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>Corehyphen;electron binding energies from selfhyphen;consistent field molecular orbital theory using a mixture of allhyphen;electron real atoms and valencehyphen;electron model atoms
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Corehyphen;electron binding energies from selfhyphen;consistent field molecular orbital theory using a mixture of allhyphen;electron real atoms and valencehyphen;electron model atoms
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机译：Corehyphen;electron binding energies from selfhyphen;consistent field molecular orbital theory using a mixture of allhyphen;electron real atoms and valencehyphen;electron model atoms
The chemistry of large systems such as clusters may be readily investigated by valencehyphen;electron theories based on model potentials, but such an approach does not allow for the examination of corehyphen;electron binding energies which are commonly measured experimentally for such systems. Here we merge our previously developed Gaussian based valencehyphen;electron model potential theory with allhyphen;electronabinitiotheory to allow for the calculation of core orbital binding energies when desired. For the atoms whose cores are to be examined, we use the real nuclear changes,allof the electrons, and the appropriate manyhyphen;electron basis sets. For the rest of the system we use reduced nuclear charges, the Gaussian based model potentials, only the valence electrons, and appropriate valencehyphen;electron basis sets. Detailed results for neutral Al2are presented for the cases of allhyphen;electron, mixed realndash;model, and modelndash;model SCFndash;MO calculations. Several different allhyphen;electron and valence electron calculations have been done to test the use of the model potentialperse, as well as the effect of basis set choice. The results are in all cases in excellent agreement with one another. Based on these studies, a set of rsquo;rsquo;doublehyphen;zetarsquo;rsquo; valence and allhyphen;electron basis functions have been used for further SCFndash;MO studies on Al3, Al4, AlNO, and OAl3. For a variety of difference combinations of real and model atoms we find excellent agreement for relative total energies, orbital energies (both core and valence), and Mulliken atomic populations. Finally, direct corehyphen;holehyphen;state ionic calculations are reported in detail for Al2and AlNO, and noted for Al3and Al4. Results for corresponding frozenhyphen;orbital energy differences, relaxed SCFndash;MO energy differences, and relaxation energies are in all cases in excellent agreement (never differing by more than 0.07 eV, usually by somewhat less). Taken as a whole, the study clearly demonstrates the accuracy of the mixed realndash;model theory.
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