# Development of density functionals for thermochemical kinetics.

@article{Boese2004DevelopmentOD, title={Development of density functionals for thermochemical kinetics.}, author={A. Daniel Boese and Jan M. L. Martin}, journal={The Journal of chemical physics}, year={2004}, volume={121 8}, pages={ 3405-16 } }

A density functional theory exchange-correlation functional for the exploration of reaction mechanisms is proposed. This 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… Expand

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#### References

SHOWING 1-10 OF 81 REFERENCES

A novel form for the exchange-correlation energy functional

- Physics
- 1998

A new approximate form for the exchange-correlation energy functional is developed. The form is based on the density matrix expansion (DME) for the exchange functional [R. M. Koehl, G. K. Odom, and… Expand

Density-functional thermochemistry. III. The role of exact exchange

- Chemistry
- 1993

Despite the remarkable thermochemical accuracy of Kohn–Sham density‐functional theories with gradient corrections for exchange‐correlation [see, for example, A. D. Becke, J. Chem. Phys. 96, 2155… Expand

Density-functional thermochemistry. V. Systematic optimization of exchange-correlation functionals

- Chemistry
- 1997

A systematic procedure for refining gradient corrections in Kohn–Sham exchange-correlation functionals is presented. The procedure is based on least-squares fitting to accurate thermochemical data.… Expand

Local hybrid functionals

- Chemistry
- 2003

We present a novel approach for constructing hybrid functionals by using a local mix of regular density functional theory (DFT) exchange and exact Hartree–Fock (HF) exchange. This local hybrid… Expand

The development of new exchange-correlation functionals

- Physics
- 1998

A procedure is presented for the possible systematic development of exchange-correlation functionals using ab initio electron densities and accurate total energies. For a training set of first row… Expand

Climbing the density functional ladder: nonempirical meta-generalized gradient approximation designed for molecules and solids.

- Physics, Medicine
- Physical review letters
- 2003

This work constructs a meta-GGA density functional for the exchange-correlation energy that satisfies exact constraints without empirical parameters, and describes both molecules and solids with high accuracy, as shown by extensive numerical tests. Expand

Density‐functional thermochemistry. IV. A new dynamical correlation functional and implications for exact‐exchange mixing

- Chemistry
- 1996

A new dynamical correlation functional is constructed subject to a small number of simple, yet key, requirements not all satisfied by existing functionals in the literature. The new functional gives… Expand

Exchange functionals with improved long-range behavior and adiabatic connection methods without adjustable parameters: The mPW and mPW1PW models

- Chemistry
- 1998

Starting from an analysis of the low-density and large gradient regions which dominate van der Waals interactions, we propose a modification of the exchange functional introduced by Perdew and Wang,… Expand

New generalized gradient approximation functionals

- Physics
- 2000

New generalized gradient approximation (GGA) functionals are reported, using the expansion form of A. D. Becke, J. Chem. Phys. 107, 8554 (1997), with 15 linear parameters. Our original such GGA… Expand

Development and assessment of new exchange-correlation functionals

- Chemistry
- 1998

We recently presented a new method for developing generalized gradient approximation (GGA) exchange-correlation energy functionals, using a least-squares procedure involving numerical… Expand