B..3.4 New basis sets in the Molpro library

A number of new basis sets have been added to the Molpro library since version 2009.1. The references for these sets can be found in the headers of the respective libmol files.

Li, Be, Na, Mg:

a) New official versions of the correlation consistent basis sets for these elements have been added, both non-relativistic and those contracted for Douglas-Kroll relativistic calculations. Specifically these are:

cc-pVnZ (n=D-5) cc-pwCVnZ (n=D-5) aug-cc-pVnZ (n=D-5) aug-cc-pwCVnZ (n=D-5)

and the above with a -DK extension. The older cc-pVnZ basis sets for these elements can still be accessed via the keywords vdz-old, etc.

b) New basis sets, including RI and MP2 auxiliary sets, have been added for F12 explicit correlation calculations:

cc-pVnZ-F12 (n=D-Q) cc-pCVnZ-F12 (n=D-Q)

The optimized CABS auxiliary sets have the same name but with a /OptRI context

For MP2 and CCSD auxiliary sets, the cc-pVnZ/MP2FIT sets of Hättig can be used, but a new cc-pV5Z/MP2FIT set has been added that is optimal for the new cc-pV5Z basis set; new aug-cc-pVnZ/MP2FIT (n=D-5) sets have been added as well. The original cc-pV5Z/MP2FIT sets of Hättig have been renamed v5z-old/mp2fit.

Cu-Zn, Y-Cd, Hf-Hg:

a) While the aug-cc-pVnZ-PP (n=D-5) and cc-pwCVnZ-PP (n=D-5) sets were already available, the combination aug-cc-pwCVnZ-PP was not yet defined. These have now been added for these elements.

b) Triple-zeta DK sets have been included now for all of these elements. Unless otherwise noted, these were optimized for 2nd-order DKH. In the cases of Hf-Hg, sets contracted for 3rd-order DKH are also now included:

cc-pVTZ-DK cc-pwCVTZ-DK aug-cc-pVTZ-DK aug-cc-pwCVTZ-DK

and the above with -DK replaced by -DK3 for DKH3 calculations in the case of Hf-Hg.

H-He, B-Ne, Al-Ar, Ga-Kr:

a) A variety of DK contracted basis sets have been added for these elements:

aug-cc-pVnZ-DK (n=D-5) cc-pCVnZ-DK (n=D-5) cc-pwCVnZ-DK (n=D-5) aug-cc-pCVnZ-DK (n=D-5) aug-cc-pwCVnZ-DK (n=D-5)

b) Official cc-pCV6Z and aug-cc-pCV6Z are now also available for Al-Ar

c) For explicitly correlated calculations, the core-valence sets have been added:

cc-pCVnZ-F12 (n=D-Q) for B-Ne, Al-Ar cc-pCVnZ-F12/OptRI (n=D-Q) for B-Ne, Al-Ar

d) cc-pVnZ-F12/OptRI (n=D-Q) as also been added for He

Turbomole def2 basis sets:

The complete Turbomole def2 basis set family has been added to the Molpro basis library (for all elements H to Rn, except Lanthanides). The def2-orbital basis sets can now be accessed as SV(P), SVP, TZVP, TZVPP, QZVP and QZVPP. In this nomenclature SVP, TZVPP, and QZVPP correspond to valence double-zeta (VDZ), valence triple-zeta (VTZ) and valence quadruple-zeta (VQZ) basis sets, respectively.

Auxiliary density fitting basis sets for all elements are available as well (e.g., TZVPP/JFIT, TZVPP/JKFIT, TZVPP/MP2FIT) and are chosen automatically in density-fitted calculations. Supposedly, the JKFIT sets are universal and also applicable in combination with the AVnZ basis sets. Initial results indicate that they also work well with the cc-pVnZ-PP and aug-cc-pVnZ-PP series of basis sets.

The orbital basis sets can also be accessed in singly and doubly augmented versions (carrying A or DA prefixes, respectively, e.g., ASVP, DASVP), and the auxiliary fitting sets in singly augmented versions (e.g., ATZVPP/MP2FIT).

The old Turbomole basis sets have been renamed; if required, they can be accessed with a def1-prefix (e..g, def1-SVP, def1-TZVPP, etc.).

molpro@molpro.net 2018-09-19