$BASIS group (optional) This group allows certain standard basis sets to be easily requested. Basis sets are specified by: a) GBASIS plus optional supplementations such as NDFUNC, b) BASNAM to read custom basis sets from your input, c) EXTFIL to read custom bases from an external file, d) or omit this group entirely, and give the basis set in the $DATA input, which is completely general. GBASIS requests various Gaussian basis sets. These include options for effective core and model core potentials. Rather oddly, GBASIS also can select semi-empirical models, and in that case requests the Slater-type orbitals for the MOPAC-type calculation. Note: The first two groups of GBASIS keywords below (except G3L and G3LX) define only the basic functions, without any polarization functions and/or diffuse functions. For example, main group elements have the basic functions for their s,p valence orbitals. Polarization and/or diffuse supplements are added separately to these GBASIS values, with keywords NPFUNC, NDFUNC, NFFUNC, DIFFS, DIFFSP, POLAR, SPLIT2, and SPLIT3, which are defined at the end of this input group. GBASIS = STO - Pople's STO-NG minimal basis set. Available H-Xe, for NGAUSS=2,3,4,5,6. = N21 - Pople's N-21G split valence basis set. Available H-Xe, for NGAUSS=3. Available H-Ar, for NGAUSS=6. = N31 - Pople's N-31G split valence basis set. Available H-Ne,P-Cl for NGAUSS=4. Available H-He,C-F for NGAUSS=5. Available H-Kr, for NGAUSS=6, note that the bases for K,Ca,Ga-Kr were changed 9/2006. = N311 - Pople's "triple split" N-311G basis set. Available H-Ne, for NGAUSS=6. Selecting N311 implies MC for Na-Ar. = G3L - Pople's G3MP2Large basis set, for H-Kr. = G3LX - Pople's G3MP2LargeXP basis set, for H-Kr. NGAUSS = the number of Gaussians (N). This parameter pertains to GBASIS=STO, N21, N31, or N311. GBASIS = MINI - Huzinaga's 3 gaussian minimal basis set. Available H-Rn. = MIDI - Huzinaga's 21 split valence basis set. Available H-Rn. = DZV - "double zeta valence" basis set. a synonym for DH for H,Li,Be-Ne,Al-Cl. (14s,9p,3d)/[5s,3p,1d] for K-Ca. (14s,11p,5d/[6s,4p,1d] for Ga-Kr. = DH - Dunning/Hay "double zeta" basis set. (3s)/[2s] for H. (9s,4p)/[3s,2p] for Li. (9s,5p)/[3s,2p] for Be-Ne. (11s,7p)/[6s,4p] for Al-Cl. = TZV - "triple zeta valence" basis set. (5s)/[3s] for H. (10s,3p)/[4s,3p] for Li. (10s,6p)/[5s,3p] for Be-Ne. a synonym for MC for Na-Ar. (14s,9p)/[8s,4p] for K-Ca. (14s,11p,6d)/[10s,8p,3d] for Sc-Zn. = MC - McLean/Chandler "triple split" basis. (12s,9p)/[6s,5p] for Na-Ar. Selecting MC implies 6-311G for H-Ne. = MINIX The minimal basis set for HF-3C, but no energy corrections added. = HF-3C The minimal basis set MINIX and three add-on energy corrections (3c). These three corrections are D3(BJ), GCP and SRB. See $DFT's dispersion corrections. * * systematic basis set families * * * These four families provide a hierachy of basis sets approaching the complete basis set limits. These families include relevant polarization and diffuse augmentations, as indicated in their names. GBASIS = CCn - Dunning-type Correlation Consistent basis sets, officially called cc-pVnZ. Use n = D,T,Q,5,6 to indicate the level of polarization. Available for H-He, Li-Ne, Na-Ar, Ca, Ga-Kr and for Sc-Zn for n=T,Q. = ACCn - As CCn, but augmented with a set of diffuse functions, e.g. aug-cc-pVnZ. Availability is the same as CCn. = CCnC - As CCn, but augmented with tight functions for recovering core and core-valence correlation, e.g. cc-pCVnZ. Available H-Ar for n=D,T,Q, also n=5 for H-Ne. = ACCnC- As CCn, augmented with diffuse as well as CCnC's tight functions, e.g. aug-cc-pCVnZ. Availability is the same as CCnC. = CCnWC the omega form of CCnC, e.g. cc-pwCVnZ, for H-Ar, for n=T only. CCnWC's tight functions are considered superior to CCnC's for recovery of core/valence correlation. = ACCnWC augmented form of CCnWC: aug-cc-pwCVnZ. See extended notes below! = PCseg-n - Polarization Consistent basis sets. n = 0,1,2,3,4 indicates the level of polarization. (n=0 is unpolarized, n=1 is ~DZP, n=2 is ~TZ2P, etc.). These provide a hierarchy of basis sets suitable for DFT and HF calculations. Available for H-Kr. = APCseg-n - These are the PCseg-n bases, with diffuse augmentation. See extended notes below! Sapporo valence basis sets: = SPK-nZP - Sapporo family of non-relativistic bases, n=D,T,Q, available H-Xe = SPK-AnZP - diffuse augmentation of the above. = SPKrnZP - Sapporo family of relativistic bases n=D,T,Q, available H-Xe. These should be used only with a relativistic transformation of the integrals, such as RELWFN=LUT-IOTC. = SPKrAnZP - diffuse augmentation of the above. See extended notes below! Sapporo core/valence basis sets: = SPK-nZC - Sapporo family of non-relativistic bases, n=D,T,Q, available H-Xe = SPK-nZCD - diffuse augmentation of the above. = SPKrnZC - Sapporo family of relativistic bases n=D,T,Q, available H-Rn. To be used only with a relativistic transformation of the integrals, such as RELWFN=LUT-IOTC. = SPKrnZCD - diffuse augmentation of the above. See extended notes below! = KTZV - Karlsruhe valence triple zeta basis, as developed by Prof.Ahlrichs, see REFS.DOC. = KTZVP- Karlsruhe valence triple zeta basis with a set of single polarization (P). = KTZVPP-Karlsruhe valence triple zeta basis with a set of double polarization (PP). The Karlsruhe sets are provided for H-Ar. Normally these families are used as spherical harmonics, see ISPHER=1 in $CONTRL. Failure to set ISPHER=1 will result in discrepancies in energy values compared to the literature or other programs, difficulties in converging SCF/DFT, CC, CI, and/or response equation iterations, and longer run times due to retention of unimportant MOs. The calculations will refuse to run without ISPHER being set. Important note about the PCseg basis set family: 1. These should be used only in spherical harmonic form. 2. The PCn basis sets included in GAMESS versions prior to March 2014 were generally contracted, but were replaced by computationally more efficient segmented contractions, and renamed to PCseg-n. The segemented contractions have the same or slightly better accuracy (especially for n=0) as the original PCn bases, which are no longer available. Important notes about the CC basis set family: 1. These should be used only in spherical harmonic form. 2. The CC5 and CC6 basis sets (and corresponding augmented versions) contain h-functions, and CC6 also contains i- functions. As of January 2013, GAMESS integral code can correctly use h & i functions, so these three call up the true basis sets. Prior to January 2013, GAMESS' integral codes was restricted to g-functions, so these three truncated away any h & i functions, to spdfg subsets, and therefore were not the true basis sets. 3. Note that the CC basis sets are generally contracted, which GAMESS can only handle by replicating the primitive basis functions, leading to a less than optimum performance in AO integral evaluation. 4. The implementation of the cc-pVnZ and cc-pCVnZ basis sets for Na-Ar include one additional tight d-function, producing the so-called cc-pV(n+d)Z and cc-pV(n+d)Z sets, which are known to improve results (see J.Chem.Phys. 114, 9244(2001) and Theoret.Chem.Acc. 120, 119(2008)). These tight d versions are invoked by GBASIS=CCn or CCnC (and also their augmented counterparts ACCn or ACC). This means the old (and less accurate) basis sets without the tight d's are not available for Na-Ar. 5. Alkali and alkali earth basis sets (Li,Be,Na,Mg) were changed April 2013 so that regular, diffuse, tight d (for Na/Mg), core/valence, and weighted core/valence sets agree with their official publication: Theor. Chem. Acc. 128, 69(2011). 6. In case you are interested in scalar relativistic effects, the CCT-DK and CCQ-DK sets optimized for use with Douglas/Kroll are available for Sc-Kr. These will be used if you type GBASIS=CCT or CCQ along with RELWFN=RESC, DK, IOTC, or LUT-IOTC, while using NR sets for elements lighter than Sc. DK versions of ACCD or ACCT are available for Sc- Zn (but not for the rest of the row, Ga-Kr). Notes about the Sapporo basis set family: 1. SPK is the international airport city code for Sapporo. 2. These should be used only in spherical harmonic form. 3. The relativistic core/valence sets are available for all atoms including the 6th row of the periodic table (H-Rn). 4. It is extremely illogical to use any of the all-electron relativistic bases without turning on scalar relativity! So, choose RELWFN=LUT-IOTC (or IOTC, DK, RESC) in $CONTRL. 5. The core/valence basis sets treat (n-1)s,(n-1)p,ns for s-block elements; (n-1)s,(n-1)p,ns,np for p block elements; (n-1)s,(n-1)p,(n-1)d,ns for d block elements, and the 4s- 4f,5s-5d,6s for f block (lanthanides). This suggests you should change the default number of core orbitals, such as NACORE in $MP2 or NCORE in $CCINP, to correlate the indicated semi-core orbitals (this is not automatic). 6. The relativistic sets ("r") are identical to the non- relativistic choices ("-") for atoms H-Ar, where scalar relativity has almost no effect on orbital shapes. 7. The relativistic bases were optimized at the 3rd order of the Douglas-Kroll transformation, with a Gaussian nuclei model. It should be fine to use them with any RESC, DK, IOTC, or LUT-IOTC calculation. 8. Because they are stored in an external file supplied with GAMESS, these can only be accessed via GBASIS in this group, not by using them in-line in $DATA. 9. The SPK basis sets were extracted from the data base of Segmented Gaussian Basis Sets, maintained by Takeshi Noro, University of Hokkaido, Sapporo, Japan: http://setani.sci.hokudai.ac.jp/sapporo/Welcome.do The mapping between the data base names and the keywords used in GAMESS is (for n=D,T,Q): data base name keyword Sapporo-nZP SPK-nZP Sapporo-nZP+diffuse SPK-AnZP Sapporo-DK-nZP SPKrnZP Sapporo-DK-nZP+diffuse SPKrAnZP Sapporo-nZP-2012 SPK-nZC Sapporo-nZP-2012+diffuse SPK-nZCD Sapporo-DK-nZP-2012 SPKrnZC Sapporo-DK-nZP-2012+diffuse SPKrnZCD * * * Effective Core Potential (ECP) bases * * * GBASIS = SBKJC- Stevens/Basch/Krauss/Jasien/Cundari valence basis set, for Li-Rn. This choice implies an unscaled -31G basis for H-He. = HW - Hay/Wadt valence basis. This is a -21 split, available Na-Xe, except for the transition metals. This implies a 3-21G basis for H-Ne. * * * Model Core Potential (MCP) bases * * * Notes: Select PP=MCP in $CONTRL to automatically use the model core potential matching your basis choice below. References for these bases, and other information about MCPs can be found in the REFS.DOC chapter. Another family covering almost all elements is available in $DATA only. GBASIS = MCP-DZP, MCP-TZP, MCP-QZP - a family of double, triple, and quadruple zeta quality valence basis sets, which are akin to the correlation consistent sets, in that these include increasing levels of polarization (and so do not require "supplements" like NDFUNC or DIFFSP) and must be used as spherical harmonics (see ISPHER). Availability: MCP-DZP: 56 elements Z=3-88, except V-Zn, Y-Cd, La, Hf-Hg MCP-TZP, MCP-QZP: 85 elements Z=3-88, except La The basis sets for hydrogen atoms will be the corresponding Dunning's cc-pVNZ (N=D,T,Q). = MCP-ATZP, MCP-AQZP - MCP-TZP and MCP-QZP core potentials whose basis sets were augmented with diffuse functions Availability: same as for MCP-TZP, MCP-QZP = MCPCDZP, MCPCTZP, MCPCQZP - based on MCP-DZP, MCP-TZP, MCP-QZP, with core-valence functions provided for the alkali and alkaline earth atoms Na through Ra. = MCPACDZP, MCPACTZP, MCPACQZP - based on MCPCDZP, MCPCTZP, MCPCQZP, with core-valence functions provided for the alkali and alkaline earth atoms Na through Ra, and augmented with diffuse functions. The basis sets were extracted from the data base Segmented Gaussian Basis Sets, maintained by Takeshi Noro, Quantum Chemistry Group, Sapporo, Japan: http://setani.sci.hokudai.ac.jp/sapporo/Welcome.do The mapping between the data base names and the names used in GAMESS is data base name GAMESS keyword MCP/NOSeC-V-DZP MCP-DZP MCP/NOSeC-V-TZP MCP-TZP MCP/NOSeC-V-QZP MCP-QZP MCP/NOSeC-V-TZP+diffuse MCP-ATZP MCP/NOSeC-V-QZP+diffuse MCP-AQZP MCP/NOSeC-CV-DZP MCPCDZP MCP/NOSeC-CV-TZP MCPCTZP MCP/NOSeC-CV-QZP MCPCQZP MCP/NOSeC-CV-DZP+diffuse MCPACDZP MCP/NOSeC-CV-TZP+diffuse MCPACTZP MCP/NOSeC-CV-QZP+diffuse MCPACQZP GBASIS = IMCP-SR1 and IMCP-SR2 - valence basis sets to be used with the improved MCPs with scalar relativistic effects. These are available for transition metals except La, and the main group elements B-Ne, P-Ar, Ge, Kr, Sb, Xe, Rn. The 1 and 2 refer to addition of first and second polarization shells, so again don't use any of the "supplements" and do use spherical harmonics. = IMCP-NR1 and IMCP-NR2 - closely related valence basis sets, but with nonrelativistic model core potentials. GBASIS = ZFK3-DK3, ZFK4-DK3, ZFK5-DK3, or ZFK3LDK3, ZFK4LDK3, ZFK5LDK3 These are a family of model core potential basis sets developed by Zeng/Fedorov/Klobukowski, for the p-block elements from 2p to 6p. The potentials were paramaterized taking into account both DK3 scalar relativistic and DK-SOC effects. The fundamental basis functions are from the Well-Tempered Basis Sets. The number after ZFK indicates the augmentation levels, e.g. ZFK3 means the diffuse functions from aug-cc-pVTZ are added, ZFK4 means from aug- cc-pVQZ, etc. The difference between ZFKn-DK3 and ZFKnLDK3 is that the common s and p exponents have been contracted as a single L-shell for the outermost s and p valence shells to save time in the "L" case. The s-block elements from 1s to 4s have also been put in the library. For H/He, all-electron aug-cc-pVnZ basis sets are used. For Li/Be, the relativistically contracted atomic natural orbital all- electron basis sets (ANO-RCC) are used. For Na/Mg, and K/Ca, unpublished MCP and basis sets based on ANO-RCC are available, although the potentials have not been extensively tested yet. No d-block elements can be used. * * * semiempirical basis sets * * * GBASIS = MNDO - selects MNDO model Hamiltonian = AM1 - selects AM1 model Hamiltonian = PM3 - selects PM3 model Hamiltonian = RM1 - selects RM1 model Hamiltonian = DFTB - selects tight binding Hamiltonian Note: The elements for which these exist can be found in the 'further information' section of this manual. If you pick one of these, all other data in this group is ignored. Semi-empirical runs actually use valence-only Slater type orbitals (STOs), not Gaussian GTOs, but the keyword remains GBASIS. Except for NGAUSS, all other keywords such as NDFUNC, etc. will be ignored for these. If you add NGAUSS, STO-NG expansions of the valence STO functions in terms of Gaussians will be added to the log file. Plotting programs such as MacMolPlt can pick up this approximation to the STOs used up from the ouput, in order to draw the orbitals. The default NGAUSS=0 suppresses this output, but values up to 6 may be given to control the accuracy of the STO-NG printing. --- supplementary functions --- NDFUNC = number of heavy atom polarization functions to be used. These are usually d functions, except for MINI/MIDI. The term "heavy" means Na on up when GBASIS=STO, HW, or N21, and from Li on up otherwise. The value may not exceed 3. The variable POLAR selects the actual exponents to be used, see also SPLIT2 and SPLIT3. (default=0) NFFUNC = number of heavy atom f type polarization functions to be used on Li-Cl. This may only be input as 0 or 1. (default=0) NPFUNC = number of light atom, p type polarization functions to be used on H-He. This may not exceed 3, see also POLAR. (default=0) DIFFSP = flag to add diffuse sp (L) shell to heavy atoms. Heavy means Li-F, Na-Cl, Ga-Br, In-I, Tl-At. The default is .FALSE. DIFFS = flag to add diffuse s shell to hydrogens. The default is .FALSE. Warning: if you use diffuse functions, please read QMTTOL in the $CONTRL input group for numerical concerns. POLAR = exponent of polarization functions = COMMON (default for GBASIS=STO,N21,HW,SBKJC) = POPN31 (default for GBASIS=N31) = POPN311 (default for GBASIS=N311, MC) = DUNNING (default for GBASIS=DH, DZV) = HUZINAGA (default for GBASIS=MINI, MIDI) = HONDO7 (default for GBASIS=TZV) SPLIT2 = an array of splitting factors used when NDFUNC or NPFUNC is 2. Default=2.0,0.5 SPLIT3 = an array of splitting factors used when NDFUNC or NPFUNC is 3. Default=4.00,1.00,0.25 The splitting factors are from the Pople school, and are probably too far apart. See for example the Binning and Curtiss paper. For example, the SPLIT2 value will usually cause an INCREASE over the 1d energy at the HF level for hydrocarbons. The actual exponents used for polarization functions, as well as for diffuse sp or s shells, are described in the 'Further References' section of this manual. This section also describes the sp part of the basis set chosen by GBASIS fully, with all references cited. Note that GAMESS always punches a full $DATA input group. Thus, if $BASIS does not quite cover the basis you want, you can obtain this full $DATA from EXETYP=CHECK, and then change polarization exponents, add Rydbergs, etc. * * * This may only be used with COORD=UNIQUE or HINT! BASNAM = an array of names of customized basis set input groups. BASNAM should obey the rule of no more than six characters starting with a letter names, and must avoid using any GBASIS string. However, the individual basis inputs can use any of the GBASIS sets by its standard name. Basis supplementations such as DIFFS or NDFUNC may only be given by explicit numerical values. This is best explained by an example where a core potential and valence-only basis set is used on a transition metal, but not its ligands: $contrl scftyp=rohf icharg=+3 mult=4 runtyp=gradient pp=read ispher=1 $end $system mwords=1 $end $guess guess=huckel $end $basis basnam(1)=metal, ligO,ligO,ligO,ligO,ligO,ligO, ligH,ligH,ligH,ligH,ligH,ligH, ligH,ligH,ligH,ligH,ligH,ligH $end $data Cr+3(H2O)6 complex...SBKJC & 6-31G(d) geometry Th CHROMIUM 24.0 .0000000000 .0 .0000000000 OXYGEN 8.0 .0000000000 .0 2.0398916104 HYDROGEN 1.0 .7757887450 .0 2.6122732372 $end ! core potential basis for Chromium $metal sbkjc $end ! normal 6-31G(d) for oxygen ligands $ligO n31 6 d 1 ; 1 0.8 1.0 $end ! unpolarized basis for hydrogens $ligH n31 6 $end $ecp Cr-ecp SBKJC O-ecp none ...snipped... there must be 6 O's given here O-ecp none H-ecp none ...snipped... there must be 12 H's given here H-ecp none $end * * * EXTFIL = a flag to read basis sets from an external file, defined by EXTBAS, rather than from $DATA. (default=.false.) It may be easier to use BASNAM to create custom basis sets! BASNAM has the bonus that your input file contains all information about the calculation, explicitly. Except for MCP basis sets, no external file is provided with GAMESS, thus you must create your own. The GBASIS keyword must give an 8 or less character string, obviously not using any internally stored names. Every atom must be defined in the external file by a line giving the chemical symbol, and this chosen string. Following this header line, give the basis in free format $DATA style, containing only S, P, D, F, G, and L shells, and terminating each atom by the usual blank line. The external file may have several families of bases in the same file, identified by different GBASIS strings. =========================================================== ==========================================================

generated on 7/7/2017