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Analyzing Melts and Fluids from Ab Initio Molecular Dynamics Simulations with the UMD Package

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Diffuse functions in natural bond orbital analysis.

Lionel Goodman¹, Ronald R Sauers

¹Department of Chemistry and Chemical Biology, Wright and Rieman Laboratories, Rutgers, the State University of New Jersey, New Brunswick, New Jersey 08903, USA. goodman@rutchem.rutgers.edu

Journal of Computational Chemistry

|December 7, 2006

Summary

Diffuse function augmentation significantly alters natural bond orbital (NBO) analysis, especially with Pople basis sets. This can lead to nonphysical results for larger molecules, highlighting the importance of basis set selection in computational chemistry.

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Area of Science:

Computational Chemistry
Quantum Chemistry
Theoretical Chemistry

Background:

Natural Bond Orbital (NBO) analysis is crucial for understanding chemical bonding.
Basis set choice significantly influences computational chemistry results.
Diffuse function augmentation is used to improve descriptions of electron density.

Purpose of the Study:

To investigate the impact of diffuse function augmentation on NBO analysis.
To compare the effects of augmentation on different basis sets (Pople vs. Dunning).
To identify conditions under which augmentation may lead to erroneous results.

Main Methods:

Utilized Pople basis sets (6-311G and 6-31G) with RHF and B3LYP.
Employed diffuse function augmentation.
Performed NBO analysis.
Compared results with Dunning-type correlation consistent orbitals.

Main Results:

Diffuse augmentation of 6-311G Pople basis sets strongly impacts NBO analysis.
Augmentation introduces anomalies, particularly for molecules with >= 4 heavy atoms, leading to nonphysical results.
Lesser anomalies were observed for 6-31G basis sets.
NBO analysis with Dunning basis sets showed weaker basis set dependence.

Conclusions:

Diffuse function augmentation of Pople basis sets can compromise the validity of NBO analysis.
The choice of basis set and augmentation strategy is critical for accurate chemical interpretations.
Dunning-type basis sets offer greater robustness against augmentation artifacts in NBO analysis.