Density Functional Theory activation energies

Sun, Y. and Chen, H. (2014) Performance of density functionals for activation energies of Re-catalyzed organic reactions. /. Chem. Theory Comput, 10, 579-588. 

Assuming that substituted Sb at the surface may work as catalytic active site as well as W, First-principles density functional theory (DFT) calculations were performed with Becke-Perdew [7, 9] functional to evaluate the binding energy between p-xylene and catalyst. Scalar relativistic effects were treated with the energy-consistent pseudo-potentials for W and Sb. However, the binding strength with p-xylene is much weaker for Sb (0.6 eV) than for W (2.4 eV), as shown in Fig. 4. 

The interaction of carbon disulfide as a substrate in carbonic anhydrase model systems has been studied using density functional theory methods. A higher activation energy of CS2 compared to C02 in the reaction with [L3ZnOH]+ was due to the reduced electrophilicity of CS2. The reversibility of the reaction on the basis of these calculations is questionable with [L3ZnSC(0)SH]+ as intermediate.572... 

Fan, L. and T. Ziegler. 1992. Nonlocal Density Functional Theory as a Practical Tool in Calculations on Transition States and Activation Energies. Applications to Elementary Reaction Steps in Organic Chemistry. J. Am. Chem. Soc. 114, 10890. 

Ab initio Hartree-Fock and density functional theory (DFT) calculations were performed to study transition geometries in the intramolecular hetero-Diels-Alder cycloaddition reactions of azoalkenes 20 (LJ = CH2, NFI, O) (Equation 1). The order of the reactivities was predicted from frontier orbital energies. DFT calculations of the activation energies at the B3LYP level were in full agreement with the experimental results described in the literature <2001JST(535)165>. 

Quantum mechanical approaches have been successfully used to predict hydrogen abstraction potentials and likely sites of metabolism of drug molecules [78-81]. AMI, Fukui functions, and density functional theory calculations could identify potential sites of metabolism. Activation energies for hydrogen abstraction were calculated by Olsen et al. [81] to be below 80 kj/mol, suggesting most CH groups can be metabolized which particular one depends on steric accessibility and intrinsic reactivities. 

Development of methods related to DFT that can treat this situation accurately is an active area of research where considerable progress is being made. Two representative examples of this kind of work are P. Rinke, A. Qteish, J. Neugebauer, and M. Scheffler, Exciting Prospects for Solids Exact Exchange Based Functional Meet Quasiparticle Energy Calculations, Phys. Stat. Sol. 245 (2008), 929, and J. Uddin, J. E. Peralta, and G. E. Scuseria, Density Functional Theory Study of Bulk Platinum Monoxide, Phys. Rev. B, 71 (2005), 155112. 

Jursic (92) studied the cycloaddition reaction of a mtinchnone with acetylene from several theoretical standpoints using density functional theory on AMI geometries. The predicted activation energy for the 1,3-dipolar cycloaddition is 11.49 kcal/mol and the elimination of carbon dioxide from the cycloadduct to give a pyrrole is 5.82 kcal/mol. Both reactions are extremely exothermic as observed experimentally. 

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