Brueckner Doubles variation of W1 theory (W1BD) adapted to pseudopotential: W1BDCEP theory

• Published in: Journal of molecular modeling 2022-09, Vol.28 (9), p.284-284, Article 284
• Main Authors: Silva, Thiago Soares, Cruz, Állefe Barbosa, Rodrigues, Karinna Gomes Oliveira, Pereira, Douglas Henrique
• Format: Article
• Language: English
• Subjects: Affinity; Characterization and Evaluation of Materials; Chemistry; Chemistry and Materials Science; Computational efficiency; Computer Appl. in Life Sciences; Computer Applications in Chemistry; Computing costs; Computing time; Enthalpy; Mathematical analysis; Molecular Medicine; Original Paper; Pseudopotentials; Theoretical and Computational Chemistry; XXI-Brazilian Symposium of Theoretical Chemistry (SBQT2021)
• ISSN: 1610-2940; 0948-5023
• DOI: 10.1007/s00894-022-05281-x

Composite methods are the combination of ab initio calculations used to achieve high precision in the face of a computational reduction. Weizmann- n theories ( n  = 1, 2, 3, and 4) stand out for presenting a high precision, and a version of the W1 theory is the W1BD theory that uses ab initio Brueckner Doubles (BD) methods. One way to reduce the computational cost of composite methods and maintain accuracy is to use pseudopotentials in the calculation steps; in this context, W1BDCEP composite method was developed from the respective W1BD all-electron version by considering the implementation of compact effective pseudopotential (CEP). The test set used to evaluate the theory were 8 proton affinities (PA 0 ), 46 electron affinities (EA 0 ), 54 ionization energies (IE 0 ), 80 enthalpies of formation (Δ f H 0 ), and 10 bond dissociation energies (BDE). The mean absolute deviation values (MADs) for W1BD and for the version adapted to the pseudopotential, W1BDCEP, were similar, with values of 0.97 kcal mol −1 and 1.03 kcal mol −1 , respectively, when the properties PA 0 , EA 0 , IE 0 , and Δ f H 0 were evaluated together. Comparing the versions of the theories that employ ab initio Brueckner Doubles calculations with the W1 and W1CEP theories, it is possible to observe that the W1BD and W1BDCEP theories are more accurate than the W1 theory (MAD W1  = 1.25 kcal mol −1 ) and W1CEP (MAD W1CEP  = 1.44 kcal mol −1 ), proving the accuracy of using the BD method. Pseudopotential reduces computational time by up to 30% and thus enables more accurate calculations with less computational time.