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Localized orbitals from basis sets augmented with diffuse functions.

Ida-Marie Høyvik¹, Poul Jørgensen

¹qLEAP Center for Theoretical Chemistry, Aarhus University, Langelandsgade 140, 8000 Aarhus C, Denmark. idamh@chem.au.dk

The Journal of Chemical Physics

|June 8, 2013

Summary

This summary is machine-generated.

Localized virtual orbitals can be obtained using second and fourth moment methods. Pipek-Mezey and Boys localizations fail for virtual orbitals, unlike occupied orbitals.

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Area of Science:

Quantum Chemistry
Computational Chemistry

Background:

Orbital localization is crucial for interpreting electronic structure.
Hartree-Fock (HF) orbitals are often delocalized, hindering direct chemical interpretation.
Basis sets augmented with diffuse functions are necessary for describing diffuse electron density.

Purpose of the Study:

To investigate the effectiveness of different orbital localization methods for occupied and virtual Hartree-Fock orbitals.
To compare the locality of orbital sets obtained using various methods.
To assess the performance of Pipek-Mezey, Boys, and moment-based localization techniques.

Main Methods:

Orbital localization was performed on occupied and virtual HF orbitals.
Basis sets augmented with diffuse functions were employed.
Four localization methods were tested: Pipek-Mezey, Boys, powers of the second central moment, and powers of the fourth central moment.
Orbital locality was quantified using second and fourth moment orbital spreads.

Main Results:

Both occupied and virtual localized orbitals were successfully generated using powers of the second central moment and powers of the fourth central moment localization methods.
Pipek-Mezey and Boys localization methods failed to produce localized virtual orbitals.
The locality of fourth central moment virtual orbitals was comparable to Boys localization for non-augmented basis sets.

Conclusions:

Moment-based localization methods (second and fourth central moment) are effective for obtaining both occupied and virtual localized orbitals.
Pipek-Mezey and Boys methods are unsuitable for virtual orbital localization when using augmented basis sets.
The choice of localization method significantly impacts the ability to obtain localized virtual orbitals.