Fully relativistic pseudopotentials

Fully relativistic pseudopotentials generated by the MBK (PRB 47, 6728 (1993)) scheme within LDA (CA19) and GGA (PBE19) which contain a partial core correction and fully relativistic effects including spin-orbit coupling.


• Li_CA19.vps
• Li_PBE19.vps

Pseudo-atomic orbitals

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 dimer, and a LiO molecule. The input files used for the orbital optimization can be found at Li_opt.dat , Li2_opt.dat , and LiO_opt.dat . Since Li_CA19.vps and Li_PBE19.vps include the 1s and 2s states (3 electrons) as the valence states, the minimal basis set is Li*.*-s2. Our recommendation for the choice of cutoff radius of basis functions is that Li8.0.pao is enough for bulks, but Li10.0.pao or Li12.0.pao is preferable for molecular systems.


• Li8.0.pao
• Li10.0.pao
• Li12.0.pao

Benchmark calculations by the PBE19 pseudopotential with the various basis functions

(1) Calculation of the total energy as a function of lattice constant in the bcc 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 Li8.0-s3p2 and Li8.0-s3p3d2 in the total energy at the minimum point is 0.013 eV/atom. An input file used for the OpenMX calculations can be found at Libcc-EvsV.dat . For comparison the result by the Wien2k code is also shown, where the calculation was performed by default setting in the Ver. 10.1 of Wien2k except for the use of R_MT x K_MAX of 12.



(2) Calculations of the band dispersion in the bcc structure, where the non-spin polarized collinear calculation with the lattice constant of 3.491 Ang. was performed using Li_PBE19.vps, Li8.0-s3p2, and Li8.0-s3p3d2, 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 Libcc-Band.dat . For comparison the result by the Wien2k code is also shown, where the calculation was performed by default setting in the Ver. 10.1 of Wien2k except for the use of R_MT x K_MAX of 12.



(3) Calculations of the total energy as a function of lattice constant of LiCl in the rock salt 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 Cl7.0-s2p2d1 and Cl7.0-s3p3d2 in the total energy at the minimum point is 0.0112 eV/atom, where Li8.0-s3p2d1 was used as basis functions for Li for both the cases. An input file used for the OpenMX calculations can be found at LiCl-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 R_MT x K_MAX of 12.




(4) Calculations of the band dispersion of LiCl in the rock salt structure, where the non-spin polarized collinear calculation with the lattice constant of 5.106 Ang. was performed using Li_PBE.vps, Cl_PBE19.vps, Li8.0-s3p2d1, and Cl7.0-s2p2d1, and the origin of the energy is taken to be the top of the valence band. The input file used for the OpenMX calculations can be found at LiCl-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 R_MT x K_MAX of 12.





(5) Calculations of a lithium dimer molecule, where Li_PBE19.vps, Li10.0-s3p2, and Li10.0-s3p3d2 were used. The input files used for the OpenMX calculations can be found at Li2.dat , Li_1.dat , Li_2.dat , Li_cp1.dat , and Li_cp2.dat ,


	Equilibrium bond length (Ang.)	Atomization energy (kcal/mol)	Atomization energy (couterpoise corrected) (kcal/mol)
Li10.0-s3p2	2.741	20.1	19.8
Li10.0-s3p3d2	2.731	20.4	20.1
Other calc.	2.730a	19.9b
Expt.	2.673c	24.4d

^a M.M. Odashima and and K. Capelle, J. Chem. Theory Comput. 5 798 (2009).
^b S. Kurth et al., Int. J. of Quantum Chem. 75, 889 (1999).
^c K.P. Huber and G. Herzberg, Constants of Diatomic Molecules (Van Nostrand Reinhold, New York, 1979).
^d J.P. Perdew, K. Burke, and M. Ernzerhof, Phys. Rev. Lett. 77, 3865 (1996).

Supplementary information for the GGA (PBE19) pseudopotential