Review Article

Advances in Understanding of Chemical Bonding: Inputs from Experimental and Theoretical Charge Density Analysis

Department of Chemistry, Indian Institute of Science Education and Research, Bhopal 462023, India
J. Phys. Chem. A, 2012, 116 (40), pp 9791–9801
DOI: 10.1021/jp306169f
Publication Date (Web): August 28, 2012
Copyright © 2012 American Chemical Society
*Fax: 0755-4092392. E-mail: dchopra@iiserb.ac.in.
Biography

Deepak Chopra is currently working as an Assistant Professor at the Indian Institute of Science Education and Research, Bhopal, since March 2009. He completed his BSc degree from Jadavpur University, Kolkata, India, followed by an MS and Ph.D. degree at the Indian Institute of Science, Bangalore, under the guidance of Professor T. N. Guru Row in January 2007. It was further followed by postdoctoral studies at the same Institute and then moved to the University of Toledo, Ohio, USA, under the supervision of Professor Alan. A. Pinkerton. His primary interests are in the areas of weak intermolecular interactions and crystal polymorphism, electron density analysis in molecular crystals, and in situ cryocrystallization of liquids.

Abstract

Abstract Image

The development of charge density analysis has undergone a major renaissance in the last two decades. In recent years, the characterization of bonding features associated with atoms in molecules and in crystals has been explored using high-resolution X-ray diffraction data (laboratory or synchrotron) complemented by high level ab initio theoretical calculations. The extraction of one electron topological properties, namely, electrostatic charges, dipole moment and higher moments, electrostatic potential, electric field gradients, in addition to evaluation of the local kinetic and potential energy densities, have contributed toward an understanding of the electron density distributions in molecular solids. New topological descriptors, namely, the source function (SF) and electron localization function (ELF) provide additional information as regards characterization of the topology of the electron density. In addition, delocalization indices have also been developed to account for bonding features pertinent to M–M bonds. The evaluation of these properties have contributed significantly toward the understanding of intra- and intermolecular bonding features in organic, inorganic, and biomolecules in the crystalline phase, with concomitant applications in the understanding of chemical reactivity and material/biological properties. In recent years, the focus has strongly shifted toward the understanding of structure–property relationships in organometallic complexes containing labile M–C bonds in the crystal structure with subsequent implications in catalysis. This perspective aims to highlight the major developments in electron density measurements in the past few years and provides pointers directed toward the potential use of this technique in future applications for an improved understanding of chemical bonding in systems that have been unexplored.

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Received 22 June 2012
Published online 28 August 2012
Published in print 11 October 2012
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