A Theoretical and Computational Analysis of Linear Free Energy Relations for the Estimation of Activation Energies
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- 作者：Jonathan E. Sutton ; Dionisios G. Vlachos
- 刊名：ACS Catalysis
- 出版年：2012
- 出版时间：August 3, 2012
- 年：2012
- 卷：2
- 期：8
- 页码：1624-1634
- 全文大小：422K
- 年卷期：v.2,no.8(August 3, 2012)
- ISSN：2155-5435
文摘
We present a theoretical and computational analysis to elucidate the relation of the Br酶nsted鈥揈vans鈥揚olanyi (BEP) and transition state scaling (TSS) correlations. We find that the TSS correlation is an approximation of the BEP correlation. The BEP correlation allows for the straightforward identification of homologous series via standard statistical tests and has better error properties than the TSS correlations. We find that the unit cell size used in the DFT calculations does not have a significant effect on the correlation parameters; however, the zero point energy correction does have a significant effect on the correlation parameters, especially for (de)hydrogenation reactions. We propose a method for using this information to estimate zero-point-energy-corrected activation energies without resorting to calculations of the zero point energy correction for every species. Finally, we find that BEP correlations derived for one parent molecule may be applicable to other molecules beyond the training set.