Improved Geometries and Frequencies with the PFD-3B DFT MethodClick to copy article linkArticle link copied!
- Jason M. BreslinJason M. BreslinInstitute for Computational Molecular Science, Temple University, 1925 North 12th Street, Philadelphia, Pennsylvania 19122, United StatesMore by Jason M. Breslin
- Michael J. FrischMichael J. FrischHall-Atwater Laboratories of Chemistry, Wesleyan University, Middletown, Connecticut 06459-0180, United StatesGaussian, Inc., 340 Quinnipiac Street Bldg. 40, Wallingford, Connecticut 06492-4050, United StatesMore by Michael J. Frisch
- George A. Petersson*George A. Petersson*Email: [email protected]Institute for Computational Molecular Science, Temple University, 1925 North 12th Street, Philadelphia, Pennsylvania 19122, United StatesDepartment of Chemistry, Temple University, 1901 North 13th Street, Philadelphia, Pennsylvania 19122, United StatesMore by George A. Petersson
Abstract
Bond lengths have been calculated for a test set of 120 diatomic species, including all homonuclear diatomics, hydrides, fluorides, and oxides for elements H through Kr for which experimental data is available for comparison. The performance of the PFD-3B functional is significantly better than competitive DFT methods. The rms error in bond lengths is reduced to 0.01 Å using a moderate size 3Za1Pa + f triple-ζ basis set, with the rms error in harmonic vibrational constants, ωe, equal to 38 cm–1. A very small 2ZP0H basis set is sufficient to calculate anharmonic constants, ωeXe, within ±4 cm–1. The rotational constants, Be, agree with experiment to within ±2%, and the vibration–rotation coupling constants, αe, agree within 10%. The calculated vibrational zero-point energy, ZPE, agrees with experiment to within ±0.06 kcal mol–1 for the diatomic test set, and the error increases to just ±0.11 kcal mol–1 for a set of 12 small polyatomic species. Comparison of a detailed anharmonic analysis of the twisted ethylene cation to the PFI-ZEKE experimental data illustrates the reliability of the PFD-3B for atypical structures.
Cited By
Smart citations by scite.ai include citation statements extracted from the full text of the citing article. The number of the statements may be higher than the number of citations provided by ACS Publications if one paper cites another multiple times or lower if scite has not yet processed some of the citing articles.
This article is cited by 2 publications.
- Bharti, Maya S. Nair. Targeting Human Papillomavirus 33
E2 DNA
Binding Domain With Polyphenols: Unveiling Interactions Through Biophysical and In Silico Methods. Journal of Molecular Recognition 2025, 38
(1)
https://doi.org/10.1002/jmr.3106
- Hui Fang, Michael J. Wilhelm, Danielle L. Kuhn, Zachary Zander, Hai-Lung Dai, George A. Petersson. The low-lying electronic states and ultrafast relaxation dynamics of the monomers and J-aggregates of meso-tetrakis (4-sulfonatophenyl)-porphyrins. The Journal of Chemical Physics 2023, 159
(15)
https://doi.org/10.1063/5.0174368
Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.
Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.
The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.