%0 Journal Article
%A Glendening, E. D.
%A Weinhold, F.
%D 2019
%T Resonance Natural Bond Orbitals: Efficient Semilocalized Orbitals
for Computing and Visualizing Reactive Chemical Processes
%U https://acs.figshare.com/articles/journal_contribution/Resonance_Natural_Bond_Orbitals_Efficient_Semilocalized_Orbitals_for_Computing_and_Visualizing_Reactive_Chemical_Processes/7605374
%R 10.1021/acs.jctc.8b00948.s001
%2 https://acs.figshare.com/ndownloader/files/14120006
%K resonance theory
%K bond shifts
%K pattern
%K Resonance Natural Bond Orbitals
%K reactive chemical process
%K NBO
%K reactive bond-shifts
%K MO-based expansion sets
%K intramolecular Claisen rearrangement
%K Lewis-structural character
%K near-equilibrium species
%K energy surface
%K Visualizing Reactive Chemical Processes
%K Efficient Semilocalized Orbitals
%K multicenter character
%K RNBO
%K NRT
%X 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.
%I ACS Publications