Chemical Bonding Theory
One of the core interests of the group is the development of modern chemical bonding theory and models that reveal the causal relationships between electronic structure, molecular geometry as well as reactivity and other properties (e.g., spectra, magnetic properties, etc.). Our development work is centered around the quantitative molecular orbital (KS-MO) theory as contained in the Kohn-Sham density functional theory (KS-DFT) and a matching canonical energy decomposition analysis (EDA) method. Other project lines focus on the charge-density rearrangement upon bond formation (VDD method). In this project line, students can work on the further development of the techniques, new models, and the creation of theoretical frameworks and their physical interpretation. Applications can be oriented towards not yet understood and/or novel bonding motifs or towards chemical reactivity theory (see other projects, below).
Kohn-Sham Density Functional Theory: Predicting and Understanding Chemistry
F. M. Bickelhaupt, E. J. Baerends
In: Reviews in Computational Chemistry; K. B. Lipkowitz and D. B. Boyd, Eds.; Wiley-VCH: New York, 2000, Vol. 15, pp. 1-86
Voronoi Deformation Density (VDD) charges. Assessment of the Mulliken, Bader, Hirshfeld, Weinhold and VDD methods for Charge Analysis
C. Fonseca Guerra, J.-W. Handgraaf, E. J. Baerends, F. M. Bickelhaupt
J. Comput. Chem. 2004, 25, 189-210
Energy Decomposition Analysis in the Context of Quantitative Molecular Orbital Theory
T. A. Hamlin, P. Vermeeren, C. Fonseca Guerra, F. M. Bickelhaupt
In: Complementary Bonding Analyses; S. Grabowski, Ed.; De Gruyter: Berlin, 2021, in press
Chemical Bond and Affinities throughout the Periodic Table
In this project, we examine the most fundamental questions about chemical bonding: What, for example, is the actual physical mechanism behind the stabilization that occurs when a bond is formed? Why do C–H bonds really become longer when the carbon atom goes from sp to sp2 to sp3 in an archetypal series such as acetylene, ethylene and ethane? And we also explore the origin of trends in the length and strength of a bond A–B as the atoms A and B vary, across the periodic system. In many cases, these fundamental questions lead to collaborations on very concrete problems of experimental colleagues, across the world.
The Nature of Nonclassical Carbonyl Ligands Explained by Kohn-Sham Molecular Orbital Theory
S. C. C. van der Lubbe, P. Vermeeren, C. Fonseca Guerra, F. M. Bickelhaupt
Chem. Eur. J. 2020, 26, 15690-15699 (issue #1000)
Nature and Strength of Lewis Acid/Base Interaction in Boron and Nitrogen Trihalides
D. Rodrigues Silva, L. de Azevedo Santos, M. Puggina de Freitas, C. Fonseca Guerra, T. A. Hamlin
Chem. Asian. J.2020,15, 4043-4054
The Role of s–p Orbital Mixing in the Bonding of Second-Period Diatomic Molecules
F. M. Bickelhaupt, J. K. Nagle, W. L. Klemm
J. Phys. Chem. A 2008, 112, 2437-2446
α-Stabilization of Carbanions: Fluorine Stabilizes more Effectively than the Heavier Halogens
F. M. Bickelhaupt, H. L. Hermann, G. Boche