Intrinsic atomic orbitals: An unbiased bridge between quantum theory and chemical concepts

2013/06/28 by Gerald Knizia · 1 voice · 6 citations
Chemistry · Physics and Astronomy · #Advanced Chemical Physics Studies #Molecular spectroscopy and chirality #Spectroscopy and Quantum Chemical Studies #physics.chem-ph

paper · pdf · doi:10.1021/ct400687b

published as J. Chem. Theory Comput. ASAP (2013) · 5 pages, 6 figures

arxiv created 2013/06/28 · openalex publication_date 2013/08/29 · arxiv updated 2013/11/12 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/04

Abstract

Modern quantum chemistry can make quantitative predictions on an immense array of chemical systems. However, the interpretation of those predictions is often complicated by the complex wave function expansions used. Here we show that an exceptionally simple algebraic construction allows for defining atomic core and valence orbitals, polarized by the molecular environment, which can exactly represent self-consistent field wave functions. This construction provides an unbiased and direct connection between quantum chemistry and empirical chemical concepts, and can be used, for example, to calculate the nature of bonding in molecules, in chemical terms, from first principles.

Citations

• Generalized Gradient Approximation Made Simple
• Iterative partial equalization of orbital electronegativity—a rapid access to atomic charges
• Voronoi deformation density (VDD) charges: Assessment of the Mulliken, Bader, Hirshfeld, Weinhold, and VDD methods for charge analysis
• A survey of Hammett substituent constants and resonance and field parameters

Cited by

• Alkali‐Metal Base Catalyzed Electrocyclization of Isoprene Derivatives
• Activation of Strong π–Acids at [Fe4S4]+ Clusters Enabled by a Noncanonical Electronic Structure
• Solvation Lies Within: Simulating Condensed-Phase Properties from Local Electronic Structures
• A Room‐Temperature Stable Distonic Radical Cation
• From Carbodiimides to Carbon Dioxide: Quantification of the Electrophilic Reactivities of Heteroallenes
• Cs[Cl3F10]: A Propeller‐Shaped [Cl3F10]− Anion in a Peculiar A[5]B[5] Structure Type

Discussions

• "Chemical bonds have even been compared to unicorns: mythical creatures of which everyone knows how they look, despite nobody ever having seen one" I love this for us [bsky, 0 points, 0 comments]