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Most Cited Journal Articles 2003-Materials Science

Following is a CAS database record representing a highly cited journal article.

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CAS indexed 6 chemical substances from this document. CAS subject entries for this document include: Proper functions.

CAPLUS COPYRIGHT 2004 ACS on STN

TITLE:	Electronic population analysis on LCAO-MO [linear combination of atomic orbital-molecular orbital] molecular wave functions. I
AUTHOR(S):	Mulliken, R. S.
CORPORATE SOURCE:	Univ. of Chicago
SOURCE:	Journal of Chemical Physics (1955), 23, 1833-40 CODEN: JCPSA6; ISSN: 0021-9606
PUBLISHER:	American Institute of Physics
LANGUAGE:	English

ABSTRACT:
An analysis in quant. form was given in terms of breakdowns of the electronic population into partial and total "gross at. populations," or into partial and total "net at. populations" together with "overlap populations." Gross at. populations distribute the electrons almost perfectly among the various at. orbitals of the various atoms in the mol. From these nos., a definite figure is obtained for the amt. of promotion (e.g. from 2s to 2p) in each atom; and also for the gross charge Q on each atom if the bonds are polar. The total overlap population for any pair of atoms in a mol. is in general made up of pos. and neg. contributions. If the total overlap population between 2 atoms is pos., they are bonded; if neg., they are antibonded. Tables of gross at. populations and overlap populations were calcd. for CO and H2O. The amt. of s-p promotion was nearly the same for the O atom in CO and in H2O (0.14 electron in CO and 0.15e in H2O). For the C atom in CO it is 0.50e. For the N atom in N2 it is 0.26e. In spite of very strong polarity in the .pi. bonds in CO, the .sigma. and .pi. overlap populations are very similar to those in N. In CO the total overlap population for the .pi. electrons is about twice that for the .sigma. electrons. The most easily ionized electrons of CO are in a mol. orbital such that its gross at. population is 94% localized on the C atom; these electrons account for the weak electron donor properties of CO.