Semiempirical Methods for Predicting Thermodynamic Properties and Kinetic Parameters

7 SEMIEMPIRICAL METHODS FOR PREDICTING THERMODYNAMIC PROPERTIES AND KINETIC PARAMETERS 

Recently, semiempirical methods based on DFT calculations have been developed for catalyst screening. These methods include linear scaling relationships [41, 42] to transfer thermochemistry from one metal to another and Brpnsted-Evans-Polanyi (BEP) relationships [43 7]. Here, these methods and also methods for estimation of the surface entropy and heat capacity are briefly discussed. Because of their screening capabilities, semiempirical methods can be used to produce a first-pass microkinetic model. This first-pass model can then be refined using more detailed theory aided by analytical tools that identify key features of the model. The empirical bond-order conservation (BOC) method, which has shown good success in developing microkinetic models of small molecules, has recently been reviewed [11] and will not be covered here. 

Linear scaling relationships correlate the heat of adsorption of molecules with the heat of adsorption of a descriptor, generally of the heteroatom of the molecule. Abild-Pedersen et al. [41] observed that the heat of adsorption of AH fragments correlates 

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