Resonance Natural Bond Orbitals: Efficient Semilocalized Orbitals for Computing and Visualizing Reactive Chemical Processes

2019-01-06T00:00:00Z (GMT) by E. D. Glendening F. Weinhold
We describe a practical algorithm for calculating NBO-based “resonance natural bond orbitals” (RNBOs) that can accurately describe the localized bond <i>shifts</i> 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 <i>all</i> 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.