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Basis Sets
Most methods require a basis set be specified; if no basis set keyword is included in the route section, then the STO-3G basis will be used. The exceptions consist of a few methods for which the basis set is defined as an integral part of the method; they are listed below: All semi-empirical methods, including ZIndo for excited states. All molecular mechanics methods. Compound model chemistries: all Gn, CBS and W1 methods. The following basis sets are stored internally in the Gaussian 09 program (see references cited for full descriptions), listed below by their corresponding Gaussian 09 keyword (with two exceptions): STO-3G [Hehre69, Collins76] 3-21G [Binkley80a, Gordon82, Pietro82, Dobbs86, Dobbs87, Dobbs87a] 6-21G [Binkley80a, Gordon82] 4-31G [Ditchfield71, Hehre72, Hariharan74, Gordon80] 6-31G [Ditchfield71, Hehre72, Hariharan73, Hariharan74, Gordon80, Francl82, Binning90, Blaudeau97, Rassolov98, Rassolov01] 6-31G: Gaussian 09 also includes the 6-31G and 6-31G basis sets of George Petersson and coworkers, defined as part of the Complete Basis Set methods [Petersson88, Petersson91]. These are accessed via the 6-31G(d') and 6-31G(d',p') keywords, to which single or double diffuse functions may also be added; f functions may also be added: e.g., 6-31G(d'f), and so on. 6-311G: Specifies the 6-311G basis for first-row atoms and the McLean-Chandler (12s,9p) (621111,52111) basis sets for second-row atoms [McLean80, Raghavachari80b] (note that the basis sets for P, S, and Cl are those called negative ion basis sets by McLean and Chandler; these were deemed to give better results for neutral molecules as well), the basis set of Blaudeau and coworkers for Ca and K [Blaudeau97], the Wachters-Hay [Wachters70, Hay77] all electron basis set for the first transition row, using the scaling factors of Raghavachari and Trucks [Raghavachari89], and the 6-311G basis set of McGrath, Curtiss and coworkers for the other elements in the third row [Binning90, McGrath91, Curtiss95]. Note that Raghavachari and Trucks recommend both scaling and including diffuse functions when using the Wachters-Hay basis set for first transition row elements; the 6-311+G form must be specified to include the diffuse functions. MC-311G is a synonym for 6-311G. D95V: Dunning/Huzinaga valence double-zeta [Dunning76]. D95: Dunning/Huzinaga full double zeta [Dunning76]. SHC: D95V on first row, Goddard/Smedley ECP on second row [Dunning76, Rappe81]. Also known as SEC. CEP-4G: Stevens/Basch/Krauss ECP minimal basis [Stevens84, Stevens92, Cundari93]. CEP-31G: Stevens/Basch/Krauss ECP split valance [Stevens84, Stevens92, Cundari93]. CEP-121G: Stevens/Basch/Krauss ECP triple-split basis [Stevens84, Stevens92, Cundari93]. Note that there is only one CEP basis set defined beyond the second row, and all three keywords are equivalent for these atoms. LanL2MB: STO-3G [Hehre69, Collins76] on first row, Los Alamos ECP plus MBS on Na-La, Hf-Bi [Hay85, Wadt85, Hay85a]. LanL2DZ: D95V on first row [Dunning76], Los Alamos ECP plus DZ on Na-La, Hf-Bi [Hay85, Wadt85, Hay85a]. SDD: D95 up to Ar [Dunning76] and Stuttgart/Dresden ECPs on the remainder of the periodic table [Fuentealba82, Szentpaly82,
SDD: D95 up to Ar [Dunning76] and Stuttgart/Dresden ECPs on the remainder of the periodic table [Fuentealba82, Szentpaly82,
Fuentealba83, Stoll84, Fuentealba85, Wedig86, Dolg87, Igel-Mann88, Dolg89, Schwerdtfeger89, Dolg89a, Andrae90, Dolg91, Kaupp91, Kuechle91, Dolg92, Bergner93, Dolg93, Haeussermann93, Dolg93a, Kuechle94, Nicklass95, Leininger96, Cao01, Cao02].
The SDD, SHF, SDF, MHF, MDF, MWB forms may be used to specify these basis sets/potentials within Gen basis input. Note that the number of core electrons must be specified following the form (e.g., MDF28 for the MDF potential replacing 28 core electrons). SDDAll: Selects Stuttgart potentials for Z > 2. cc-pVDZ, cc-pVTZ, cc-pVQZ, cc-pV5Z, cc-pV6Z: Dunnings correlation consistent basis sets [Dunning89, Kendall92, Woon93, Peterson94, Wilson96] (double, triple, quadruple, quintuple-zeta and sextuple-zeta, respectively). These basis sets have had redundant functions removed and have been rotated [Davidson96] in order to increase computational efficiency. These basis sets include polarization functions by definition. The following table lists the valence polarization functions present for the various atoms included in these basis sets: Atoms H He Li-Be B-Ne Na-Ar Ca Sc-Zn Ga-Kr cc-pVDZ 2s,1p 2s,1p 3s,2p,1d 3s,2p,1d 4s,3p,1d 5s,4p,2d 6s,5p,3d, 1f 5s,4p,2d cc-pVTZ 3s,2p,1d 3s,2p,1d 4s,3p,2d,1f 4s,3p,2d,1f 5s,4p,2d,1f 6s,5p,3d,1f 7s,6p,4d,2f,1g 6s,5p,3d,1f cc-pVQZ 4s,3p,2d,1f 4s,3p,2d,1f 5s,4p,3d,2f,1g 5s,4p,3d,2f,1g 6s,5p,3d,2f,1g 7s,6p,4d,2f,1g 8s,7p,5d,3f,2g,1h 7s,6p,4d,2f,1g cc-pV5Z 5s,4p,3d,2f,1g 5s,4p,3d,2f,1g 6s,5p,4d,3f,2g,1h 6s,5p,4d,3f,2g,1h 7s,6p,4d,3f,2g,1h 8s,7p,5d,3f,2g,1h 9s,8p,6d,4f,3g,2h,1i 8s,7p,5d,3f,2g,1h cc-pV6Z 6s,5p,4d,3f,2g,1h not available not available 7s,6p,5d,4f,3g,2h,1i not available not available not available not available
These basis sets may be augmented with diffuse functions by adding the AUG- prefix to the basis set keyword (rather than using the + and ++ notationsee below). SV, SVP, TZV, TZVP [Schaefer92, Schaefer94], QZVP [Weigend05] of Ahlrichs and coworkers. MIDI! of Truhlar and coworkers [Easton96]. The MidiX keyword is used to request this basis set. EPR-II and EPR-III: The basis sets of Barone [Barone96a] which are optimized for the computation of hyperfine coupling constants by DFT methods (particularly B3LYP). EPR-II is a double zeta basis set with a single set of polarization functions and an enhanced s part: (6,1)/[4,1] for H and (10,5,1)/[6,2,1] for B to F. EPR-III is a triple-zeta basis set including diffuse functions, double d-polarizations and a single set of f-polarization functions. Also in this case the s-part is improved to better describe the nuclear region: (6,2)/[4,2] for H and (11,7,2,1)/[7,4,2,1] for B to F. UGBS: The universal Gaussian basis set of de Castro, Jorge and coworkers [Silver78, Silver78a, Mohallem86, Mohallem87, daCosta87, daSilva89, Jorge97, Jorge97a, deCastro98]. Additional polarization functions may be added by including a suffix to this keyword: U B nP V O GS || where n is an integer indicating whether to add 1, 2 or 3 polarization functions for each function in the normal UGBS basis set. The second item is a code letter indicating which function should be augmented polarization functions: P adds them to all functions, V adds them to all valence functions, and O requests the scheme used in Gaussian 03 (see below). For example, the UGBS1P keyword requests this basis set with one additional polarization function to all orbitals, and UGBS2V adds two additional polarization function to all valence orbitals. The O suffix adds the same functions as the UGBSnP keywords in Gaussian 03. UGBS1O adds a p function for each s, a d function for each p, and so on; UGBS2O adds a p and d function for each s, a d and f function for each p, and UGBS3O adds a p, d and f for each s, etc. Diffuse functions may be added as usual with + or ++; the first of these may be specified as 2+ to add two diffuse functions for heavy atoms. MTSmall of Martin and de Oliveira, defined as part of their W1 method (see the W1U keyword) [Martin99]. The DGDZVP, DGDZVP2 and DGTZVP basis sets used in DGauss [Godbout92, Sosa92]. CBSB7: Selects the 6-311G(2d,d,p) basis set used by CBS-QB3 high accuracy energy method [Montgomery99]. The notation specifies two additional d polarization functions on second rows atoms, one d function on first row atoms and a p function on hydrogens (note that this three-field polarization function syntax is not supported by Gaussian 09).
functions and one set of f functions on heavy atoms, and supplemented by 2 sets of p functions on hydrogens. When the AUG- prefix is used to add diffuse functions to the cc-pVxZ basis sets, one diffuse function of each function type in use for a given atom is added [Kendall92, Woon93]. For example, the AUG-cc-pVTZ basis places one s, one d, and one p diffuse functions on hydrogen atoms, and one d, one p, one d, and one f diffuse functions on B through Ne and Al through Ar. Adding a single polarization function to 6-311G (i.e. 6-311G(d)) will result in one d function for first and second row atoms and one f function for first transition row atoms, since d functions are already present for the valence electrons in the latter. Similarly, adding a diffuse function to the 6-311G basis set will produce one s, one p, and one d diffuse functions for third-row atoms. When a frozen core calculation is done using the D95 basis, both the occupied core orbitals and the corresponding virtual orbitals are frozen. Thus while a D95** calculation on water has 26 basis functions, and a 6-31G** calculation on the same system has 25 functions, there will be 24 orbitals used in a frozen core post-SCF calculation involving either basis set. The following table lists polarization and diffuse function availability and the range of applicability for each built-in basis set in Gaussian 09: Basis Set 3-21G 6-21G 4-31G 6-31G 6-311G D95 D95V SHC CEP-4G CEP-31G CEP-121G LanL2MB LanL2DZ SDD, SDDAll cc-pVDZ cc-pVTZ cc-pVQZ cc-pV5Z cc-pV6Z SV SVP TZV and TZVP QZVP MidiX EPR-II, EPRIII UGBS MTSmall DGDZVP DGDZVP2 DGTZVP CBSB7 Applies to H-Xe H-Cl H-Ne H-Kr H-Kr H-Cl except Na and Mg H-Ne H-Cl H-Rn H-Rn H-Rn H-La, Hf-Bi H, Li-La, Hf-Bi all but Fr and Ra H-Ar, Ca-Kr H-Ar, Ca-Kr H-Ar, Ca-Kr H-Ar, Ca-Kr H, B-Ne H-Kr H-Kr H-Kr H-Rn H, C-F, S-Cl, I, Br H, B, C, N, O, F H-Lr H-Ar H-Xe H-F, Al-Ar, Sc-Zn H, C-F, Al-Ar H-Kr included in definition +,++ included in definition included in definition included in definition included in definition included in definition included in definition included in definition included in definition included in definition included in definition UGBS(1,2,3)P +,++,2+,2++ added via AUG- prefix (H-Ar, Sc-Kr) added via AUG- prefix (H-Ar, Sc-Kr) added via AUG- prefix(H-Ar, Sc-Kr) added via AUG- prefix (H-Na, Al-Ar ScKr) added via AUG- prefix (H, B-O) Polarization Functions * or ** * or ** through (3df,3pd) through (3df,3pd) through (3df,3pd) (d) or (d,p) * * (Li-Ar only) * (Li-Ar only) * (Li-Ar only) +,++ +,++ +,++ +,++ Diffuse Functions +
STO-3G and 3-21G accept a * suffix, but this does not actually add any polarization functions.
Other basis sets may also be input to the program using the ExtraBasis and Gen keywords. The ChkBasis keyword indicates that the basis set is to read from the checkpoint file (defined via the %Chk command). See the individual descriptions of these keywords later in this chapter for details.