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Least-squares analysis of overlapped bound-free absorption spectra and predissociation data in diatomics: The *C*(^{1}Π_{ u }) state of I_{2}

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10.1063/1.3616039

### Abstract

Absorption spectra are recorded at low resolution but high quantitative precision for I_{2} vapor at 35 °C and 64 °C. These and literature spectra are analyzed by least-squares quantum spectral simulation of the overlapped *A* ← *X*, *B* ← *X*, and *C*(^{1}Π_{ u }) ← *X* transitions, with the aid of a pseudocontinuum model for the discrete regions of the *A* ← *X* and *B* ← *X*spectra. The analysis yields improved descriptions of the small-*R* regions of the *A*- and *B*-state potentials, which are known precisely at larger *R* from discrete spectroscopy. The *C* potential is determined at small *R* from its *C* ← *X*absorption, at intermediate *R* from literature data for *B* → *C*predissociation, and at large *R* from its known van der Waals well. The estimates of the electronic transition moment function |*μ* _{ e }(*R*)| for the *B*–*X* transition expand upon precise results from a recent determination by a different method. For the *C*–*X* and *A*–*X* transitions, the *R*-dependence of the transition moment functions resembles that found previously for these systems in Br_{2}. Of the spectroscopic properties, the *C* ← *X*spectrum is most altered from the previous analysis, being now ∼20% weaker. For *B* → *C*predissociation, no derived *C* potential has yielded computed rates in adequate statistical agreement with the analyzed experimental data.

© 2011 American Institute of Physics

Received 08 April 2011
Accepted 05 July 2011
Published online 01 August 2011

Article outline:

I. INTRODUCTION

II. EXPERIMENTAL WORK AND DATA ASSESSMENT

III. METHOD OF ANALYSIS

A. Theory summary

B. Potential curves

C. Least-squares algorithm

IV. RESULTS AND DISCUSSION

A. Preliminary analysis of absorption spectra

B. *B* → *C*predissociation

C. Dependence on *B*-state point of attachment

D. Recommended results

V. CONCLUSION

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/content/aip/journal/jcp/135/5/10.1063/1.3616039

2011-08-01

2014-04-24

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