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# Further Evidence for Chemical Fractionation from Ultraviolet Observations of Carbon Monoxide1footnote 11footnote 1Based on observations obtained with the NASA/ESA 𝐻𝑢𝑏𝑏𝑙𝑒 𝑆𝑝𝑎𝑐𝑒 𝑇𝑒𝑙𝑒𝑠𝑐𝑜𝑝𝑒 through the Space Telescope Science Institute, which is operated by the Association of Universities for Research in Astronomy, Inc., under NASA contract NAS5-26555.

## 1 Introduction

Carbon monoxide is the second most abundant molecule, after H2, in interstellar clouds and is seen in dark cloud envelopes through observations at ultraviolet wavelengths (Smith & Stecher 1969; Morton 1975). High-quality spectra acquired with the Goddard High Resolution Spectrograph (GHRS) on the Hubble Space Telescope allow detailed studies of the CO abundance and the relative abundances of the various forms containing carbon and oxygen isotopes (Sheffer et al. 1992; Lambert et al. 1994; Lyu, Smith, & Bruhweiler 1994). For instance, Lambert et al. deduced the relative abundances of 12C16O, 13C16O, 12C18O, and 12C17O. One goal of these studies is to extract information on physical conditions for the gas probed by CO absorption. The earlier efforts with GHRS of Sheffer et al. (1992), Lambert et al. (1994), and Lyu et al. (1994) had as a focus the sight line toward $`\zeta `$ Oph \[RA(2000) $`=`$ 16h 37m 10s; DEC(2000) $`=`$ $``$10 34 02′′\]; here, we present results on two other sight lines, $`\rho `$ Oph A \[RA(2000) $`=`$ 16h 25m 35s; DEC(2000) $`=`$ $``$23 26 49′′\] and $`\chi `$ Oph \[RA(2000) $`=`$ 16h 27m 01s; DEC(2000) $`=`$ $``$18 27 22′′\], in the same portion of the sky.

From observations of dark cloud cores via CO emission (e.g., Penzias 1981; Langer & Penzias 1993) and of diffuse clouds via CH+ absorption (Stahl et al. 1989; Centurion & Vladilo 1991; Crane, Hegyi, & Lambert 1991; Stahl & Wilson 1992; Vladilo, Centurion, & Cassola 1993; Centurion, Cassola, & Vladilo 1995), ambient isotopic ratios for C and O can be obtained because CO in cloud cores and CH+ in diffuse clouds are not fractionated. \[Throughout this paper we consider (chemical) fractionation as any process that alters isotopic ratios from ambient values.\] In cloud cores the severe attentuation of ultraviolet radiation removes all possible routes for fractionation, while the non-thermal conditions leading to CH+ production are believed to equilibrate CH+ isotopomers. The ratios found from these studies of material in the solar neighborhood are: 12C/13C $``$ 65, 16O/18O $``$ 500, and 16O/17O $``$ 2600. These 12C/13C and 16O/18O ratios are consistent with the recommendations of Wilson & Rood (1994) who claimed H2CO gives a lower limit, and CO an upper limit. Wilson & Rood obtained respective average values of $`77\pm 7`$ and $`560\pm 25`$. The measurements reported here also probe material near the Sun.

In cloud envelopes, however, the isotopic ratios in CO are altered by chemical fractionation. Isotopic exchange reactions (13C+ $`+`$ 12CO $``$ 12C+ $`+`$ 13CO) can enhance the abundance of 13CO relative to 12CO when gas temperatures are low (Watson, Anicich, & Huntress 1976) because 13CO has a lower zero-point energy. On the other hand, the more abundant variants are enhanced relative to less abundant ones when selective isotopic photodissociation dominates (Bally & Langer 1982; Chu & Watson 1983). Since CO photodissociation takes place via line absorption, the more abundant forms of CO have lines that are more optically thick, resulting in self shielding against further photodissociation for these isotopic variants. van Dishoeck and Black (1988), Kopp et al. (1996), and Warin, Benayoun, & Viala (1996) incorporated these processes into detailed models, and here we compare the predictions of these models with our observations.

In our earlier studies of CO fractionation in the diffuse clouds toward $`\zeta `$ Oph (Sheffer et al. 1992; Lambert et al. 1994), significant enhancement of 12C16O relative to 13C16O was found, with a ratio about a factor of 2 larger than the interstellar value of 65 – 70. Lyu et al. (1994), from the same data set analyzed by Sheffer et al., derived a much smaller 12C16O-to-13C16O ratio that was indistinguishable from the ambient value. One potential cause for the different conclusions comes from the set of oscillator strengths ($`f`$-values) for the $`AX`$ system of bands used to extract column densities. The analysis of Lambert et al. (1994) was based on the measurements of Chan, Cooper, & Brion (1993) from electron-energy-loss spectra, while the work of Lyu et al. (1994) adopted the $`f`$-values of Eidelsberg et al. (1992) from absorption measurements with a synchrotron source. Lambert et al. (1994) noted that their data with a higher signal-to-noise ratio yielded a more satisfactory curve of growth when the results of Chan et al. (1993) were utilized. Recent laboratory results (Smith et al. 1994; Federman et al. 1997a; Jolly et al. 1997, Zhong et al. 1997; Stark et al. 1998; Eidelsberg et al. 1999), based on a variety of experimental techniques including absorption of synchrotron radiation, are consistent with those of Chan et al., and therefore the appropriate set of $`f`$-values to use is no longer an issue. Furthermore, Lambert et al. derived 12C16O/12C18O and 12C16O/12C17O ratios that were also about a factor of two greater than the ambient ratios for the oxygen isotopes, a result expected if their conclusions about carbon fractionation were correct. Still, it is unsettling that two groups reached such different conclusions about CO fractionation, and one of the reasons for acquiring the observations toward $`\rho `$ Oph A and $`\chi `$ Oph was to compare the predictions of van Dishoeck & Black (1988) for diffuse clouds with differing physical conditions. As described below, this objective was met.

Ratios of the CO isotopic variants in diffuse and translucent clouds have been obtained via millimeter-wave techniques as well. Langer, Glassgold, & Wilson (1987) mapped a region around $`\zeta `$ Oph in 12CO and presented a tentative detection of 13CO toward the star. Their 12CO/13CO ratio of about 80$`{}_{10}{}^{}{}_{}{}^{+70}`$ is formally consistent with our earlier ultraviolet measure. More recently, Kopp et al. (1996) mapped the gas in the vicinity of $`\zeta `$ Oph in both isotopomers and obtained lower limits of about 45 to 65 for the more diffuse directions. Gredel, van Dishoeck, & Black (1994) surveyed millimeter-wave emission from southern translucent clouds with $`A_V`$ between 1 and 4 mag. While the 12CO/13CO ratios of antenna temperature, which may be affected by optical depth in the 12CO line, are low, the 12C16O/12C18O and 13C16O/12C18O ratios are similar to or greater than the ambient interstellar values. The ratios involving the oxygen isotopes suggest that selective isotopic photodissociation is operating in these southern clouds.

It is not a simple matter to compare results from ultraviolet absorption and millimeter-wave emission lines. Absorption samples an infinitesmal pencil beam while emission is an average over the finite telescope beam. Furthermore, emission lines are more prone to uncertainties in excitation, radiative transfer, and abundance. Liszt & Lucas (1998) overcame these difficulties by measuring millimetric absorption against background compact extragalactic sources. They found a 12CO/13CO ratio between 15 and 54 that decreases with increasing $`N`$(12CO). Such a result indicates that isotope exchange prevails in their sample of relatively diffuse clouds with $`N`$(12CO) as large as $`2\times 10^{16}`$ cm-2.

The paper is organized in the following manner. The next Section provides details of the ultraviolet measurements acquired with GHRS as well as ground-based observations of CH+, which provided the ambient 12C/13C ratio. Section 3 presents our results while Section 4 describes our analysis. In the latter section, results on the excitation of the fine structure levels in the ground state of C I and on absorption from vibrationally excited H2 are included as an aid in constraining the appropriate physical conditions for the clouds. The data on C I and H2 were extracted from the spectra used for CO absorption. The resulting column densities for C I appear in Zsargó, Federman, & Cardelli (1997), who derived a self-consistent set of C I $`f`$-values for future analyses. \[The recent update by Federman & Zsargó (2001) does not alter these column densities because column densities and Doppler parameters were inferred from lines with well-known $`f`$-values.\] The relative populations in the fine structure levels are used to derive estimates for gas density and temperature (e.g., Jenkins, Jura, & Loewenstein 1983; Lambert et al. 1994) in the present work. Estimates of the flux of ultraviolet radiation permeating the gas are possible from analyses of vibrationally excited H2 (Federman et al. 1995; Meyer et al. 2001). Next, simple arguments highlight the importance of selective isotopic photodissociation for the three Sco-Oph sight lines. General comparisons with the theoretical predictions of van Dishoeck & Black (1988), Kopp et al. (1996), and Warin et al. (1996) are made in the Discussion, where we suggest areas for further improvement in the theoretical models. Such improvements in our models (van Dishoeck & Black 1988) are beyond the scope of this paper. Throughout this paper we note specific isotopes as needed; otherwise, the general chemical formula is used. Similarly, explicit notation is given for all CO bands that are not part of the $`AX`$ Fourth Positive System, which is designated only by $`v^{}`$0. An Appendix provides observational results for lines of elements heavier than zinc that are seen in our spectra.

## 2 Observations and Data Reduction

### 2.1 Ultraviolet Measurements

Only a brief description of our reduction procedure is given here; details can be found in our earlier papers (e.g., Lambert et al. 1995). Spectra were acquired with grating G160M of the GHRS and covered three wavelength intervals – 1252 to 1294 Å, 1385 to 1426 Å, and 1443 to 1488 Å. Each exposure consisted of 4 FP-SPLITs and several exposures were obtained at each nominal wavelength setting, but slightly offset from each other. The most important step in the reduction involved the realization of the highest possible signal-to-noise (S/N) ratio from the data. We applied the procedures outlined by Cardelli & Ebbets (1994) for the minimization of noise due to granularity, etc. on each FP-SPLIT subexposure. The final spectrum for a wavelength interval was derived from merging the individual FP-SPLITs in wavelength space. Table 1 provides a listing of the exposures for each star, as well as other pertinent information, such as central wavelength and the number of counts. The total number of counts for an interval, the S/N ratio attained in the merged spectra, and the CO bands covered by the interval are also shown. The exposure times were 1632s, except for z2b9020g where one FP-SPLIT subexposure failed. The resultant S/N ratio in our final spectra is on average very similar to the tabulated values computed from (total counts)0.5.

Two-Ångström segments centered on each CO band were extracted and the stellar continuum was rectified with routines available in the IRAF environment distributed by NOAO. The rectification process still retained residuals that constitute the largest errors in the profiles of the strong bands ($`v^{}`$ $`=`$ 2–5). While uncertainties in equivalent width ($`W_\lambda `$) as large as 25% are possible, the self-consistent column densities for the suite of bands suggests smaller systematic errors. A further problem arose while rectifying the spectra of $`\chi `$ Oph. Since $`\chi `$ Oph is a Be star, its continuum varies much more than do those of $`\rho `$ Oph A and $`\zeta `$ Oph. This introduced the largest source of error in the band profiles for the star because the acceptable rectified continuum depends to some extent on the person performing the task. Our final continua reflect the consensus of at least two rectifiers (Y.S. and S.R.F.). Figures 1 and 2 show respective spectra revealing absorption from 12CO and 13CO toward our targets. The observations are indicated by filled circles, and the fits (described below) to extract the 12CO/13CO ratio are shown as solid lines. Table 2 displays the $`W_\lambda `$ values for the CO bands derived from the fully reduced spectra of $`\rho `$ Oph A and $`\chi `$ Oph. These include the intersystem bands, $`a^{}X`$ 14$``$0 and $`eX`$ 5$``$0. The root-mean-square (rms) variation in the continuum and the number of pixels across a band were employed in a conservative computation of the uncertainty in $`W_\lambda `$. The CO bands in the spectra of $`\rho `$ Oph A are much stronger (optically thicker) than those of $`\chi `$ Oph and $`\zeta `$ Oph.

Absorption from C I and vibrationally excited H2 were seen in our spectra. The derivation of $`W_\lambda `$ for lines of neutral carbon toward both stars is presented in Zsargó et al. (1997). For absorption from $`v^{\prime \prime }`$ $`=`$ 3 in the lowest electronic state of H2, we employed a strategy much like the one discussed above for CO. Absorption involving the R(0), R(1), R(2), R(3), P(2), and P(3) lines was clearly detected in the spectrum of $`\rho `$ Oph A (see Figure 3). The presence of the P(2) line manifested itself by an asymmetry in the line at 1279.478 Å of C I from $`J`$ $`=`$ 2. Vibrationally excited H2 was not detected toward $`\chi `$ Oph. The results for measures of $`W_\lambda `$ appear in Table 3, which includes the results of Federman et al. (1995) for $`\zeta `$ Oph for reference. Our observations of all the expected lines in essence provide confirmation of vibrationally excited H2 in diffuse clouds, as suggested earlier by Federman et al. (1995). \[The data of Meyer et al. (2001) are likely probing gas under more extreme conditions.\] A steeply varying stellar continuum prevented the derivation of upper limits for R(0) and R(1) toward $`\chi `$ Oph; furthermore, while the lack of an asymmetry in the C I line at 1279.478 Å indicated that P(2) is not present, a useful upper limit could not be obtained.

### 2.2 Ground-based Measurements

High-resolution observations of 12CH+ and 13CH+ absorption toward $`\rho `$ Oph A and $`\chi `$ Oph were obtained at McDonald Observatory with an echelle spectrograph on the 2.7 m Harlan J. Smith Telescope in 1995 May. The stellar spectra were imaged onto a Texas Instruments CCD with 15 $`\mu `$m pixels. An interference filter was used to limit the spectral coverage to the single order containing the lines near 4230 Å. Bias and flat-field images were acquired each night and Th-Ar comparison spectra were interspersed among the stellar spectra. Dark frames were taken the first night as a check on background levels during the longest exposure. In all, $`\rho `$ Oph A ($`B`$ $`=`$ 5.26) was observed for 20 hours and $`\chi `$ Oph ($`B`$ $`=`$ 4.70) for 14 hours.

The raw data were reduced with standard IRAF procedures. After bias subtraction, flat fielding and removal of scattered light and cosmic rays, the spectra were extracted. Wavelength calibration was based on lines seen in the Th-Ar comparison spectra. The spectral resolution, which was derived from the full width at half maximum (FWHM) of the Th-Ar lines averaged over all the nights, was determined to be $`33.1\pm 0.3`$ mÅ, which is significantly larger than the thermal width for the Th lines ($``$ 2 mÅ). For $`\rho `$ Oph A, fitting of the continuum level around the CH+ lines was straightforward. However, for $`\chi `$ Oph, an underlying stellar emission line caused some concern. Centurion et al. (1995; hereafter CCV) used a synthetic stellar line (which they assign to Fe II $`\lambda `$4233.167) to extract and normalize the spectrum of the star HD110432 in the direction of the Southern Coalsack. An unfortunate fact of our spectrum was that only part of the stellar line was included, and so we performed a normal continuum division, restricted to a limited wavelength interval in order to minimize the influence of baseline structure. Since for $`\chi `$ Oph the interstellar line is located on the blue wing of the stellar line, rather than in the self-reversal core (cf. CCV), we do not believe that our extraction procedure added significantly to the derived uncertainties. The rms dispersion in the rectified continuum yielded a signal-to-noise ratio per pixel of about 650 for both stars. The rectified spectra appear in Figure 4.

After normalization/rectification, the $`W_\lambda `$ for the 12CH+ and 13CH+ lines were derived from Gaussian fits. Two methods utilizing the STSDAS routine NGAUSS were employed. In the first, we adopted an isotope shift of $`0.272`$ Å, as measured from the 12CH+ line. This value is based on the laboratory measurements by Bembenek (1997) for 13CH+ and those of Carrington & Ramsay (1982) for 12CH+. We kept the widths of the 13CH+ and 12CH+ lines the same in our syntheses. The results of this analysis appear in Table 4, where $`W_\lambda `$, $`v_{LSR}`$, and the Doppler parameter ($`b`$-value) are given. The LSR velocities obtained here are within 1 km s-1 of those derived by Crane, Lambert, & Sheffer (1995) from ultra-high-resolution observations; the $`b`$-values also agree very well. The relatively large $`b`$-values seen for CH+ lines are likely a consequence of its production involving an endothermic reaction (e.g., Lambert & Danks 1986). As for the $`W_\lambda `$, our determinations and those of Lambert & Danks (1986) are very similar, as are the results of Crane et al. for $`\chi `$ Oph. For $`\rho `$ Oph A, the measurements of Crane et al. yield an $`W_\lambda `$ about 2-$`\sigma `$ larger. The values of $`W_\lambda `$ yield column density ratios, $`N(^{12}\mathrm{CH}^+)`$/$`N(^{13}\mathrm{CH}^+)`$, of $`120\pm 54`$ and $`65\pm 19`$, respectively, for the gas toward $`\rho `$ Oph A and $`\chi `$ Oph from a curve-of-growth analysis with $`f`$ $`=`$ $`5.5\times 10^3`$ and $`b`$ $`=`$ 2.5 km s-1. Use of a smaller $`b`$-value, 2 km s-1, introduces a negligible change because the optical depth at line center for 12CH+ is less than 0.5. The uncertainties in the ratios are dominated by the precision of the 13CH+ measures. The result for $`\chi `$ Oph is in the range (60 – 70) determined for other sight lines, but that for $`\rho `$ Oph A is a bit high (consistent at the 1-$`\sigma `$ level, however).

In the second method, we fixed the relative wavelength offset between the isotopomers at $`0.265`$ Å. This isotopic shift is based on the measurements of CCV for CH+ toward HD110432, rather than the value of $`0.26`$ Å obtained from theoretical calculations by Auguson and Herbig (1967) and used in earlier studies (e.g., Centurion & Vladilo 1991). The quoted uncertainty of about 2 to 3 mÅ in each laboratory measurement (Carrington & Ramsay 1982; Bembenek 1997) indicates that the shift derived from astronomical spectra is consistent with the laboratory value at about the 1.5-$`\sigma `$ level. With a shift of $`0.265`$ Å we find $`109\pm 36`$ and $`61\pm 20`$ for $`\rho `$ Oph A and $`\chi `$ Oph. In summary, the ratios derived here indicate that the 12C/13C ratio is approximately 65, as in other, more precise determinations for the general interstellar medium (e.g., Langer & Penzias 1993; CVV) and for the Rho Ophiuchi Molecular Cloud in particular (Bensch et al. 2001).

## 3 Relative Abundances of CO Isotopomers

Three steps were employed in the extraction of the relative abundances among the isotopic variants of CO. The extraction was based on synthesis of the measured bands through the minimization of the rms difference between the observed band and the fit. The $`f`$-values of Chan et al. (1993) were adopted, as was the case in Lambert et al. (1994). The first step involved fits to absorption from the weaker 10$``$0 and 11$``$0 bands in order to set the initial column density. For this column density, simultaneous fits of the stronger bands yielded rotational excitation temperatures ($`T_{rot}`$ $`=`$ $`T_{10}`$, $`T_{21}`$, and $`T_{32}`$) and the $`b`$-value. The final step involved fitting the 13CO bands, which are not very sensitive to changes in $`T_{rot}`$ and $`b`$-value because these bands are optically thin. As consistency checks on these derived rotational excitation temperatures, $`T_{rot}`$ also was estimated from the 10$``$0 and 11$``$0 bands of 12CO and the 2$``$0, 3$``$0, and 4$``$0 bands of 13CO under the assumption that $`T_{10}=T_{21}=T_{32}`$. These determinations yield similar excitation temperatures for 12CO, within the mutual uncertainties, and show that the rotational excitation in 12CO and 13CO is essentially the same. One added complication with the 2$``$0 and 3$``$0 bands for 13CO was the presence of the C18O band. For the synthesis of the 13CO bands toward $`\rho `$ Oph A, where all bands were much stronger than those toward $`\chi `$ Oph, the 13C16O/12C18O ratio was inferred as well. Figures 1 and 2 also show the synthetic spectra and the residuals between the observed and synthetic profiles. For completeness, the data are displayed with theoretical curves of growth, which are based on our results in Table 5, in Figure 5. All data can be described very well by these curves of growth, which were computed for a given $`N`$(CO) with the appropriate wavelengths for the various lines comprising the bands. Allowance was also made for absorption from 12C18O in the strongest bands.

This procedure provided the necessary information for our study of chemical fractionation in CO; the results appear in Table 5. The values for $`N(^{12}\mathrm{CO})`$ are the most precise among available ones for the sight lines to $`\rho `$ Oph A and $`\chi `$ Oph. We note that the CO ($`AX`$) bands toward $`\rho `$ Oph A are stronger than the ones seen in the spectrum of $`\zeta `$ Oph (Sheffer et al. 1992; Lambert et al. 1994; Lyu et al. 1994). The 12CO column density is not as large, however, because the $`b`$-values are greater. Our determination of the column density toward $`\rho `$ Oph A is about a factor of 3 greater than the value inferred from $`Copernicus`$ data of the $`B`$$`X`$ 0$``$0 band at 1150 Å (Snow & Jenkins 1980). Most of the difference arises from the fact that they adopted a $`b`$-value of 1.2 km s-1 where we deduced $`b`$ $`=`$ 0.6 km s-1. Because we fitted several bands simultaneously, whose wavelengths fall on different parts of the blaze function for G160M, our $`b`$-values are less susceptible to the variations in spectral resolution across the blaze noted by Lyu et al. (1994). As for $`\chi `$ Oph, the $`Copernicus`$ measurements of Frisch (1980) on the $`C`$$`X`$ 0$``$0 band near 1088 Å, using a band oscillator strength of 0.123 (Federman et al. 2001), yield a value for $`N(^{12}\mathrm{CO})`$ that agrees nicely with ours. We also extracted the $`Copernicus`$ data on $`\rho `$ Oph A and $`\chi `$ Oph for both the $`BX`$ and $`CX`$ 0$``$0 bands from the MAST archive at the Space Telescope Science Institute and used routines in IRAF for an improved comparison with the GHRS results. Table 6 shows the comparison of measured and derived values of $`W_\lambda `$; the derived values are based on the $`f`$-values of Federman et al. (2001) and the cloud parameters \[$`N`$(12CO), $`T_{10}`$, $`T_{21}`$, and $`b`$-value\] from the synthesis of the $`AX`$ bands. The correspondence between the values is very good. The relatively slight differences for the $`CX`$ band are mainly the result of imprecise subtraction of the Cl I line at 1088 Å. The $`W_\lambda `$ for the $`CX`$ band toward $`\rho `$ Oph A from Federman et al. (1980) is significantly less than that reported here; an incorrect continuum placement is likely the cause.

While the above comparison shows that the derived cloud parameters are rather robust, we now comment on the velocities, $`b`$-values, and excitation temperatures in Table 5. The heliocentric velocities associated with the weighted blend of the Q(1) and Q(2) lines for the 2$``$0 through 5$``$0 bands agree with those obtained by Crane et al. (1995) to within about 2 km s-1. Since thermal velocities do not contribute significantly to the line width, we would expect similar $`b`$-values for different species. Indeed, the $`b`$-values of $``$ 0.60 to 0.70 km s-1 agree with other measures based on ultra-high-resolution observations. Measurements of K I $`\lambda `$ 4044 toward $`\chi `$ Oph (Knauth et al. 2003) indicate a similar value. The K I column density from $`\lambda `$ 7699 (Welty & Hobbs 2001) can be made consistent with the results from $`\lambda `$ 4044 by assuming one velocity component with a $`b`$-value of about 0.70 km s-1. Moreover, Welty & Hobbs suggest that the strongest component toward $`\rho `$ Oph A has a $`b`$-value of approximately 0.60 km s-1. For the direction toward $`\rho `$ Oph A, synthesis of the strong and weak band profiles yielded different rotational excitation temperatures. While the 2$``$0 to 5$``$0 12CO bands indicate $`T_{10}`$ of 2.7 K, the weaker 10$``$0 and 11$``$0 bands, as well as 2$``$0 to 5$``$0 bands of 13CO, are better fitted with $`T_{10}`$ between $`7.7\pm 2.5`$ and $`10.3\pm 2.9`$ K. (The larger excitation temperatures are more consistent with $`T_{21}`$ and $`T_{32}`$ derived from the strong bands of 12CO.) If the effect is substantiated by more precise determinations, it could be understood in terms of how deeply the observations probe into the cloud: optically thin bands, which sample most of the volume, reveal higher excitation temperatures in the core, but saturated bands are sensitive to outside regions of the cloud. This effect can arise from a density gradient which also appears in our analysis of C I levels and vibrationally excited H2 described below. The effect of a decreasing CO excitation temperature toward the edge of the cloud can also result from less trapping of CO millimeter lines in the periphery compared with the amount of trapping in the cloud’s core (e.g., Bernes 1979; Hogerheijde & van der Tak 2000). An explicit radiation transfer code would be needed to confirm this scenario. In its stead, we also suggest that some combination of two clouds with differing physical conditions, such as the two dominant components seen by Welty & Hobbs (2001) in K I absorption, might account for $`T_{10}`$ variations in the bands. Crane et al. (1995) found two CH components toward $`\rho `$ Oph A as well, one with a small $`b`$-value like that inferred by CO and the other with a larger $`b`$-value.

Two intersystem bands of CO, $`a^{}X`$ 14$``$0 and $`eX`$ 5$``$0, are present in our spectra of $`\rho `$ Oph A and the stronger $`a^{}X`$ band is seen toward $`\chi `$ Oph. Table 2 gives the measured values of $`W_\lambda `$. Federman et al (1994a) derived an $`f`$-value for the $`a^{}X`$ band which was $`(31\pm 7)`$% smaller than that computed by Morton & Noreau (1994), while the $`f`$-value for the $`eX`$ band was ($`89\pm 16`$)% smaller. Fitting the bands with the parameters deduced from the $`A`$$`X`$ bands suggests $`f`$($`a^{}X`$) of ($`0.7\pm 0.2`$) $`f`$(MN) and $`f`$($`eX`$) of ($`1.1\pm 0.3`$) $`f`$(MN), where $`f`$(MN) is the value quoted by Morton & Noreau (1994). Our more precise determinations from spectra of X Per taken with the Space Telescope Imaging Spectrograph (Sheffer, Federman, & Lambert 2002) reveal respective $`f`$-value ratios of 0.94 $`\pm `$ 0.15 and 0.78 $`\pm `$ 0.12. The combination of the results for these directions suggests that the band oscillator strength quoted by Morton & Noreau should be decreased some 10 – 30%. Improved analysis that includes multiple curve crossings (Rostas et al. 2000; Eidelsberg & Rostas 2003) substantiates the astronomical findings.

## 4 Analysis

### 4.1 Density from Atomic and Molecular Excitation

The relative populations of the fine structure levels in the ground state of C I yield estimates for gas density and temperature (e.g., Jenkins et al. 1983). The populations are mainly affected by collisional (de)excitation and far infrared radiative decay, and to a lesser extent by ultraviolet pumping and the subsequent decay from the excited electronic level. We previously analyzed the distribution of these levels in our study of the gas toward $`\zeta `$ Oph (Lambert et al. 1994). Here we apply the same technique to the data on C I toward $`\rho `$ Oph A and $`\chi `$ Oph. Zsargó et al. (1997) derived column densities for each level; the resulting ratios, $`N(J^{})`$/$`N(J)`$, are $`N(1)`$/$`N(0)`$ $`=`$ $`0.430\pm 0.024`$ and $`0.422\pm 0.019`$, respectively, for $`\rho `$ Oph A and $`\chi `$ Oph, and $`N(2)`$/$`N(0)`$ $`=`$ $`0.238\pm 0.014`$ and $`0.235\pm 0.011`$ for the two sight lines. The abundances (relative to total protons) of the collision partners (H, o-H2, and p-H2) are also needed; these were obtained from Savage et al. (1977). For He, we assumed an abundance of 10%. As in all analyses of excitation, if the temperature is known, the density of collision partners ($`n_c`$) is inferred. For neutral interstellar gas, $`n_c`$ $``$ $`n`$(H) $`+`$ $`n`$(H2).

The results of our analysis appear in Figure 6, where the allowed ranges in density and temperature are shown for 2-$`\sigma `$ excursions about the observed column density ratios. One facet is immediately clear: The results for $`N(1)`$/$`N(0)`$ (dashed lines) suggest lower densities than do the results for $`N(2)`$/$`N(0)`$ (dot-dashed lines). The earlier analysis by Jenkins et al. (1983), based on spectra from the $`Copernicus`$ satellite, did not reveal this dichotomy. Their column density ratios, though generally consistent with our estimates, probably had uncertainties too large to discern any difference. We also note that Jenkins et al. and Federman, Welty, & Cardelli (1997b) found this dichotomy toward the nearby line of sight to $`\beta ^1`$ Sco, while Zsargó & Federman (2003) detected the two velocity components in high-resolution ECH-A data on 1, $`\delta `$, and $`\sigma `$ Sco. Ultra-high resolution spectra reveal additional, weaker components in K I absorption toward $`\rho `$ and $`\chi `$ Oph (Welty & Hobbs 2001). Moreover, for our two directions, the $`b`$-values deduced from curves of growth for the lines originating from $`J`$ $`=`$ 0 and 1 are larger than the $`b`$-value for the $`J`$ $`=`$ 2 lines (Zsargó et al. 1997). From this information, we infer that absorption from the lower fine structure levels are probing (1) more extended portions of the neutral gas where the average density is expected to be lower or (2) an additional low density component.

The use of the rotational excitation temperature for the $`J`$ $`=`$ 0 and 1 levels in H2 \[$`T_{01}(\mathrm{H}_2)`$\] as a measure of the kinetic temperature allows us to derive values for the gas density. Adopting the 2-$`\sigma `$ range in values of Savage et al. (1977), which are also indicated in Fig. 6, yields densities for the gas toward both of our targets of $``$ 100 and 200 – 400 cm-3 from $`N(1)`$/$`N(0)`$ and $`N(2)`$/$`N(0)`$, respectively. The estimates are rather robust. There is little change when applying substantial differences in the relative fractions of collision partners; the inferred densities are mainly influenced by the observed relative fine structure populations. For $`\rho `$ Oph A, the effects of increasing the amount of UV pumping are illustrated in Fig. 6 as well. A 10-fold increase in UV flux, as suggested by our H2 measurements, lowers the density estimate a small, but noticeable amount.

We can derive other estimates for gas density from analysis of the distribution of rotational levels in the ground state of C2 or CO. Excitation of C2 involves a combination of collisions, radiative decay between rotational levels, and near infrared pumping to the $`A`$ electronic state, followed by radiative cascades among vibrational and rotational levels of the ground state. According to van Dishoeck & Black (1982), the amount of excitation can be represented by $`n_c\sigma `$/$`I_{ir}`$, where $`\sigma `$ is the collisional cross section and $`I_{ir}`$ is the enhancement in IR flux over the typical interstellar value. The observational data on C2 of Danks & Lambert (1983) and van Dishoeck & de Zeeuw (1984), along with the theoretical predictions of van Dishoeck & Black (1982), lead to the estimates shown in Figure 6 as enclosed areas. These were obtained through a $`\chi `$-squared minimization procedure, weighted by the precision of the observational data on column density for a given level. We adopted a cross section of $`2\times 10^{16}`$ cm-2, an oscillator strength of $`1\times 10^3`$, and $`I_{ir}`$ of 1.

The results from C2 excitation are generally consistent with those from the $`N(1)`$/$`N(0)`$ ratio for C I, which is a bit of a surprise. The estimates from C2 are very sensitive to assumptions concerning excitation. Recent determinations (Langhoff et al. 1990; Erman & Iwamae 1995; Lambert et al. 1995) of the oscillator strength for the $`AX`$ 2$``$0 band, $`f_{20}`$, are 20 to 40% larger than the adopted value. A larger $`f`$-value would increase the density estimate (van Dishoeck & Black 1982) a corresponding amount. The adopted cross section is in the middle of the range suggested by van Dishoeck & Black. Quantal calculations (Lavendy et al. 1991; Robbe et al. 1992; Phillips 1994) span the suggested range, with larger cross sections giving lower densities. A reexamination of C2 excitation, utilizing the more recent determinations of $`f_{20}`$ and collisional cross sections, appears necessary.

Finally, the excitation of CO can be studied. This excitation is controlled by collisions, radiative decay, absorption of the cosmic background radiation, and resonant scattering of CO lines from nearby molecular clouds (Wannier, Penprase, & Andersson 1997). The latter process appears to be the dominant one, and as a result, only upper limits on density are possible. This conclusion is based on the $`J`$ $`=`$ $`10`$ maps of the Sco-Oph region by de Geus, Bronfman, & Thaddeus (1990). We selected the channel with $`v_{LSR}`$ between 3 and 5 km s-1 and estimated the filling factors for the gas at the projected positions of $`\rho `$ Oph A and $`\chi `$ Oph. The excitation temperature, $`T_{10}`$, due solely to resonant scattering of emission from the molecular cloud is $`7.3\pm 1.0`$ and $`3.2\pm 0.4`$ K, respectively. These values are comparable to, or greater than, the values inferred from profile synthesis of the UV absorption bands. Therefore, all that can be said about density is that is it less than about 1000 cm-3. The fact that $`T_{10}`$ is not larger than $`T_{21}`$ or $`T_{32}`$, as would be expected for subthermal conditions in relatively diffuse gas, is further proof that resonant scattering of line radiation dominates CO excitation along the two sight lines.

### 4.2 UV Flux from H2 Excitation

In cold ($`T`$ $`<`$ 1000 K) gas, the population of the $`v`$ $`=`$ 3 level of the ground electronic state is governed by the flux of ultraviolet radiation permeating the cloud (Black & van Dishoeck 1987). Absorption from the $`J`$ $`=`$ 0, 1, and 2 levels in the vibrational ground state – the ones with the greatest populations – of ultraviolet photons leaves the H2 molecules in excited electronic states, but rapid decay returns the molecules to various vibrational levels of the ground electronic state (e.g., Black & Dalgarno 1976). Collisional (de)excitation is not effective in (de)populating $`v`$ $`=`$ 3 because the densities and temperatures are too low. Thus, from the amount of absorption we can infer the ultraviolet flux (Federman et al. 1995).

The measurements of vibrationally excited H2 toward $`\rho `$ Oph A are not easily modeled. The amount of H I along the line of sight is very large, which, together with the large amount of H2 in $`v`$ $`=`$ 3, suggests that there is low density gas close to the star. \[Use of the revised H I column ($`4.3\times 10^{21}`$ cm-2) of Diplas & Savage (1994) in the analysis does not remove the difficulties encountered here.\] On the other hand, the CO column density is quite high and $`T_{10}(\mathrm{H}_2)`$ is only 46 K (Savage et al. 1977), indicating the presence of denser, lower temperature gas along the line of sight. Rotational excitation in C2 is consistent with a total density of a few hundred cm-3, although the quality of the data is not very high (see Fig. 6). \[The total density, $`n_{tot}`$ $`=`$ $`n`$(H I$`+`$ 2$`n`$(H2) $`>`$ $`n_c`$, is the parameter of interest in chemical modeling. For our sight lines, $`n_{tot}`$ is about 1.5 $`n_c`$.\]

The results from a set of models for $`\rho `$ Oph A appear in Table 7, where the first five entries are the input parameters for the models: the enhancement factor for the UV flux ($`I_{UV}`$), $`n_{tot}`$, the gas temperature ($`T`$), the polytropic index, and the means of populating the levels during H2 formation. All our models are based on an adopted $`b`$-value of 1.0 km s-1. The initial model had constant $`n_{tot}`$ and $`T`$ with $`n_{tot}`$ $`=`$ 300 cm-3, $`T`$ $`=`$ 45 K, and $`I_{UV}`$ $`=`$ 4. This model reproduces the H2 $`v`$ $`=`$ 0 observations quite well, but it fails to reproduce those for H I and H2 $`v`$ $`=`$ 3. Increasing the radiation field to $`I_{UV}`$ $`=`$ 10 brings the column density for H2 in $`v`$ $`=`$ 3, $`J`$ $`=`$ 0 into agreement with observations, but this fails for the higher rotational levels. The H2 levels $`v`$ $`=`$ 3, $`J`$ $`=`$ 1-3 clearly indicate a much higher rotational temperature, between 100 and 500 K; the second model shows the effects of increasing the temperature to 100 K. This improves the comparison with the rotational levels in $`v`$ $`=`$ 3, but now the column densities for $`v`$ $`=`$ 0 are not consistent with observations. An attempt based on polytropic models with a temperature gradient from about 400 K at the edge to 45 K or 100 K in the center still could not reproduce all the data. Given the limited set of data, especially the lack of data for the high-lying rotational levels in $`v`$ $`=`$ 0, we can only state that there seems to be at least two components along the line of sight. A warm component of low density gas is exposed to a radiation field that is enhanced by a factor of $``$ 10 over the standard radiation field (Draine 1978); presumably, this gas is located close to the B2 V star, about 0.2 pc away. As noted in our work on $`\zeta `$ Oph (Federman et al. 1995), the current models do not include line overlap, which can result in an overestimate of the pumping rate by up to a factor of 2. Thus, the $`I_{UV}`$ inferred here for this component should be regarded as a lower limit. The second component, containing most of the H2 $`v`$ $`=`$ 0, as well as CO and C2, must be much colder and denser. This picture suggests that we are observing a photodissociation region in the reflection nebula associated with $`\rho `$ Oph via absorption lines. The two components may correspond to the dominant components in K I (Welty & Hobbs 2001) and the two seen in CH spectra (Crane et al. 1995). Both K I and CH probe material over a larger range in density than either CO or C2.

The direction to $`\chi `$ Oph was modeled by van Dishoeck & Black (1986); their best model (G) yielded predictions for the amount of H2 in $`v`$ $`=`$ 3 which exceed our upper limits by factors of 2-4 or so (see Table 7). Therefore, the value for $`I_{UV}`$ used in the calculations must be reduced accordingly, from which we infer that the strength of the ultraviolet field is comparable to the average interstellar field ($`I_{UV}`$ of 1 to 2). As shown in Table 7, new calculations with reduced field strengths confirm this supposition. The results of the simplified analysis of Federman et al. (1994b) now agree better with the refined models described here.

### 4.3 CO Fractionation

With the addition of the present results for $`\rho `$ Oph A and $`\chi `$ Oph, there are three sight lines in Sco OB2 with accurately determined values for the $`N(^{12}\mathrm{CO})`$/$`N(^{13}\mathrm{CO})`$ ratio. We have $`125\pm 23`$ for $`\rho `$ Oph A, $`117\pm 35`$ for $`\chi `$ Oph, and $`167\pm 15`$ for $`\zeta `$ Oph (the latter from Lambert et al. 1994). The amount of fractionation is comparable in the gas toward $`\rho `$ Oph A and $`\chi `$ Oph and it is larger toward $`\zeta `$ Oph. These ratios are greater than the ambient 12C/13C ratio of about 65; self shielding of the more abundant isotopomer clearly causes the observed fractionation. The results can be understood in a qualitative way through the realization that larger column densities increase the effects of self shielding, while larger fluxes of ultraviolet radiation increase the photodissociation rate. In other words, the ‘reduced column density’ $`N(^{12}\mathrm{CO})`$/$`I_{UV}`$ is a measure of the amount of fractionation. Taking $`N`$(12CO) from Table 5 and $`I_{UV}`$ from the previous section, along with the results for $`\zeta `$ Oph from Lambert et al. (1994), $`N`$(12CO) $`=`$ $`2.5\times 10^{15}`$ cm-2, and Federman et al. (1995), $`I_{UV}`$ $`=`$ 1 to 2, we obtain values of $`N(^{12}\mathrm{CO})`$/$`I_{UV}`$ of about $`1.9\times 10^{14}`$, $`1.93.8\times 10^{14}`$, and $`1.32.5\times 10^{15}`$ cm-2 for $`\rho `$ Oph A, $`\chi `$ Oph, and $`\zeta `$ Oph, respectively. The ‘reduced column density’ follows the trend seen in the observed amount of fractionation. For the directions considered here, selective isotopic photodissociation is the process controlling the relative abundances of the 12CO and 13CO isotopomers; the present results on C18O are not precise enough for definitive statements.

A more quantitative means of comparison involves analysis based on eqn. (15) in Lambert et al. (1994):

$$F_{13}=\frac{\mathrm{\Gamma }_{13}}{\mathrm{\Gamma }_{12}}\left[1+\frac{3.2\times 10^{12}}{\mathrm{\Gamma }_{13}}\left(\frac{n_{tot}}{200}\right)\left(\frac{\delta _\mathrm{C}}{0.1}\right)\right]\times \left[1+\frac{6.4\times 10^{12}}{\mathrm{\Gamma }_{12}}\left(\frac{n_{tot}}{200}\right)\left(\frac{\delta _\mathrm{C}}{0.1}\right)\right]^1.$$

In this expression, the amount of fractionation, $`F_{13}`$, is \[$`n`$(12CO)/$`n`$(13CO)\]/\[$`n`$(12C)/$`n`$(13C)\] and the photodissociation rate for isotopomer $`i`$ is $`\mathrm{\Gamma }_i`$. The numerical coefficients in square brackets are based on the rate constants for isotopic charge exchange, while $`\delta _\mathrm{C}`$ represents the elemental carbon abundance relative to the value for the Sun. A factor of 0.4 more closely matches the interstellar measurements of Cardelli et al. (1993a). The photodissociation rates come from the calculations of shielding functions by van Dishoeck & Black (1988) $``$ see their Table 5, which includes the effects of CO self shielding and mutual shielding from H2. The necessary columns of H2 are taken from Savage et al. (1977). The amount of grain attenuation is based on Model 2 described by van Dishoeck & Black (1986). For $`\rho `$ Oph A and $`\chi `$ Oph, we multiplied the grain optical depth by 0.7 to accommodate larger than average values for the ratio of total to selective extinction (Federman et al. 1994). We approximate local densities $`n`$(X) with column densities. We considered $`I_{UV}`$ of 1 toward $`\chi `$ and $`\zeta `$ Oph and $`I_{UV}`$ $`=`$ 10 toward $`\rho `$ Oph A. For $`n_{tot}`$, we adopted 300 cm-3 for the gas toward $`\rho `$ Oph A and $`\chi `$ Oph, as inferred above, and 200 cm-3 for the gas toward $`\zeta `$ Oph (Lambert et al. 1994). Finally, since van Dishoeck & Black (1988) considered a slab geometry, the column densities used here are one half the measured ones.

With the use of an ambient isotope ratio of 65 for carbon, our measurements indicate values for $`F_{13}`$ of 1.9 $`\pm `$ 0.4, 1.8 $`\pm `$ 0.6, and 2.6 $`\pm `$ 0.3 for the directions $`\rho `$ Oph A, $`\chi `$ Oph, and $`\zeta `$ Oph. The uncertainties in the observed values are based on the uncertainties in the 12CO/13CO ratios and an assumed 10% uncertainty in the 12C/13C ratio, taken in quadrature. The quantities in square brackets are approximately 1 when $`n_{tot}`$ of a few hundred cm-3 is adopted, as found from C I and C2 excitation. The main exceptions are the calculations for $`\chi `$ and $`\zeta `$ Oph where the bracket involving $`\mathrm{\Gamma }_{12}`$ is about 2.0. In other words, this re-enforces the notion that the three sight lines are controlled by photodissociation. We find $`F_{13}`$ to be 1.8, 1.0, and 1.2 for the respective sight lines. Considering the simplications made (e.g., column for local density), the accuracy of the observational results (10-30%), and the results using Table 5 of van Dishoeck & Black (1988) (20-30%), the agreement between calculations and observations is good. The correspondence for $`\chi `$ and $`\zeta `$ Oph could be improved by combined changes in $`I_{UV}`$ and $`n_{tot}`$ of about a factor of 4; this would be accomplished by increasing $`I_{UV}`$ and decreasing $`n_{tot}`$. It is satisfying that our simple analyses utilizing observational input are able to reproduce the enhanced 12CO/13CO ratios seen by us. A more detailed modeling effort is beyond the scope of this paper.

## 5 Discussion

### 5.1 H2 Excitation

When the populations of vibrationally excited H2 are controlled by optical pumping via absorption of UV photons, the ortho (odd $`J`$) to para (even $`J`$) ratio in excited states differs from the ratio for the vibrational ground state (Sternberg & Neufeld 1999). While their work focuses on warm photodissociation regions, where the ortho to para ratio in the ground state is the thermal value, the same ideas apply to cool gas where the population in $`J`$ $`=`$ 0 is large. The effect is clearly seen in our data for $`\rho `$ Oph A and the data of Federman et al. (1995) for $`\zeta `$ Oph. The respective ortho to para ratios for the $`v`$ $`=`$ 3 state toward the two stars are $`2.7\pm 0.9`$ and $`4.1\pm 2.2`$, and the corresponding ratios for the ground state are $`0.7\pm 0.3`$ and $`1.2\pm 0.4`$. For the $`v`$ $`=`$ 3 state, we summed over all possible rotational levels, including statistical weights, but only considered the $`J`$ $`=`$ 0 and 1 levels of the ground state because they have much larger columns than higher-lying levels.

The difference in ortho to para ratio between vibrational levels arises from enhanced optical depth in lines from $`J`$ $`=`$ 0 of the ground state. Since optical pumping populates the rotational levels of vibrationally excited states via a two-step process, the change in rotational quantum number is 0 or 2. The larger optical depth of lines originating from $`J`$ $`=`$ 0, the most populous (para) level, reduces the abundance of para rotational levels in $`v`$ $`=`$ 3. This leads to a larger ortho to para ratio for $`v`$ $`=`$ 3.

Excitation of H2 also occurs during its formation on grains. During formation about 4.4 eV of binding energy is distributed among substrate excitation, molecular excitation, and translational energy. The partition among the channels is poorly understood. For instance, it is not clear whether the nascent molecules are vibrationally hot and rotationally cold $``$ high $`v`$ and low $`J`$ (see Duley & Williams 1993) $``$ or the opposite (Hunter & Watson 1978; Wagenblast 1992). More recent experimental (Gough et al. 1996) and theoretical (Kim, Ree, & Shin 1999) work on H2 excitation during formation on carbonaceous surfaces suggests most of the energy goes into vibrational motion. Internal excitation of H2 could be discerned from observations of high-lying rotational levels in the ground state and of vibrationally excited H2. Since high-lying rotational levels in the ground state are needed to assess the importance of the predicted distributions (Federman et al. 1995), but such data do not exist for $`\rho `$ Oph A, more definitive statements cannot be made at this time. The large number of ro-vibrational levels probed by observations of HD 37903 (Meyer et al. 2001) may provide the answer to this important question.

In our studies of molecular chemistry in diffuse clouds (e.g., van Dishoeck & Black 1989; Federman et al. 1997c; Knauth et al. 2001), we have begun to appreciate the importance of using the extinction curve for the sight line in the analysis. As for the two directions examined here, the extinction curve for both stars is lower than ‘typical’ at the shortest wavelengths (Fitzpatrick & Massa 1990; Snow, Allen, & Polidan 1990; Green et al. 1992). In the present work, we did not attempt to model more than H2 in any detail. Under these circumstances, different extinction curves could be incorporated into the scaling term $`I_{UV}`$. It is also worth mentioning that calculations adopting bi-directional radiation fields, like those of Lyu et al. (1994), with one half the flux incident on each side of the cloud yield results similar to the ones presented here.

### 5.2 CO Fractionation

There are now three sight lines, all in Sco-Oph, where 12CO is enhanced relative to other isotopomers by approximately a factor of two over the ambient 12C/13C ratio. We are confident in our results for a number of reasons. First, other analyses that yielded smaller relative amounts of 12CO from the CO data toward $`\zeta `$ Oph were based either on a set of $`f`$-values now known to be inaccurate (Lyu et al. 1994) or on data of the same bands for 12CO and 13CO (Levshakov & Kegel 1994) which are prone to optical depth corrections in the more abundant isotopomer. The former point is addressed in more detail below. Second, our synthesis code does not always give results indicating enhanced amounts of 12CO. In a paper on photodissociation regions toward sources of reflection nebulae (Knauth et al. 2001), our code used for profile synthesis confirmed the lower 12CO/13CO ratio ($``$ 40) seen toward 20 Aql (Hanson, Snow, & Black 1992) from an independent extraction of $`IUE`$ spectra.

An especially critical one is the third reason. New measurements of $`f`$-values for Rydberg transitions of CO are larger than once thought (Federman et al. 2001). \[These are the $`f`$-values giving excellent fits to the CO bands seen in $`Copernicus`$ spectra, upon adoption of the parameters derived from the $`AX`$ bands, as discussed in Section 3 and in Federman & Lambert (2002).\] Although only a few transitions of importance in CO photodissociation have been re-examined to date, in all cases the $`f`$-values for Rydberg transitions are about a factor of two larger than those compiled by Eidelsberg et al. (1991) from the measurements of Letzelter et al. (1987). This may explain why ab initio modeling efforts, such as those of van Dishoeck & Black (1986), van Dishoeck & Black (1988), Kopp et al. (1996), and Warin et al. (1996), are unable to produce 12CO/13CO ratios much in excess of the ambient 12C/13C ratio. Use of a larger $`f`$-value would increase the optical depth of dissociating transitions, which in turn leads to more self shielding for the more abundant isotopomer. Moreover, larger optical depths in lines leading to CO dissociation would improve the correspondence between model predictions and submillimeter-wave observations of dense photodissociation regions (Hollenbach & Tielens 1999). Further work is needed to derive accurate $`f`$-values for all transitions involved in CO photodissociation.

More self shielding for 12CO would also provide a better correspondence in the CO abundance between model and observations. For instance, the theoretical predictions of van Dishoeck & Black (1986) are too small by factors of a few, even after accounting for the smaller values for $`I_{UV}`$ derived from vibrationally excited H2. An enhancement in CO production would help alleviate the problem as well. A key reaction is C+ $`+`$ OH $``$ CO+ $`+`$ H. Dubernet, Gargaud, & McCarroll (1992) performed quantal calculations on this reaction and obtained a rate constant of about $`5\times 10^9`$ cm3 s-1, which is substantially larger than the estimate given in Prasad & Huntress (1980) and is about a factor of 2 larger than the value given by Federman & Huntress (1989) based on average dipole orientation (ADO) theory.

While a self-consistent picture seems to be emerging, we briefly discuss the apparent contradictory results of Lyu et al. (1994) and Liszt & Lucas (1998). It is our contention that the differences between Lyu et al. and our earlier work (Sheffer et al. 1992; Lambert et al. 1994) for $`\zeta `$ Oph lie in the adopted $`f`$-values. As noted in the Introduction, Lambert et al. found a more satisfactory curve of growth with the $`f`$-values of Chan et al. (1993). All agree that the column density of 12CO is best determined by the 11$``$0 and 12$``$0 bands, which are essentially optically thin. For these bands, the $`f`$-values of Eidelsberg et al. (1992) are 50% larger than those of Chan et al. With their preferred curve of growth, Lyu et al. infer $`N`$(12CO) $`=`$ $`1.8\times 10^{15}`$ cm-2; this value becomes $`2.7\times 10^{15}`$ cm-2 when using Chan et al.’s $`f`$-values, much more in line with the results of Lambert et al. ($`2.5\times 10^{15}`$ cm-2). We also point out that the two sets of results for the 5$``$0 band of 13CO agree nicely. There is another way to check the 12CO/13CO ratios: the ratio of $`f`$-values for 13CO and 12CO bands with the same $`W_\lambda `$. Lambert et al. provided a comparison in their Table 5, which indicates a ratio greater than 125. The same comparison can be made with our data displayed in Table 2. For both $`\rho `$ Oph A and $`\chi `$ Oph, the $`W_\lambda `$ for the 11$``$0 band of 12CO is the same as that for the 4$``$0 band of 13CO. The ratio of $`f`$-values is 134, consistent with our isotopomeric ratios.

Finally, we comment on the work of Liszt & Lucas (1998), where the 12CO/13CO ratio decreases with increasing $`N`$(12CO) for column densities sampled by our UV measurements. First, our results specifically concern the clouds in Sco-Oph; other clouds, like that toward 20 Aql, have much smaller ratios (Hanson et al. 1992; Knauth et al. 2001). Second, there are no direct measures of extinction or C+ abundance for their extragalactic sight lines. Enhancements in 13CO relative to 12CO require a significant flux of UV radiation to produce the C+ needed for isotopic charge exchange (but not too large to heat the gas via photoelectrons coming off grains). A more accurate determination of the extinction would also help clarify why complex molecules such as HCN (e.g., Lucas & Liszt 1994) are detected, when standard chemical models of diffuse molecular gas (e.g., van Dishoeck & Black 1986) suggest very low abundances.

In summary, ultraviolet observations of CO and its isotopic variants toward $`\rho `$ Oph A and $`\chi `$ Oph were analyzed in conjunction with measurements on absorption from C I and vibrationally excited H2. Significant enhancements in the amount of 12CO relative to the other isotopomers were found. The amount of H2 in $`v`$ $`=`$ 3 toward $`\rho `$ Oph A indicates an ultraviolet flux about 10 times the average interstellar flux permeates this direction; for the $`\chi `$ Oph sight line, the flux cannot be greater than twice the average interstellar value. Analysis of C I (and C2) excitation reveals modest densities for the material seen in absorption. Resonant scattering of emission lines from nearby molecular clouds controls the distribution of CO rotational levels, thereby limiting the usefulness of CO excitation for inferring density. Simple arguments based on the processes involved in selective isotopic photodissociation are able to reproduce the observed 12CO/13CO ratios. Incorporation of an improved set of $`f`$-values for dissociating transitions in large scale models will likely lead to better agreement with our observations.

A. Abundances of Heavy Elements

In addition to lines of CO, H2, C I, S I, Co II, and Ni II reported here and in Zsargó et al. (1997), Mullman et al. (1998), and Zsargó & Federman (1998), our spectra of $`\rho `$ Oph A and $`\chi `$ Oph reveal absorption from Ga II, As II, and Sn II. The results are given in Table 8, where $`W_\lambda `$ and $`N`$(X) are listed. The sources of $`f`$-values used in deriving column densities are Morton (1991) for Ga II, Cardelli et al. (1993b) for As II, and Schectman et al. (2000) for Sn II. A curve of growth with a $`b`$-value of 2.5 km s-1 was used; such a $`b`$-value is common for the dominant ion (Savage, Cardelli, & Sofia 1992). Two components, separated by about 10 km s-1, are discerned in the spectra of $`\chi `$ Oph. These are the major complexes found in Na I D (Welty, Hobbs, & Kulkarni 1994). Furthermore, knowledge of the total proton column density yields an elemental abundance. We adopted a combination of the H2 data of Savage et al. (1977) and H I data of Diplas & Savage (1994) for $`\rho `$ Oph A, $`N_H`$ $`=`$ $`5.0\times 10^{21}`$ cm-2, and the results of Bohlin, Savage, & Drake (1978) for $`\chi `$ Oph, $`2.26\times 10^{21}`$ cm-2. The fractional abundances ($`10^{10}`$) are similar to those seen toward $`\zeta `$ Oph (Cardelli, Savage, & Ebbets 1991; Cardelli et al. 1993b) and in other H2-rich sight lines (Cardelli 1994 for Ga II; Sofia, Meyer, & Cardelli 1999 for Sn II).

The archive of $`Copernicus`$ data developed by George Sonneborn and available at the Multiwavelength Archive at the Space Telescope Science Institute was used in this research. Support for this work was provided by NASA through grant number GO-5389.02-93A from the Space Telescope Science Institute, which is operated by the Association of Universities for Research in Astronomy, Incorporated, under NASA contract NAS5-26555 and through Long Term Space Astrophysics grant NAG5-4957 to the University of Toledo. We acknowledge the helpful suggestions of an anonymous referee.  Table 1 GHRS Observations    Star Filename Wavelength Counts Total Counts S/N Ratio CO bands      (Å)      $`\rho `$ Oph Aa z2b95106 1465.60 10547 $`\mathrm{}`$ $`\mathrm{}`$ $`\mathrm{}`$   z2b95107 1467.04 10363 $`\mathrm{}`$ $`\mathrm{}`$ $`\mathrm{}`$   z2b95108 1461.30 10045 $`\mathrm{}`$ $`\mathrm{}`$ $`\mathrm{}`$   z2b9510a 1471.35 6445 37400 193 2$``$0, 3$``$0   z2b9510b 1403.67 6983 $`\mathrm{}`$ $`\mathrm{}`$ $`\mathrm{}`$   z2b9510c 1405.12 6489 $`\mathrm{}`$ $`\mathrm{}`$ $`\mathrm{}`$   z2b9510e 1408.00 5989 19461 140 4$``$0, 5$``$0   z2b9510f 1271.36 8917 $`\mathrm{}`$ $`\mathrm{}`$ $`\mathrm{}`$   z2b9510g 1272.83 8030 $`\mathrm{}`$ $`\mathrm{}`$ $`\mathrm{}`$   z2b9510i 1275.75 7786 24733 157 10$``$0, 11$``$0  $`\chi `$ Ophb z2b90206 1465.60 15141 $`\mathrm{}`$ $`\mathrm{}`$ $`\mathrm{}`$   z2b90207 1467.04 15388 $`\mathrm{}`$ $`\mathrm{}`$ $`\mathrm{}`$   z2b90208 1461.30 15358 $`\mathrm{}`$ $`\mathrm{}`$ $`\mathrm{}`$   z2b9020a 1471.35 14415 60302 246 2$``$0, 3$``$0   z2b9020b 1403.67 15559 $`\mathrm{}`$ $`\mathrm{}`$ $`\mathrm{}`$   z2b9020c 1405.12 14975 $`\mathrm{}`$ $`\mathrm{}`$ $`\mathrm{}`$   z2b9020e 1408.00 15279 45813 214 4$``$0, 5$``$0   z2b9020f 1271.36 22992 $`\mathrm{}`$ $`\mathrm{}`$ $`\mathrm{}`$   z2b9020g 1272.83 17850 $`\mathrm{}`$ $`\mathrm{}`$ $`\mathrm{}`$   z2b9020h 1275.75 23780 64622 254 10$``$0, 11$``$0     a GHRS exposures of HD147933 with G160M conducted on 1995 June 17. b GHRS exposures of HD148184 with G160M conducted on 1995 February 11-12.  Table 2 CO Measurements    Molecule CO Band $`W_\lambda `$    (mÅ)    $`\rho `$ Oph A $`\chi `$ Oph    12CO $`AX`$ 2$``$0 $`87.7\pm 1.6`$ $`48.9\pm 1.2`$   3$``$0 $`80.9\pm 2.0`$ $`44.6\pm 1.2`$   4$``$0 $`62.5\pm 2.0`$ $`39.9\pm 1.2`$   5$``$0 $`53.3\pm 1.9`$ $`28.3\pm 1.6`$   10$``$0 $`10.0\pm 1.4`$ $`2.0\pm 0.6`$   11$``$0 $`4.6\pm 1.6`$ $`1.6\pm 1.0`$   $`a^{}X`$ 14$``$0 $`13.8\pm 1.5`$ $`3.6\pm 0.5`$   $`eX`$ 5$``$0 $`3.6\pm 0.9`$ $`0.8\pm 0.6`$  13CO $`AX`$ 2$``$0 $`10.3\pm 1.5`$ $`2.6\pm 1.0`$   3$``$0 $`11.0\pm 1.6`$ $`2.2\pm 1.1`$   4$``$0 $`4.9\pm 1.3`$ $`1.5\pm 0.8`$   5$``$0 $`4.1\pm 1.0`$ $`0.8\pm 1.0`$      Table 3 Results for Vibrationally Excited H2    Line $`W_\lambda `$   (mÅ)   $`\rho `$ Oph A a $`\chi `$ Oph $`\zeta `$ Oph b    R(0) $`1.07\pm 0.19`$ $`\mathrm{}`$ $`0.34\pm 0.16`$  R(1) $`2.09\pm 0.27`$ $`\mathrm{}`$ $`0.33\pm 0.16`$  R(2) $`2.00\pm 0.35`$ $``$ $`0.52`$ $``$ $`0.30`$  R(3) $`2.12\pm 0.35`$ $``$ $`0.68`$ $`\mathrm{}`$  P(1) $``$ $`0.70`$ $`\mathrm{}`$ $`\mathrm{}`$  P(2) $`0.81\pm 0.26`$ $`\mathrm{}`$ $`\mathrm{}`$  P(3) $`1.43\pm 0.28`$ $``$ $`0.53`$ $`\mathrm{}`$     a Weighted average of independent determinations by J.A.C. and S.R.F. b From Federman et al. (1995).  Table 4 Results for 12CH+ and 13CH+ a    Star Molecule $`W_\lambda `$ $`v_{LSR}`$ $`b`$    (mÅ) (km s-1) (km s-1)    $`\rho `$ Oph A 12CH+ $`12.25\pm 0.09`$ 4.5 2.2   13CH+ $`0.11\pm 0.05`$ $`\mathrm{}`$ 2.2  $`\chi `$ Oph 12CH+ $`10.45\pm 0.16`$ 2.6 2.1   13CH+ $`0.17\pm 0.05`$ $`\mathrm{}`$ 2.1     a Results based on separation of $`0.272`$ Å and the line width for 13CH+ was constrained to be the same as that for 12CH+.  Table 5 Results from Fitting the CO Bands    Parameter $`\rho `$ Oph A $`\chi `$ Oph    $`N`$(12CO) (cm-2) ($`1.92\pm 0.25`$) $`\times 10^{15}`$ ($`3.8\pm 1.0`$) $`\times 10^{14}`$  $`v_{helio}`$ (km s-1) $`4.4\pm 1.6`$ $`10.3\pm 1.5`$  $`b`$ (km s-1) $`0.60\pm 0.02`$ $`0.66\pm 0.04`$  $`T_{10}`$ (K) $`2.7\pm 0.1`$a $`3.0\pm 0.3`$b  $`T_{21}`$ (K) $`7.6\pm 0.5`$a $`5.2\pm 0.6`$b  $`T_{32}`$ (K) $`8.4\pm 0.5`$a $`7.5\pm 3.7`$b  $`N`$(12CO)/$`N`$(13CO) $`125\pm 23`$ $`117\pm 35`$  $`N`$(C16O)/$`N`$(C18O) $`1100\pm 600`$ $`\mathrm{}`$     a $`T_{10}`$, $`T_{21}`$, $`T_{32}`$ $`=`$ $`10.3\pm 2.9`$ K from the 10$``$0 and 11$``$0 bands, while the 2$``$0 to 5$``$0 bands of 13CO give $`7.7\pm 2.5`$ K. b $`T_{10}`$, $`T_{21}`$, $`T_{32}`$ $`=`$ $`4.7\pm 2.2`$ K from the 10$``$0 and 11$``$0 bands, while the 2$``$0 to 4$``$0 bands of 13CO give $`4.4\pm 2.9`$ K.  Table 6 Comparison of Results for the $`BX`$ and $`CX`$ Bands    Star $`W_{BX}`$ (mÅ)  $`W_{CX}`$ (mÅ)     Present Fit Other  Present Fit Other  $`\rho `$ Oph A $`27.3\pm 4.8`$ 32.4 $`\mathrm{}`$  $`54.6\pm 5.9`$ 65.1 $`22\pm 7`$ a  $`\chi `$ Oph $`9.6\pm 3.7`$ 11.9 b $`\mathrm{}`$  $`42.1\pm 4.1`$ 43.9 $`44\pm 2.5`$ c     a Federman et al. 1980. b Since the P branch is within the noise, the $`W_\lambda `$ for the R branch is given. c Frisch 1980.  Table 7 Modeling Results for Vibrationally Excited H2    Species Model Observed   1 2 3 4 5   $`\rho `$ Oph A a        $`I_{UV}`$ 4.0 10.0 10.0 10.0 8.0 $`\mathrm{}`$  $`n_{tot}`$ (cm-3) 300.0 300.0 300.0 300.0b 300.0b $`\mathrm{}`$  $`T`$ (K) 45.0 100.0 100.0 100.0b 45.0b $`\mathrm{}`$  Index $`1.00`$ $`1.00`$ $`1.00`$ $`1.20`$ $`1.18`$ $`\mathrm{}`$  Form. model STc ST Wd ST ST $`\mathrm{}`$  H 4.8(20)e 6.6(20) 6.6(20) 1.0(21) 1.1(21) 6.5(21)  H2 3.7(20) 3.7(20) 3.7(20) 3.7(20) 3.7(20) 3.7(20)  H2 $`v=0`$:        $`J=0`$ 3.1(20) 1.4(20) 1.4(20) 1.2(20) 2.1(20) ($`3.0\pm 1.0`$)(20)  $`J=1`$ 6.4(19) 2.3(20) 2.3(20) 2.5(20) 1.6(20) ($`7.1\pm 3.0`$)(19)  $`J=2`$ 1.7(17) 2.7(18) 2.7(18) 4.9(18) 1.6(18) $`\mathrm{}`$  $`J=3`$ 1.1(16) 5.0(16) 5.0(16) 1.7(17) 7.9(16) $`\mathrm{}`$  $`J=4`$ 1.5(15) 2.1(15) 2.3(15) 2.3(15) 1.8(15) $`\mathrm{}`$  $`J=5`$ 2.9(14) 7.0(14) 7.2(14) 7.7(14) 5.2(14) $`\mathrm{}`$  H2 $`v=3`$:        $`J=0`$ 5.4(11) 7.0(11) 7.0(11) 6.8(11) 5.6(11) ($`8.2\pm 2.0`$)(11)  $`J=1`$ 7.4(11) 2.3(12) 2.3(12) 2.6(12) 1.6(12) ($`2.0\pm 0.5`$)(12)  $`J=2`$ 1.3(12) 1.7(12) 1.7(12) 1.7(12) 1.4(12) ($`1.7\pm 0.4`$)(12)  $`J=3`$ 6.4(11) 2.0(12) 1.9(12) 2.2(12) 1.4(12) ($`2.7\pm 0.5`$)(12)      Table 7 Cont. Modeling Results for Vibrationally Excited H2    Species Model Observed     1 f 2 g 3 h   $`\chi `$ Oph      H2 $`v=3`$:      $`J=0`$ 1.0(12) 1.6(11) 3.0(11) $`\mathrm{}`$  $`J=1`$ 1.4(12) 2.2(11) 4.2(11) $`\mathrm{}`$  $`J=2`$ 2.4(12) 3.8(11) 7.1(11) $``$ 4.8(11)  $`J=3`$ 1.2(12) 1.9(11) 3.5(11) $``$ 8.9(11)     a All models have the standard extinction curve with grain model 2. b Temperature and density gradient: values refer to center of cloud. c ST: statistical distribution of 1.5 eV over all levels upon formation. d W: Wagenblast 1992: fraction 0.73 in $`v`$ $`=`$ 5, $`J`$ $`=`$ 9 and 0.27 in $`J`$ $`=`$ 10. e 4.8(20) $`=`$ $`4.8\times 10^{20}`$ cm-2. f $`\chi `$ Oph model G: $`T`$ $`=`$ 45 K, $`I_{UV}`$ $`=`$ 9, $`n_{tot}`$ $`=`$ 300 cm-3 (van Dishoeck & Black 1986). g Model G with $`I_{UV}`$ $`=`$ 1. h Model G with $`I_{UV}`$ $`=`$ 2.  Table 8 Results for Ga II, As II, and Sn II    Species Line $`f`$-value $`\rho `$ Oph A  $`\chi `$ Oph   (Å)  $`W_\lambda `$ $`N`$(X) ($`\times 10^{11}`$)  $`W_\lambda `$ $`N`$(X) ($`\times 10^{11}`$)     (mÅ) (cm-2)  (mÅ) (cm-2)  Ga II 1414.40 1.80 a $`11.28\pm 0.35`$ $`4.38\pm 0.17`$  $`0.81\pm 0.16`$ $`0.26\pm 0.05`$ b     $`\mathrm{}`$ $`\mathrm{}`$  $`5.41\pm 0.16`$ $`1.87\pm 0.06`$ b  As II 1263.77 0.32 c $`1.23\pm 0.35`$ $`2.78\pm 0.81`$  $`0.67\pm 0.24`$ $`1.50\pm 0.55`$  Sn II 1400.44 1.04 d $`4.69\pm 0.33`$ $`2.82\pm 0.22`$  $`0.41\pm 0.16`$ $`0.24\pm 0.09`$ b     $`\mathrm{}`$ $`\mathrm{}`$  $`3.02\pm 0.16`$ $`1.76\pm 0.10`$ b     a From Morton 1991. b There are two velocity components, separated by approximately 10 km s-1. c From Cardelli et al. 1993b. d From Schectman et al. 2000.


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# A new hypothesis of sunspot formation

## 1 INTRODUCTION

Sunspots are observed as moderate-dark formations on the Sun surface. Today there exist many hypotheses, which are framed from different premises and able to explain different groups of features in sunspot generation and its development. Those hypotheses can be classified into several groups: hydrodynamic, magnetic, and magnetic-hydrodynamic explanations. Until 30s of the last century, the hydrodynamic and thermodynamic hypotheses had been developed; they explained generation of sunspots and their reduced temperature by adiabatic processes of gas expansion and cooling. A comprehensive review and analysis of the hydrodynamic and adiabatic hypotheses were performed by Sitnik .

In 1908, Hall discovered the magnetic field in sunspots. From this point, magnetic and magnetic-hydrodynamic theories have been developed. Usually they postulate an existence of general magnetic field and its amplification in the spot zones due to self-excitation processes. The general magnetic field induces the electric current in a moving ionized gas and this induced field enhances or attenuates the primary field (”solar hydromagnetic dynamo” of ”dynamo-effect”). Now the existence of a strong magnetic field is considered as a key feature of sunspots, as a primary phenomenon that controls their generation, physical and dynamic characteristics. The review and analysis of magnetic and magnetic-hydrodynamic theories is available in literature; in particular, the references to these reviews can be found in several books (Bray and Loughhead ; Obridko ) and in the later papers of other authors.

However, those theories fail to explain some observable phenomena. According to Obridko , there exist some difficulties concerning energy transfer in a spot and problem of sport brightness (temperature). The generated spots with penumbras have a universal brightness (temperature), which is independent of their size and other parameters. The observed brightness for spots lies in a very narrow range. The objects with a transitional brightness are unstable and decay promptly. The balance of mechanisms providing, on one hand, a reduced spot brightness, but, on another hand, a non-zero brightness, must be very strict. The fundamentals of this balance are not clear yet from the theoretical point of view. All the known mechanisms of development of the spot magnetic field (diffusion model), spot cooling, and energy transfer may provide this balance near any state; this means that we must observe a continuum of spot brightness (or its temperature).

The magnetic field plays a passive role in photosphere strata and does not participate directly in energy transfer. It makes a contribution in a change of substance distribution, and this changes the conditions for radiation energy transfer. However, significant concentrations of substance are possible that are close in temperature, because the magnetic field does not influence directly the radiation transfer. A spot is a secondary stable state of solar substance (Obridko ).

The phenomenon of discretization is very important in energy aspects. All stable states have different energies, and fast transitions between them are possible only if matched with release/consumption of energy that must be significant for different nonstationary phenomena in solar atmosphere.

There exists a problem of flux deficit in the spot. The problem can be formulated as follows: the spot umbra produces 15-20% of the flux generated by the undisturbed zones of the solar photosphere. Where does the rest of energy flux difference go: does it transform into other forms of energy or it is just distributed uniformly of the solar surface?

Gurevich and Lebedinsky  were the first who put forward the idea that the radiant energy in a spot transforms into the magnetic field energy, but they did not propose any specific mechanism for that. Later, many researchers tried to explain the energy flux imbalance by energy transformation into other nontraditional forms: magnetic field, Evershed effect, motion of magnetic knots, different types of waves, etc.

Besides, we see a problem of effective conversion of heat energy into ordered mechanical energy. There exists a series of facts that indicate an intimate connection of sunspots with convection of different scales: a tendency that sunspots appear at the junctions of supergranules; a similarity in general view and properties of light elements in the spot umbra and granulation.

All the magnetic and magnetic-hydrodynamic theories use (in this or that way) the Lenz’s rule: the induced current takes the direction that its magnetic field counteracts the changes in the magnetic flux that caused this induction. Actually, the Lenz’s rule is an another presentation of the Le Chatelier principle (any system in equilibrium under external impact proceeds an automatic adjustment to compensate this impact) being applied to a particular case of electromagnetic phenomena.

The review of literature and problems concerning mechanism of sunspot formation convinced us that formation of sunspots is accompanied by heat processes that cannot be accounted by Lenz’s rule; therefore the existing magnetic and magnetic-hydrodynamic theories fail to explain the effect of constant sunspot temperature. Obviously, this consideration is incomplete and does not cover all the sides of this process. If we consider the evolution of this process with the heat aspects and Le Chatelier principle, we have to assume that a certain overheating of Sun surface stimulates the processes that apt to decrease the body temperature in the given place, and there is a need to channel out the excessive energy; it is consumed to creation of the magnetic field in the spot.

The process of liquid boiling when overheat stimulates its cooling is a close analogy to this process. Cooling takes place due to formation of a vapor bubble, and the energy goes to intensive generation of vapor phase.

In this paper we consider an analogy between formation of sunspots and liquid boiling. We want to apply the expedient that has been well-proved in physics: the knowledge accumulated in one field is being transferred to another scope of study and we check up how common are the regularities in these fields. The considered analogy must be not contrary to the results of observation.

## 2 OBSERVATION OF SUNSPOTS

The process of sunspot formation proceeds several stages, Obridko : at first, one or several pores develop in a form of local darkening of intergranulation substance at the junctions of supergranules with the plumes over these pores. Then the elongated darkening zones of inter-granular substance develop and the pores merge. Later a patch of dark substance (or group of pores) starts condensing and the spot umbra appears. For a large spot, there can be several of those nucleate umbras. The plumes can be observed over the spots, but plumes disappear earlier than the spots dissipate.

The process of sunspot formation starts at a certain temperature and finishes when a certain level of temperature is reached, i.e. this is a threshold phenomenon. A fully developed spot has the sizes multiple to the size of supergranules, and the spots with intermediate size are usually less stable. Through the hierarchical system of self-organization of structures, it changes the regime of natural convection. The magnetic field appears before the sunspots and disappears after them.

## 3 OBSERVATION ON NUCLEATE-FREE BOILING IN A THIN LAYER OF LIQUID

With a growth in the heat flux, the natural convection mode is replaced by boiling mode for regular liquids. It is exactly the boiling mode that can be described by a boiling temperature (at a given pressure). Studying the mechanism of bubble formation, Moore and Mesler  discovered temperature pulsation under the vapor bubbles. This pulsation develops because for a boiling mode the local heat flux might be several orders higher than the general heat flux conveyed by the heating surface; and this causes a local cooling of the surface.

In the outer manifestation, the process of sunspot formation is quite different from conventional process of nucleate boiling. According to the Kutateladze’s  definition, the boiling is a process of evaporation in the liquid bulk. We do not see any bubbles during sunspot formation; however, the author of this paper had observed the process of nucleate-free boiling in a thin layer under vacuum - there was no bubbles, but the funnel-like and crater-like structures were formed which could move over the heating surface (Gogonin et al., ; Zhukov ; Dorokhov and Zhukov ). The funnel-shape structures might be formed not only in a thin layer over the heated surface, but also on a surface of overheated thick liquid layer.

The most detail study was performed with a thin oil layer with the depth of 2 mm. Two cases were studied: with the pressure above the layer equal to 200 Pa and 5-10 Pa. As the heat flux increases, two processes can be observed: they are different in manifestation, but the same in their essence. For the pressure of 200 Pa, a flash boiling took place, but it was not observed for the pressure of 5-10 Pa, but another process was observed, with the diagram depicted in Fig. 1.

Fig. 1a shows a cross-section of the convection cell and streamlines. Over the cell, a sketch of a velocity profile of vapor is depicted. The hot liquid ascends in the center of cell, and the colder liquid descends at the boundaries. On the free interface of convection cells, a temperature gradient is usually observed (Berdnikov and Kirdyashkin ). As the liquid is heated to the temperature close to the boiling temperature, it starts to evaporate intensively on the top interface. In this moment, the reactive force of phase transition has different magnitudes in sites with different heating. In the sites with hotter liquid it is higher, Kutateladze , and its action makes the layer thinner and produces a “funnel” (Fig. 1,b). Existence of “funnels” is supported by the reactive force of the phase transition.

The fact that liquid evaporation rate from the “funnel” surface is higher than in other places was evidenced by visual observation of mist jets rising from a “funnel” (it is visible in rays of light). The hotter zones have more dense population of “funnels”. This is also a place for formation of “craters” covered with ultra thin layer of oil (Fig. 1,c).

The observed processes are depicted in Fig. 2. In the place where the crater has passed, the liquid becomes colder due to intensive evaporation; first one cannot see any ordered motion of oil flow in this trace, but later convection cells develop up there. After a time, the “funnels” develop on the place of these cells. In the zones with a dense population of “funnels”, a crater may be born again. The process tend to reproduce; and the number, size, and nucleation frequency of “craters” become higher with a growth of the specific heat flux.

But for entire range of heat fluxes, for the regime of joint existence of “funnels” and “craters”, the “craters” were always covered with an ultra fine level of oil. At last, at high specific heat fluxes, one can observe a regime with most of surface covered with “craters” and with moving narrow “bridges” of oil moving between them and providing wetting of “craters” (Fig. 2,c). At the heat flux corresponding to the beginning of this process, the “craters” are covered with an ultra thin layer of oil.

In our experiments, we measured the temperature of the heating surface with a thermocouple placed at the distance of 0.1 mm from the surface. The thermocouple readings were recorded with a plotter. The evolution of surface temperature under the 2-mm thickness oil is plotted in Fig. 3 for the specific heat flux $`q10,000`$ W/m2 and the pressure before heating fixed at the level of 5-10 Pa. At the initial period, there is no “craters” in the oil layer and the temperature of heating surface increases by exponent (section 1-2). After $`t15`$ sec, “craters” develop in the layer and the surface temperature decreases (section 2-3). Since $`t20`$ sec, the temperature of surface remains almost constant. Since $`t27`$ sec, the thermocouple imbedded into the bottom demonstrates a passing of a “crater”, and temperature drops drastically (section 4-5), and then recovers (section 5-6). The next peak on this plotting corresponds to passing of another “crater” (section 6-7). After $`t40`$ sec, the temperature of surface again increases exponentially up to the initial level that was in the system before development of “craters” in the layer (section 7-8). The moment of passing of a “crater” over the thermocouple was tracked down by visual observations.

Since the form of event is too different from the regular boiling of liquids (e.g. no vapor bubbles), the researchers (Gogonin at al., ) classified this as an evaporation process, which takes place indeed. However, we can observe some features inherit to regular process of nucleate boiling:

1. With the growth of heat flux, this regime follows the regime of convective heat transfer and it is more intensive.
2. One can observe temperature pulsation of sites under the structural features of this process (“craters” and “funnels”).
3. The surface under the structural features (the basement of “craters” and “funnels”) is covered with an ultra thin layer of liquid.

Taking into consideration these features, the author of the present paper classifies the process described by Gogonin et al.  as surface nucleate-free boiling in a thin layer of liquid in the form of film evaporation. The essence of this mode that a liquid is being heated through a horizontal surface under vacuum. Local thinning of the layer takes place and the structures develop in the form of “funnels” (Fig.1,b) and travelling “craters” (Fig. 1,c), which are caused by the impact of reactive force of phase transition in a non-uniform interface of liquid (Zhukov ; Dorokhov and Zhukov ).

## 4 COMPARATIVE ANALYSIS OF PHENOMENA

The table summarizes the comparison between formation of sunspots and process of nucleate-free boiling in a thin layer of liquid: the dynamics, conditions of formation, periodicity of processes, result of impact, place in the hierarchy of self-organization of complex systems, etc.

One can see from this compendium that the phenomena of sunspot formation and nucleate-free boiling in a thin layer have many common features: dynamics and conditions of formation, geometry characteristics, structures on the surface, influence of the formation site, periodicity. They also take the same place in the hierarchy of self-organization for complex systems (rows 1-9 of the Table). The differences are in the type of medium and the mechanism of energy channelling from the heating surface (rows 10, 11).

Pores and sunspots, as well as “funnels” with “craters” emerging during nucleate-free boiling in a thin layer, develop in places with local overheating of surface. Beyond a certain temperature (the saturation temperature) at the given pressure, the fluid transforms into a metastable state. If the system has a local overheating above the saturation temperature, this can be considered as an external impact. According to the Le Chatelier principle, any equilibrium system being subjected to an external impact, tries to change in a way that counteracts that impact. This means that in places of local overheating the structures must be formed that provide removal of heat from the heating surface and produce cooling of the heating surface. This creates pulsation in the surface temperature. The process of funnel and crater formation in nucleate-free boiling in a thin layer and creation of pores and sunspots are all the threshold-like process: it starts after exceeding of a certain temperature and stops after cooling down to a certain level, i.e., it exists in a narrow range of temperatures. The process is accompanied by energy consumption and restructuring of flow pattern. Therefore, all the surface of a spot, regardless its size, takes a uniform temperature (the model of protective shell (Obridko )).

The developed spot has the size multiple to the size of supergranulation, and all the sunspots with intermediate sizes are much less stable (Obridko ), because with a nucleation of a temperature nonuniformity inside the Sun, it is “carried away” up to the surface due to convective flow of solar within supergranules and giant granules. While that, one or several neighbor supergranules must have a higher temperature. The solar spot cools down the surface with the size multiple to the size of a supergranules.

As it has been pointed out, the difference between the formation of sunspots and surface nucleate-free boiling in a thin layer of liquid is in the nature of working medium and the method for removal of excessive energy from the heating surface (rows 10, 11 in the Table.). Indeed, those two items are related tightly and reflect the fact that energy transformation into another form is a complex process in these processes. For liquids, the process of boiling means consumption of energy, generation of a new phase (vapor), and an increase in volume. Simultaneously, the pressure of the vapor phase grows; for vacuum boiling (explosive boiling) this fact is quite common, and a twofold pressure growth can be observed.

During a nonstationary process of bubble formation (or crater) the local temperature of the surface and liquid drops down and the volumetric pressure increases ($`T_A`$, $`P_V`$). The pressure in volume has a direct correspondence with the boiling temperature $`T_S(P_V)`$ that increases with the pressure, because there exists a relation between the saturation temperature and the vapor pressure. Therefore, we have the following: $`T_A,T_S(P_V)`$. Obviously, boiling (formation of bubbles of craters) ceases at $`T_A=T_S(P_V)`$. Therefore, a decrease in the temperature of the bubble (crater) formation and pressure growth ($`T_A,P_V`$ ) must inhibit boiling and transfer the liquid into equilibrium state for a time (during this time, the bubble detaches or the crater collapses), and later the surface is heated up again and the process repeats.

According to the very general principle formulated by Le Chatelier, any system in equilibrium tends to rearrange for weakening of the external impact. The heating of a patch of the solar surface stimulates the process that must reduce the temperature of this patch. The same way as liquid boiling channels out the excessive energy on vapor generation, the solar energy is consumed on generation of a magnetic field (this hypothesis was put forward by Gurevich and Lebedinsky ). The same as in boiling liquids, the heated surface must be cooled down, and this brings up the magnetic field pressure

$$P_V(H)=\frac{H^2}{8\pi }$$

That is, ($`T_A`$ , $`P_V(H)`$ ). If we consider further this analogy, then the increasing magnetic field (similar to the vapor pressure) suppresses the growth of a sunspot. This analogy allows us to explain the accurate balancing of the temperature and magnetic field strength around certain values. However, this paper does not give the answer about an unambiguity of the $`P(H)T`$ relationship for solar substance (which is a natural consequence of this analogy). But it is a known fact that the spots can be observed on other stars, and they are similar to sunspots. Many stars have the brightness of different levels and the spot temperature and magnetic field strength must be different from value of the Sun. This creates an opportunity to generalize data in $`P(H)T`$ coordinates (magnetic field strength - brightness), but that kind of generalization is beyond the scope of this article.

## 5 CONCLUSION

This paper put forward a new thermodynamic hypothesis of sunspot formation. An analogy was considered between the processes of sunspot formation and phenomena of surface nucleate-free boiling in a thin layer of liquid. This hypothesis goes in line with the Le Chatelier principle and gives explanation why the brightness (temperature) of spots keeps close to a certain level.

## List of captions

Fig.1. Dynamics of “crater” formation: a - convective cell, b - “funnel”, c - “crater”.

Fig.2. Photos of the processes that were observed in the thin layer of oil VM -1 with the thickness of 2 mm: a - “funnel”; b - “crater” (shown with a cross); c - two “craters” with a bridge between them (arrow). Scale 1 cm.

Fig.3. Surface temperature pulsation during nucleate-free boiling in a thin layer at low heat flux.


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# Distinguishability of complete and unextendible product bases

## I Acknowledgements

The main part of this work was completed at IBM T.J. Watson research center. I would like to thank the Quantum information group at IBM for their hospitality, Dr. David DiVincenzo for useful discussion, advice and careful reading of the manuscript, Dr. Charles Bennett and Dr. Barbara Terhal for helpful discussions.