Why is the dual descriptor a more accurate local reactivity descriptor than Fukui functions?

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• 作者：Jorge Ignacio Martínez-Araya
• 关键词：Dual descriptor ; Nucleophilic Fukui function ; Electrophilic Fukui function ; Local reactivity descriptor
• 刊名：Journal of Mathematical Chemistry
• 出版年：2015
• 出版时间：February 2015
• 年：2015
• 卷：53
• 期：2
• 页码：451-465
• 全文大小：1,799 KB
• 参考文献：1. C. Morell, A. Grand, A. Toro-Labbé, New dual descriptor for chemical reactivity. J. Phys. Chem. A 109, 205-12 (2005) CrossRef
  2. C. Morell, A. Grand, A. Toro-Labbé, Theoretical support for using the \(\Delta f(\mathbf{r})\) descriptor. Chem. Phys. Lett. 425, 342-46 (2006) CrossRef
  3. R.G. Parr, W. Yang, / Density-Functional Theory of Atoms and Molecules (Oxford University Press, New York, 1989)
  4. P. Geerlings, F. De Proft, W. Langenaeker, Conceptual density functional theory. Chem. Rev. 103, 1793-874 (2003) CrossRef
  5. H. Chermette, Density functional theory: a powerful tool for theoretical studies in coordination chemistry. Coord. Chem. Rev. 178-80 Part 1, 699-21 (1998).
  6. H. Chermette, Chemical reactivity indexes in density functional theory. J. Comput. Chem. 20, 129-54 (1999) CrossRef
  7. P.A. Johnson, L.J. Bartolotti, P.W. Ayers, T. Fievez, P. Geerlings, hemical density and chemical reactions: a unified view from conceptual DFT, in / Modern Charge-Density Analysis, chapter 21, ed. by C. Gatti, P. Macchi (Springer, New York, 2012), pp. 715-64
  8. C. Cárdenas, N. Rabi, P.W. Ayers, C. Morell, P. Jaramillo, P. Fuentealba, Chemical reactivity descriptors for ambiphilic reagents: dual descriptor, local hypersoftness, and electrostatic potential. J. Phys. Chem. A 113, 8660-667 (2009) CrossRef
  9. P.W. Ayers, C. Morell, F. De Proft, P. Geerlings, Understanding the Woodward-Hoffmann rules by using changes in electron density. Chem. Eur. J. 13, 8240-247 (2007) CrossRef
  10. C. Morell, P.W. Ayers, A. Grand, S. Gutiérrez-Oliva, A. Toro-Labbé, Rationalization of Diels-Alder reactions through the use of the dual reactivity descriptor \(\Delta f(\mathbf{r})\) . Phys. Chem. Chem. Phys. 10, 7239-246 (2008) CrossRef
  11. C. Morell, A. Hocquet, A. Grand, B. Jamart-Grégoire, A conceptual DFT study of hydrazino peptides: assessment of the nucleophilicity of the nitrogen atoms by means of the dual descriptor \(\Delta f(\mathbf{r})\) . J. Mol. Struct. THEOCHEM 849, 46-1 (2008) CrossRef
  12. J.I. Martínez, J.L. Moncada, J.M. Larenas, The dual descriptor to measure local reactivity on Buckminster fullerenes: an analysis within the framework of conceptual DFT. J. Mol. Model. 16, 1825-832 (2010) CrossRef
  13. J. Martínez, V. Cruz, J. Ramos, S. Gutiérrez-Oliva, J. Martínez-Salazar, A. Toro-Labbé, On the nature of the active site in bis(imino)pyridyl iron, a catalyst for olefin polymerization. J. Phys. Chem. C 112, 5023-028 (2008) CrossRef
  14. J.I. Martínez-Araya, Revisiting caffeate’s capabilities as a complexation agent to silver cation in mining processes by means of the dual descriptor: a conceptual DFT approach. J. Mol. Model. 18, 4299-307 (2012) CrossRef
  15. J.I. Martínez-Araya, Explaining reaction mechanisms using the dual descriptor: a complementary tool to the molecular electrostatic potential. J. M
• 作者单位：Jorge Ignacio Martínez-Araya (1) (2)
  
  1. Departamento de Ciencias Químicas, Facultad de Ciencias Exactas, Universidad Andres Bello, Avenida República 275, Santiago, Chile
  2. Dirección de Postgrado e Investigación, Sede Providencia, Universidad Autónoma de Chile, Carlos Antúnez 1920, Código Postal 7500566, Providencia-Santiago, Chile
  
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Physical Chemistry
  Theoretical and Computational Chemistry
  Mathematical Applications in Chemistry
  
• 出版者：Springer Netherlands
• ISSN：1572-8897

文摘

A mathematical analysis reveals that dual descriptor is a more accurate tool than nucleophilic and electrophilic Fukui functions. Although Fukui function has the capability of revealing nucleophilic and electrophilic regions on a molecule, the dual descriptor is able to unambiguously expose truly nucleophilic and electrophilic regions, but along with the latter, dual descriptor is less affected by the lack of relaxation terms than the Fukui function when the frontier molecular orbital approximation is applied. This implies that the dual descriptor can be considered a more reliable descriptor to measure local reactivity than Fukui function. This statement is demonstrated in the present work.