Chemical Concepts from Quantum Mechanics / Edition 1 available in Hardcover
- Pub. Date:
- Royal Society of Chemistry, The
Extracting chemical information from modern wave functions and from experimental high-resolution electron densities is a challenging but valuable task. Many chemical concepts have been introduced at an intuitive level, often in the distant past, and hence need to be continuously confronted and scrutinised against a wealth of data obtained from modern computer calculations and increasingly automated X-ray equipment. This new book looks at the issues involved in bridging the expanding gap between widely used chemical concepts and modern accurate physical and computational data on molecules. It offers a valuable insight into research and opinion regarding this topic. Faraday Discussions document a long-established series of Faraday Discussion meetings which provide a unique international forum for the exchange of views and newly acquired results in developing areas of physical chemistry, biophysical chemistry and chemical physics. The papers presented are published in the Faraday Discussion volume together with a record of the discussion contributions made at the meeting. Faraday Discussions therefore provide an important record of current international knowledge and views in the field concerned.
Table of Contents
Spiers Memorial Lecture - Quantum chemistry: The first seventy years; Anatomy of bond formation. Bond length dependence of the extent of electron sharing in chemical bonds from the analysis of domain-averaged Fermi holes; Bonding indicators from electron pair density functionals; Source function description of metal-metal bonding in d-block organometallic compounds; Forces in molecules; On the definition of local spin in relativistic and nonrelativistic quantum chemistry; General Discussion; Calculation of negative electron affinity and aqueous anion hardness using Kohn-Sham HOMO and LUMO energies; The physical basis of the hard/soft acid/base principle; Use of DFT-based reactivity descriptors for rationalizing radical addition reactions: applicability and difficulties; Carboranes: chemical concepts derived from the AIM study of the experimental and theoretical electron density distribution functions; On the accurate estimation of intermolecular interactions and charge transfer: the case of TTF-CA; General Discussion; The physical origin of large covalent-ionic resonance energies in some two-electron bonds; Quantifying resonance through a Lewis Valence Bond approach: application to haloallyl and carbonyl cations; The unusual electronic mechanism of the [1,5] hydrogen shift in (Z)-1,3-pentadiene predicted by modern valence bond theory; On the interpretation of valence bond wavefunctions; Current-density maps as probes of aromaticity: Global and Clar ring currents in totally resonant polycyclic aromatic hydrocarbons; Electron sharing indexes at the correlated level. Application to aromaticity calculations; Critical analysis of the local aromaticity concept in polyaromatic hydrocarbons; General Discussion; Direct estimate of conjugation and aromaticity in cyclic compounds with the EDA method; Charge transfer, chemical potentials, and the nature of functional groups: answers from quantum chemical topology; Energy partitioning schemes: a dilemma; Highly polar bonds and the meaning of covalency and ionicity-structure and bonding of alkali metal hydride oligomers; The dithiolene ligand-innocent or non-innocent? A theoretical and experimental study of some cobalt-dithiolene complexes; General Discussion; Concluding remarks