Fourier Transform Emission Spectroscopy of Some New Bands of ReN R. S. Ram Department of Chemistry, University of Arizona, Tucson, AZ and P. F. Bernath Department of Chemistry, University of York, Heslington, York, UK YO10 5DD

Introduction Chemical importance Transition metal-containing diatomics represent simple metal systems where d electrons participate in the bonding. These molecules provide models for understanding the bonding and reactivity in transition metal systems. Recent interest in transition metal nitrides are in part due to their importance in catalysis. Experimental observations test the predictions of ab initio calculations. Astrophysical importance Transition metal atoms and nitrogen have relatively large abundances in many stars. If found, the spectra of transition metal nitrides would provide data on the abundance of nitrogen in cool stars.

Previous work First observation of a [  =1] – X0 + transition at cm -1. [R.S. Ram, P.F. Bernath, W.J. Balfour, J. Cao, C.X.W. Qian and S.J. Rixon, JMS 168, 350 (1994)] LIF observation of visible spectrum of ReN in the nm region. [W.J. Balfour, J. Cao, C.X.W. Qian and S. J. Rixon, JMS 183, 113(1997)] Several transitions were observed by laser excitation spectroscopy. Ground state was assigned as X 3  - (0 + ) labeled as X0 +. Possible configurations of low-lying electronic states discussed. LIF and dispersed fluorescence study of ReN. [J. Cao, W.J. Balfour and C.X.W. Qian, JPC 101, 6741 (1997)] Deperturbation analysis of the [  =1] - X0 + system at cm -1. Tentative location of the low-lying 3  - 1, 3  3, 3  2, 3  1 and 1  + states from dispersed fluorescence.

Periodic Table Re is in group 7, like Mn, and ReN is isoelectronic with WO (Hund’s case a′ X 3 Σ - ground state).

Balfour and co-workers 12 valence electrons ReN: 1δ 2 3σ 2 g. s. configuration; X 3 Σ - term for Hund’s case (a), and X0 + and A1 for case (a′). Formal triple bond for ReN, but no ab initio calculations are available.

Balfour and co-workers

Experimental Rhenium hollow cathode discharge with 3.0 Torr of Ne and 5 mTorr N V, 457 mA current Spectra observed with the Fourier transform spectrometer of the National Solar Observatory at Kitt Peak cm cm -1 UV beam splitter Si diode detectors Filter: RG495 Filter: CuSO 4 Resolution: 0.02 cm -1 Scans: 6 (60 minutes)Scans: 8 (60 minutes)

The following two new ReN bands have been identified in the visible region: 0 + – A cm – A cm -1 Observed by Balfour et al.  [JMS 183, 113 (1997)] Present observations

A compressed portion of the new visible bands of ReN

A portion of the A1, 0-0 band of ReN at cm -1

Constants (in cm -1 ) for the observed states of ReN ConstantsA TvTv (11) (11) (12) BvBv (15) (15) (15) 10 7 × D v 3.384(21)4.281(25)3.787(22) 10 4 × q v (39)-- Numbers in parentheses are one standard deviation in the last digits Present term value for the A1 stateValue from Balfour et al. (1997) (11) cm (100) cm -1

Summary Two new ReN bands having a common lower state have been observed in the cm -1 region using Fourier transform emission spectroscopy A1 (0-0)22110 cm A1 (0-0)22224 cm -1 The upper state of the 0 + state at cm -1 is common to the upper state of the [24.7]0 + state [Balfour et al. (1997)], which places the A1 state at cm -1. A rotational analysis of these bands provide spectroscopic constants for the new states. No theoretical predictions are available for these states.

Acknowledgments NASA laboratory astrophysics program Walter Balfour NSERC, Canada National Solar Observatory Mike Dulick