ISSN:
0020-7608
Keywords:
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Quantum Chemistry can today boast the fact that ordinary chemists - by means of personal computers and programs available - can study many theoretical properties of molecules by solving the Schrödinger equation and get an advance idea of how to properly arrange their experiments to find new features. For small molecules, they can use ab initio programs of the Hartree-Fock type, and for large molecules, they can use semiempirical programs available. To achieve higher accuracy and to include electron correlation properly, however, one has in the ab initio approach to use configurational interaction methods and giant computers, whereas in the semiempirical methods, the effect of correlating is often taken into account in the adjustable parameters forming the basis for this approach. In connection with the ab initio methods, it is further emphasized that the resolvent methods combined with the partitioning technique provide an excellent conceptual and mathematical framework for getting solutions of any accuracy desired, but that most of the programming of this approach remains to be done. Ordinary wave mechanics is valid at absolute zero of temperature, and - in order to include such important chemical concepts as temperature, entropy, free energy, etc. - one has to go over to general quantum theory and the Liouvillian formalism. One can stil start from the Coulombic Hamiltonian, but it becomes of importance to include the nuclear motion properly and preferably on the same level as that of the electronic motion. It is further emphasized that the irreversibility problem is not yet fully solved, that the theory of the interaction between matter and electromagnetic fields still needs some improvements, and that the question of the proper introduction of relativistic corrections in the quantum theoretical treatment of molecular systems involving heavier atoms still has a great deal to desire. © 1994 John Wiley & Sons, Inc.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/qua.560510614
