Simultaneous Determination of Structures, Vibrations, and Frontier Orbital Energies from a Self-Consistent Range-Separated Hybrid Functional.
A self-consistent optimally tuned range-separated hybrid density functional (scOT-RSH) approach is developed. It can simultaneously predict accurate geometries, vibrational modes, and frontier orbital energies. This is achieved by optimizing the range-separation parameter, γ, to both satisfy the ionization energy theorem and minimize interatomic forces. We benchmark our approach against an established hybrid functional, B3LYP, using the G2 test set. scOT-RSH greatly improves the accuracy of occupied frontier orbital energies, with a mean absolute error (MAE) of only 0.2 eV relative to experimental ionization energies compared to 2.96 eV with B3LYP. Geometries do not change significantly compared to those obtained from B3LYP, with a bond length MAE of 0.012 Å compared to 0.008 Å for B3LYP, and a 6.5% MAE for zero-point energies, slightly larger than that of B3LYP (3.1%). scOT-RSH represents a new paradigm in which accurate geometries and ionization energies can be predicted simultaneously from a single functional approach.
†Department of Physics, University of Ontario Institute of Technology, Oshawa, Ontario L1H 7K4, Canada.
Isaac
I
Tamblyn
‡Department of Materials and Interfaces, Weizmann Institute of Science, Rehovoth 76100, Israel.
Sivan
S
Refaely-Abramson
¶Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.|§Department of Physics, University of California, Berkeley, California 94720, United States.|∥Kavli Energy Nanosciences Institute at Berkeley, Berkeley, California 94720, United States.
Jeffrey B
JB
Neaton
‡Department of Materials and Interfaces, Weizmann Institute of Science, Rehovoth 76100, Israel.
Leeor
L
Kronik
density functional theory; ionization energy; optimal tuning; range-separated hybrid functionals; structural optimization; zero-point energy