Development of Novel Density Functionals for Thermochemical Kinetics

Abstract

A new density functional theory (DFT) exchange-correlation functional for the exploration of reaction mechanisms is proposed. This new functional, denoted BMK (Boese-Martin for Kinetics), has an accuracy in the 2 kcal/mol range for transition state barriers but, unlike previous attempts at such a functional, this improved accuracy does not come at the expense of equilibrium properties. This makes it a general-purpose functional whose domain of applicability has been extended to transition states, rather than a specialized functional for kinetics. The improvement in BMK rests on the inclusion of the kinetic energy density together with a large value of the exact exchange mixing coefficient. For this functional, the kinetic energy density appears to correct `back' the excess exact exchange mixing for ground-state properties, possibly simulating variable exchange.

J. Chem. Phys., in press (303431JCP, scheduled for August 15, 2004 issue); supplementary data available at http://theochem.weizmann.ac.il/web/papers/BMK.html

References in corpus (11)

• Climbing the Density Functional Ladder: Non-Empirical Meta-Generalized Gradient Approximation Designed for Molecules and Solids
• Correlation consistent valence basis sets for use with the Stuttgart-Dresden-Bonn relativistic effective core potentials: the atoms Ga-Kr and In-Xe
• Towards standard methods for benchmark quality ab initio thermochemistry --- W1 and W2 theory
• W3 theory: robust computational thermochemistry in the kJ/mol accuracy range
• Assessment of W1 and W2 theories for the computation of electron affinities, ionization potentials, heats of formation, and proton affinities
• The Role of the Basis Set: Assessing Density Functional Theory
• Benchmark {\em ab initio} energy profiles for the gas-phase S${}_N$2 reactions Y${}^{-}$ + CH${}_3$X $\to$ CH${}_3$Y + X${}^{-}$ (X,Y = F,Cl,Br). Validation of hybrid DFT methods
• From ab initio quantum chemistry to molecular dynamics: The delicate case of hydrogen bonding in ammonia
• Vibrational Spectra of the Azabenzenes Revisited: Anharmonic Force Fields
• Anharmonic force field and vibrational frequencies of tetrafluoromethane (CF${}_4$) and tetrafluorosilane (SiF${}_4$)
• A fully ab initio quartic force field of spectroscopic quality for SO_3

Cited by in corpus (37)

• Computer Modeling of Halogen Bonds and Other $\sigma$-Hole Interactions
• Libxc: a library of exchange and correlation functionals for density functional theory
• How accurate is density functional theory at predicting dipole moments? An assessment using a new database of 200 benchmark values
• A general framework for scintillation in nanophotonics
• Empirical Double-Hybrid Density Functional Theory: A 'Third Way' In Between WFT and DFT
• Performance of ab initio and density functional methods for conformational equilibria of CnH2n+2 alkane isomers (n=2-8)
• Benchmark thermochemistry of the C_nH_{2n+2} alkane isomers (n=2--8) and performance of DFT and composite ab initio methods for dispersion-driven isomeric equilibria
• Delocalization errors in density functional theory are essentially quadratic in fractional occupation number
• Long-range corrected hybrid meta-generalized-gradient approximations with dispersion corrections
• What types of chemical problems benefit from density-corrected DFT? A probe using an extensive and chemically diverse test suite
• Recent achievements in ab initio modelling of liquid water
• Assessment of Various Density Functionals and Basis Sets for the Calculation of Molecular Anharmonic Force Fields
• Anharmonic force fields and thermodynamic functions using density functional theory
• Assessing Excited State Energy Gaps with Time-Dependent Density Functional Theory on Ru(II) Complexes
• Atomization energies of the carbon clusters Cn (n=2--10) revisited by means of W4 theory as well as density functional, Gn, and CBS methods
• Density Functional Theory for Electronic Excited States
• Choosing a density functional for static molecular polarizabilities
• Basis set effects on the hyperpolarizability of CHCl_3: Gaussian-type orbitals, numerical basis sets and real-space grids
• Benefits of Range-separated Hybrid and Double-Hybrid Functionals for a Large and Diverse Dataset of Reaction Energies and Barrier Heights
• Construction of a general semilocal exchange-correlation hole model: Application to nonempirical meta-GGA functionals
• Third order Møller-Plesset theory made more useful? The role of density functional theory orbitals
• Double-hybrid density-functional theory with meta-generalized-gradient approximations
• Short- and long-range corrected hybrid density functionals with the D3 dispersion corrections
• Some Observations on the Performance of the Most Recent Exchange-Correlation Functionals for the Large and Chemically Diverse GMTKN55 Benchmark
• Grappa -- A Machine Learned Molecular Mechanics Force Field
• Reference CC3 Excitation Energies for Organic Chromophores: Benchmarking TD-DFT, BSE/$GW$ and Wave Function Methods
• Reproducibility of density functional approximations: how new functionals should be reported
• Accurate non-empirical range-separated hybrid van der Waals density functional for complex molecular problems, solids, and surfaces
• Canonical and DLPNO-based composite wavefunction methods parametrized against large and chemically diverse training sets. 2. Correlation consistent basis sets, core-valence correlation, and F12 alternatives
• Revisiting fundamental properties of TiO${}_2$ nanoclusters as condensation seeds in astrophysical environments
• Analytical harmonic vibrational frequencies with VV10-containing density functionals: Theory, efficient implementation, and benchmark assessments
• On the sensitivity of computed partial charges toward basis set and (exchange-)correlation treatment
• Using Electronegativity and Hardness to Test Density Functional Universality
• In-Depth Exploration of Catalytic Sites on Amorphous Solid Water: I. The Astrosynthesis of Aminomethanol
• Density functional benchmark for quadruple hydrogen bonds
• Pathways to Interstellar Amides via Carbamoyl (NH2CO) Isomers by Radical-Neutral Reactions on Ice Grain Mantles
• Revisiting the performance of time-dependent density functional theory for electronic excitations: Assessment of 43 popular and recently developed functionals from rungs one to four