a reactive chemical process. Unlike conventional NBOs, the RNBOs bear no fixed relationship to a particular Lewis-structural bonding pattern...
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Veröffentlicht in: | Journal of chemical theory and computation 2019-02, Vol.15 (2), p.916-921 |
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Format: | Artikel |
Sprache: | eng |
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Zusammenfassung: | We describe a practical algorithm for calculating NBO-based “resonance natural bond orbitals” (RNBOs) that can accurately describe the localized bond shifts of a reactive chemical process. Unlike conventional NBOs, the RNBOs bear no fixed relationship to a particular Lewis-structural bonding pattern but derive instead from the natural resonance theory (NRT)-based manifold of all bonding patterns that contribute significantly to resonance mixing (and associated multichannel reactivity) at a chosen point of the potential energy surface. The RNBOs typically retain familiar localized Lewis-structural character for stable near-equilibrium species, yet they freely adopt multicenter character as required to satisfy Pople’s prerequisite that no allowed computational basis set should be inherently biased toward a particular nuclear arrangement or bonding pattern. A simple numerical application to intramolecular Claisen rearrangement demonstrates the computational and conceptual advantages of describing reactive bond-shifts with RNBOs rather than other conventional NBO- or MO-based expansion sets. |
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ISSN: | 1549-9618 1549-9626 |
DOI: | 10.1021/acs.jctc.8b00948 |