# The Amount of Interstellar Carbon Locked in Solid Hydrogenated Amorphous Carbon

## 1. Introduction

It is now well established on the basis of astronomical and laboratory-based infrared (IR) spectroscopy that some form of solid, hydrogenated carbonaceous material is present in the diffuse interstellar medium (ISM). The absorption feature at $`2950cm^1`$ characteristic of the C-H stretching mode in hydrogenated carbonaceous materials is clearly and consistently revealed by observational studies of dusty lines of sight, from early near-IR spectrophotometric observations of the Galactic center by Soifer, Russell, & Merrill (1976) to the most recent observations of Cygnus OB2 #12, the prototypical diffuse ISM line of sight, by Whittet et al. (1997) using the Infrared Space Observatory (ISO). Other relevant observational works include: the observation of Cygnus OB2 #12 by Adamson, Whittet, & Duley (1990), the near-IR spectral surveys of Galactic center sources and other diffuse ISM probes by Sandford et al. (1991) and Pendleton et al. (1994), and the near-IR spectroscopy of the proto-planetary nebula CRL 618 by Chiar et al. (1998). Without considering observational and laboratory work outside the $`35002500cm^1`$ spectral region, the spectral profile of the $`2950cm^1`$ C-H stretching feature itself is not consistent with any simple hydrocarbon molecule – including polycyclic aromatic hydrocarbons (PAHs) – or mixtures thereof (e.g. Bellamy 1975). It is the signature of some form of cold (but not frozen) hydrogenated carbonaceous material which we will call HAC.

HACs comprise a wide range of materials composed only of carbon and hydrogen, but which vary in $`sp^1:sp^2:sp^3`$ hybridization ratios and H/C ratio. There is substantial empirical and experimental evidence to indicate that for C-H networks the carbon hybridization ratios, which determine the structural and optical properties of the material, and the H/C ratio are related; they do not vary independently. We point to the reviews of HAC by Robertson (1986); the “random covalent network” model by Angus & Jansen (1988); the “defected graphite” model by Tamor & Wu (1990); and the experimental characterizations of various HACs by Dischler, Bubenzer & Koidl (1983); McKenzie et al. (1983); Tsai & Bogy (1987); Gonzalez-Hernandez, Chao & Pawlik (1988); and Tamor, Wu et al. (1989). It is clear from these works that for HAC in general, regardless of production method: 1) the $`sp^3/sp^2`$ ratio, optical gap and the real part of the index of refraction all increase with increasing H/C ratio; 2) the density and the imaginary part of the index of refraction both decrease with increasing H/C ratio; 3) HACs seldom contain a significant concentration of $`sp^1`$ hybridized carbon; 4) the maximum value of H/C is near 1.5; and 5) HACs photoluminesce with an efficiency and energy of peak emission that depend on the H/C ratio. In total, these works demonstrate that amorphous, carbonaceous solids in general have predictable, well-determined optical and physical properties, despite having fundamental parameters like the H/C ratio and the $`sp^3/sp^2`$ ratio which are wide ranging. Thus it is possible and indeed practical to investigate and draw conclusions about the interstellar HACs from HAC analogs which are produced by methods and under conditions far different than the interstellar case. So, while the astrophysical production method of HAC may be the photolysis of organic ices as proposed by Bernstein et al. (1995) or Greenberg et al. (1995) (among others), or may be by direct deposition onto silicate cores as suggested by Jones, Duley, & Williams (1990), results of experiments on HAC materials produced by plasma-enhanced chemical-vapor deposition (PECVD), arc-evaporation, or laser ablation, for example, are directly applicable to the astrophysical problem under consideration.

It is imperative to determine more precisely the nature of interstellar HAC in the light of recent reconsiderations of the abundance of solid- and gas-phase carbon in the diffuse ISM. It now seems likely that the cosmic abundance of carbon (and other heavy elements) is perhaps as low as $`0.50.75`$ of the solar abundance, which had long been thought to be representative of abundances in the ISM. Snow & Witt (1995) review the existing literature on the carbon abundance in the sun, in a number of recently formed B stars, and in F and G stars similar to the sun, and conclude that the abundance of carbon relative to hydrogen in the ISM is $`225\pm 50ppM`$. In addition, the amount of carbon in the gas phase has recently been redetermined more precisely by Cardelli et al. (1996) through observations with the Goddard High-Resolution Spectrograph of the weak C II\] $`\lambda 2325\mathrm{\AA }`$ absorption line along lines of sight with greatly different ratios of atomic to molecular hydrogen. They derive a gas-phase carbon abundance relative to hydrogen of $`140\pm 50ppM`$. Thus it appears that the amount of carbon available to form solid material in the ISM – a parameter that is crucial to all dust-models of interstellar extinction (e.g., Mathis 1996; Li & Greenberg 1997) – is likely to be only about $`80ppM`$ of hydrogen, to within an uncertainty of about a factor of two.

Thus, the first goal of this current work is to present a rigorous determination of the portion of the solid-phase of carbon in the diffuse ISM that must be locked in the form of HAC to give rise to the observed absorption in the interstellar $`2950cm^1`$ C-H stretching feature.

Further, it is important to understand the role interstellar HAC grains play in the extinction of starlight, given the presence of HAC in the general diffuse ISM. In order to proceed, the complex index of refraction of HACs as a function of energy in the ultraviolet (UV) and visible regions of the electromagnetic spectrum must be known, in addition to the amount of this material that is present. Assumptions about the structural nature of the grains (i.e., core/mantle or uniform composition) and the size/shape distributions for the grains must also be made, but laboratory investigation is of little help here. Tabulated optical constants of materials presented as analogs to the diffuse ISM carbonaceous material, ranging from “organic refractory” materials to HACs and other forms of amorphous carbon, are plentiful in the literature and are used as needed in models of interstellar extinction. For example, see Smith (1984); Duley (1984); Bussoletti et al. (1987); Alterovitz et al. (1991); Jenniskens (1993); Colangeli (1995); and Schnaiter et al. (1998, 1999).

The list of “optical constants” works just cited, it is important to note, does not completely overlap with the list of “IR spectroscopy papers” cited in the previous paragraphs. So, while there has been a great deal of work in the areas of IR and UV/visible spectroscopies of HAC materials, the works are in large measure disjoint. The very recent works of Jaeger et al. (1998) and Schnaiter et al. (1998, 1999) deserve special mention as they begin to consider the problems of grain composition, structure, and optical properties collectively.

A second goal of this current work, then, is to present the complex index of refraction as a function of energy in the UV/visible for a HAC material with an IR absorption spectrum that is quantitatively consistent with the latest IR observations of dust in the diffuse ISM, particularly the ISO spectrum of Cyg. OB2 #12 by Whittet et al. (1997), a data set that was until now not available in the literature.

In addition to absorbing and scattering starlight, it has been suggested that HAC grains are the carrier of the broad, red emission band known as extended red emission (ERE) (e.g., Duley 1985; Witt & Schild 1988; Witt 1994). ERE has been detected in a variety of dusty astrophysical environments, including: reflection nebulae, planetary nebulae, dark nebulae, Galactic cirrus clouds, an H II region, the halo of M82, and a nova. Most recently, Gordon, Witt, & Friedmann (1998) have shown that ERE is also a phenomenon associated with general diffuse interstellar medium dust (see this work for references to the numerous original ERE detections). They also conclude that the quantum efficiency of the ERE process is in excess of 10%. Witt, Gordon, & Furton (1998) argue that this extremely high efficiency, among other things, forces a reconsideration of the notion that ERE is due to interstellar HAC grains. This same argument has also been made by Ledoux et al. (1998). At the very least, this finding demands a careful measurement of the photoluminescence (PL) efficiency of HAC materials that are otherwise viable analogs to the interstellar carbonaceous material.

The experimental aspects of this work concerning the PECVD of and subsequent characterization by UV/visible/IR absorption spectroscopies, optical PL spectroscopy, and UV/visible spectroscopic ellipsometry are described in §2. A rigorous determination of the amount of carbon locked in interstellar HAC grains is presented in §3.1. The characteristics that any viable interstellar HAC analog must posess, in light of the analysis presented in §3.1, are discussed in §3.2. The optical role HAC grains are likely to play in the extinction of UV/visible starlight, and in the dust luminescence processes known as ERE in the diffuse ISM is considered in §3.3. All of this is followed by a brief conclusion in §4.

## 2. Experimental Considerations, Analysis and Results

In our laboratories at the University of Toledo and Rhode Island College, we have been involved in depositing and characterizing thin films of HAC and related materials for almost a decade. We use both RF- and DC-based PECVD systems to produce thin, solid films from mixtures of gas-phase precursors. We rely on UV/visible/IR absorption spectroscopies, visible and near-IR PL spectroscopy, among other techniques such as spectroscopic ellipsometry and electron microscopy, for analysis and characterization of these thin-film materials. In this work, we present a thorough characterization of a single HAC sample, from among the many samples we have produced and analyzed, as a viable analog to the interstellar hydrogenated, carbonaceous material. The deposition method and conditions, along with a summary of the derived optical and physical properties are presented in §2.1. The measurement and analysis that were completed to derive the physical and optical properties of this sample, including its electronic band-gap, density, H/C ratio, $`sp^3/sp^2`$ ratio, PL efficiency, complex index of refraction, and IR ($`40001000cm^1`$) mass-absorption coefficient are presented in §§2.2-2.5.

### 2.1. HAC Sample Preparation and Summary of Derived Physical and Optical Properties

This interstellar HAC analog was produced using a DC-based PECVD system of a somewhat unique design. Although DC PECVD is electronically simpler than RF PECVD, it does not lend itself as well to depositing materials (either conducting or insulating) onto insulating substrates, which are most commonly used (i.e., fused silica and salt). The system we have designed minimizes this problem. It consists of a vacuum chamber pumped by a roughing pump and a diffusion pump, with a four-channel precursor gas mixing manifold. Electronically, the chamber itself is grounded and the sample is deposited onto the substrate placed on a support about $`5mm`$ beneath a $`3.0cm`$ diameter nickel-chromium screen which serves as the cathode. All of this is surrounded by a chimney-like glass tube about $`7cm`$ in diameter, open at the bottom and very near the top of the chamber, in order to confine the plasma and to minimize possible contamination of the deposited samples by contaminants on the metal walls of the vacuum chamber. During the deposition process, the conducting screen is pulled to a negative DC potential which is variable between $`02000V`$ by a high-voltage power supply and a current-limiting resistor. The screen maintains the plasma, which causes deposition onto the substrate just below as ionized molecular fragments of the precursor gas mixture “overshoot” it. The screen itself is coated during the deposition process as well. For this reason, a clean screen is used for each deposition and, as a drawback, the deposition process is self-limiting because the current through the plasma into the screen decreases as the screen becomes coated by the insulating material, eventually becoming too low to support the plasma. HAC films can be deposited with thickness up to about $`200nm`$ in a single deposition lasting about $`30min`$; thicker films can be deposited by interrupting the process to replace the cathode screen.

In general, samples deposited under identical conditions have indentical physical and optical properties. The materials that result are thin, solid, homogeneous films; they are not porous or particulate in nature.

The deposition conditions for the HAC sample presented in this work are as follows: the precursor gas was 99.99% pure methane, at a pressure of $`200mTorr`$ with a flow-rate of $`5.0sccm`$; the electric potential was $`1000VDC`$ which established a current of $`3.0mA`$ initially. The total deposition time was $`60min`$, consisting of two sequential $`30min`$ depositions between which the cathode screen was changed. The several films produced in this way turned out to be about $`300nm`$ thick. A sodium chloride substrate was used for subsequent IR spectroscopic analysis of the sample; a fused silica substrate was used for subsequent UV/visible analyses. There was no indication that the HAC material deposited differently onto the salt substrate than onto the fused silica substrate.

The UV/visible absorption spectrum of this HAC sample was recorded over the wavelength range $`900190nm`$ with a Perkin-Elmer 552 dual beam spectrophotometer; the absorbance spectrum and a corresponding “Tauc” plot, as described in §2.2, are shown in Figure 1. The optical PL spectrum covering the $`500950nm`$ wavelength range was recorded with an Ocean Optics S2000 fiber-fed CCD spectrometer using the $`488nm`$ line of an argon-ion laser as the source of excitation. The PL spectrum shown in Figure 2 was reduced to quantum efficiency as described in §2.3. The sample was analyzed by spectroscopic ellipsometry over the wavelength range $`3001000nm`$ with a J.A. Woollam Company SASE-1.1 ellipsometer. This analysis, which is discussed in much more detail in §2.4, was completed with the help of Dr. Margaret Tuma of the NASA Lewis Research Center; we are grateful for her assistance. The indices of refraction ($`n`$ and $`k`$) derived from this analysis are shown in Figure 3. Finally, the IR absorption of this sample was recorded over the frequency range $`40001000cm^1`$ with a Nicolet 510P FT-IR spectrometer (the low-frequency limit is imposed by the salt substrate); this spectrum, reduced to mass-extinction coefficient as described in §2.5 is shown in Figure 4.

A summary of the physical and optical properties of this HAC sample, derived from the measurements indicated in the previous paragraph is presented in Table 1. The details of each analysis are presented in the following subsections.

### 2.2. HAC Sample Band-gap and Physical Properties

A number of laboratory studies have demonstrated the electronic band-gap of HAC to be a useful parameter related to many of its optical and physical properties (e.g., Robertson 1986; Angus & Jansen 1988; Tamor, Haire et al. 1989; Tamor & Wu 1990; and Witt, Ryutov, & Furton 1997). The electronic band-gap of any amorphous semiconductor is conveniently characterized via the method outlined by Tauc (1973). This method prescribes that the band-gap is equal to the $`x`$-intercept of a plot of $`(\alpha E)^{\frac{1}{2}}`$ versus $`E`$ ($`\alpha `$ is the absorption coefficient, $`E`$ is energy), provided that the conduction and valence band edges are parabolic in energy, a condition that has proven to be more or less satisfied for most HACs. Figure 1 shows a plot of the UV/visible optical depth spectrum for the HAC sample, along with a plot of $`(\tau E)^{\frac{1}{2}}`$ derived from the optical depth spectrum according to $`\tau =\alpha t=\mathrm{ln}(\frac{I}{I_o})`$. The $`x`$-intercept of the $`(\tau E)^{\frac{1}{2}}`$ plot is $`E_g=1.9eV`$. Note that plots of $`(\tau E)^{\frac{1}{2}}`$ and $`(\alpha E)^{\frac{1}{2}}`$ versus $`E`$ differ only in slope, not in $`x`$-intercept.<sup>1</sup><sup>1</sup>1Note also that $`\alpha t=\mathrm{ln}(\frac{I}{I_o})`$ is only an approximate relation; $`\alpha `$ really needs to be determined more carefully. The use of this approximation in the “Tauc plot” is justified, however, given the assumptions made in this formalism.

One physical property that is well-parameterized by $`E_g`$ is mass density. For example, Figure 3 in Tamor, Wu, et al. (1989) reveals an approximately inverse relationship between mass density and band-gap. The density of HAC with $`E_g=1.9eV`$, the case here, is about $`1.5g/cm^3`$. We also verified this by direct measurement; the mass of HAC deposited onto the substrate was determined with a microbalance (mass after deposition minus mass before deposition), then with the sample thickness determined by the ellipsometric analysis described below, the HAC sample density of $`1.5g/cm^3`$ was verfied to within the precision of the measurements. The uncertainty in this measurement is approximately $`0.1g/cm^3`$.

A review of the literature shows that the $`sp^3/sp^2`$ carbon hybridization ratio, the H/C atom ratio, and the band-gap all are well correlated for HACs in general. Table I in Kaplan, Jansen, & Machonkin (1985); Figure 7 in Angus & Hayman (1988); and Figure 4 in Tamor & Wu (1990) are representative of this correlation. From these figures we determine that $`sp^3/sp^2=0.5\pm 0.1`$ and H/C$`=0.5\pm 0.1`$ for this HAC sample with $`E_g=1.9eV`$. The estimated errors for these quantities stem from the uncertainty in $`E_g`$, and from the precision with which the data in the tables and figures cited above can be interpolated. We also determined the H/C atom ratio directly from an analysis of the C-H stretch absorption feature via the method prescribed by Jacob & Unger (1996); the detailis of this derivation are desribed in §2.5. We find, consistent with the results above, that H/C$`0.5`$.

### 2.3. HAC Sample Photoluminescence

It is well known that HACs luminesce upon exposure to blue and near-UV radiation, with an overall efficiency and energy of peak emission that depend strongly and directly on the band-gap of the material (e.g., Watanabe, Hasegawa, & Kurata 1982; Silva, et al. 1996; Witt, Ryutov, & Furton 1997).

The optical PL spectrum for this HAC sample was recorded over the wavelength range $`500950nm`$ with an Ocean Optics S2000 fiber-fed CCD spectrometer. The excitation source was the $`488nm`$ line of an argon-ion laser. This fiber/spectrometer combination has been calibrated to absolute units via a NIST-traceable standard lamp. Furthermore, the spectrum, which is shown in Figure 2, has been reduced to approximately represent the PL photon quantum efficiency (QE) by dividing the observed PL photon count by the number of absorbed excitation laser photons, as computed from the measured laser intensity and the measured sample absorbance at the laser wavelength. This method is approximate because the radiative transport of the exciting and emitted photons, including scattering and self-absorption, is not accounted for. The error introduced by this simplification is smaller than the other errors associated with the PL observation and absolute calibration. Overall, this HAC sample has an integrated PL QE of $`0.05\pm 0.02`$, with a wavelength of peak emission around $`700nm`$.

### 2.4. HAC Sample Index of Refraction

The complex index of refraction ($`nik`$) of this HAC sample and its thickness were determined over the wavelength range $`3001000nm`$ by spectroscopic ellipsometry. In this techniqure, the relative amplitudes and phase-shifts between parallel and perpendicularly polarized light reflected from the surface of a thin film sample are measured as functions of wavelength; these functions are denoted $`\mathrm{\Psi }(\lambda )`$ and $`\mathrm{\Delta }(\lambda )`$, respectively. Rather sophisticated modeling is required, however, to reduce the $`\mathrm{\Psi }(\lambda )`$ and $`\mathrm{\Delta }(\lambda )`$ data to the sample thickness and its optical constants $`n(\lambda )`$ and $`k(\lambda )`$ (Aspnes 1985). Despite this difficulty, spectroscopic ellipsometry is arguably the best technique to determine index of refraction for thin-film samples, and one which has not been applied to HAC materials in great measure.

The ellipsometric analysis of this HAC sample (the measurement of $`\mathrm{\Psi }(\lambda )`$ and $`\mathrm{\Delta }(\lambda )`$) was performed with a J.A. Woollam Company SASE-1.1 spectroscopic ellipsometer by Dr. Margaret Tuma at the NASA Lewis Research Center. The reduction of $`\mathrm{\Psi }(\lambda )`$ and $`\mathrm{\Delta }(\lambda )`$ to $`n(\lambda )`$ and $`k(\lambda )`$ (and sample thickness) was completed by one of the authors (JWL); the method of analysis is described in some detail below since the results are heavily model dependent.

Equations describing the reflection and transmission of light incident at some angle on a thin film of an optically isotropic and homogeneous material with complex index of refraction $`nik`$ deposited on a substrate are derived from Maxwell’s equations. The amplitude and phase of the reflected beam, which are analyzed by the ellipsometer, are different for light polarized parallel to the plane of incidence than for light polarized perpendicular to the plane of incidence. The ratio $`\frac{R_{}}{R_{}}`$ defines two functions of wavelength – $`\mathrm{\Psi }(\lambda )`$ and $`\mathrm{\Delta }(\lambda )`$ – according to the relation

$$\frac{R_{}(\lambda )}{R_{}(\lambda )}=e^{i\mathrm{\Delta }(\lambda )}\mathrm{tan}\mathrm{\Psi }(\lambda ).$$
(1)   
Since $`R_{}(\lambda )`$ and $`R_{}(\lambda )`$ are complicated functions of $`n`$ and $`k`$, so are $`\mathrm{\Psi }(\lambda )`$ and $`\mathrm{\Delta }(\lambda )`$. The equations for $`\mathrm{\Psi }(\lambda )`$ and $`\mathrm{\Delta }(\lambda )`$ in terms of $`n`$ and $`k`$ can not be algebraically inverted to give $`n`$ and $`k`$ in terms of $`\mathrm{\Psi }(\lambda )`$ and $`\mathrm{\Delta }(\lambda )`$ except under the simplest of circumstances. Thus, the determination of $`n(\lambda )`$ and $`k(\lambda )`$ (and the sample thickness) from $`\mathrm{\Psi }(\lambda )`$ and $`\mathrm{\Delta }(\lambda )`$ measured by the ellipsometer is a problem which requires a numerical solution.

We developed a non-linear least-squares fitting technique using MATHMATICA to determine $`n(\lambda )`$, $`k(\lambda )`$ and the film thickness for this HAC sample. In our method, $`n(\lambda )`$ and $`k(\lambda )`$ were assumed to be parameterized functions of wavelength, and the values of the parameters were determined so as to minimize the difference between the $`\mathrm{\Psi }(\lambda )`$ and $`\mathrm{\Delta }(\lambda )`$ measured at a given angle of incidence and those computed using the parameterized $`n(\lambda )`$ and $`k(\lambda )`$ functions. The thickness was also a parameter adjusted during the fitting process. The general form for the parameterized functions describing $`n(\lambda )`$ and $`k(\lambda )`$ were determined by trial and error fitting to $`n`$ and $`k`$ data presented by Smith (1984) for a number of HAC samples ranging from highly hydrogenated and transparent to graphitic and more opaque. It was found that the following functional forms for $`n(\lambda )`$ and $`k(\lambda )`$ were the simplest that could fit, given the choice of appropriate parameters, all of the data given by Smith (1984):

$`n(\lambda )`$ $`=`$ $`n_o+n_1\lambda ^1+n_2\lambda ^2,`$ (2)   
$`k(\lambda )`$ $`=`$ $`k_oexp(k_1\lambda +k_2\lambda ^1).`$ (3)   
Values for the parameters describing $`n(\lambda )`$ and $`k(\lambda )`$ that minimized the least squares difference between measured and computed $`\mathrm{\Psi }(\lambda )`$ and $`\mathrm{\Delta }(\lambda )`$ were determined for the HAC sample and for the fused silica substrate itself at four angles of incidence evenly spaced between $`60^{}70^{}`$. The values of $`n`$ and $`k`$ derived for the fused silica blank agreed well with literature values, thus verifying the technique, and it was found for the HAC sample that one set of parameters could reproduce all the experimental data to a level of $`\chi ^210^3`$. The solutions were also found to be unique. The functions that emerged as solutions were generally insensitive to the initial guesses for the parameters, and were unchanged by the addition of other parameters (i.e., $`n_3`$, $`n_4`$, …, $`k_3`$, $`k_4`$, …). The values for the parameters of Equations 2 and 3 describing $`n(\lambda )`$ and $`k(\lambda )`$ for this HAC sample are shown in Table 2; the thickness of the film was found to be $`300\pm 30nm`$. Plots of $`n(\lambda )`$ and $`k(\lambda )`$ are shown in Figure 3.

It should be noted that our determinations of $`n(\lambda )`$ and $`k(\lambda )`$ are certain to approximately $`1020\%`$ at any given wavelength, and that they compare favorably to other published data for similar HAC materials (e.g., Smith 1984; Alterovitz et al. 1991) and for organic grain mantle materials (Chlewicki & Greenberg 1990; Jenniskens 1993).

### 2.5. HAC Sample IR Mass-extinction Coefficient

The IR absorption spectrum of this interstellar HAC analog was recorded over the frequency range $`40001000cm^1`$ with a Nicolet 510P FT-IR spectrometer. The sample was deposited onto a NaCl substrate for this analysis. The resulting spectrum, percent transmission as a function of frequency, was quantified by reducing it to spectral mass-absorption coefficient as follows. First, the raw absorption spectrum was divided by an absorption spectrum of the NaCl substrate itself and baseline corrected. This was done in order to highlight the principle absorption features, and to suppress continuum absorption by the HAC which is primarily due to scattering and interference from the HAC/NaCl interface and the exposed surfaces. The baseline-corrected spectrum was then converted to optical depth and reduced to mass-absorption according to the relation

$$\kappa (\nu )=\frac{ln(I/I_o)}{\rho t},$$
(4)   
where $`\rho `$ and $`t`$ are the sample density and thickness determined as previously described. The final spectrum is shown in Figure 4. The small, double feature at $`2350cm^1`$ and the high-frequency structure in the $`20001500cm^1`$ range and above $`3500cm^1`$ are not associated with the HAC sample; they arise from water vapor and CO<sub>2</sub> not completely purged from the spectrometer when the spectrum was recorded.

Inspection of this plot reveals that the single, strongest absorption feature in this type of HAC is the $`2950cm^1`$ C-H stretching band, with a maximum mass-absorption coefficient of $`1.4\times 10^3cm^2/g`$. Other absorption features are also apparent at the low-frequency end of the spectrum, but at levels significantly weaker than the main C-H stretching peak; these bands are due to C-H wagging and C-C stretching modes.

The integrated absorption strength for this sample in the $`2950cm^1`$ feature is $`\kappa =46cm^2/g`$, which corresponds to an intrinsic, integrated band strength of $`\sigma =1.7\times 10^{21}cm^2`$ per C-H bond.<sup>2</sup><sup>2</sup>2See §3.1 for the details of this calcualtion. From Figure 1 in Jacob & Unger (1996) we thus find that H/C for this sample is about 0.5 as presented in §2.2. It should be pointed out that only bound hydrogen is included in this ratio.

## 3. Discussion

Carbon is the most abundant element capable of maintaining itself in solid form under the conditions that prevail in the diffuse ISM. Various forms of solid carbon are invoked as sources or carriers of a variety of phenomena; for example, graphite and amorphous carbon grains for the $`220nm`$ bump (Mathis 1994; Mennella et al. 1998), HAC grains for ERE and for near-IR continuum emission (Duley 1985), and gas-phase HAC fragments for diffuse interstellar bands (Duley 1995). However, the only direct evidence that some form of solid carbonaceous material is present in the diffuse ISM is the detection of the $`2950cm^1`$ absorption feature due to C-H bonds along dusty lines of sight (e.g., Soifer, Russell, & Merrill 1976; Adamson, Whittet, & Duley 1990; Sandford et al. 1991; Pendleton et al. 1994; Whittet et al. 1997). This detection and identification are firm. The extent to which HAC can account for other astrophysical phenomena depends on its optical and physical properties, as derived from laboratory investigations of these materials.

The most superficial comparison that can be made between laboratory-produced HAC and the true interstellar HAC, but nonetheless an important one, is of the profile of the C-H stretch feature. Indeed, comparisons of this sort are plentiful in the literature (e.g., Sandford et al. 1991; Duley 1994; Greenberg et al. 1995; Schnaiter et al. 1998). We provide our own such comparison in Figure 5, which shows the $`27503050cm^1`$ relative optical depth spectrum for the interstellar HAC analog presented here, along with that observed toward the Galactic center source IRS 6 and toward Cyg. OB2 #12. The IRS 6 data were provided by Y. Pendleton and are published in Pendleton et al. (1994) the Cyg. OB2 #12 data recorded by ISO were provided by D.C.B. Whittet and are published in Whittet et al. (1997). It is clear from this figure that the two interstellar profiles are similar and are both well represented by the profile of the interstellar HAC analog (see also Chiar et al. (1998) for additional, very recent comparisons of this sort). Principal uncertainties in the data are associated with determining the appropriate baseline to use to extract the profile of the feature from the astronomical spectra.

It is, however, not sufficient to identify a laboratory-produced material as an analog to some interstellar material based on the observation of a single absorption feature. What other absorption features are produced by dust in the diffuse ISM? This question is most unambiguously answered by the recent observation of Cyg. OB2 #12 by Whittet et al. (1997) using ISO. Absorption along this line of sight is believed to arise nearly entirely from dust in the diffuse ISM.<sup>3</sup><sup>3</sup>3At least some of the absorption along the lines of sight to IR-bright Galactic center sources such as IRS 6 is known to arise from molecular cloud edges (McFadzean et al. 1989). Perhaps the most striking fact about the ISO Cyg. OB2 #12 observation is the lack of any strong absorption features in addition to the Si-O band at $`1000cm^1`$ and the C-H band at $`2950cm^1`$, except possibly a very weak feature at $`1600cm^1`$, either due to C-C stretching or C-H wagging vibrations. This, however, is useful evidence in itself which serves to exclude a large number of interstellar carbonaceous grain analog materials that have been proposed to date. Note, in this respect, that the IR absorption spectrum of the interstellar HAC analog presented here (Figure 4) is dominated by C-H stretching absorption at $`2950cm^1`$, with much less prominent absorption in the $`10001800cm^1`$ region which would be still less conspicuous at the signal-to-noise of the ISO Cyg. OB2 #12 observation.

In addition to comparing the profiles of IR absorption features observed along lines of sight through the diffuse ISM with those produced by laboratory analogs, it is possible and indeed necessary to address the question of absorption-band strength. How much carbon needs to be locked in the form of interstellar HAC in order to explain the strength of the interstellar $`2950cm^1`$ feature? This question is crucial in light of the recent determinations of the amount of solid carbon likely to be available to form interstellar HAC material (Snow & Witt 1995).

### 3.1. The Amount of Carbon in Diffuse ISM HAC Grains

In principle it is straight forward to determine the amount of carbon locked in diffuse ISM HAC grains from a quantitative analysis of the $`2950cm^1`$ interstellar absorption feature due to C-H bonds. One measures the total optical depth in the band (either by integrating over the band profile or by simply noting the maximum optical depth of the feature) and determines the number of C-H bonds necessary to produce the absorption using laboratory measurements of the intrinsic absorption strength or cross section per C-H bond. Indeed, several groups have done this, most notably Sandford et al. (1991) (hereafter S91) and Duley et al. (1998) (hereafter D98). But, in practice, there are significant difficulties with the laboratory measurement and interpretation of the C-H stretching absorption-band strength which have been overlooked.

S91 analyzed the $`2950cm^1`$ C-H absorption feature observed toward several bright IR sources believed to be probes of the diffuse ISM. They concluded that the amount of carbon necessary to produce the observed optical depth is $`10\%`$, to within a factor of two, of the cosmic abundance of carbon as presented in Allen (1973) ($`370ppM`$ H), or roughly $`2080ppM`$ of hydrogen. They relied, however, on C-H absorption-band strengths (and feature widths) measured in small hydrocarbon molecules (C<sub>5</sub>H<sub>12</sub>, C<sub>6</sub>H<sub>14</sub>, and cyclo-C<sub>6</sub>H<sub>14</sub>), when there is no a priori reason to expect the C-H stretching band strength in small molecules to be the same as that in solid matter. D98 measured the C-H absorption band strength for a single HAC produced by laser ablation of carbon in a low pressure, hydrogen-rich atmosphere and analyzed the IR observations of lines of sight toward the Galactic center by Pendleton et al. (1994) to conclude that $`7297ppM`$ H of carbon is necessary to explain the optical depth in the interstellar $`2950cm^1`$ feature. But here, the assumption is made that the C-H stretching band strength is independent of the H/C ratio in HAC, when there is in fact evidence to the contrary (Jacob & Unger 1996, hereafter JU96). It is clear from both of these studies that the laboratory determinations of the intrinsic absorption strengths of various C-H modes contribute a large uncertainty to the determination of the amount of carbon locked in interstellar HAC.

The literature concerning the quantitative analysis of IR absorption features is especially confusing to the uninitiated; there are about as many units for characterizing the intrinsic strength of an IR mode as there are papers doing so. The following paragraphs serve to connect two frameworks relevant to this current work.

The relation most commonly used in the astronomical literature, and the one used by S91, among others is

$$N=\frac{1}{A}\tau _{max}\mathrm{\Delta }\nu ,$$
(5)   
where N is the column density of absorbers, $`\tau _{max}`$ is the maximum optical depth in an IR absorption feature and $`\mathrm{\Delta }\nu `$ is the full-width at half maximum of the feature in wavenumbers. $`A`$ is a constant with units $`cmpergroup`$ or $`cmperbond`$. Equation 5 is an approximate relation, derived from the more formal, rigorous definition for the number density of C-H bonds,

$$n=\frac{1}{\sigma }_{feature}\frac{\alpha (\nu )}{\nu }𝑑\nu ,$$
(6)   
where $`\alpha (\nu )`$ is the absorption coefficient as a function of frequency and the normalization constant $`\sigma `$ is the integrated cross section per absorber, in units $`cm^2perabsorber`$. Some physical-chemistry studies of IR band strengths report band cross sections, not the $`A`$-value of Equation 5, most notably in this context the work of JU96. Note that there is an approximate relation between $`A`$ and $`\sigma `$

$$A\sigma \overline{\nu },$$
(7)   
where $`\overline{\nu }`$ is the average or central frequency of the absorption band.

In connection with determining the amount of carbon locked in interstellar HAC, the work of JU96 is of utmost relevance. These authors determined the integrated absorption cross section per C-H bond experimentally in a large number of HAC samples covering a range in H/C ratio from about 0.3 to about 1.<sup>4</sup><sup>4</sup>4They define a constant $`A`$ which is not the Sandford et al. $`A`$, but that is the reciprocal of the integrated band cross section. They found that the cross section varied linearly with H/C such that $`1\times 10^{21}\sigma 5\times 10^{21}cm^2`$ for $`0.3`$H/C$`1.`$<sup>5</sup><sup>5</sup>5There is some scatter in the data presented by JU96, and possibly an indication of a saturation of the $`2950cm^1`$ band strength at high levels of hydrogenation, but these attributes do not significantly affect the discussion and conclusions that follow. This result complicates the analysis of the interstellar $`2950cm^1`$ feature because it reveals that the H/C ratio in interstellar HAC grains must be estimated in order to determine how much carbon these grains contain, since the intrinsic band strength is a function of the H/C ratio.

Before proceeding to discuss the results of JU96 more thoroughly, it is instructive to compare their results to those of S91 and D98. Both of these groups determined $`A`$-values for four principal $`sp^3`$ C-H stretching modes: –CH<sub>3</sub> symmetric and asymmetric, and $`>`$CH<sub>2</sub> symmetric and asymmetric. Their results are summarized in Table 3; $`A`$-values were converted to cross sections using Equation 7.

The results in Table 3 are consistent with those of JU96. The relatively low value of $`\sigma _{D98}`$ is consistent with their determination of H/C in the range $`0.30.4`$ for the sample. The relatively high value of $`\sigma _{S91}`$ is consistent with the fact that the hydrocarbon molecules they analyzed were saturated, with H/C in excess of unity. The interstellar HAC analog presented in our work has $`H/C0.5`$ and we determine the integrated absorption cross section, according to Equation 6, to be $`\sigma =1.7\times 10^{21}cm^2`$, which is also consistent with the results of JU96.

These results clearly demonstrate the problem which complicates the analysis of the interstellar $`2950cm^1`$ feature: the intrinsic cross section per C-H bond depends strongly on the H/C ratio of the interstellar HAC grains, which is not well determined. The only data that give an indication of the H/C ratio in the interstellar material is the profile of the C-H stretch feature itself. Materials with very low hydrogen content (and very low $`sp^3/sp^2`$ ratios) have profiles dominated by $`sp^2`$-modes which occur at frequencies near and above $`3000cm^1`$; materials with high hydrogen content (and higher $`sp^3/sp^2`$ ratios) have profiles dominated by $`sp^3`$-modes, as seems to be the astrophysical situation. But the profile is not very sensitive for HACs with H/C greater than about 0.3, perhaps because there is a preference for hydrogen to bond to $`sp^3`$-hybridized carbon. So, the profile of the C-H stretch feature alone is not sufficient to remove the complication.

The mass-absorption coefficient $`\kappa `$ for the C-H stretch feature is the quantity that directly relates the strength of the observed interstellar band to the amount of carbon locked in interstellar HAC grains. $`\kappa `$ is defined to be the cross section per unit mass of material

$$\kappa =\frac{\sigma }{m_{CH}},$$
(8)   
where $`m_{CH}`$ is the mass of material per C-H bond since $`\sigma `$ is the cross section per C-H bond. But, the definition

$$\kappa ^{}(\nu )=\frac{\alpha (\nu )}{\rho },$$
(9)   
where $`\alpha (\nu )`$ is the absorption coefficient as a function of frequency and $`\rho `$ is the mass-density, is also commonly used. These equations define $`\kappa `$’s which are different but related – as reviewed below.

Equation 6, which rigorously defines $`\kappa `$, can be approximated by

$$n\frac{1}{\sigma }\alpha _{max}\frac{\mathrm{\Delta }\nu }{\overline{\nu }},$$
(10)   
where $`\alpha _{max}`$ is the maximum absorption coefficient in the feature, and $`\mathrm{\Delta }\nu `$ and $`\overline{\nu }`$ are the feature width and central frequency, respectively. For the interstellar C-H feature, $`\mathrm{\Delta }\nu /\overline{\nu }\frac{1}{30}`$. Given that $`n=\rho /m_{CH}`$ is the number-density of C-H bonds, combining Equations 9 and 10 gives

$$\kappa \frac{1}{30}\kappa ^{}(2950)$$
(11)   
as the relation between $`\kappa `$ determined from $`\sigma `$ according to Equation 8 and $`\kappa ^{}`$ at the interstellar $`2950cm^1`$ feature maximum defined by Equation 9.

Thus Equation 11 can be used to relate $`\kappa `$, the integrated mass-absorption coefficient, to $`\kappa ^{}(2950)`$ which is most commonly used in the astronomy literature.

The mass-absorption coefficient for the C-H stretch feature in HAC materials depends on the H/C ratio. In Equation 8, both $`\sigma `$ and $`m_{CH}`$ are functions of the H/C ratio; specifically, it can be shown that

$$m_{CH}=m_H+\frac{m_C}{\mathrm{H}/\mathrm{C}},$$
(12)   
where $`m_H`$ and $`m_C`$ are the mass of the hydrogen and carbon atoms, respectively. Using this relation, the values for $`\sigma `$ determined by JU96, and Equation 11, the mass-absorption coefficient as a function of H/C ratio can be computed as presented in Table 4. It is clear from these data that the mass-absorption coefficient for the C-H band in HAC materials varies by over a factor of 20 for $`0.2`$H/C$`1`$

What is the mass-absorption coefficient for interstellar HAC grains as determined observationally? The mass-absorption coefficient $`\kappa ^{}`$ defined by Equation 9 can be thought of as the optical depth per the column mass-density of absorbers. Accordingly, it can be stated in terms of relevant astrophysical quantities as follows:

$$\kappa ^{}(2950)=\frac{\tau (2950)}{N(\mathrm{H})}\left(\frac{N(\mathrm{C})}{N(\mathrm{H})}\right)_{\delta HAC}^1\left(\frac{\mathrm{C}/\mathrm{H}}{m_{CH}}\right),$$
(13)   
where $`N(\mathrm{X})`$ is column density of element $`X`$, $`\left(\frac{N(\mathrm{C})}{N(\mathrm{H})}\right)_{\delta HAC}^1`$ is the amount of carbon relative to hydrogen depleted into the HAC grains (the quantity we wish to determine), and C/H is that of the HAC material itself.

In what follows, we will use Equation 13 to analyze exclusively the line of sight toward Cyg. OB2 #12, the prototypical diffuse ISM line of sight. Similar results are obtained for lines of sight toward the Galactic center. The maximum optical depth in the $`2950cm^1`$ feature observed toward Cyg. OB2 #12 is $`\tau (2950)0.04`$ with $`A_V=10.2mag`$. Using $`\tau _V=4.92\times 10^{22}N(\mathrm{H})`$ given by Mathis (1996), we find $`\tau (2950)/N(\mathrm{H})=2.1\times 10^{24}cm^2`$ (which is consistent with other lines of sight as well). The ratio $`\left(\frac{\mathrm{C}/\mathrm{H}}{m_{CH}}\right)`$, derived from the values in Table 4, ranges from $`4.5\times 10^{22}g^1`$ to $`5.0\times 10^{22}g^1`$, so a constant value of $`4.7\times 10^{22}g^1`$ is representative of HACs to within the uncertainty of the observations. Thus, the mass-absorption coefficient for the interstellar C-H stretch feature is

$$\kappa ^{}(2950)=\left(0.10cm^2g^1\right)\left(\frac{N(\mathrm{C})}{N(\mathrm{H})}\right)_{\delta HAC}^1$$
(14)   
which depends only on the amount of carbon relative to hydrogen depleted into HAC grains. Notice that the system of variables: $`\left(\frac{N(\mathrm{C})}{N(\mathrm{H})}\right)_{\delta HAC}`$, H/C for HAC, and $`\kappa ^{}(2950)`$ is underconstrained. There are three variables, but only two constraints: the relation between H/C for HAC and $`\kappa ^{}(2950)`$ summarized in Table 4, and the relation between $`\left(\frac{N(\mathrm{C})}{N(\mathrm{H})}\right)_{\delta HAC}`$ and $`\kappa ^{}(2950)`$ given in Equation 14. Table 5 summarizes this. The first column lists values for the amount of carbon relative to hydrogen locked in interstellar HAC grains $`\left(\frac{N(\mathrm{C})}{N(\mathrm{H})}\right)_{\delta HAC}`$; the second column shows the corresponding, required values of $`\kappa ^{}(2950)`$. The third column gives values for the HAC H/C ratio associated with the $`\kappa `$’s in the second column, interpolated from Table 4. Note the approximate inverse relationship between the amount of carbon locked in HAC grains and the H/C ratio the HAC material would need to have in order to explain the observed optical depth in the interstellar $`2950cm^1`$ feature.

Thus we are lead to the conclusion that the amount of carbon locked in interstellar HAC grains is in the range of $`80ppM`$ hydrogen (or more, depending on the gas-phase abundance and depletion of carbon) to possibly less than $`20ppM`$ hydrogen, depending on the degree of hydrogenation of the material. Note that this result is similar to that presented by S91 with one significant difference: the large range in their estimate of $`\left(\frac{N(\mathrm{C})}{N(\mathrm{H})}\right)_{\delta HAC}`$ is, by their own acknowledgment, due to uncertainties in the observations and in band-strengths they rely on. This is not the case here; the large range in $`\left(\frac{N(\mathrm{C})}{N(\mathrm{H})}\right)_{\delta HAC}`$ is due to a fundamental lack of information to close the problem.

We can, however, draw important conclusions from this analysis, and can use these results to place limits on the interstellar HAC grain problem. On the surface, it is clear that interstellar HAC grains must be hydrogenated at least to the level H/C$`0.5`$, and at this limit most of the available solid carbon would need to be in form of HAC grains. The other limit is not so precisely delineated. It is clear that if the HAC grains are extremely highly hydrogenated, to the maximum H/C$`11.5`$, then the amount of carbon needed to produce the observed optical depth in the $`2950cm^1`$ feature would be small, perhaps as low as $`20ppM`$ hydrogen. But, as we discuss in §3.3, this seems unlikely because these HACs photoluminesce efficiently in the blue-green and such emission has never been observed in interstellar environments.

### 3.2. Viable Interstellar HAC Analogs

The data in Table 5 can be used to evaluate the viability of other potential interstellar HAC analogs. From a purely qualitative standpoint, any material proposed as an analog to the hydrogenated carbonaceous component of the diffuse ISM must produce absorption in the IR that is dominated by the C-H stretch feature at $`2950cm^1`$, given the recent ISO observation of Cyg. OB2 #12 by Whittet et al. (1998). The lack of other strong features along this line of sight (excepting the Si-O band at $`1000cm^1`$) is meaningful. In light of this, the suggestion that solids such as the organic refractory EUREKA materials of Greenberg et al. (1995), for example, are analogs to the carbonaceous component of the diffuse ISM must not be taken too literally because they show significant absorption due to bonds other than C-H and C-C. These materials do, however, offer intriguing insight into a possible interstellar HAC production method.

From a quantitative standpoint, the results of the previous section provide a key criterion to which all interstellar HAC analogs must be held. Given that only $`80ppM`$ of carbon relative to hydrogen is likely to be depleted from the gas phase to form solid carbonaceous material (Snow & Witt 1995), any laboratory analog to the interstellar HAC material must have a mass-absorption coefficient at the peak of the C-H stretch feature in excess of $`10^3cm^2/g`$, and in order to do so must be hydrogenated to a level of H/C$`>0.5`$.

The interstellar HAC analog presented in this work, with H/C $`0.5`$ and $`\kappa ^{}(2950)=1.4\times 10^3cm^2/g`$, appears to be a limiting material in the sense that it produces absorption in the C-H stretch feature with a strength that would require all of the available solid carbon to be in form of this type of material. Other interstellar HAC analogs presented to date, however, appear in this analysis to require more the solid carbon than is available in order to account for the interstellar $`2950cm^1`$ feature (Borghesi et al. 1985; Ogmen & Duley 1988; Colangeli et al. 1995; Jaeger et al. 1998). Of course, uncertainty in the true amount of solid-phase carbon in the ISM constrains each of these interstellar HAC analogs to different degrees; each must be considered on a case by case basis. However, that materials with lower mass-absorption coefficients in the $`2950cm^1`$ band require more solid-phase carbon to account for the observed strength of this feature – perhaps more than is available – remains a valid conclusion.

While determination of IR mass-absorption spectra for interstellar grain analogs is a necessary quantification, it has only been done by a limited number of groups. Bussoletti et al. (1987) and Colangeli et al. (1995) produced and analyzed a variety of HAC materials (denoted BE, ACAR, ACH2, etc…), derived by arc-evaporation of graphite, and determined mass-absorption spectra for them through the near-IR along with other properties, including indices of refraction, which, incidently, have been used subsequently by Mathis (1996) to compute his most recent dust model. For these materials, however, $`\kappa ^{}(2950)`$ is only on the order of $`100150cm^2/g`$ – clearly too low to account for the interstellar $`2950cm^1`$ feature. More recently, Schnaiter et al. (1998) produced a variety of matrix-isolated nano-sized carbon grains and, among other things, determined the mass-absorption coefficient in the C-H stretch feature. They found $`\kappa ^{}(2950)`$ to range from near zero to around $`600cm^2/g`$ for the most highly hydrogenated materials they produced. The mostly highly hydrogenated of these materials may possibly be able to account for the $`2950cm^1`$ feature, given the uncertainty in the true amount of solid-phase carbon that is available. Finally, D98 produced an interstellar HAC analog by laser ablation of graphite in a low-pressure, hydrogen-rich atmosphere, and analyzed the strength of the C-H stretch feature. Although they do not specifically compute $`\kappa ^{}(2950)`$, it is apparently approximately $`450cm^2/g`$, based on the H/C ratio they quote and the “$`A`$-value” (of Equation 5) they determine; again considerably lower than necessary to account for all of the absorption in the interstellar $`2950cm^1`$ feature. So, although a number of carbonaceous materials have been presented in the literature over the past few years as sources of the interstellar $`2950cm^1`$ feature, and thus as interstellar HAC analogs, the HAC presented in this work is the first to be shown to be quantitatively consistent with IR observations in the $`40001000cm^1`$ spectral region of lines of sight which unambiguously sample only the diffuse ISM.

### 3.3. The Optical Role of HAC Grains in the Diffuse ISM

Given the presence in the diffuse ISM of some form of hydrogenated carbonaceous solid, as betrayed by the interstellar $`2950cm^1`$ feature, it is necessary to consider carefully the roles it may and may not play in other UV/visible/IR phenomena. HAC is included as a source of opacity in the current dust models of Mathis (1996) and Li & Greenberg (1997), and has been proposed as the source or carrier of the broad, red dust luminescence band known as ERE (e.g., Duley 1985; Witt 1994), near-IR ($`13\mu m`$) non-thermal continuum radiation (Jones, Duley, & Williams 1990), and the $`220nm`$ bump (Colangeli et al. 1993; Schnaiter et al. 1998), in addition to being the assumed source of the interstellar $`2950cm^1`$ feature. The extent to which HAC grains can indeed fill all of these roles must continue to be reviewed in light of new astronomical and laboratory data.

Although HAC is assumed to be a major source of opacity in the near-UV and visible (Li & Greenberg 1997), its optical constants in this spectral region are by far the poorest determined of most astrophysically important materials. In addition, the recent recent dust models of Li & Greenberg 1997 and Mathis (1996) require that the imaginary part of the index of refraction for the material causing visible/near-UV absorption needs to be as high as $`0.4`$. If so, then the material causing this absorption is not the HAC responsible for the interstellar $`2950cm^1`$ feature, for the simple reason that HACs which produce significant optical depth per carbon atom in the C-H stretch band are not nearly this absorbing in the visible. As demonstrated in Figure 3, our HAC sample, which matches the interstellar C-H feature both in profile and in mass-absorption coefficient (at a minimum level), is essentially transparent in the visible, with $`k`$ rising to about $`0.4`$ only in the near-UV. Further, we consider this a limiting material because increasing its visual opacity would require lowering its bandgap below its present value ($`1.9eV`$), decreasing its mass-absorpton coefficient in the C-H stretch band to where more than $`80ppM`$ solid phase carbon would be required to match the C-H band strength, and shifting its C-H band profile toward frequencies higher than observed. HAC, then, is not the sole source of absorption in the visible/near-UV.

A recent paper by Adamson et al. (1998), describing spectropolarimetric observations of the interstellar $`2950cm^1`$ feature observed toward the Galactic center source Sgr. A IRS7, provides an additional clue to the nature of the carrier of this absorption band. They find this feature to be unpolarized with an upper limit well below that expected on the basis of a model in which the carrier bonds are associated with the aligned silicate grains (i.e., silicate-core/HAC-mantle grains). This suggests the possibility that the IR-active HAC grains are extremely small – below the Rayleigh limit. If this is the case, then it seems again that the HAC material is very highly hydrogenated with a correspondingly high C-H stretch mass-absorption coefficient. Interestingly enough, small HAC grains have recently been shown in the lab by Schnaiter et al. (1998) to produce broad absorption around $`220nm`$, thus making them candidates for the carrier of the interstellar $`220nm`$ extinction feature. They concluded, in fact, that small HAC grains locking up about $`100ppM`$ carbon relative to hydrogen could explain the observed strength of the $`220nm`$ bump. In addition, these laboratory-produced HAC grains have a mass-absorption coefficient in the $`2950cm^1`$feature of $`\kappa ^{}(2950)600cm^2/g`$, which is near but lower than the required $`10^3cm^2/g`$. It thus appears that small HAC grains are a promising source of both the $`220nm`$ bump and the $`2950cm^1`$ C-H feature. But, they would need to lock up essentially all the solid-phase carbon if the recent works of Schnaiter et al. 1998 and Schnaiter et al. 1999 are final. It is important to note that the HAC sample presented in this current work does not produce structure in the $`190250nm`$ spectral region.

Finally, it has been suggested that HAC grains are the carrier of ERE observed in a variety of astrophysical environments (Duley, Seahra, & Williams 1997). More recently, however, Gordon, Witt, & Friedmann (1998) and Szomoru & Guhathakurta (1998) have shown that ERE is also produced by dust in the diffuse ISM with a quantum efficiency so high as to call into question its HAC origin. By comparing the absorbed fraction of the interstellar radiation field, integrated over the $`91.2550nm`$ range, with the observed ERE intensity over the same lines of sight, Gordon, Witt, & Friedmann (1998) conclude and Szomoru & Guhathakurta confirmed that $`(10\pm 3)\%`$ of all absorbed photons lead to the production of ERE photons. Since the ERE carrier is most likely only one of several dust components contributing to the absorption in the UV/visible wavelength range, the true quantum efficiency of the ERE process must be larger than 10%, and could be as high as 40% to 50%.

The quantum efficiency of PL in HAC (Silva et al. 1996; Rusli, Robertson, & Amaratunga 1996; Witt, Ryutov, & Furton 1997) is closely correlated with the bandgap, which in turn is correlated with the H/C ratio. High-efficiency PL occurs in HAC only if the bandgap is large, of order $`3eV`$, which implies, under UV illumination, blue-green luminescence instead of red emission. The absence of blue emission in astronomical sources (Rush & Witt 1975; Witt & Boroson 1990) argues thus against the presence of such high-bandgap HAC and the large H/C ratios this would imply. Materials such as the HAC sample discussed in this paper can contribute to the ERE in the correct wavelength range, but only with a modest quantum efficiency of about 5%. At best, it would be a partial contributor to the ERE observed in the diffuse ISM. Other possible sources for the ERE, such as silicon nanoparticles (Witt, Gordon, & Furton 1998; Ledoux et al. 1998) or large PAH molecules (d’Hendecourt et al. 1986) must therefore be considered as main contributors. Further, the absence of blue emission in ERE sources also argues against the presence of HACs with H/C$`>0.5`$. This limits at the low end the amount of carbon contained in interstellar HAC grains because of the existence of the correlation between the H/C ratio and the band mass-absorption coefficient (see Table 5). We conclude, therefore, that the amount of carbon locked up in HAC is nearer $`80ppM`$ than $`20ppM`$ of hydrogen.

## 4. Summary

In summary, we have produced and thoroughly characterized a HAC sample that is, on the basis of a quantitative comparison of the IR absorption spectra of the HAC and of the diffuse ISM, a viable analog to the true interstellar HAC material. Both spectra are dominated by the C-H stretching feature at $`2950cm^1`$, with much weaker absorption in the $`20001000cm^1`$ range due to C-C stretching and C-H wagging modes (in addition to the Si-O band in the interstellar spectrum). This HAC has a density of $`1.5g/cm^3`$, an electronic band-gap of $`1.9\pm 0.1eV`$, H/C and $`sp^3/sp^2`$ ratios both near $`0.5`$, a peak mass-absorption coefficient in the $`2950cm^1`$ band of $`\kappa ^{}(2950)=1.4\times 10^3cm^2/g`$, and an integrated PL quantum efficiency of $`0.05\pm 0.02`$ with peak emission near $`700nm`$. We have also determined via spectroscopic ellipsometry the complex index of refraction for this HAC in the wavelength range $`3001000nm`$, finding $`n`$ to be nearly constant near $`1.7`$ and $`k`$ to rise exponentially from near zero in the visible to around $`0.4`$ in the near-UV.

We carefully analyzed the profile and strength of the $`2950cm^1`$ C-H stretching absorption band in HAC and the diffuse ISM. We review the results of Jacob & Unger (1996), showing that the intrinsic strength of the $`2950cm^1`$ feature per C-H bond, and thus the amount of carbon that needs to be bound in HAC in the diffuse ISM, is a strong function of the degree of hydrogenation of the material. HACs with H/C$`0.5`$, like the sample described in this work, are minimally able to provide the observed optical depth in the interstellar $`2950cm^1`$ feature, requiring approximately $`80ppM`$ carbon relative to hydrogen – essentially all the available solid-phase carbon. HACs with H/C much lower than $`0.5`$ require increasingly more than $`80ppM`$ of carbon relative to hydrogen, and thus do not appear to be viable interstellar HAC analogs. HACs with H/C much higher than $`0.5`$, while able to account for the $`2950cm^1`$ feature optical depth with less carbon, perhaps as little as $`20ppM`$ of hydrogen, also do not appear to be viable analogs because these materials as a rule exhibit blue-green photoluminescence with an efficiency on the order of $`10\%`$ – such dust emission has never been observed. So, we conclude that interstellar HAC must be hydrogenated to a level of about $`0.50.7`$ and that this material locks up most of the available solid-phase carbon.

Finally, we consider other optical roles interstellar HAC is likely to play in the diffuse ISM. We conclude that HAC is not the dominant source of the ERE band, which has now been conclusively detected in the diffuse ISM, because HAC’s PL spectrum and quantum efficiency differ significantly from ERE. We also conclude that HAC is not the sole source of opacity in the visible and near-UV because HACs with $`k>>0`$ in this spectral region require far more carbon than is available in the solid phase to account for the observed $`2950cm^1`$ band optical depth. In addition, it is important to note that the bulk-solid HAC which we have produced does not show any structure in the spectral vicinity of $`220nm`$.

The authors are grateful to Yvonne Pendleton and Doug Whittet for providing observational data, Margaret Tuma for assistance with the spectroscopic ellipsometry of our HAC sample, and Thomas Henning for a thorough critique of the manuscript. This work was supported by NASA grants to the University of Toledo and by subcontract to Rhode Island College.