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Changes in Transition Probability due to the Interaction of Rotation and Vibration in Diatomic Band Spectra

Abstract

THE distributions of rotational and vibrational intensities in band spectra are frequently used for measurement of effective temperatures in, for example, flames1 and stellar spectra. In such calculations it has become customary to treat independently the derivation of rotational and vibrational transition probabilities, although the possibility of error has been noted2,3. Major errors attributed to an interaction occur with the weak (0, 1) band of OH at 3428 A. as shown by the incompatible rotational ‘temperatures’ obtained from a plot such as Fig. 1, calculated on the assumption that only rotational transition probability affects intensity within a band. The gradients of the three straight lines correspond to temperatures of 2,290, 1,420 and 750° K. for R, Q and P 1 branches respectively. The curved portions at low energies are due to unresolved satellite branches. Similar treatment of a stoichiometric flame, using the intensities of Bass and Broida4, give for the (0,1) band R branches a temperature of 4,180° K., and for the P branches 1,380° K.; even the S branch of the (0,0) band at 3064 A. gives 3,560° K. The estimated temperature of the flame was 2,750° K. Further discrepancies for other bands of the system have been reported5. The (0,1) band is very weak, and these effects cannot be attributed to self-absorption.

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References

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LEARNER, R., GAYDON, A. Changes in Transition Probability due to the Interaction of Rotation and Vibration in Diatomic Band Spectra. Nature 183, 242–243 (1959). https://doi.org/10.1038/183242a0

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