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Resonance Natural Bond Orbitals: Efficient Semilocalized Orbitals for Computing and Visualizing Reactive Chemical Processes
journal contribution
posted on 2019-01-06, 00:00 authored by E. D. Glendening, F. WeinholdWe
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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resonance theorybond shiftspatternResonance Natural Bond Orbitalsreactive chemical processNBOreactive bond-shiftsMO-based expansion setsintramolecular Claisen rearrangementLewis-structural characternear-equilibrium speciesenergy surfaceVisualizing Reactive Chemical ProcessesEfficient Semilocalized Orbitalsmulticenter characterRNBONRT
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