Journal of Physical Chemistry, Vol.100, No.14, 5660-5667, 1996
Chemiluminescent Emission from the Reaction of Manganese Vapor (Mn-X) and Halogen Molecules (Cl-2,F-2)
The chemiluminescent reactions between an agglomerated flux of entrained manganese vapor (atoms and small manganese molecules) and halogen vapor (chlorine or fluorine) have been investigated under multiple collision conditions. Both reaction groups produce emission features that are readily correlated with manganese atom transitions, manganese(I) halide molecular emission, and broad features centered at 464, 530, and 720 nm which might be attributed to the manganese cluster halides or to manganese dimer. Chemical reactions involving manganese atoms and small manganese clusters are required to explain the observed emission features. The energetics of several possible metal atom, dimer, and trimer reactions are considered and correlated with the observed emission features. The energetics of some of these reactions are used to estimate the a(5) Sigma-X(7) Sigma energy separation in MnF. This value, 2500 +/- 500 cm(-1), is consistent with the value of 1743 cm(-1) determined for MnH and a value of 3000 +/- 500 cm(-1) estimated previously for MnF. Vibrationally resolved emission features are observed for five previously investigated MnF transitions. While limited information was obtained for the system a (350 nm), c (504 nm), or d (690 nm) transitions, revised vibrational analyses for the b (495 nm) and the e (832 nm) band systems of MnF are presented. The b system bands are found to be blue degraded, with a vibrational analysis suggesting that the observed transition terminates in the X(7) Sigma ground state. Twenty bands belonging to the origin sequence of the e system have been identified and fit using a nonlinear least squares analysis. Energetic arguments dictate that the lower state of this transition must be either the ground state or an electronic state differing little in energy from the ground state. The location of the observed broad emission features common to both the chlorine and fluorine systems are in reasonable agreement with absorption bands reported previously for Mn-2 isolated in rare gas matrices. While their correlation with Mn-2 is a viable possibility, the features in the 464 nm region would seem to be more reasonably associated, at least in part, with Mn2F* (Mn2Cl*) emission products. Emission profiles suggest that there are significant differences in the bond lengths for those states involved in the transitions giving rise to the broad emission features.
Keywords:ELECTRON-SPIN-RESONANCE;RARE-GAS MATRICES;ROTATIONAL ANALYSIS;METAL-CLUSTERS;MN-2+;SPECTROSCOPY;SPECTRA;OXIDATION;STATES;DIMERS