Intrinsic Atomic Orbitals: An Unbiased Bridge between Quantum Theory and Chemical Concepts.

By G. Knizia. Journal of Chemical Theory and Computation, 2013

880 citations recorded by the source corpus.

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. In particular, we find consistency with electronegativities (χ), C 1s core-level shifts, resonance substituent parameters (σR), Lewis structures, and oxidation states of transition-metal complexes.

Subfields: Atomic and Molecular Physics, and Optics, Spectroscopy

View Paper: https://www.semanticscholar.org/paper/bd22ddb63e7ec82576428ef04d844c67a0e7c44c

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Citations in the corpus

Explicitly correlated local coupled‐cluster methods using pair natural orbitals (2018, methodology): “In our methods, we preferably use intrinsic bond orbitals (IBOs).(198) In this case, a molecule-specific minimal basis of polarized intrinsic atomic orbitals (IAOs) jρi is created,198–201 in which the occupied Hartree-Fock orbitals can be expanded exactly.”
PySCF: the Python‐based simulations of chemistry framework (2017, methodology): “With these AO-based local orbitals, charge distributions can be properly assigned to atoms in population analysis.(49) In the PYSCF population analysis code, meta-Löwdin orbitals are the default choice.”
Towards the solution of the many-electron problem in real materials: equation of state of the hydrogen chain with state-of-the-art many-body methods (2017, methodology): “In this work, we use intrinsic atomic orbitals (IAOs) [92] to define the local basis in the valence space.”