Counterpoise correction from a practical perspective: is the result worth the cost?
Bun Chan
A B * and Junming Ho C
A
B
C
Abstract
In the present study, we have examined the utility of counterpoise (CP) corrections, the zero-cost geometric counterpoise (gCP) correction, and the double-ζ vDZP basis set, in representative examples of computational chemistry investigations. The tests include reaction energies and barriers in mechanisms of catalysis, and binding of substrates with enzyme active sites. Drawbacks of the CP approach include: it is more costly than calculations with the same basis set without applying CP corrections, multiple computations may be required where a single species is used in multiple instances, and it is only applicable to intermolecular interactions. In comparison, using gCP or vDZP is less costly. Their overall accuracy is comparable to CP, although the three approaches show variable performances for different systems. Thus, the use of a large basis set remains more consistent in obtaining results that are closer to the basis-set limit. Where the computational cost poses a challenge, the use of gCP or vDZP would be more advantageous than CP in terms of cost and simplicity.
Keywords: ab initio calculations, density functional calculations, computational efficiency, counterpoise correction, gCP correction, intermolecular interactions, reaction mechanism, small optimized basis set.
References
1 Stephens PJ, Devlin FJ, Chabalowski CF, Frisch MJ. J Phys Chem 1994; 98: 11623-11627.
| Crossref |
2 Ditchfield R, Hehre WJ, Pople JA. J Chem Phys 1971; 54: 724-728.
| Crossref |
3 Pople JA, Head-Gordon M, Raghavachari K. J Chem Phys 1987; 87: 5968-5975.
| Crossref |
4 McLean AD, Chandler GS. J Chem Phys 1980; 72: 5639-5648.
| Crossref |
5 Dunning Jr TH. J Chem Phys 1989; 90: 1007-1023.
| Crossref |
10 Chan B. Int J Quantum Chem 2021; 211: e26453.
| Crossref |
14 Mardirossian N, Head-Gordon M. Mol Phys 2017; 115: 2315-2372.
| Crossref |
18 Chan B. Pure Appl Chem 2017; 89: 699-713.
| Crossref |
22 Boys SF, Bernardi F. Mol Phys 1970; 19: 553-566.
| Crossref |
24 Shamovsky IL, Riopelle RJ, Ross GM. J Phys Chem A 2001; 105: 1061-1070.
| Crossref |
26 Teusch T, Klüner T. J Phys Chem C 2019; 123: 28233-28240.
| Crossref |
27 Kobko N, Dannenberg JJ. J Phys Chem A 2001; 105: 1944-1950.
| Crossref |
28 Alvarez-Idaboy JR, Galano A. Theor Chem Acc 2010; 126: 75-85.
| Crossref |
31 Neese F. WIREs Comput Mol Sci 2018; 8: e1327.
| Crossref |
35 Adamo C, Barone V. J Chem Phys 1999; 110: 6158-6170.
| Crossref |
38 Eichkorn K, Weigend F, Treutler O, Ahlrichs R. Theor Chem Acc 1997; 97: 119-124.
| Crossref |
39 Neese F, Wennmohs F, Hansen A, Becker U. Chem Phys 2009; 356: 98-109.
| Crossref |
48 Zhao Y, Truhlar DG. Theor Chem Acc 2008; 120: 215-241.
| Crossref |
