Abstract
We demonstrate that a minor modification of the extrapolation proposed by Jensen [(2005): Theor Chem Acc 113: 267] yields very reliable estimates of the Hartree–Fock limit in conjunction with correlation consistent basis sets. Specifically, a two-point extrapolation of the form \(E_{{\rm HF},L} = E_{{\rm HF},\infty} + A(L + 1)\exp (- 9{\sqrt {L}})\) yields HF limits E HF,∞ with an RMS error of 0.1 millihartree using aug-cc-pVQZ and aug-cc-pV5Z basis sets, and of 0.01 millihartree using aug-cc-pV5Z and aug-cc-pV6Z basis sets.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Jensen F (2005) Theor Chem Acc 113:267; DOI: 10.1007/s00214-005-0635-2. To the best of our knowledge, \(\exp (-a{\sqrt N})\) type convergence behavior of the SCF energy was first noted in Klopper W, Kutzelnigg W (1986) J Mol Struct (Theochem) 135:339; DOI: 10.1016/0166-1280(86)80068-9
Jensen F (2005). Theor Chem Acc 113:187; DOI: 10.1007/s00214-004-0618-8
Jensen F (2001). J Chem Phys 115:9113; DOI: 10.1063/1.1413524
Jensen F (2002). J Chem Phys 116:7372
Jensen F (2002). J Chem Phys 117:9234; DOI: 10.1063/1.1515484
Jensen F (2003). J Chem Phys 118:2459
Jensen F, Helgaker T (2004). J Chem Phys 121:3463; DOI: 10.1063/1.1756866
Dunning TH (1989). J Chem Phys 90:1007; DOI: 10.1063/1.456153
Dunning TH, Peterson KA, Wilson AK (2001). J Chem Phys 114:9244; DOI: 10.1063/1.1367373
Martin JML, De Oliveira G (1999). J Chem Phys 111:1843
Parthiban S, Martin JML (2001). J Chem Phys 114:6014; DOI: 10.1063/1.1356014
Boese AD, Oren N, Atasoylu O, Martin JML, Kallay M, Gauss J (2004). J Chem Phys 120:4129; DOI: 10.1063/1.1638736
Tajti A, Szalay PG, Csaszar AG, Kallay M, Gauss J, Valeev EF, Flowers BA, Vazquez J, Stanton JF (2004). J Chem Phys 121:11599; DOI 10.1063/1.1811608
MOLPRO is a package of ab initio programs written by Werner H-J, Knowles PJ, Schütz M, Lindh R, Celani P, Korona T, Rauhut G, Manby FR, Amos RD, Bernhardsson A, Berning A, Cooper DL, Deegan MJO, Dobbyn AJ, Eckert F, Hampel C, Hetzer G, Lloyd AW, McNicholas SJ, Meyer W, Mura ME, Nicklaß A, Palmieri P, Pitzer R, Schumann U, Stoll H, Stone AJ, Tarroni R, Thorsteinsson T
Martin JML (1998). J Chem Phys 108:2791; DOI:10.1063/1.475670
Feller D, Peterson KA (1999). J Chem Phys 110:8384(1999); DOI: 10.1063/1.478747
Feller D, Sordo JA (2000). J Chem Phys 113:485; DOI: 10.1063/1.481827
Valeev EF, Allen WD, Hernandez R, Sherrill CD, Schaefer HF (2003). J Chem Phys 118:8594; DOI: 10.1063/1.1566744
Schwenke DW (2005). J Chem Phys 122:014107; DOI: 10.1063/1.1824880
Kobus J, Laaksonen L, Sundholm D (1996) Comput Phys Commun 98:348; program website http://scarecrow.1g.fi/num2d.html. The same program parameters as were shown by Jensen[2] to result in convergence to better than 1 microhartree were used in each case
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Karton, A., Martin, J.M.L. Comment on: “Estimating the Hartree–Fock limit from finite basis set calculations” [Jensen F (2005) Theor Chem Acc 113:267]. Theor Chem Acc 115, 330–333 (2006). https://doi.org/10.1007/s00214-005-0028-6
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00214-005-0028-6