New density functionals with broad applicability for thermochemistry, thermochemical kinetics, noncovalent interactions, transition metals, and spectroscopy
Presenter
October 1, 2008
Keywords:
- Density
MSC:
- 11R45
Abstract
This lecture reports on work carried out in collaboration with
Yan Zhao.
We have developed a suite of density functionals. All four
functionals are accurate for noncovalent interactions and
medium-range correlation energy. The functional with broadest
capability, M06, is uniquely well suited for good performance
on both transition-metal and main group-chemistry; it also
gives good results for barrier heights. Another functional,
M06-L has no Hartree-Fock exchange, which allows for very fast
calculations on large systems, and it is especially good for
transition-metal chemistry and NMR chemical shieldings. M08-2X
and an earlier version, M06-2X, have the very best performance
for main-group thermochemistry, barrier heights, and
noncovalent interactions. M06-HF has no one-electron
self-interaction error and is the best functional for charge
transfer spectroscopy. A general characteristic of the whole
suite is the optimized inclusion of kinetic energy density and
higher separate accuracy of medium-range exchange and
correlation contributions with less cancellation of errors than
previous functionals [1-4]; for example, the functionals are
compatible with a range of Hartree-Fock exchange and, although
one or another of them may be more highly recommended for one
or another property or application, all four are better on
average than the very popular B3LYP functional. A few sample
applications, including catalytic systems [5,6] and
nanomaterials [7], will also be discussed. Recent work on
lattice constants, band gaps, and an improved version of M06-2X
will be summarized if time permits.
[1] "Design of Density Functionals by Combining the Method of
Constraint Satisfaction with Parametrization for
Thermochemistry, Thermochemical Kinetics, and Noncovalent
Interactions," Zhao, Y. ; Schultz, N. E.; Truhlar, D. G.; J.
Chem. Theory Comput. 2006, 2, 364-382.
[2] "A New Local Density Functional for Main Group
Thermochemistry, Transition Metal Bonding, Thermochemical
Kinetics, and Noncovalent Interactions," Zhao, Y.; Truhlar, D.
G. J. Chem. Phys. 2006, 125, 194101/1-18.
[3] “The M06 Suite of Density Functionals for Main Group
Thermochemistry, Thermochemical Kinetics, Noncovalent
Interactions, Excited States, and Transition Elements: Two New
Functionals and Systematic Testing of Four M06-Class
Functionals and 12 Other Functionals,” Zhao, Y.; Truhlar, D. G.
Theor. Chem. Acc. 2008, 120, 215-241.
[4] "Density Functionals with Broad Applicability in
Chemistry," Zhao, Y.; Truhlar, D. G. Acc. Chem. Res. 2008 41,
157-167.
[5] “Attractive Noncovalent Interactions in Grubbs
Second-Generation Ru Catalysts for Olefin Metathesis," Zhao,
Y.; Truhlar, D. G. Org. Lett. 2007, 9, 1967-1970.
[6] "Benchmark Data for Interactions in Zeolite Model Complexes
and Their Use for Assessment and Validation of Electronic
Structure Methods," Zhao, Y.; Truhlar, D. G. J. Phys. Chem. C
2008, 112, 6860-6868.
[7] "Size-Selective Supramolecular Chemistry in a Hydrocarbon
Nanoring," Zhao, Y.; Truhlar, D. G. J. Am. Chem. Soc.2007, 129,
8440-8442.