The
structural phase stabilities of iron disulfide (FeS2),
titanium dioxide (TiO2), and polymorphs of manganese
oxides (MnO2) are known to be challenging problems for
the semilocal exchange-correlation (xc) approximations of the Density
Functional Theory. Popular and nonempirical semilocal xc functionals
fail badly for at least one of these solids. For example, the strongly
constrained and appropriately normed (SCAN) meta-GGA xc functional
fails to predict the correct ground state for FeS2 (pyrite
and marcasite polymorphs) and TiO2 (rutile and anatase
polymorphs) structures but yields accurate formation energies and
the correct ground state of all MnO2 polymorphs. In this
work, we find that the recently proposed meta-GGA constructed from
the cuspless hydrogen exchange hole density (MGGAC) [Phys.
Rev. B
2019, 100, 155140] can
predict the correct ground state of polymorphs of FeS2,
TiO2, and MnO2. Moreover, when compared to the
experimental results, we also obtain the quantitatively good agreement
from the MGGAC functional for the structural properties and bandgaps
of those solids, and this agreement indicates the feasibility of this
method.
The exchange hole, which is one of the principal constituents of the density functional formalism, can be used to design accurate range-separated hybrid functionals in association with appropriate correlation. In this regard, the exchange hole derived from the density matrix expansion has gained attention due to its fulfillment of some of the desired exact constraints. Thus, the new long-range corrected density functional proposed here combines the meta generalized gradient approximation level exchange functional designed from the density matrix expansion based exchange hole coupled with the ab initio Hartree-Fock exchange through the range separation of the Coulomb interaction operator using the standard error function technique. Then, in association with the Lee-Yang-Parr correlation functional, the assessment and benchmarking of the above newly constructed range-separated functional with various well-known test sets shows its reasonable performance for a broad range of molecular properties, such as thermochemistry, non-covalent interaction and barrier heights of the chemical reactions.
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