




basis sets for one and twocomponent
calculations with gatchina smallcore shapeconsistent
relativistic pseudopotentials
a.a.rusakov, a.zaitsevskii









The following Gaussian basis sets are to be used with
the semilocal (radially local) version of relativistic pseudopotentials
developed by the PNPI quantum chemistry group
(N.S. Mosyagin, A.N. Petrov, A.V. Titov, and I.I. Tupitsyn,
Progr. Theor. Chem. Phys.,
B 15, 229251 (2006),
http://www.qchem.pnpi.spb.ru/recp).
These pseudopotentials correspond to small (60 and 92 electrons for sixth and seventh row
elements respectively) atomic cores and are optimized to reproduce "valence" shells
(n1)d ns np.
The procedure used to generate the correlation consisted basis sets
for onecomponent relativistic calculations was
essentially that described in [K.A. Peterson, C. Puzzarini,
Theor. Chem. Acc. 114, 283296 (2005)]; moreover, exponential parameters for
relatively diffuse and highangularmomentum functions for sixthrow elements were taken
from the cited work and [K.A. Peterson, J. Chem. Phys. 119, 11099 (2003)].
The bases for one and twocomponent RDFT calculations and
the pseupotential parameters are provided as well. The twocomponent RDFTspecific Gaussian basis sets
were constructed employing a multistep optimization procedure,
including optimization of both exponents and contraction
coefficients. The calculations employed
twocomponent SCF calculations (either HartreeFock or DFT).
Optimization of the inner of s, p, and d subsets
was performed at the atomic level.
The exponents of outermost s, p, and d functions, as well as
polarization f functions were optimized,
to make the resulting basis set flexible enough
to account for various types of the chemical environment.
This was achieved by minimizing the sum of molecular energies
for the pool of molecules including those with different bond types.





