Mod:Hunt Research Group/orca6 PPs
Contents
Using Multiple Built-in Basis Sets in One File
This section explains how to use different basis sets for different elements in ORCA and also to add pseudopotentials on heavy elements. Below is a file for methyl iodide (CH3I) where the def2SVP basis set is used for all elements and the def2-ECP is used for iodine. The main basis set (def2-SVP) has been defined in the route line starting with a ! while specific basis sets can be mentioned in the %basis block. Remember to put an 'end' to each line in the block and and 'end' for %basis as well. Instead of using "RIJCOSX def2/J def2-SVP/C" for the auxiliary basis set, you can use the keyword "AutoAux" without the quotes to let ORCA determine the best auxiliary basis set automatically. NoAutoStart keyword tells ORCA not to use any previously present .gbw file to read info. If this keyword is not there, and a .gbw file exists in the folder with the input file, ORCA will try to read MOs and other information from that file.
%MaxCore 1000 %pal nprocs 16 end # Optimization of CH3I !B3LYP NoAutoStart TightSCF def2-SVP RIJCOSX def2/J def2-SVP/C %basis NewECP I "def2-ECP" end # Define ECP for Iodine atom end * xyz 0 1 C 0.00000000 0.00000000 -1.79947500 H 0.00000000 1.03191700 -2.12804700 H -0.89366600 -0.51595800 -2.12804700 H 0.89366600 -0.51595800 -2.12804700 I 0.00000000 0.00000000 0.32417000 *
Keywords for ECPs
It is important to note here that there are certain keywords for ECP's as given in ORCA 6.0 manual (Table 4.3 on page 46). You can call those ECPs (pseudopotentials) with those specific keywords. Some of those keywords are copied below:
Pseudopotential Keyword def2-XVP def2-ECP aug-cc-pVnZ SK-MCDHF-RSC LANL2DZ HayWadt
Similarly, to use a different basis set for a heavy element (I in our case), we have to request it in %basis block with NewGTO keyword. We have to use the Auxiliary basis set for this as well with NewAuxCGTO. See the below example of CH3I where the aug-cc-pVTZ basis set has been used for all the elements and the aug-cc-pVTZ-PP basis set has been used for iodine. Similarly, the ECP also needs to be requested for iodine that is aug-cc-pVTZ-PP and requested via the keyword SK-MCDHF-RSC here.
%MaxCore 1000 %pal nprocs 16 end # Optimization of CH3I !B3LYP NoAutoStart TightSCF aug-cc-pVTZ RIJCOSX aug-cc-pVTZ/C %basis NewGTO I "aug-cc-pVTZ-PP" end NewAuxCGTO I "aug-cc-pVTZ-PP/C" end NewECP I "SK-MCDHF-RSC" end end * xyz 0 1 C 0.00000000 0.00000000 -1.79947500 H 0.00000000 1.03191700 -2.12804700 H -0.89366600 -0.51595800 -2.12804700 H 0.89366600 -0.51595800 -2.12804700 I 0.00000000 0.00000000 0.32417000 *
Keyword to Print the Basis Set in the output File
The keyword to print the basis set in ORCA output file is PrintBasis. It has been used in the custom basis set example below.
Using a Custom Basis Set in ORCA
In ORCA we can also use a custom basis set from an external source like basissetexchange. For that we can use the following format by requesting NewGTO in the %basis block. Below example shows a basis set request for Carbon.
NewGTO C ''Copy basis set here from basissetexchange'' end
In the example below for a CH3I molecule, the calculation requests aug-cc-pVTZ for Carbon and Hydrogen, aug-cc-pVTZ-PP basis set for Iodine, and the associated pseudopotential for Iodine via NewECP keyword.
%MaxCore 1000 %pal nprocs 16 end # CCSD(T) Single Point Energy of CH3I !DLPNO-CCSD(T) NoAutoStart TightSCF TightPNO AutoAux printbasis %basis NewGTO C S 10 1 8.236000E+03 5.310000E-04 2 1.235000E+03 4.108000E-03 3 2.808000E+02 2.108700E-02 4 7.927000E+01 8.185300E-02 5 2.559000E+01 2.348170E-01 6 8.997000E+00 4.344010E-01 7 3.319000E+00 3.461290E-01 8 9.059000E-01 3.937800E-02 9 3.643000E-01 -8.983000E-03 10 1.285000E-01 2.385000E-03 S 1 1 9.059000E-01 1.000000E+00 S 10 1 8.236000E+03 -1.130000E-04 2 1.235000E+03 -8.780000E-04 3 2.808000E+02 -4.540000E-03 4 7.927000E+01 -1.813300E-02 5 2.559000E+01 -5.576000E-02 6 8.997000E+00 -1.268950E-01 7 3.319000E+00 -1.703520E-01 8 9.059000E-01 1.403820E-01 9 3.643000E-01 5.986840E-01 10 1.285000E-01 3.953890E-01 S 1 1 1.285000E-01 1.000000E+00 S 1 1 0.0440200 1.0000000 P 1 1 3.827000E-01 1.000000E+00 P 5 1 1.871000E+01 1.403100E-02 2 4.133000E+00 8.686600E-02 3 1.200000E+00 2.902160E-01 4 3.827000E-01 5.010080E-01 5 1.209000E-01 3.434060E-01 P 1 1 1.209000E-01 1.000000E+00 P 1 1 0.0356900 1.0000000 D 1 1 1.097000E+00 1.000000E+00 D 1 1 3.180000E-01 1.000000E+00 D 1 1 0.1000000 1.0000000 F 1 1 7.610000E-01 1.0000000 F 1 1 0.2680000 1.0000000 end NewGTO H S 1 1 3.258000E-01 1.000000E+00 S 5 1 3.387000E+01 6.068000E-03 2 5.095000E+00 4.530800E-02 3 1.159000E+00 2.028220E-01 4 3.258000E-01 5.039030E-01 5 1.027000E-01 3.834210E-01 S 1 1 1.027000E-01 1.000000E+00 S 1 1 0.0252600 1.0000000 P 1 1 1.407000E+00 1.000000E+00 P 1 1 3.880000E-01 1.000000E+00 P 1 1 0.1020000 1.0000000 D 1 1 1.057000E+00 1.0000000 D 1 1 0.2470000 1.0000000 end NewGTO I S 11 1 5.546500E+03 1.560000E-04 2 8.382140E+02 9.860000E-04 3 1.821870E+02 2.792000E-03 4 3.121230E+01 -4.325100E-02 5 1.953140E+01 2.341340E-01 6 8.240990E+00 -7.509430E-01 7 2.194550E+00 8.829680E-01 8 1.109110E+00 4.620610E-01 9 3.746410E-01 2.228600E-02 10 1.770800E-01 -4.353000E-03 11 8.106100E-02 1.102000E-03 S 1 1 3.746410E-01 1.000000E+00 S 1 1 1.770800E-01 1.000000E+00 S 11 1 5.546500E+03 -7.300000E-05 2 8.382140E+02 -5.080000E-04 3 1.821870E+02 -1.158000E-03 4 3.121230E+01 1.219300E-02 5 1.953140E+01 -8.785400E-02 6 8.240990E+00 3.382000E-01 7 2.194550E+00 -5.765500E-01 8 1.109110E+00 -4.092980E-01 9 3.746410E-01 5.674590E-01 10 1.770800E-01 6.124890E-01 11 8.106100E-02 1.432310E-01 S 1 1 1.001000E-01 1.000000E+00 S 1 1 4.120000E-02 1.0000000 P 9 1 1.889880E+02 5.850000E-04 2 2.128680E+01 3.692300E-02 3 1.003960E+01 -2.353240E-01 4 3.451800E+00 3.414830E-01 5 1.974560E+00 5.347880E-01 6 1.024200E+00 2.651410E-01 7 4.494370E-01 2.578700E-02 8 1.866480E-01 5.220000E-04 9 7.348100E-02 6.060000E-04 P 1 1 5.981000E-01 1.000000E+00 P 9 1 1.889880E+02 -2.560000E-04 2 2.128680E+01 -1.168200E-02 3 1.003960E+01 8.319200E-02 4 3.451800E+00 -1.569700E-01 5 1.974560E+00 -2.245180E-01 6 1.024200E+00 -1.144510E-01 7 4.494370E-01 3.753560E-01 8 1.866480E-01 5.751360E-01 9 7.348100E-02 2.459170E-01 P 1 1 9.618000E-02 1.000000E+00 P 1 1 3.590000E-02 1.0000000 D 9 1 1.326620E+02 5.720000E-04 2 3.760540E+01 4.402000E-03 3 1.038910E+01 -4.092200E-02 4 6.490170E+00 9.966100E-02 5 3.454510E+00 3.226630E-01 6 1.844130E+00 4.003430E-01 7 9.624780E-01 2.683060E-01 8 4.728530E-01 8.484700E-02 9 1.932000E-01 7.632000E-03 D 1 1 4.728530E-01 1.000000E+00 D 1 1 1.932000E-01 1.000000E+00 D 1 1 7.820000E-02 1.0000000 F 1 1 4.064000E-01 1.000000E+00 F 1 1 1.848000E-01 1.0000000 end NewAuxCGTO I "aug-cc-pVTZ-PP/C" end NewECP I N_core 28 lmax g s 3 1 40.03337600 49.98964900 2 2 17.30057600 281.00655600 2 3 8.85172000 61.41673900 2 p 4 1 15.72014100 67.41623900 2 2 15.20822200 134.80769600 2 3 8.29418600 14.56654800 2 4 7.75394900 28.96842200 2 d 4 1 13.81775100 35.53875600 2 2 13.58780500 53.33975900 2 3 6.94763000 9.71646600 2 4 6.96009900 14.97750000 2 f 4 1 18.52295000 -20.17661800 2 2 18.25103500 -26.08807700 2 3 7.55790100 -0.22043400 2 4 7.59740400 -0.22164600 2 g 1 1 1.00000000 0.00000000 2 end end * xyz 0 1 C 0.00000000 0.00000000 -1.79947500 H 0.00000000 1.03191700 -2.12804700 H -0.89366600 -0.51595800 -2.12804700 H 0.89366600 -0.51595800 -2.12804700 I 0.00000000 0.00000000 0.32417000 *
