Density functional theory catalytic reaction rate

Numerous quantum mechanic calculations have been carried out to better understand the bonding of nitrogen oxide on transition metal surfaces. For instance, the group of Sautet et al have reported a comparative density-functional theory (DFT) study of the chemisorption and dissociation of NO molecules on the close-packed (111), the more open (100), and the stepped (511) surfaces of palladium and rhodium to estimate both energetics and kinetics of the reaction pathways [75], The structure sensitivity of the adsorption was found to correlate well with catalytic activity, as estimated from the calculated dissociation rate constants at 300 K. The latter were found to agree with numerous experimental observations, with (111) facets rather inactive towards NO dissociation and stepped surfaces far more active, and to follow the sequence Rh(100) > terraces in Rh(511) > steps in Rh(511) > steps in Pd(511) > Rh(lll) > Pd(100) > terraces in Pd (511) > Pd (111). The effect of the steps on activity was found to be clearly favorable on the Pd(511) surface but unfavorable on the Rh(511) surface, perhaps explaining the difference in activity between the two metals. The influence of... 

Dinuclear complexes of trans- and cis-geometry (trans-complexes are more thermodynamically stable) have the ArZ-Pd-ZAr structural unit, which is needed to operate in the catalytic cycle. The observed rate constant of the addition reaction of PhsSes to alkyne was linearly dependent on the concentration of dinuclear complexes [Pd(SePh)4(PPh3)2] [108]. Theoretical study at the density functional theory level has shown that alkyne insertion in the dinuclear complex preferentially involves the terminal ZAr group rather than the bridging ZAr group coordinated in mode [112]. A deficiency of the phosphine ligand under catalytic conditions resulted in rapid... 

Rate constants can be estimated by means of transition-state theory. In principle all thermodynamic data can be deduced from the partion function. The molecular data necessary for the calculation of the partion function can be either obtained from quantum mechanical calculations or spectroscopic data. Many of those data can be found in tables (e.g. JANAF). A very powerful tool to study the kinetics of reactions in heterogeneous catalysis is the dynamic Monte-Carlo approach (DMC), sometimes called kinetic Monte-Carlo (KMC). Starting from a paper by Ziff et al. [16], several investigations were executed by this method. Lombardo and Bell [17] review many of these simulations. The solution of the problem of the relation between a Monte-Carlo step and real time has been advanced considerably by Jansen [18,19] and Lukkien et al. [20] (see also Jansen and Lukkien [21]). First principle quantum chemical methods have advanced to the stage where they can now offer quantitative predictions of structure and energetics for adsorbates on surfaces. Cluster and periodic density functional quantum chemical methods are used to analyze chemisorption and catalytic surface reactivity [see e.g. 24,25]. 

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