University of Chicago Laboratory of Molecular Structure and Spectra Technical Report: 1968 Page: 271
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where to obtain d6/dR at R, da+/dR must be taken at 1yR.
The fact that the effects of the Rydberg electron on AG1 and
Re are relatively larger and more persistent in H2 than in He2 (see
Tables 1 and 2) can be accounted for. Namely, from Eq. 14 with
+= 0, (Re- Re+) must be proportional to d6/dR divided by k; and
since the k values are only about half as large for H2 as for He2,
+ +
R - R , and therefore also AG1 - AG1 in view of the Mecke-Birge
e e2 2
14
rules relating Re to me are more strongly affected by core-
splitting for H2 than for He2. By the same reasoning, it it under-
standable that for molecules with still larger force constants
(e.g. N2, NO) the apparent bonding effects of even the lowest-energy
Rydberg MO's are found to be very small: AG and Re for N2 and NO
are very close to their values for the free ions.
4. Analysis of Rydberg Term Values.--We now seek to interpret
observed term defect (i.e. 6) data for Rydberg states of H2 and He2
corresponding to the n* data of Tables 1 and 2. Evidence on the
variation of 6 values with R can also be obtained by using two
further sets of data, namely united-atom 6 values to represent
R = O, and d6/dR values computed from the AG1 and R data of Tables
- e
1 and 2 using Eq. 14. Tables 3 and 4 summarize all such information
for n values up to 3. The molecular 6 values given in these tables
have been computed from mean T values of corresponding singlet and
triplet Rydberg states which have been corrected so as to represent
mean vertical vibration-free T values at an R equal to R of the
- -e -271
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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/m1/283/?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.