Solid-State Organic Chemistry at University of Kentucky

University of Kentucky | College of Pharmacy

Tonglei Li

analyze, compute & design
	solid-state organic/drug chemistry

Quantum mechanics (QM) is a major driving force for almost every scientific field in the 20th century. For the last two decades, density functional theory (DFT) has seen a dramatic surge in its own development and applications. With the highlight of the 1998 Nobel Prize to Kohn and Pople, applications of QM and DFT have become a routine practice not only for theoretical chemists, but also for bench scientists and engineers.

DFT claims that electronic energy is a functional of electron density. Accordingly, derivatives of the energy over electron density and external potential, which is defined by nucleus positions and charges, result in some insighful concepts, including Fukui function, hardness, softness, and electron chemical potential. These concepts can find their root in many classical theories. It is widely regarded that the hardness indicates a resistance to charge transfer, while the softness measures the ease of transfer and is associated with high polarizability. DFT-based concepts and their combinations have been discussed in many applications including molecular properties (electrophilicity, aromaticity, conformation, etc.), reactivity and catalysis, illustrating the theory that electron is the fundamental quantity for describing atomic and molecular ground states. What is the most valuable for this project is the proof of Pearson’s HSAB (hard and soft acids and bases) and the maximum hardness principles by the conceptual DFT. The HSAB principle states that hard acids prefer hard bases and soft acids prefer soft bases, thermodynamically and kinetically. The maximum hardness principle claims that molecular systems tend to states of high hardness. Nicely tightened to the classic principles from the electronic level, the DFT-defined hardness and softness have been shown to control the energy change of a molecular process.

Key References:

P. Hohenberg and W. Kohn (1964) Inhomogeneous Electron Gas, Physical Review B 136:864

W. Kohn, A. D. Becke, and R. G. Parr (1996) Density Functional Theory of Electronic Structure, Journal of Physical Chemistry 100:12974-12980

R. G. Parr and W. T. Yang (1995) Density-Functional Theory of the Electronic-Structure of Molecules, Annual Review of Physical Chemistry 46:701-728

P. Geerlings, F. De Proft, and W. Langenaeker (2003) Conceptual Density Functional Theory, Chemical Reviews 103:1793-1873

K. Fukui (1982) Role of Frontier Orbitals in Chemical-Reactions, Science 218:747-754

R. G. Parr and W. T. Yang (1984) Density Functional-Approach to the Frontier-Electron Theory of Chemical-Reactivity, Journal of the American Chemical Society 106:4049-4050

R. G. Parr, R. A. Donnelly, M. Levy, and W. E. Palke (1978) Electronegativity - Density Functional Viewpoint, Journal of Chemical Physics 68:3801-3807

F. De Proft, S. B. Liu, and P. Geerlings (1998) Calculation of the Nuclear Fukui Function and New Relations for Nuclear Softness and Hardness Kernels, Journal of Chemical Physics 108:7549-7554

P. W. Ayers and R. G. Parr (2001) Variational Principles for Describing Chemical Reactions. Reactivity Indices Based on the External Potential, Journal of the American Chemical Society 123:2007-2017

P. W. Ayers and R. G. Parr (2000) Variational Principles for Describing Chemical Reactions: The Fukui Function and Chemical Hardness Revisited, Journal of the American Chemical Society 122:2010-2018

R. F. Nalewajski (2003) Electronic Structure and Chemical Reactivity: Density Functional and Information-Theoretic Perspectives, Advances in Quantum Chemistry 43:119-184

R. F. Nalewajski (2000) Coupling Relations between Molecular Electronic and Geometrical Degrees of Freedom in Density Functional Theory and Charge Sensitivity Analysis, Computers & Chemistry 24:243-257

R. G. Parr and W. Yang. Density-Functional Theory of Atoms and Molecules. New York, NY: Oxford University Press, 1989.

G. Klopman (1968) Chemical Reactivity and Concept of Charge- and Frontier-Controlled Reactions, Journal of the American Chemical Society 90:223-234

R. G. Parr and R. G. Pearson (1983) Absolute Hardness - Companion Parameter to Absolute Electronegativity, Journal of the American Chemical Society 105:7512-7516

W. T. Yang and R. G. Parr (1985) Hardness, Softness, and the Fukui Function in the Electronic Theory of Metals and Catalysis, Proceedings of the National Academy of Sciences of the United States of America 82:6723-6726

R. G. Pearson (1963) Hard and Soft Acids and Bases, Journal of the American Chemical Society 85:3533-3539

R. G. Pearson (1966) Acids and Bases, Science 151:172-177

R. G. Parr and P. K. Chattaraj (1991) Principle of Maximum Hardness, Journal of the American Chemical Society 113:1854-1855

Home | Publications | Group Members | Equipment | Information

DISCLAIMER: This is a personal web site. The ideas and information expressed on it have not been approved or authorised by the University either explicitly or implicitly. They are purely for the purposes of research collaboration, education, and/or personal usage. Any links to external Web sites are provided as a courtesy. They should not be construed as an endorsement by the University or this Laboratory.