PMID- 25429927
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20150611
LR  - 20141128
IS  - 1089-7690 (Electronic)
IS  - 0021-9606 (Linking)
VI  - 141
IP  - 20
DP  - 2014 Nov 28
TI  - Towards improved local hybrid functionals by calibration of exchange-energy 
      densities.
PG  - 204101
LID - 10.1063/1.4901238 [doi]
AB  - A new approach for the calibration of (semi-)local and exact exchange-energy 
      densities in the context of local hybrid functionals is reported. The calibration 
      functions are derived from only the electron density and its spatial derivatives, 
      avoiding spatial derivatives of the exact-exchange energy density or other 
      computationally unfavorable contributions. The calibration functions fulfill the 
      seven more important out of nine known exact constraints. It is shown that 
      calibration improves substantially the definition of a non-dynamical correlation 
      energy term for generalized gradient approximation (GGA)-based local hybrids. 
      Moreover, gauge artifacts in the potential-energy curves of noble-gas dimers may 
      be corrected by calibration. The developed calibration functions are then 
      evaluated for a large range of energy-related properties (atomization energies, 
      reaction barriers, ionization potentials, electron affinities, and total atomic 
      energies) of three sets of local hybrids, using a simple one-parameter 
      local-mixing. The functionals are based on (a) local spin-density approximation 
      (LSDA) or (b) Perdew-Burke-Ernzerhof (PBE) exchange and correlation, and on (c) 
      Becke-88 (B88) exchange and Lee-Yang-Parr (LYP) correlation. While the 
      uncalibrated GGA-based functionals usually provide very poor thermochemical data, 
      calibration allows a dramatic improvement, accompanied by only a small 
      deterioration of reaction barriers. In particular, an optimized BLYP-based 
      local-hybrid functional has been found that is a substantial improvement over the 
      underlying global hybrids, as well as over previously reported LSDA-based local 
      hybrids. It is expected that the present calibration approach will pave the way 
      towards new generations of more accurate hyper-GGA functionals based on a local 
      mixing of exchange-energy densities.
FAU - Arbuznikov, Alexei V
AU  - Arbuznikov AV
AD  - Institut fur Chemie, Technische Universitat Berlin, Theoretische Chemie, Sekr. 
      C7, Strasse des 17. Juni 135, D-10623 Berlin, Germany.
FAU - Kaupp, Martin
AU  - Kaupp M
AD  - Institut fur Chemie, Technische Universitat Berlin, Theoretische Chemie, Sekr. 
      C7, Strasse des 17. Juni 135, D-10623 Berlin, Germany.
LA  - eng
PT  - Journal Article
PL  - United States
TA  - J Chem Phys
JT  - The Journal of chemical physics
JID - 0375360
EDAT- 2014/11/29 06:00
MHDA- 2014/11/29 06:01
CRDT- 2014/11/29 06:00
PHST- 2014/11/29 06:00 [entrez]
PHST- 2014/11/29 06:00 [pubmed]
PHST- 2014/11/29 06:01 [medline]
AID - 10.1063/1.4901238 [doi]
PST - ppublish
SO  - J Chem Phys. 2014 Nov 28;141(20):204101. doi: 10.1063/1.4901238.