Iodine revisited

The Journal of Chemical Physics

Volumn 55, Issue 1, 1971, Pages 288-309

  Mulliken, Robert S ^a,b  

^a UNIVERSITY OF CHICAGO   (United States)

^b UNIVERSITY OF TEXAS AT AUSTIN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0004975106     PISSN: 00219606     EISSN: None     Source Type: Journal    
DOI: 10.1063/1.1675521     Document Type: Article

References (118)

1. For the most accurate evaluation of the molecular constants and U(R) curve for state X, see
2. For the B state, see (a)
3. For any [formula omitted] configuration, Recknagel shows that the energy is [formula omitted] C, [formula omitted] [formula omitted] [formula omitted] and [formula omitted] for the [formula omitted] [formula omitted] [formula omitted] [formula omitted] [formula omitted] and [formula omitted] states, respectively, where a, b, c are various specific integrals.
4. For a [formula omitted] configuration as in the 2310 configuration of [formula omitted] Recknagel shows that the energy is [formula omitted] C, [formula omitted] [formula omitted] [formula omitted] [formula omitted] for the respective states [formula omitted] [formula omitted] [formula omitted] [formula omitted] [formula omitted] and [formula omitted]
5. case the 2332 states [formula omitted] and/or [formula omitted] and [formula omitted]) were lower in energy than 1441, [formula omitted] as has sometimes been suggested, the correlations in Fig. 1 would have to be changed, but these possibilities are here deemed rather strongly improbable (cf. Sec. VI).
6. The validity of this assumption is uncertain.
7. For [formula omitted] the value 7.2 a.u. calculated by
8. See Refs. 41 and 46 in
9. See Ref. 16
10. 19 in which it was assumed that the predissociating state is 2332, [formula omitted]
11. See reference to it on p. 555 of Ref. 28.
12. As discussed above, most probably the [formula omitted] curve which crosses the B curve is that from 1441, [formula omitted] but possibly it is the 2332, [formula omitted] or [formula omitted] curve.
13. The 2341, [formula omitted] for which [formula omitted] would also be very weakly possible. The selection rule [formula omitted] (hence [formula omitted]) holds for spectroscopic transitions between two case a [formula omitted] states; see
14. 21 shows the 2341, [formula omitted] curve as running entirely below the B curve, which would be very unfavorable for collisional predissociation.
15. The estimated vertical energy of 2341, [formula omitted] is only 0.3 eV above that of [formula omitted] in Table I, and a reversed order is almost as likely as not.
16. 26a
17. Other interactions with higher-energy states should be included in a complete configuration-interaction calculation, but we may assume these to be about the same for [formula omitted] and [formula omitted]
18. References 36 and 37 are in good agreement on the value [formula omitted] as estimated from their absorption curves.
19. The dipole strengths for [formula omitted] and [formula omitted] are given as 2D because of the twofold degeneracy of [formula omitted] and [formula omitted] where D refers to a single component.
20. 33 forbidding [formula omitted] in case a and thereby indicating weakness in case c) shows that his argument is invalid.
21. The matrix element between [formula omitted] and [formula omitted] is zero; they are mixed only indirectly via [formula omitted]
22. 46 of 0.43 for the oscillator strength of 1441, [formula omitted] with [formula omitted] for this transition (see Sec. VI for discussion).
23. The vertical energies at [formula omitted] of state X should be somewhat less than those given by [formula omitted] since the first peak of the vibrational wavefunction at the inner limb of the upper U(R) curve, which approximately determines the position of [formula omitted] is somewhat outside the point of intersection of the vibrational energy level with the U(R) curve. This difference has been ignored here in Table I in the case of the 1441, [formula omitted] state.
24. A transition of this type (2310, [formula omitted] [formula omitted]) is known in [formula omitted]
25. At shorter wavelengths are several systems some, at least, of which are Rydberg bands (for a pictorial representation, see Ref. 47).
26. Other values are 0.2 according to
27. 2.3 according to
28. The same effect has been observed by others, e.g., R. Millikan (private communication).
29. particular, note the discordant interval [formula omitted] between the [formula omitted] and 53 969 bands in the [formula omitted] column where all the neighboring intervals are near [formula omitted] likewise the discordant interval [formula omitted] between the 53 827 and 53 923 bands in the [formula omitted] column where all the neighboring intervals are near [formula omitted]
30. Transitions [formula omitted] and [formula omitted] should be much weaker since there is a strict selection rule [formula omitted] in case a, hence [formula omitted] if [formula omitted] as here [cf.
31. Preceded by a few weaker anti-Stokes lines beginning at 1860 Å.
32. Oldenberg reported some overlapping of continuous background and diffuse bands beginning at λ 2042.
33. 71 did.
34. [formula omitted] cannot be exactly determined from these data since for the longer exciting wavelengths, heated iodine was used, and excitation must have come from initially vibrating molecules. Here absorption must be in the KM and PR bands.
35. Reference 90, Eqs. (23) and (25).
36. The change in [formula omitted] in Eq. (13) is less important for [formula omitted] than the change in [formula omitted] since [formula omitted] is not very sensitive to [formula omitted]
37. Here the quantity [formula omitted] is small, so that the harmonic approximation is accurate enough for present purposes.
38. 57 on iodine in argon, and this system has been attributed to a molecule IN.
39. With respect to expected shortcutting into excited atoms, see the last paragraph of Sec. III.
40. According to a calculation by N. S. Ham (see Ref. 37, footnote on p. 756), [formula omitted] is [formula omitted] and [formula omitted] so that [formula omitted] would be [formula omitted] and [formula omitted] and for [formula omitted] and [formula omitted] there is a 9.5percent; mixing.