Rotational line strengths in a 5Σ – 5Π transition with application to the A – X system of CrO

1984 ◽  
Vol 62 (12) ◽  
pp. 1610-1615 ◽  
Author(s):  
U. Sassenberg ◽  
A. S.-C. Cheung ◽  
A. J. Merer

Detailed calculations of the line strengths in a 5Σ – 5Π transition as a function of J show that the relative branch intensities in the A – X system of CrO, which do not follow the published formulae for 5Σ(b) – 5Π(a) transitions, can be explained very well in terms of strong spin uncoupling in the 5Π state, with a single perpendicular transition moment dominating. It is emphasized that spin uncoupling affects line strengths by an amount that increases very rapidly with multiplicity, so that algebraic formulae for the pure coupling cases quickly lose their value. An unusual cancellation effect occurs in the main branches of a 5Σ – 5Π transition, nine of which have intensities that drop to zero and then rise again with increasing J.

1971 ◽  
Vol 49 (21) ◽  
pp. 2693-2703 ◽  
Author(s):  
J. B. Tatum ◽  
J. K. G. Watson

Rotational line strengths (Hönl–London factors) are calculated for 3Σ±–3Σ± electric dipole transitions, allowing for nonzero values of the splitting constant λ. If the 3Σ states are intermediate between Hund's coupling cases (a) and (b) only one transition moment is required, whereas if there is a tendency to case (c) four transition moments may be required. The resulting formulas are compared with the observed spectra of the diatomic molecules of the Group VI elements. The same formulas are valid for 3Σ±–3Σ± magnetic dipole transitions.


Pramana ◽  
1985 ◽  
Vol 24 (3) ◽  
pp. 503-512
Author(s):  
T K Balasubramanian ◽  
V P Bellary

1993 ◽  
Vol 79 (5) ◽  
pp. 911-941 ◽  
Author(s):  
H. Bervas ◽  
S. Le Boiteux ◽  
L. Labrunie ◽  
B. Attal-Tretout

1986 ◽  
Vol 64 (1) ◽  
pp. 36-44 ◽  
Author(s):  
C. M. L. Kerr ◽  
J. K. G. Watson

Electronic transitions of the type 3Δ–3Σ are forbidden in the absence of spin–orbit or orbit–rotation coupling, but spin–orbit perturbations produce three transition moments, two perpendicular (Y1 and Y2) and one parallel (Z1) while low-order orbit–rotation couplings introduce three further perpendicular transition moments (X1, X2, and X3). Formulas are presented for the rotational line strengths in a 3Δ(a)–3Σ(int) transition in terms of these parameters and are applied to recent data of Coquart and Ramsay for the Herzberg III system [Formula: see text] of molecular oxygen. It is shown that all six parameters are significant, and that there are noticeable departures from the first-order relations Y1 = Y2, Z1 = 0, X1 = X2 = X3. The observation of orbit–rotation intensity effects led to the first identification of lines of the Ω′ = 3 subbands of the 4–0 to 7–0 bands of the Herzberg III system, which are forbidden for the spin–orbit mechanism. The wave numbers of these lines are in satisfactory agreement with the analysis of the A′3Δu → a1Δg emission by Slanger and Huestis.


1973 ◽  
Vol 51 (12) ◽  
pp. 1300-1301 ◽  
Author(s):  
J. L. Féménias ◽  
C. Athénour ◽  
R. Stringat

Van Vleck's RAM method is used for calculating rotational line strengths in electric dipole transitions between electronic states of diatomic molecules arising from coupling cases which involve the nuclear spin.


1990 ◽  
Vol 68 (2) ◽  
pp. 231-237 ◽  
Author(s):  
B. R. Lewis ◽  
S. T. Gibson

Rotational line strengths are given for 3Σ+(int) – 3Σ−(int) transitions arising from spin–orbit coupling. Observed branch intensities for the forbidden β3Σu+ – X3Σg− transition of O2 may be explained by assuming spin–orbit mixing of β3Σu+ with the B3Σu− and E3Σu− states. On the other hand, observed branch intensities for the Herzberg I A3Σu+ – X3Σg− transition of O2 may be explained only by assuming mixing with 3Σ and 3Π states. In neither case do earlier formulae, derived assuming a single 3Π perturber, apply.


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