University of Chicago Laboratory of Molecular Structure and Spectra Technical Report: 1968 Page: 265
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We shall not attempt to compute 6 values, but will obtain
pen
empirical values of 6pen for H2 by taking 6(R) - 6c.s.(R) using
empirical values of 6 and computed values of 6 . We shall find
C.S.
that the values of 6 obtained in this way are reasonable.
pen
On the basis of Eqs. 7-9, it is seen that the change in the
effective core field on splitting the core must produce in H2 the
following effects which are also characteristic in H2+ (see Part V,
Sec. 2); for penetrating MO's in H2, however, the energy effects of
penetration, which are absent in H2 , are superposed.
(1) For MO's with X = 2, i.e. ns, npwr, nd6, and so on, 6 is
CoS.
negative, AT is negative, and the energy change due to core split-
ting is positive, increasing as R increases.
(2) For MO's with 2 > 0 and X < 1, 6c.s. is positive and the energy
change due to core splitting is increasingly negative as R increases.
Both effects may be considered as due primarily to the changes
in the effective field of the core which result when it is split.
But also, the difference between (1) and (2) is related to the
fact that MO's with X = are unpromoted MO's, while those with
X < 2 are promoted MO's, which go to LCAO forms of lower n as
+ 10
R -+ m in H2 . As we shall see below, the Rydberg MO's of H2
conform well to expectations (1) and (2) above.
Reasoning similar to that just given for H2 shows that for
the Rydberg states of He2, with core 16 l, Eqs. 5-9 should hold
g u
11
to a rather similar extent to that in H2. For diatomic molecules
with larger cores, the situation becomes in general more complicated.265
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University of Chicago. Laboratory of Molecular Structure and Spectra. University of Chicago Laboratory of Molecular Structure and Spectra Technical Report: 1968, report, 1969~; Chicago, Illinois. (https://digital.library.unt.edu/ark:/67531/metadc228352/m1/277/?q=green+energy: accessed July 18, 2024), University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu; crediting UNT Libraries Government Documents Department.