Fully relativistic pseudopotentials generated by
the MBK (PRB 47, 6728 (1993)) scheme within LDA (CA13) and GGA (PBE13) which contain
a partial core correction and fully relativistic effects including spin-orbit coupling.
The number below the symbol means a cutoff radius (a.u.) of the confinement
potential. These file includes fifteen radial parts for each angular
momentum quantum number l (=0,1,2,3). The basis functions were generated by variationally
optimizing the corresponding primitive basis functions in the single atom, the CaO molecule,
and the FCC bulk. The input files used for the orbital optimization can be found at
Ca_opt.dat ,
CaO_opt.dat ,
and
Cafcc_opt.dat .
Since Ca_CA13.vps and Ca_PBE13.vps include the 3s, 3p, and 4s (10 electrons)
as the valence states, the minimal basis set is Ca*.*-s2p1.
Our recommendation for the choice of cutoff radius of basis functions is that
Ca9.0.pao is enough for bulks, but Ca11.0.pao or Ca13.0.pao is preferable
for molecular systems.
Benchmark calculations by the PBE13 pseudopotential with the various basis functions
(1) Calculation of the total energy as a function of lattice constant in the fcc structure,
where the total energy is plotted relative to the minimum energy for each case. a0
and B0 are the equilibrium lattice constant and bulk modulus obtained by fitting to
the Murnaghan equation of state. The difference between Ca9.0-s4p3d2 and Ca9.0-s4p3d3f1
in the total energy at the minimum point is 0.0044 eV/atom.
An input file used for the OpenMX calculations can be found at
Cafcc-EvsV.dat .
For comparison the result by the Wien2k code is also shown, where
the calculation was performed by default setting in the Ver. 9.1 of Wien2k except for
the use of RMT x KMAX of 12.
(2) Calculations of the band dispersion in the fcc structure,
where the non-spin polarized collinear calculation with the lattice constant of 5.580 Ang.
was performed using Ca_PBE13.vps and Ca9.0-s4p3d2,
and the origin of the energy is taken to be the Fermi level.
The input file used for the OpenMX calculations can be found at
Cafcc-Band.dat .
For comparison the result by the Wien2k code is also shown, where
the calculation was performed by default setting in the Ver. 9.1 of Wien2k
except for the use of RMT x KMAX of 12.
(3) Calculations of the CaO molecule with S=1,
where Ca_PBE13.vps, O_PBE13.vps, Ca11.0-s4p3d2, Ca11.0-s4p3d3f1, and
O6.0-s3p2d2 were used.
The input files used for the OpenMX calculations can be found at
CaO.dat ,
Ca_CP.dat ,
O_CP.dat ,
Ca.dat ,
and
O.dat ,
Equilibrium bond length (Ang.)
Atomization energy (eV)
Atomization energy (couterpoise corrected) (eV)
Ca11.0-s4p3d2, O6.0-s3p2d2
1.827
5.359
5.326
Ca11.0-s4p3d3f1, O6.0-s3p2d2
1.818
5.431
5.392
Other calc.
1.816 a
5.15 a
Expt.
1.822 b
>4.80 b
a H.J. Kulik and N. Marzaria, J. Chem. Phys. 133, 114103 (2010). b Taken from Ref. (a)
Supplementary information for the GGA (PBE13) pseudopotential
