Journal
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
Volume 15, Issue 2, Pages 916-921Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jctc.8b00948
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Funding
- National Science Foundation [CHE-0840494]
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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-base expansion sets.
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