Interstellar CN And CH+ In Diffuse Molecular Clouds: C-12/C-13 Ratios And Cn Excitation

We present very high signal-to-noise ratio absorption-line observations of CN and CH+ along 13 lines of sight through diffuse molecular clouds. The data are examined to extract precise isotopologic ratios of (CN)-C-12/(CN)-C-13 and (CH+)-C-12/(CH+)-C-13 in order to assess predictions of diffuse cloud chemistry. Our results on (CH+)-C-12/(CH+)-C-13 confirm that this ratio does not deviate from the ambient C-12/C-13 ratio in local interstellar clouds, as expected if the formation of CH+ involves nonthermal processes. We find that (CN)-C-12/(CN)-C-13, however, can be significantly fractionated away from the ambient value. The dispersion in our sample of (CN)-C-12/(CN)-C-13 ratios is similar to that found in recent surveys of (CO)-C-12/(CO)-C-13. For sight lines where both ratios have been determined, the (CN)-C-12/(CN)-C-13 ratios are generally fractionated in the opposite sense compared to (CO)-C-12/(CO)-C-13. Chemical fractionation in CO results from competition between selective photodissociation and isotopic charge exchange (ICE). An inverse relationship between (CN)-C-12/(CN)-C-13 and (CO)-C-12/(CO)-C-13 follows from the coexistence of CN and CO in diffuse cloud cores. However, an ICE reaction with CN may mitigate the enhancements in (CN)-C-12/(CN)-C-13 for lines of sight with low (CO)-C-12/(CO)-C-13 ratios. For two sight lines with high values of (CO)-C-12/(CO)-C-13, our results indicate that about 50% of the carbon is locked up in CO, which is consistent with the notion that these sight lines probe molecular cloud envelopes where the transition from C+ to CO is expected to occur. An analysis of CN rotational excitation yields a weighted mean value for T-01((CN)-C-12) of 2.754 +/- 0.002 K, which implies an excess over the temperature of the cosmic microwave background (CMB) of only 29 +/- 3 mK. This modest excess eliminates the need for a local excitation mechanism beyond electron and neutral collisions. The rotational excitation temperatures in (CN)-C-13 show no excess over the temperature of the CMB.