Hartree–Fock orbitals significantly improve the reaction barrier heights predicted by semilocal density functionals

Janesko, Benjamin G.; Scuseria, Gustavo E.

doi:10.1063/1.2940738

Cited by 110 publications

(130 citation statements)

References 51 publications

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“…This is also true for other functionals like B2PLYP and BHandHLYP, thus further confirming the role of HF exchange in determining reaction barriers. 23,63,64 At the same time, B1LYP and B3LYP provide significantly high deviations, in contrast with the results obtained for the PT reaction database. Stable in the ranking are the PBE0-DH and ωB97D functionals, both providing comparable deviations (see Table 4).…”

Section: Resultscontrasting

confidence: 80%

DFT and Proton Transfer Reactions: A Benchmark Study on Structure and Kinetics

Mangiatordi

Brémond

Adamo

2012

J. Chem. Theory Comput.

117

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A significant number of different exchange correlation functionals, ranging from generalized gradient approximations to double hybrids, has been tested on a difficult playground represented by proton transfer reactions. In order to have a complete picture of their performances, both energetics and structural features have been compared and the obtained ranking compared with those issued from the standard test for kinetics (i.e., the DBH24/08 set). Among all of the functionals, the ωB97X, BMK, B1LYP, and PBE0-DH approaches are those providing a good error balance on all four trials. Beyond these figures, the obtained results allow for some general considerations, such as those on the role of Hartree-Fock exchange in reaction barriers or the relation between structure and energetics.

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Section: Resultscontrasting

confidence: 80%

DFT and Proton Transfer Reactions: A Benchmark Study on Structure and Kinetics

Mangiatordi

Brémond

Adamo

2012

J. Chem. Theory Comput.

117

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“…In particular, HF‐DFT is a nonvariational method that uses density from the SCF calculations with HF and computes a post‐HF correction using a GGA functional of BLYP or PBE . Indeed, there are early attempts along this line …”

Section: Theorymentioning

confidence: 99%

Analytic derivatives for the XYG3 type of doubly hybrid density functionals: Theory, implementation, and assessment

Zhang

2013

J Comput Chem

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We present a theoretical development of the equations required to perform an analytic geometry optimization of a molecular system using the XYG3 type of doubly hybrid (xDH) functionals. In contrast to the well-established B2PLYP type of DH functionals, the energy expressions in the xDH functionals are constructed by using density and orbital information from another standard Kohn-Sham (KS) functional (e.g., B3LYP) for doing the self-consistent field calculations. Thus, the xDH functionals are nonvariational in both the hybrid density functional part and the second-order perturbation part, each of which requires formally to solve a coupled-perturbed KS equation. An implementation is reported here which combines the two parts by defining a total Lagrangian such that only a single set of the Z-vector equations need to be solved. The computational cost with our implementation is of the same order as those for the conventional Møller-Plesset theory to the second order (MP2) and B2PLYP. Systematic test calculations are provided for covalently bonded molecules as well as compounds involving the intramolecular nonbonded interactions for the main group elements. Satisfactory performance of the xDH functionals demonstrates that the extra computer time on top of the conventional KS procedure is well-invested, in particular, when the standard KS functionals and MP2 as well, are problematic.

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“…The clear improvement in the CDFT-CI barrier heights can be traced to two sources. First, we note that a large fraction of the error in DFT barrier height predictions is known to arise from electron self-interaction error (SIE) [115,116]. Because the constraints force the electrons to localize in every underlying diabatic state, the effects of SIE on the CDFT-CI results are mitigated [62,64], improving the barrier heights.…”

Section: Explicit Solventmentioning

confidence: 99%

The Diabatic Picture of Electron Transfer, Reaction Barriers, and Molecular Dynamics

Voorhis

Kowalczyk

Kaduk

et al. 2010

Annu. Rev. Phys. Chem.

296

367

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Diabatic states have a long history in chemistry, beginning with early valence bond pictures of molecular bonding and stretching through the construction of model potential energy surfaces to the modern proliferation of methods for computing these elusive states. In this review we summarize the basic principles that define the diabatic basis and demonstrate how they can be applied in the specific context of constrained density functional theory. Using illustrative examples from electron transfer and chemical reactions, we show how the diabatic picture can be used to extract qualitative insight and quantitative predictions about energy landscapes. The review closes with a brief resumé of the challenges and prospects for the further application of diabatic states in chemistry.

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Hartree–Fock orbitals significantly improve the reaction barrier heights predicted by semilocal density functionals

Cited by 110 publications

References 51 publications

DFT and Proton Transfer Reactions: A Benchmark Study on Structure and Kinetics

DFT and Proton Transfer Reactions: A Benchmark Study on Structure and Kinetics

Analytic derivatives for the XYG3 type of doubly hybrid density functionals: Theory, implementation, and assessment

The Diabatic Picture of Electron Transfer, Reaction Barriers, and Molecular Dynamics

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