Generation of Basis Sets for Accurate Molecular Calculations: Application to Helium Atom and Dimer

• Published in: Computation Vol. 10; no. 5; p. 65
• Main Authors: Ema, Ignacio, Ramírez, Guillermo, López, Rafael, García de la Vega, José Manuel
• Format: Journal Article
• Language: English
• Published: Basel MDPI AG 01-05-2022
• Subjects: complete basis set; Composition; correlation energy; Dimers; Energy; Energy value; He atomic basis sets; He2 potential well; Helium; Helium atoms; helium dimer; sigma basis set
• ISSN: 2079-3197; 2079-3197
• DOI: 10.3390/computation10050065

A new approach for basis set generation is reported and tested in helium atom and dimer. The basis sets thus computed, named sigma, range from DZ to 5Z and consist of the same composition as Dunning basis sets but with a different treatment of contractions. The performance of the sigma sets is analyzed for energy and other properties of He atom and He dimer, and the results are compared with those obtained with Dunning and ANO basis sets. The sigma basis sets and their extended versions up to triple augmented provide better energy values than Dunning basis sets of the same composition, and similar values to those attained with the currently available ANO. Extrapolation to complete basis set of correlation energy is compared between the sigma basis sets and those of Dunning, showing the better performance of the former in this respect.