The effect of electronic correlation on molecular wavefunctions |
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| Affiliation: | 1. Department of Chemistry, FPV, University of SS Cyril and Methodius, 91701 Trnava, Slovakia;2. Department of Chemistry, School of Life Sciences, University of Sussex, Brighton BN1 9QJ, United Kingdom;3. Institute of Nanotechnology, Karlsruhe Institute of Technology (KIT), Postfach 3640, 76021, Germany;4. IPCMS-CNRS, Université de Strasbourg, 23, rue du Loess, f-67034 Strasbourg, France;1. Department of Physics, Faculty of Science, Qom University of Technology, Qom, Iran;2. Faculty of Physics, University of Kashan, Kashan, Iran;3. Educator, Farhangian University, Tehran, Iran;4. Faculty of Petroleum and Gas, Yasouj University, Gachsaran 75813-56001, Iran;1. Graduate School of Information Sciences, Hiroshima City University, Hiroshima 731-3194, Japan;2. Institute for Protein Research, Osaka University, Suita 565-0871, Japan;1. Department of Pediatrics, Case Western Reserve University, Cleveland, OH 44106, USA;2. Pediatric Respiratoray Medicine, University of Virginia School of Medicine, Charlottesville, VA 22908, USA;3. Department of Anesthesia, University of Iowa Hospitals and Clinics, Iowa, IA, USA;4. Galleon Pharmaceuticals, Inc., 213 Witmer Road, Horsham, PA, USA;5. Division of Pulmonary, Critical Care and Sleep Medicine, University Hospital Case Medical Center, Case Western Reserve University, Cleveland, OH, USA;6. Department of Biomedical Engineering, Case Western Reserve University, Cleveland, OH, USA;7. Department of Pharmacology, Case Western Reserve University, Cleveland, OH, USA;8. Functional Electrical Stimulation Center, Case Western Reserve University, Cleveland, OH, USA |
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| Abstract: | ![]()
The minimal basis set Hartree-Fock and full-CI wavefunctions of some molecules (N2, CO, BH2, CH4) are analyzed in terms of their valence-bond components. The internal valence correlation has dramatic effects on this distribution. The coefficients of the ionic forms decrease very rapidly with ionicity; the largest coefficients concern neutral determinants with maximum spreading of the p electrons which are multiplied by important factors (3 to 10) by the CI. The neutral components with two electrons is the same p AO are increased to a lesser extent. Correlation decreases the charge fluctuation in a dramatic way. On the other hand the atomic spin fluctuation increases under correlation. When the main atomic configuration is not the ground state one (as in BH2 or CH4) the correlation does not increase the components of the atomic ground states, and has little effect on hybridization. These various trends reflect a compromise between the necessity of bond building between electrons of opposite spins and the tendency of the atoms to increase their components in their low energy configurations. |
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