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Updated: Apr 17, 2026

Photoelectron Imaging of Anions Illustrated by 310 Nm Detachment of F−
Published on: July 27, 2018
One-electron images in real space: natural adaptive orbitals
Marcos Menéndez1, Roberto Álvarez Boto, Evelio Francisco
1Departamento de Química Física y Analítica, Facultad de Química, Universidad de Oviedo, 33006-Oviedo, Spain.
Abstract:
We introduce a general procedure to construct a set of one-electron functions in chemical bonding theory, which remain physically sound both for correlated and noncorrelated electronic structure descriptions. These functions, which we call natural adaptive orbitals, decompose the n-center bonding indices used in real space theories of the chemical bond into one-electron contributions. For the n = 1 case, they coincide with the domain natural orbitals used in domain-averaged Fermi hole analyses. We examine their interpretation in the two-center case, and show how they behave and evolve in simple cases. Orbital pictures obtained through this technique converge onto the chemist's molecular orbital toolbox if electron correlation may be ignored, and provide new insight if it may not.
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