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# Chemical Abundances in Twelve Red Giants of the Large Magellanic Cloud from High-Resolution Infrared Spectroscopy1footnote 11footnote 1Based on observations obtained at the Gemini Observatory, which is operated by the Association of Universities for Research in Astronomy, Inc., under a cooperative agreement with the NSF on behalf of the Gemini partnership: the National Science Foundation (United States), the Particle Physics and Astronomy Research Council (United Kingdom), the National Research Council (Canada), CONICYT (Chile), the Australian Research Council (Australia), CNPq (Brazil), and CONICET (Argentina).

## 1 Introduction

The Large Magellanic Cloud (LMC), one of the nearest galaxies and a much smaller system than the Milky Way, is a prime target in which to probe chemical evolution in stellar populations. Unlike the Milky Way, where large fractions of the volume are obscured by dust, the sightlines into most of the LMC are relatively clear, rendering entire populations of stars visible. The LMC’s distance demands that detailed stellar abundance studies be based on spectra from 4-8 meter class telescopes and be restricted to rather luminous stars.

Pioneering abundance studies have been conducted on LMC stellar samples already. One basic measure of overall chemical evolution in a stellar system is an age-metallicity relation. In the LMC, Olszewski et al. (1991) and Dopita (1996) provide extensive results, with the Olszewski et al. work based on clusters and Dopita’s results derived from planetary nebulae. More recently, Geisler et al. (1997) and Bica et al. (1998) have provided additional results from clusters. In summary, the LMC age-metallicity relation appears to reflect a rapid enrichment phase more than 10 Gyr ago, followed by apparent chemical quiescence until about 2 Gyr ago, when another enrichment period (still ongoing) began.

Additional insights into chemical evolution can be provided by studying elements arising from different nucleosynthetic origins, e.g. Type II supernovae (SN II), Type Ia supernovae (SN Ia), or asymptotic giant branch (AGB) stars. Studies of this type require high-resolution spectra and are still a challenging endeavor to undertake in the LMC. Published abundance distributions for the LMC include Russell & Dopita (1992), Barbuy, Pacheco, & Castro (1994), Hill, Andrievsky, & Spite (1995), Luck et al. (1998), Korn et al. (2000), Hill et al. (2000), Spite et al. (2001), and Korn et al. (2002). The analysed stars include main sequence and supergiant B-stars, supergiant K- to F-stars, and Cepheid variables. For the younger stars ($``$ 108 yr), these papers find a typical iron abundance of \[Fe/H\]$``$ -0.3 for LMC field stars. The oxygen-to-iron abundance ratio in the LMC may be measurably lower than this same ratio at the same \[Fe/H\] abundance in the Galaxy. The trend of \[O/Fe\] as a function of \[Fe/H\] can be a crucial relation in establishing star formation histories in a stellar population. Oxygen is made preferentially in the most massive stars, while iron comes from both massive, core-collapse supernovae (SN II) and the (presumably) binary Type Ia supernovae. The run of the O/Fe ratio with Fe/H in a stellar system is, therefore, a measure of the history of SN II to SN Ia rates, and, hence, the star formation history of the LMC. Carbon and nitrogen abundances may also be lower when compared to Galactic stars at the same \[Fe/H\]. As C, N, and O (with Ne) are the most abundant heavy elements, their abundances carry much weight in setting the overall metallicity, Z, in a galaxy.

Most of the previous abundance determinations of C, N and O in the LMC have rested on atomic lines, some of which are quite weak, or hampered possibly by non-LTE processes. Because of the importance of the O/Fe ratio to the disentangling of the LMC’s star fomration history, this study set out to measure oxygen, as well as carbon and nitrogen abundances, in a sample of LMC red giants by observing molecular unblended lines of OH, CO, and CN from high-resolution infrared (IR) spectra. Using the 8.3m Gemini South reflector, along with the Phoenix high-resolution IR spectrometer, abundances of the isotopes 12C, 13C, 14N, and 16O could be determined along with abundances of Fe, Na, Sc, and Ti.

## 2 Observations & Data Reduction

High-resolution infrared (IR) spectra were obtained of target red-giant stars using the 8.3 m Gemini South reflecting telescope and the NOAO Phoenix spectrometer (Hinkle et al. 1998; 2000; 2002). This instrument is a cryogenically cooled echelle spectrograph that uses order separating filters to isolate individual echelle orders. The detector is a 1024x1024 InSb Aladdin II array. The size of the detector in the dispersion direction limits the wavelength coverage in a single exposure to about 1550 km s-1, or $``$120Å at 2.3 $`\mu `$m and $``$80 Å at 1.6 $`\mu `$m. One edge of the detector is blemished so the wavelength coverage on all but the brightest sources is typically trimmed a few percent to avoid this area. The InSb material limits the range of sensitivity to the 1-5$`\mu `$m wavelength region. However, the thermal brilliance of the sky requires that the observation of fainter sources, e.g. LMC giants, be limited to the non-thermal 1-2.4$`\mu `$m region. The spectra discussed here were observed with the widest (0.35 arcsecond) slit resulting in a spectral resolution of R=$`\lambda `$/$`\mathrm{\Delta }`$$`\lambda `$= 50,000.

The program star positions, K-magnitudes, and (J-K) colors are listed in Table 1. The positions are taken from the 2-Micron All-Sky Survey (2MASS) database (http://irsa.ipac.caltech.edu). The first seven stars listed in Table 1 were selected based upon a color-magnitude diagram constructed using the 2MASS database for two 15’ fields in the LMC. The LMC red giant branch is clearly visible in a K versus (J-K) diagram and all program field giants were found to be LMC members based on their radial velocities. The identifying names given to the field stars here were assigned by us as either field 1 or field 2, followed by the star number from our list for that field, i.e. 2.4525 is from field 2 and is number 4525 from that list. In addition to the field stars selected from the 2MASS survey, one star is a bright field supergiant (HV 2568), while four stars in Table 1 were taken from Aaronson & Mould’s (1985) IR photometric study of LMC clusters. NGC1898 AM5 is found not to be a member of the cluster (as will be seen from our radial velocity and abundance analysis), but a foreground or background LMC giant.

Each program star was observed along the slit at two, three, or four separate positions separated by 5” on the sky: the delivered image FWHM at the spectrograph varied from 0.25”-0.80” during the nights that spectra were taken, so stellar images at different positions on the slit were well separated on the detector. Equal integration times were used for a particular program star during a particular set of observations. With this observing strategy, sky and dark backgrounds are removed by subtracting one integration from another (the star being at different positions on the detector array). During each night, 10 flat-field and 10 dark images were recorded for each given wavelength setting of the echelle grating. A hot star, with no intrinsic spectral lines in the regions observed, was also observed each night in each observed wavelength region. If telluric lines were present in the spectral interval, the hot star was observed at airmasses bracketing the program stars and suitable combinations of the hot star spectra were used to divide out the telluric lines from program star spectra. If no telluric lines fell in the observed region, the hot star was observed only once as a monitor of fringing and general test of data reduction quality. All program stars were observed at two echelle tilts through two different filters: one filter was K4308, with wavelength coverage from 23345 to 23455Å, and the other was H6420, with wavelength coverage from 15505 to 15575Å. Table 2 provides an observational log, showing the number and integration time for each observation, as well as the approximate signal-to-noise (S/N) of each final, reduced spectrum (with reduction as described below).

The array image frames were reduced to one-dimensional, wavelength calibrated spectra with the IRAF444The IRAF software is distributed by the National Optical Astronomy Observatories under contract with the National Science Foundation. set of routines. For a given night and wavelength setting, dark and flat-field frames were averaged and the dark frame was subtracted from the flat-field. The average, dark-subtracted flat-field was normalized and the pairs of differenced program star frames were divided by the normalized flat-field. The aperture containing the stellar signal was defined and traced for each star frame, followed by extraction of the spectrum. For the 23400Å spectra, wavelength calibrations were computed by using a set of telluric wavelengths obtained from the hot star spectra. In the 15540Å region, where there are no telluric lines, wavelengths were set using photospheric lines from the red giants themselves, so no radial-velocity information can be extracted from the spectra observed in this region. The wavelength calibration fits yielded residuals of typically 0.01–0.02Å.

Sample reduced spectra are shown in Figure 1 for both spectral regions in one of the field red giants (2.3256). The top panel shows the 15540Å region and the bottom panel the 23400Å region. The 23400Å region contains a number of telluric absorption lines and this spectrum has been ratioed with the hot star HIP27603 in order to remove telluric absorption lines. The effective airmass of the telluric standard star is adjusted by differently weighted averages of the different integrations on this star until the telluric absorption cancels out as well as possible from the program star. In practice virtually no evidence of such absorption is visible in the program star spectra. In both regions, a number of the spectral lines or features used in the abundance analysis are identified. This figure illustrates both the quality of the spectra and the variety of lines available for study.

## 3 Analysis

The analysis uses a combination of photometry and spectroscopy to determine fundamental stellar parameters (effective temperature, surface gravity, microturbulent velocity, and overall stellar metallicity) and detailed chemical compositions. The high-resolution spectra are analyzed using plane-parallel, LTE model atmospheres that are generated using two different versions of the MARCS code: an older version based largely upon the program as described in Gustaffson et al. (1975), and a more recent version, OSMARCS (Plez, Brett, & Nordlund 1992; Edvardsson et al. 1993; Asplund et al. 1997), which contains more extensive molecular opacities. Abundances derived from both types of models are compared to give some indication of potential model atmosphere systematic effects. The model atmospheres are coupled to the most recent version of the LTE spectrum synthesis code MOOG (Sneden 1973) in order to derive abundances.

### 3.1 Stellar Effective Temperatures

The effective temperatures of the stars are chosen using broadband color (J-K)-Teff calibrations. Table 1 listed the stars observed along with their K-magnitudes and (J-K) colors. The 2MASS database is the source of the magnitudes and colors for the field giants, while Aaronson & Mould (1985) were used for the cluster members. The 2MASS magnitudes and colors have been transformed to the system defined by Bessell and Brett (1988), as we use Teff-calibrations from Bessell, Castelli, & Plez (1998), who use the color system defined in Bessell & Brett (1988). The 2MASS corrections are those defined by Carpenter (2001) in his Appendix A and are fairly small: a constant 0.04 magnitude offset in K, and a small color term that is about 0.03 magnitude in (J–K). Table 3 lists the absolute bolometric magnitudes based upon a distance modulus of 18.5 and K-band bolometric corrections from Bessell et al. (1998): no corrections for reddening in the IR were included here.

Bessell et al. (1998) show that Teff-(J-K) relations have a small metallicity dependence and we use their calibration for \[Fe/H\]= -0.50, which is what is expected for the typical LMC field (Cole, Smecker-Hane, & Gallagher 2000): Table 3 lists these effective temperatures. Other color effective temperature relations are available in the literature. We compare one other source (McWilliam 1990) to the calibrations used here. The mean difference between the effective temperatures from the Bessell et al. (1998) calibration minus those from the McWilliam (1990) calibration is +90$`\pm `$51K, suggesting that the temperature scales agree at a level of about 100 K.

### 3.2 Surface Gravities, Microturbulent Velocities, & Iron Abundances

The stellar surface gravity can usually be derived from either ionization equilibria (where, for example, Fe I and Fe II lines are forced to yield the same abundance) or from estimates of stellar luminosity and mass. No ionized atomic lines are detectable in the relatively small IR spectral windows observed here, so gravities are defined by luminosity and mass estimates from the standard relation

(g/g)= (M/M)$`\times `$(Teff/Teff($``$))4$`\times `$(L/L).

For LMC red giants, bolometric magnitudes (Table 3) and, hence, absolute luminosities are known with some accuracy; the distance modulus adopted is 18.5 $`\pm `$ 0.2. Mass estimates are obtained using evolutionary tracks. Figure 2 shows plots of Mbol versus Teff for the LMC red giants from this work and model tracks from Schaerer et al. (1993), with the model tracks computed for the metallicity expected for most of LMC program stars (\[Fe/H\]= -0.35). Models are shown for 1.0, 2.0, 3.0, 4.0, 5.0, 7.0, and 10.0M and these tracks stop at the tip of the first ascent of the red giant branch (RGB). Karakas & Lattanzio (2002, private communication) kindly provided tracks for 1.0, 1.9, 3.0, and 4.0M models that included evolution along the asymptotic giant branch (AGB) and into the thermally pulsing (TP-AGB) phase of evolution (with these models also computed for an LMC metallicity). The two separate sets of models from Schaerer et al. (1993) and Karakas & Lattanzio (2002) agree well from evolution on the ZAMS and onto the RGB; on the AGB and TP-AGB, the tracks become rather complicated and these tracks are not plotted in Figure 2 for the sake of clarity.

The top panel of Figure 2 provides a broad view of stellar evolution and includes the positions of a few other samples of LMC stars from previously published abundance studies, whose results will be compared to those derived here. The Korn et al. (2002) paper is an analysis of 4 main-sequence B-star members of the young cluster NGC2004, while Korn et al. (2000) studied 5 somewhat evolved B-star members in two clusters (NGC2004 again and NGC1818). Hill et al. (1995) derived abundances in 9 field nonvariable (or very slightly variable) F-supergiants. What Figure 2 makes clear is that compared to these earlier LMC studies, the stars sampled here are of rather lower mass. The earlier abundances mentioned above are derived from LMC stars with masses of $``$10M, while the red giants analyzed here have masses closer to $``$2-4M. The mass and evolutionary regimes are quite different and thus our study can add complementary abundance information to what has been derived already for the LMC.

The bottom panel of Figure 2 shows, in more detail, the exact location of the target stars from this study. Except for the massive supergiant, HV2586, the red giants fall in a narrow region crossed by either first ascent giants, or early AGB stars with masses in the range of $``$2-4M. Individual masses were estimated for each LMC red giant and these approximate masses are listed in Table 3: these masses were obtained by comparisons to both the Schaerer et al. (1993) and Karakas & Lattanzio (2002) tracks. The star NGC1898 AM6 is worth a special note as it will turn out to be significantly more metal-poor than the other stars in this sample (with \[Fe/H\]= -1.13). Model tracks with \[Fe/H\]= -0.35, at a given mass, are too red for this giant and more appropriate tracks indicate that it is a lower-mass giant with M$``$1.0M. The surface gravities used for the abundance analysis were then calculated from the mass estimates and are listed in Table 3, rounded to the nearest solar mass. Since no program star, except the obviously massive supergiant HV2586, appears likely to be above 4M, and none apparently at masses lower than 2M (except for the metal-poor cluster member NGC1898 AM6), it is likely that errors in the surface gravity do not exceed $``$0.2 dex, which would not cause a significant error (i.e., $``$ 0.15 - 0.20 dex) in derived abundances.

Modeling the behavior of spectral lines with one-dimensional model atmospheres requires the definition of the microturbulent velocity, $`\xi `$. The value of $`\xi `$ is set by the condition that lines of differing line-strengths from the same species result in the same abundances. In the IR spectral windows observed here, the numerous 12C16O, hereafter 12CO lines in the 23400Å window can be used, as the various rotational lines from the (3-1) vibration series exhibit a variety of line-strengths (see Figure 1). The detailed selection of the 12CO lines is discussed in Section 3.4, but Figure 3 shows an example of the determination of the microturbulent velocity for the cluster-member red giant NGC2203 AM1. The left panels show values of slopes versus $`\xi `$ for the abundance versus reduced equivalent-widths (top panel) and abundance versus excitation potential slopes(bottom panel). Both plots show a zero slope at nearly the same value of the microturbulence, indicating that the Teff used for this star is a reasonably good value, as the abundance versus excitation potential is sensitive to the temperature, thus, a unique value of $`\xi `$ provides a simultaneous fit to both line-strength and excitation potential. The right panels illustrate the quality of the spectral-line data by showing the derived abundances versus both reduced equivalent-width (top panel) and versus excitation potential (bottom panel) for the best-fit value of $`\xi `$= 3.3 km s-1. Both trends show effectively zero slopes and small scatter ($`\pm `$0.05 dex in the 12C abundance). The derived microturbulent velocities are listed in Table 3.

The right panels in Figure 3 also illustrate an experiment conducted on line formation in the model atmospheres. The 12CO lines are formed over a range of optical depths in the atmosphere, with strong lines being formed preferentially higher compared to weaker lines. The filled circles in these panels show results for a “standard” model atmosphere used in the abundance analysis: standard here means the atmosphere extends to optical depths, defined at $`\lambda `$=5000Å as low as $`\tau `$5000= 10-4, at which point the atmosphere is truncated. The open squares show abundances from the 12CO lines for a model that has been truncated at $`\tau `$5000= 10-3: as some of the 12CO lines are the strongest lines in the spectra, if substantial contributions to their absorption were occurring near $`\tau `$5000$``$ 10-4, truncating the models here would result in incorrect abundances. Clearly, truncating at either 10-3 or 10-4 in optical depth has no significant effect ($``$0.01-0.02 dex) on derived abundances, and the optical depth structures of the models are adequate.

Earlier abundance studies of Galactic red giants that overlap somewhat the effective temperatures and gravities of the stars studied here were Smith & Lambert (1985, 1986, 1990) and it is instructive to compare values of the microturbulence derived from those papers and the microturbulent velocities measured here; the Smith & Lambert analyses relied on near-IR Fe I lines as the primary indicators with which to set $`\xi `$, while using the 12CO lines as secondary checks. The top panel of Figure 4 is a plot of $`\xi `$ versus absolute bolometric magnitude for the LMC red giants and the Galactic stars from the Smith & Lambert papers. It appears that the lower luminosity giants have a typical $`\xi `$= 2.0 km s-1, but at luminosities greater than Mbol$``$ -2.5, there is a trend of increasing values of $`\xi `$ with increasing absolute magnitude, as well as increasing amounts of scatter. The LMC red giants fall right within the scatter as defined by the Galactic giants, with the LMC sample tending to be composed of stars of slightly higher luminosities than the samples of Galactic stars studied by Smith & Lambert (1985, 1986, 1990), but exhibiting the same basic behavior in terms of the microturbulence. The bottom panel of Figure 4 is in a similar vein to the top panel: here $`\xi `$ is plotted versus log g. Microturbulent velocities for the Milky Way giants cluster around 2.0 km s-1 for the higher gravity stars (log g $``$ 1.0), but then $`\xi `$ increases both in magnitude and scatter as gravity decreases. The overlap between Galactic and LMC giants is essentially perfect.

The metallicity is estimated from the 15540Å window where three Fe I lines are measurable as largely unblended features. The next section covers the linelist selections for the various species in detail, but the \[Fe/H\] values listed in Table 3 are from these three lines, using gf-values set by fits to the IR Arcturus spectra atlas (Hinkle, Wallace, & Livingston 1995) using the Fe abundance determined from optical Fe I and Fe II lines (Smith et al. 2000). The parameters for $`\alpha `$ Boo (Arcturus) adopted here are those derived by Smith et al. (2000): Teff= 4300K, log g= 1.7, $`\xi `$= 1.6 km s-1, and \[Fe/H\]= -0.72.

The last column of Table 3 lists the heliocentric radial velocities of the program stars as determined from the sample of nine 12CO lines used to set the microturbulence. From the radial velocities it is found that all program stars are LMC members; Prevot et al. (1985) find velocities of field stars in the LMC to range from $``$+250 to +310 km s-1. The two clusters in our sample were also observed by Olszewski et al. (1991) for both radial velocities and metallcities (not the same stars as observed here, however). In the case of NGC2203, Olszewski et al. (1991) find a mean radial velocity of +243 km s-1, which is close to the +253 km s-1 found for the two member stars in this sample. They also derive a cluster metallicity of \[Fe/H\]= -0.53: a value similar to what we find for AM1 (-0.67) and AM2 (-0.61). For NGC1898, Olszewski et al. (1991) observe a mean cluster velocity of +210 km s-1 and a metallicity of \[Fe/H\]= -1.37. This radial velocity and abundance are close to what we find for AM6 (V= +219 km s -1 and \[Fe/H\]= -1.1). For the other star, AM5, we find V= +255 km s-1 and \[Fe/H\]= -0.50: quite different from Olszewski et al. (1991) or what we find for AM6. This star is almost certainly a cluster non-member, however, its velocity indicates that it is a member of the LMC. It is either a foreground or background LMC red giant in the field of NGC1898.

### 3.3 The Atomic Lines Used: Fe I, Na I, Sc I, and Ti I

In the two spectral intervals sampled, a handful of atomic lines are detectable which are largely unblended and single. These lines are listed in Table 4, along with the measured equivalent widths from the twelve program LMC red giants. The excitation energies are from the Kurucz & Bell (1995) lists, while the gf-values have been adjusted to provide the same abundances from these lines in $`\alpha `$ Boo (Hinkle et al. 1995) as found from the analysis of this standard star in conjunction with analyses of $`\omega `$ Cen red giants (Smith et al. 2000). Table 4 lists the line data and equivalent widths for all 12 of the program stars.

### 3.4 The Molecular Lines Used for the CNO Abundances: CO, OH, and CN

The IR windows were chosen to provide molecular lines from which to derive the C, N, and O abundances. The 23400Å region includes lines of the CO first-overtone vibrationa-rotation bands. The 15540Å region includes lines of the OH first-overtone vibration-rotation bands and the CN Red system. Partial pressures of C and O are coupled through the formation of CO and to a lesser extent of OH and H2O. The partial pressure of N is controlled almost exclusively by formation of N2. Minor influences of other molecules was taken fully into account. A simultaneous analysis of CO and OH lines provides the C and O elemental abundances. Analysis of the CN lines and the C abundance give the N abundance.

The wavelengths, excitation potentials, and gf-values for the CO vibration-rotation lines are from Goorvitch (1994), with the $`\mathrm{\Delta }`$$`\upsilon `$=2 lines in the 23400Å region being used. The 12CO lines measured span a range in line strength and $`\chi `$, and were used to set the microturbulence as well as provide a check on the adopted Teff from the (J-K) photometry. The CO dissociation energy was taken as D0= 11.090eV. In addition to the 12CO lines, the 13CO (2-0) bandhead falls at the red edge of the 23400Å setting in all but one program star, and synthesis of this bandhead was used to derive a 13C abundance (tabulated as a 12C/13C ratio).

The spectral region near 15540Å was selected as it contains a number of relatively isolated and unblended OH lines, as used in previous oxygen analyses by Balachandran & Carney (1996), Melendez, Barbuy, & Spite (2001), and Meléndez & Barbuy (2002). Asplund & Garcia Pérez (2001) have pointed out that strong OH lines may be sensitive to the effects of temperature differences and granulation that are found in the 3D model atmospheres, but not in the 1D models; however their calculations covered effective temperatures that are considerably hotter (Teff= 5800-6200K) than those found here. Nissen et al. (2002) point out that the granulation effects on the OH lines from the 3D models are expected to decline with decreasing effective temperature. Meléndez & Barbuy (2002) confirmed that oxygen abundances derived from the stronger lines are higher than for the weaker OH lines, again however, for stars that are distinctly hotter than those sampled here. The differences found by Meléndez & Barbuy (2002) are more pronounced for more metal-poor stars and disappear for stars with \[Fe/H\]$``$ -1. The combination of lower effective temperatures and higher metallicities in the stars sampled here why this effect is not found in our oxygen abundances. The wavelengths, excitation potentials, and gf-values are from Goldman et al. (1998), with the dissociation energy being D0= 4.392eV (Huber & Herzberg 1979).

Nitrogen abundances are based on five CN lines in the 15540Å spectral region (these CN lines are weaker than the CO and OH lines, but are well-defined and typically unblended). The CN lines were chosen from a linelist extracted from a masterlist compiled by B. Plez as described in Hill et al. (2002). The CN dissociation energy is D0= 7.77 eV (Costes et al. 1990).

The molecular line data, as well as the measured equivalent widths are listed in Table 4.

### 3.5 Errors from Stellar Parameter Uncertainties and Final Abundances

As already discussed in Section 3.1, uncertainties exist in Teff of at least $``$100K and gravities may be uncertain by about $`\pm `$0.2 dex. Fits to the 12CO lines to determine $`\xi `$ constrain this parameter to $`\pm `$0.2 to 0.3 km s-1. In order to investigate how these parameter uncertainties manifest themselves into abundance changes, the model for the program star 2.4525, which has an effective temperature near the middle of the program star distribution, was perturbed by +100K in Teff, +0.2 dex in log g, and +0.2 km s-1, respectively, and abundances computed for each perturbation. These abundance changes are listed in Table 5 for each species used in the abundance analysis. These changes can be assumed to be quasi-linear for small changes in the stellar parameters across the range of values found for this sample of red giants and be used to assess the overall uncertainties in the abundance analysis.

Systematic effects are always possible, for example, due to the choice of type of model atmosphere. This possibility was investigated by comparing abundances derived from two different sets of model atmospheres, one from the older MARCS program and the other from the newer OSMARCS code. In none of the stellar parameters spanned by the program stars was it found that derived abundance differences exceeded 0.10 dex. In the deeper layers (where $`\tau `$5000$``$ 0.6) the two sets of models agree in temperature and pressure. In regions where spectral lines form (typically $`\tau `$5000$``$ 0.1), differences are still essentially zero at Teff= 3800K, but the OSMARCS models become slightly warmer (by about 40K), and have higher gas pressures (by about 20%) for Teff= 3600K. The lines affected most by the differing models at this effective temperature were from OH (note the temperature sensitivity in Table 5), however, the effects were small and of no significant consequence to the abundances reported here.

Final abundances, based upon the OSMARCS models, are listed in Table 6 in the system of A(x)= log $`ϵ`$(x)= log\[n(x)/n(H)\] + 12. The 13C abundances are reported in the traditional form of 12C to 13C ratios. For species with abundances derived from three or more lines, the standard deviation of the mean is also shown: this provides some rough estimate of the quality of the spectra used in the analysis. All abundances were based ultimately on spectrum synthesis, although the equivalent widths listed in Table 4 were used for a first-cut abundance analysis. Included in Table 6 are the adopted abundances in the Sun for the elements studied, as well as for the well-studied, metal-poor red giant $`\alpha `$ Boo. The $`\alpha `$ Boo abundances for Fe, Na, Sc, and Ti are those from Smith et al. (2000); the atomic-line gf-values were adjusted so as to yield these abundances in $`\alpha `$ Boo from an analysis of these lines in the IR Atlas spectrum of this star (Hinkle et al. 1995). The abundances in $`\alpha `$ Boo for C, N, and O (including 13C) were derived from the same spectral regions and lines of CO, OH, and CN as used in the analysis of the LMC program stars.

Examples of two spectral syntheses in LMC red giants are shown in Figure 5. The top panel shows one region containing three 12CO lines (of differing strengths) and a Sc I line. The spectrum displayed is that from LMC 1.6 and three separate 12C and Sc abundances are illustrated in the syntheses. The comparisons between observed and model spectra are excellent. The bottom panel shows two of the OH lines in NGC1898 AM6 with, again, three different oxygen abundances in the synthetic spectra. Examples of observed and synthetic spectra of the blended 13CO(2-0) bandhead are displayed in Figure 6. The top panel shows the LMC field giant 2.1158, which has an estimated mass of $``$ 3M (Figure 2 and Table 3). Syntheses with three different isotopic carbon ratios are shown, with 12C/13C= 17 providing the best fit. The cluster member AM6 of NGC1898 is shown in the bottom panel to illustrate 13CO in a lower-mass ($``$ 1 M), lower-metallicity (\[Fe/H\]= -1.1) giant. In this star, a much lower isotopic ratio is derived, with 12C/13C= 3.5.

### 3.6 The Abundances

## 4 Discussion

Observational understanding of a stellar system’s chemical evolution must pursue a selection of elements whose stellar surface abundances are considered to reflect faithfully the composition of the gas from which the stars formed. Here, Na, Sc, Ti, and Fe may plausibly be deemed such a selection. Below, we discuss some implications of our abundances, primarily, by contrasting abundance ratios relative to Fe in the LMC, the Galaxy, and other systems.

On the other hand, surface abundances of C and N in red giants are well recognized to be affected by convective mixing as red giants. This mixing rearranges the C and N abundances and obscures the original abundances which betray the chemical evolution of the stellar system. We compare C and N in LMC and Galactic red giants.

Oxygen is likely unaffected by the convective mixing until the giant evolves to the asymptotic giant branch. Here, we assume O is a probe of chemical evolution, and discuss the O/Fe ratio in the LMC and the Galaxy.

### 4.1 The LMC Iron Abundances

The red-giant sample here consists of nine stars that are not associated with any clusters and are thus categorized as field stars, and three stars that are members of clusters (1 in NGC1898 and 2 in NGC2203). Recently, Cole, Smecker-Hane, & Gallagher (2000) have begun to map the field metallicity distribution in the LMC, and present values of \[Fe/H\] (derived from Ca II IR-triplet measurements) for 38 field red giants. Their distribution for \[Fe/H\] is shown in the top panel of Figure 7. This metallicity distribution peaks at about \[Fe/H\]= -0.5, with a fairly sharp cutoff at -0.25, and a diminishing tail down to \[Fe/H\] of about -1.6. Our sample of field stars is small and the resulting \[Fe/H\] distribution is shown in the bottom panel of Figure 7; clearly the overlap in metallicity between the two samples is perfect. The details of the shape of the metallicity distribution function for the field stars studied here cannot be well-defined with only nine stars, so a detailed comparison with the Cole et al. (2000) results requires a larger sample, but the overall agreement is encouraging.

The two clusters sampled in this study have both had their metallcities measured by Olszewski et al. (1991), who also used the Ca II IR-triplet method. For NGC1898, they find \[Fe/H\]= -1.37, while we find \[Fe/H\]= -1.13 for member AM5. With estimated total uncertainties of $``$0.16 dex in Fe I as derived from this study, plus the uncertainties from the Olszewski et al. (1991) work, a difference of 0.24 dex signifies quite good agreeement for this cluster. The other cluster common to both studies is NGC2203, which has an average \[Fe/H\]= -0.64 from 2 members analyzed here (AM1 and AM2), while Olszewski et al. (1991) find \[Fe/H\]= -0.53: again quite good agreement between two very different types of analyses.

### 4.2 Sodium, Scandium, and Titanium Abundances

Commonly, results of stellar abundance analyses are expressed as the quantity \[X/Fe\]. The Na, Sc, and Ti abundances in Table 6 give mean values \[Na/Fe\] = -0.30, \[Sc/Fe\] = 0.0, and \[Ti/Fe\] = -0.18 with a star-to-star scatter most probably dominated by measurement errors. These results compare fairly favorably with measurements from LMC F-G supergiants and Cepheids: for example, Hill et al. (1995) give (\[Na/Fe\], \[Sc/Fe\], \[Ti/Fe\]) = (-0.2, -0.1, 0.0) for \[Fe/H\] $``$ -0.3 supergiants referenced to the Galactic supergiant Canopus, and Luck et al. (1998) give (-0.15, -0.14, 0.07) for similar Cepheids with respect to Galactic Cepheids. Use of Galactic comparisons minimizes systematic errors. At the same \[Fe/H\] as the LMC stars, Galactic stars show slightly positive values of \[Na/Fe\] and \[Ti/Fe\] but a \[Sc/Fe\] close to zero At the same \[Fe/H\] as the LMC stars, Galactic stars show slightly positive values of \[Na/Fe\] and \[Ti/Fe\] but a \[Sc/Fe\] close to zero The mild Na and Ti underabundances of the LMC stars relative to Galactic stars of the same \[Fe/H\] is likely attributable to the same factors responsible for the lower \[O/Fe\] (see below). In addition, the underabundances of Na and Ti, relative to Fe, are also found in the few dwarf spheroidal galaxies with published abundances, e.g. Shetrone, Cote, & Sargent (2001).

### 4.3 Carbon and Nitrogen Abundances

Carbon and nitrogen abundances are altered during mixing in red giants, as material exposed to the CN-cycle is brought to the star’s surface. The 12C abundance decreases, the 14N abundance increases, and the 12C/13C ratio decreases, but the sum of the 12C, 13C, and 14N is conserved. This mixing in first ascent and early-AGB red giants is not expected to alter the 16O abundance.

Figure 8 investigates the 12C and 14N abundances in the LMC red giants in comparison to other samples of stars, both in the LMC and in the Galaxy. The abundances of 14N are plotted versus the abundances of 12C. The solar symbol is located at A12C=8.41 (Allende Prieto, Lambert, & Asplund 2002–from their 1D MARCS model) and A14N=7.93 (Holweger 2001) and the dashed line represents equal changes in both carbon-12 and nitrogen-14. The solid curves are various “mixing curves” in which initial abundances of carbon and nitrogen are changed in such a way that their sum remains constant: as 12C decreases, 14N increases to mimic red-giant mixing of material consisting of increasing exposure to the CN-cycle. The open circles show the 12C and 14N abundances in Galactic disk M-giants from Smith & Lambert (1985; 1986; 1990) and these giants are well-represented by a CN-cycle mixing curve defined by approximate solar carbon and nitrogen initial abundances. The four-pointed crosses are s-process enriched MS and S stars, also from the Smith & Lambert papers and are plotted as different symbols because the photospheres of these giants have presumably been contaminated by material from the third dredge-up, associated with 4He-burning thermal pulses along the AGB. Such stars quite possibly have had primary 12C added to their surfaces and might be expected to evolve away from a simple CN-cycle mixing curve. What should be noted concerning the MS/S stars, however, are the few examples which show very large 14N abundances. These objects are AGB stars that have undergone hot-bottom burning (e.g. D’Antona & Mazzitelli 1996), where some amount of primary 12C produced during thermal pulses on the AGB is converted to 14N, via the CN-cycle, at the base of a deep convective envelope.

The LMC red giants analyzed here are plotted in Figure 8 as filled circles and fall in a much different region than the Galactic red giants. The two mixing curves that define approximately the region in the carbon-nitrogen plane where the LMC giants fall begin at lower initial carbon and nitrogen abundances. As initial values, we used the recent paper by Korn et al. (2002) that presents abundances for 4 true main-sequence B-star members of the young LMC cluster NGC2004. They conducted a non-LTE abundance analysis and their results for C and N are shown as the open squares in Figure 8. Using initial C and N abundances that bracket the Korn et al. (2002) abundances, the resulting CN-mixing curves provide excellent approximations to the behavior of the field LMC red giants. One of the results for LMC initial abundances, as indicated by Korn et al. (2002), was a lower value for both \[C/Fe\] and \[N/Fe\] in the LMC: such mixing lines, beginning at values of $``$-0.3 dex in \[C/Fe\] and \[N/Fe\], go right through the regions defined by the red giant abundances. An additional conclusion from the comparison of the carbon and nitrogen abundances in both the main-sequence B-stars and the red giants, is that simple CN mixing does an excellent job of describing the dredge-up in this sample of red giants; no evidence of deeper mixing, or of hot bottom burning, is found: these processes might lower the star’s 16O abundance through conversion of some 16O to 14N through the ON-cycles.

The constraint on possible oxygen depletions can be strengthened further by investigating the C/N abundance ratios. Most of the LMC giants in Figure 8 fall at values of \[12C/Fe\] that are about 0.6 to 0.8 dex below their probable initial values (as suggested by the Korn et al. 2002 results). At these levels of carbon-12 depletions, for the case of only CN-cycle mixing, the expected C/N ratios would be about 6 or less; all of the measured C/N ratios calculated from the abundances in Table 6 fit this constraint. The C/N ratio will increase over this value if additional nitrogen is added from the conversion of 16O to 14N via the ON cycles. Because oxygen is the most abundant member of the CNO trio, even a relatively modest depletion will measurably increase the nitrogen abundance. Given a plausible initial oxygen abundance as determined by Korn et al. (2002), a decrease in 16O of 0.2 dex would increase the C/N ratio to values of 8-10 in the regime of carbon depletions observed in the present sample of LMC red giants; such a large ratio is not found in any of the program stars. The LMC red giants studied here appear to have effectively unaltered 16O.

The 12C/13C ratio is another abundance indicator that is sensitive to stellar mixing on the red giant branch. The initial ratio is expected to be quite large ($``$ 40-90), while first dredge-up lowers this ratio to $``$ 18-26 for stars in the mass range from M$``$ 1-8M according to standard stellar models (e.g., Charbonnel 1994; but also Iben 1964). It has been known for some time that low-mass field giants exhibited lower 12C/13C ratios than predicted by standard models, with Keller, Sneden, & Pilachowski (2002) providing recent results of a discussion of this effect. Masses for giant-star members of clusters can be determined more accurately than masses for field giants, and the effect of lower 12C/13C ratios in lower-mass giants has been quantified by Gilroy (1989) using open clusters. Her results of 12C/13C versus giant mass are plotted in Figure 9 as the open squares. Above a mass of about 2.0-2.5M, the values of 12C/13C are 22-30 and agree reasonably well with standard stellar models of first dredge-up. In the lower-mass giants, however, Gilroy (1989) finds steadily decreasing 12C/13C ratios with decreasing mass, in contradiction to standard models. The 12C/13C ratios derived here for the LMC red giants are also plotted in Figure 9 as the filled circles. The masses for the LMC giants are estimated to only $`\pm `$0.5M and are based on the model tracks from Figure 2: these masses should be viewed as crude estimates. Nevertheless, there is a general trend of lower 12C/13C ratios with lower masses that tracks the Gilroy (1989) trend rather well, although offset to lower isotopic carbon-12 to -13 ratios for a given mass. Charbonnel (1994) and Charbonnel, Brown, & Wallerstein (1998) investigate the lower 12C/13C values in the lower-mass red giants and suggest that extra-mixing, possibly driven by meridional circulation and rotationally induced turbulence can explain the lower 12C/13C ratios. In their model, extra-mixing is inhibited by mean molecular weight gradients, which increase with increasing metallicity, so they predict more extensive mixing (and lower 12C/13C ratios for a given-mass giant) at lower metallicities. The offset between Gilroy’s (1989) trend and the LMC trend may be due to this metallicity effect.

The 12C/13C ratio of 45 in NGC2203 AM2 deserves some mention. Although the errorbars on this measurement are large, it still falls well above the trend of 12C/13C with mass found for the other LMC red giants. One possibility is that this star has begun dredge-up as an AGB star and some 12C (produced from 4He-burning) has been added to the photosphere. If the 12C abundance were increased by 0.15 dex due to such dredge-up, the observed current 12C/13C ratio of 45 would have been 30 before the addition of extra 12C: within the scatter of the other red giants. Until more LMC red giants are observed, such an explanation of the anomalous position of NGC2203 AM2 in Figure 9 is speculation.

### 4.4 The Oxygen Abundances

On the assumption that the oxygen abundance is left unaltered by the convective mixing, an assumption supported by the 12C, 13C, and 14N abundances of the LMC red giants, the O/Fe ratio may be used as a tracer of chemical evolution. The \[O/Fe\] values run from -0.3 to +0.3 with a hint that they increase with decreasing \[Fe/H\]. Oxygen to iron abundances from a large number of Galactic and LMC studies, presented as \[O/Fe\] versus \[Fe/H\], are brought together in Figure 10: the LMC red-giant results from this study are plotted as filled circles. The Galactic samples of field stars shown in this figure are taken from Edvardsson et al. (1993), shown as open circles, Nissen & Edvardsson (1992) shown as open triangles, Cunha, Smith, & Lambert (1995) shown as open hexagons, and Smith, Cunha, & King (2001) shown as open squares (the Galactic results are plotted as smaller symbols simply to keep these numerous points from falling on top of each other and obliterating their visibility). The open pentagons at low metallicity are the recent results for Galactic stars from Melendez & Barbuy (2002) using the IR OH v-r lines: this paper also includes the earlier results from Melendez, Barbuy, & Spite (2001). Other low-metallicity results for \[O/Fe\] are from Barbuy (1988) and Nissen et al. (2002), shown as asterisks and three-pointed stars, respectively. Additional \[O/Fe\] values for the LMC are shown as comparisons to the red giants observed here: the filled triangles are from Korn et al. (2002) for main-sequence B-stars, the filled squares are from Hill et al. (1995) for F-supergiants, and the filled pentagons are from Hill et al. (2000) and Spite et al. (2001) for old clusters and globular clusters. Figure 10 shows that, over the metallicity range of \[Fe/H\]$``$ -1.0 to -0.2, the LMC stars fall about 0.2-0.3 dex below stars in the Milky Way. The fact that main-sequence B-stars, F supergiants, and cool, red giants all yield the same results from independent analyses using very different sets of lines (O II and Fe III for B stars, weak O I 6158Å lines and Fe II for F supergiants, and Fe I plus OH for the red giants) suggests strongly that this is now a well established trend.

The common interpretation of the different \[O/Fe\] - \[Fe/H\] relations is that star formation in the LMC occurred in an early burst. Interruption of star formation reduced the input of oxygen into the interstellar gas. In this interval, SN Ia delivered iron and so brought the O/Fe down. In the Galaxy, star formation was less affected by bursts, and O/Fe remained at its “high” value to a higher \[Fe/H\] than in the LMC. The solid curves shown in Figure 10 are a simple interpretation of the differing values of \[O/Fe\] in the Milky Way versus the LMC. These curves were generated by taking yields from supernovae of types II and Ia and adding the processed elements into a unit mass of gas over time. The rate at which the abundances grow with time depends on the supernovae rate per unit mass of gas. This rate is normalized by assuming a rate of one SN II per 100 years and one SN Ia per 300 years in the Milky Way, with the mass taken to be 1011M. Oxygen mass yields for SN II were taken from Arnett (1999) and convolved with a Salpeter mass function to yield an average mass of 1.5M ejected per SN II. Iron yields for SN II were similar to that from Timmes, Woosley, & Weaver (1995), and set at 0.15M per SN II. With the rates and yields set for the Milky Way SN II, it remained to set both the Fe yield from SN Ia and the time delay for their initial contribution to chemical evolution. In order to fit the Milky Way trend as shown in Figure 10, it was necessary to set the SN Ia Fe yield to 0.7M per SN Ia and to use a time delay of 1.5 Gyr: both of these values are reasonable in such a simple approximation. The resulting curve does a fairly good job of following the values of \[O/Fe\] versus \[Fe/H\] in the Milky Way, with the final point on the calculated curve shown being reached after a time of 12 Gyr. The other curve shown was generated as an approximation to the LMC trend of \[O/Fe\] versus \[Fe/H\]. Although not a unique solution, this curve was generated by simply lowering the SN II rate per unit mass in the LMC by a factor of 3 and the SN Ia rate by a factor of 2 (the SN II and Ia O and Fe yields and SN Ia time delay were the same). This very simple numerical model indicates the \[O/Fe\] abundance ratios in the LMC can be understood as arising from both a slower rate of SN II per unit mass (caused presumably by a lower average star formation rate per unit mass of gas) and a slightly enhanced ratio of SN Ia rates to SN II rates in the LMC. These results are in rough agreement with those suggested by the analytical chemical evolution models of Pagel & Tautvaisiene (1998).

## 5 Conclusions

Abundances of seven elements (C, N, O, Na, Sc, Ti, and Fe) have been measured in twelve red-giant members of the LMC from high-resolution IR spectra obtained with Gemini South plus Phoenix. Using IR spectra it is possible to extract quantitative chemical abundances for a number of elements in somewhat lower-mass stars (M$``$ 2-4M red giants) in the LMC than previous high-resolution optical spectroscopic studies of main-sequence B-stars or F to K supergiants (with M$``$ 8-10M). The IR abundance analyses add complementary stellar mass targets to the earlier works. In addition, the molecular lines of such species as CO, OH, or CN in the IR spectra allow for the determination of the abundances of specific CNO isotopic species, such as 12C, 13C, 14N, and 16O here, or 17O, 18O, and 15N in future studies.

The iron abundances sampled here range from \[Fe/H\]= -1.1 to -0.3. Both \[Na/Fe\] and \[Ti/Fe\] are found to be consistently lower than their Galactic values by $``$ -0.1 to -0.5 over the metallicity range sampled in the LMC. These characteristic underabundances of Na and Ti seem to also occur in a number of dwarf spheroidal galaxies (Shetrone et al. 2002).

The LMC red giants in this sample all show evidence of the mixing of CN-cycle material to their surfaces via the first dredge-up, with 14N enhanced by +0.4 to +0.8 dex over its estimated initial values, and 12C decreased by -0.3 to -0.5 dex. No evidence is found, in these predominantly first ascent giants or early AGB stars, of the extreme nitrogen enrichments ($``$ +1.0 dex or more) that might result from second dredge-up or hot bottom burning. The 12C/13C ratios in the LMC red giants are found to decrease with decreasing giant star mass in a manner similar to that found for Galactic red giants (Gilroy 1989); however, the LMC trend appears to be shifted to lower 12C/13C ratios for a given red-giant mass. This shift may be due to the increased mixing associated with lower-metallicity giants as suggested by Charbonnel et al. (1998).

A comparison of \[O/Fe\] versus \[Fe/H\] between the LMC and the Milky Way finds that the LMC trend falls below by about 0.2 dex over the range of \[Fe/H\]= -1.1 to -0.3. Good agreement in \[O/Fe\] as derived from a sample of F-supergiants (Hill et al. 1995), main-sequence B-stars (Korn et al. 2002), and the red giants analyzed here suggests that the difference between the LMC and the Milky Way is real. Lower values of \[O/Fe\] in the LMC can be explained by both a lower supernovae rate (caused by a lower star formation rate) and a lower ratio of supernovae type II to supernovae type Ia.

We thank the staff of Gemini South for their excellent assistance with these observations. Nick Suntzeff is to be thanked for insightful comments concerning the distance to the LMC. This work is supported in part by the National Science Foundation through AST99-87374 (V.V.S.).


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# Bader’s interatomic surface and Bohmian mechanics.

## I Introduction

In a previous work  we analyzed the statistical meaning of Bader’s interatomic surface (or zero flux surface of the electronic density gradient), i.e.

$$\rho (𝐫)𝐧=0,𝐫S(𝐫)$$
(1)
(where $`𝐧`$ is the unit vector perpendicular to $`S(𝐫)`$ at each point $`𝐫`$ of the surface $`S`$).

We used the approximation of Thomas-Fermi for the electron density and related properties and showed that the partitioning of the whole system in subsystems which are in mutual statistical equilibrium is consistent with Bader’s partitioning of atoms in molecules. The Theory of Atoms in Molecules is well known, thus we do not review it and suggest the reader to consult the following references , while for technical applications see for example . The central point of our previous work was to define the electronic chemical potential within the approximation of the simple Thomas-Fermi model and then consider two cases, electron as non interacting particles, and electrons as classical interacting particles. Next, by imposing the condition of statistical equilibrium at each point of the surface of separation between two subsystems, which means the gradient of the electronic chemical potential at the surface to be zero along the crossing direction (normal to the surface), we could comment on the consistency between Bader’s definition and the statistical definition of atomic subsystem in a multiatomic system. In this work we extend the previous analysis to a more sophisticated Thomas-Fermi model which takes into account exchange energy (Dirac) and the inhomogeneity of the electron density, i.e. the Weizsacker correction to the Thomas-Fermi kinetic energy; the resulting model is known as Thomas-Fermi-Dirac-Weizsacker (TFDW) (see pg 127-136 of ). We apply the procedure developed in our previous work and find some interesting connections with bohmian mechanics (for details about bohmian mechanics see for example  and references therein). This is an interesting result since an attempt to interpret Bader’s theory in terms of bohmian mechanics has already been done for the part relative to the chemical bond ; our current results can be integrated with those and lead to a simple interpretation of some chemical concepts in a statistical context with evident advantages for molecular modeling and its applications.

## II Thomas-Fermi-Dirac-Weizsacker model

The introduction in the simple Thomas-Fermi energy functional

$$E_{TF}=C_V\rho (𝐫)^{5/3}\underset{i=1,M}{}Z_i_V\frac{\rho (𝐫)}{|𝐫𝐑_i|}𝑑𝐫+\frac{1}{2}_V\frac{\rho (𝐫)\rho (𝐫^{})}{|𝐫𝐫^{}|}𝑑𝐫𝑑𝐫^{}$$
(2)
(where C is a proper dimensional constant, $`V`$ is the total volume of the system, the first term represents the kinetic energy within the Thomas-Fermi approximation, the second term describes the total interaction between electrons and nuclei ($`Z_i,𝐑_i`$ represents the charge and position of the $`i`$-th nucleus, while $`i=1,M`$)) of the exchange energy term $`C_x\rho (𝐫)^{4/3}𝑑𝐫`$ where $`C_x`$ is the appropriate dimensional constant and the Weizsacker correction term to the kinetic energy $`\frac{\mathrm{}^2}{8m}\frac{|\rho (𝐫)|^2}{\rho (𝐫)}𝑑𝐫`$, leads to the, so called, TFDW energy functional:

$$\begin{array}{cc}E_{TFDW}=C_V\rho (𝐫)^{5/3}_{i=1,M}Z_i_V\frac{\rho (𝐫)}{|𝐫𝐑_i|}𝑑𝐫+\frac{1}{2}_V\frac{\rho (𝐫)\rho (𝐫^{})}{|𝐫𝐫^{}|}𝑑𝐫𝑑𝐫^{}\hfill & \\ C_x\rho (𝐫)^{4/3}𝑑𝐫+\frac{\mathrm{}^2}{8m}\frac{|\rho (𝐫)|^2}{\rho (𝐫)}𝑑𝐫\hfill & \end{array}.$$
(3)
Within this approximation the electronic chemical potential $`\mu (𝐫)`$ is derived via a variational procedure as

$$\mu (𝐫)=\frac{\delta E_{tot}[\rho (𝐫)]}{\delta \rho (𝐫)}.$$
(4)
and this leads to the following relation:

$$\begin{array}{cc}\mu (𝐫)=\frac{5}{3}C\rho (𝐫)^{2/3}_{i=1,M}\frac{Z_i}{|𝐫𝐑_i|}+\frac{1}{2}_V\frac{\rho (𝐫^{})}{|𝐫𝐫^{}|}𝑑𝐫^{}\hfill & \\ \frac{4}{3}C_x\rho (𝐫)^{1/3}+\frac{\mathrm{}^2}{8m}\left[\frac{|\rho (𝐫)|^2}{\rho (𝐫)^2}2\frac{|^2\rho (𝐫)|}{\rho (𝐫)}\right].\hfill & \end{array}$$
(5)
Now we impose the statistical equilibrium $`\mu (𝐫)=constant`$ at the interatomic surface $`S^{}`$ along the normal crossing direction, i.e.

$$_𝐧\mu (𝐫)=0$$
(6)
$$𝐫S^{}(𝐫).$$
(7)
In order to understand a possible meaning of Bader’s surface $`S`$ in a statistical context, let us suppose that $`S`$ and $`S^{}`$ coincide, which means that we suppose Bader’s topological partitioning criterion is equivalent to a statistical partitioning criterion of $`\rho (𝐫)`$, this will allow us to apply the properties of $`S`$ to Eq.6 (of course $`S`$ in Eq.1 and $`S^{}`$ in Eq.7 are not necessarily the same and will comment on this case later on); i.e. taking into account that $`\rho (𝐫)𝐧=0,𝐫S(𝐫)`$ we obtain

$$_𝐧\left[\underset{i=1,M}{}\frac{Z_i}{|𝐫𝐑_i|}+\frac{1}{2}_V\frac{\rho (𝐫^{})}{|𝐫𝐫^{}|}𝑑𝐫^{}+\frac{\mathrm{}^2}{8m}\left[\frac{|\rho (𝐫)|^2}{\rho (𝐫)^2}2\frac{|^2\rho (𝐫)|}{\rho (𝐫)}\right]\right]=0.$$
(8)
Since $`_{i=1,M}\frac{Z_i}{|𝐫𝐑_i|}+\frac{1}{2}_V\frac{\rho (𝐫^{})}{|𝐫𝐫^{}|}𝑑𝐫=\varphi (𝐫)`$ is the classical electrostatic potential, Eq.8 expresses the condition that the generalized force which takes into account non-local (and non-classical) effects must vanish at the surface of separation. The interpretation of the above result is the same furnished in our previous work, with the exception that now we do not simply have the classical electrostatic force but an additive term, as one could have easily guessed a priori. However what makes this result interesting is the fact that the term $`\frac{\mathrm{}^2}{8m}\left[\frac{|\rho (𝐫)|^2}{\rho (𝐫)^2}2\frac{|^2\rho (𝐫)|}{\rho (𝐫)}\right]=Q(𝐫)`$ represents the Bohm potential (see ). This consideration, will allow us to interpret the results found so far in terms of bohmian mechanics.

## III Bader’s theory and Bohmian Mechanics

We supposed that $`S`$ and $`S^{}`$ are the same, i.e. Bader’s interatomic surface corresponds to a surface of separation between two statistical subsystems in equilibrium. $`S`$ (or $`S^{}`$) does not explicitly show the nature of the bond at the separation, but only define the topological domain of each atom. This means that this analysis furnishes one chemical information (defines atomic entities) but does not show how they are related to each other in chemical terms. In their work  Levit and Sarfatti shows that Bohm’s quantum potential can give a direct interpretation, at least for atoms not beyond the third row as underlined by Hamilton , of bonding and reactivity in a multiatomic system. In the light of what stated above let us consider the concept expressed by Eq.8, i.e. the electrostatic potential $`\varphi (𝐫)`$ must be equal to minus Bohm potential $`Q(𝐫)`$ at every point of the surface $`S`$. This means that from the topology of $`\varphi (𝐫)`$ one can work out the bonding nature and reactivity at each point of the separation surface, i.e. along $`S`$ bonding and reactivity can be determined in terms of classical electrostatic interaction.

One can notice that in general, in case $`S`$ and $`S^{}`$ are not the same (i.e.$`\rho (𝐫)0`$), it is possible to say that along $`S^{}`$ bonding and reactivity are equivalently described by a quantum (Bohm potential) or a classical ($`E_{TF}`$) approach.

Although the model used is highly simplified, as extensively discussed in our previous work, the conclusions above are very interesting because furnish basic indications about the nature of chemical properties in a statistical context stimulating a further development at higher level of theory.

As stated in our previous work, rigorously speaking, the force which acts at the surface of an atom is the Ehrenfest force and the results obtained here are valid only within the approximation done for exchange and density’s inhomogeneity. At higher level of approximation for exchange and correlation, the physical picture may be very different; nevertheless starting from our results one could build a more complete and rigorous picture. We have found also another connection with bohmian mechanics in terms of single particle dynamics. In this case we have to consider the quantum wavefunction to be imaginary and in polar form $`\psi (𝐫)=R(𝐫,t)e^{iS(𝐫,t)}/\mathrm{}`$, or the more familiar $`\psi (𝐫)=(\rho (𝐫,t)^{1/2})e^{iS(𝐫,t)}/\mathrm{}`$ where $`\rho (𝐫,t)`$ is the one particle time dependent electron density as considered so far. The point particles of mass $`m`$ in the configuration space will be governed by the following dynamics:

$$v_n=\frac{\mathrm{}}{m}Im\frac{_n\psi }{\psi }$$
(9)
where $`v_n`$ is the velocity of the particle along the direction $`𝐧`$. Applying the Shröedinger equation and considering the stationary case, using the property $`v_n=\frac{v_n}{n}`$ where $`\frac{}{n}`$ is the derivative with respect to the direction normal to the surface $`S`$, from equation (2) in Ref. we obtain:

$$\frac{v_n^2}{n}=_n\left(\frac{1}{m}\varphi (𝐫)+Q(𝐫)\right)$$
(10)
($`_n=𝐧`$, and $`𝐧`$ as specified before is the vector normal to $`S`$ at each point). Considering $`S`$ and $`S^{}`$ coinciding, from Eq.8 and Eq.10 one obtains:

$$v_n\frac{v_n}{n}=0$$
(11)
Eq.11 is satisfied either in case the velocity of the particle normal to $`S`$ is zero or in case the flux of kinetic energy is zero. In the first case we have a natural interpretation on interatomic surface, i.e. the particle does not cross the border and so belongs to a particular topological domain, in the second case, this expresses the fact that the flux of classical kinetic energy in the Thomas-Fermi formulation $`\frac{\rho }{\rho ^{1/3}}`$ and the flux of the quantum kinetic energy $`v_n\frac{v_n}{n}`$ through the surface $`S`$ are both zero. These properties of $`S`$ are very interesting and, as the properties previously shown, stimulate further investigation of the classical-quantum connections of $`S`$. However one must notice that although this latter result is intriguing, it applies only to complex wavefunctions; this means that for practical application in current research, where ground state calculations are mainly done, this result cannot be used unless particular cases are investigated (e.g. systems in magnetic fields).

## IV Discussion and Conclusions

We analyzed the statistical meaning of interatomic surface in Bader’s formulation from a statistical point of view within the approximation of Thomas-Fermi-Dirac-Wiezsacker. It emerged an interesting connection with bohmian mechanics in interpreting properties of points at the surface $`S`$ in terms of bonding and reactivity. It must be also clear that this analysis is valid in the limit of the approximations done, more sophisticated models could lead to different results and certainly not to a direct interpretation in terms of bohmian mechanics. However it would be interesting to understand why and how the modification of properties of $`S`$ occur at higher level of theory using our previous analysis as a starting point. Another important problem is to understand how $`S`$ and $`S^{}`$ are connected for real cases; our analysis was based on the hypothesis that they do coincide, so that we could comment on the consistency of Bader’s surface with a statistical definition but this hypothesis is not obvious and if they differ it would be interesting to understand at which level of approximation they do coincide. Since Bader’s procedure to obtain $`S`$ is based on a rigorous method within quantum mechanics, the exact relation between $`S`$ and $`S^{}`$ at different levels of statistical theory could lead to clearer formulation of quantum properties in statistical terms with obvious advantages for practical applications. In conclusion, we think that our analysis is important for a formulation in statistical terms of the chemical properties at atomistic level and because represents a stimulating challenge for further developments.


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# References

Hydrogen Bond Dynamics Near A Micellar Surface: Origin of the Universal Slow Relaxation at Complex Aqueous Interfaces
Sundaram Balasubramanian1, Subrata Pal2, and Biman Bagchi2
1 Chemistry and Physics of Materials Unit,

Jawaharlal Nehru Centre for Advanced Scientific Research,

Jakkur, Bangalore 560064, India.

2Solid State and Structural Chemistry Unit, Indian Institute of Science,

Bangalore 560012, India.

Abstract

The dynamics of hydrogen bonds among water molecules themselves and with the polar head groups (PHG) at a micellar surface have been investigated by long molecular dynamics simulations. The lifetime of the hydrogen bond between a PHG and a water molecule is found to be much longer than that between any two water molecules, and is likely to be a general feature of hydrophilic surfaces of organized assemblies. Analyses of individual water trajectories suggest that water molecules can remain bound to the micellar surface for more than a hundred picosecond. The activation energy for such a transition from the bound to a free state for the water molecules is estimated to be about 3.5 kcal/mole.

The study of hydrogen bond dynamics has proven to be a very useful tool  to understand the origin of many fascinating dynamical properties of water which are due to its extended hydrogen bond network . However, the same properties exhibit quite different behavior for water molecules at the surfaces of self-organized assemblies and biological macromolecules . Recent time domain spectroscopic measurements have shown that their dynamics is considerably slower than their counterparts in bulk water, sometimes slower by more than two orders of magnitude! While the reorientation of water molecules and solvation of ions or dipoles in bulk water proceeds with an average time constant of less than a picosecond (ps), the same at protein surfaces gets extended to hundreds of picoseconds . Such slow dynamics has been observed in proteins , microemulsions , micelles , lipid vesicles and bilayers .

The slow dynamics of water molecules at heterogeneous surfaces seems to be universal and could be a collective effect originating from the surface and/or from the nature of the hydrogen bond network at the surface. The work of Cheng and Rossky  have already shown that water molecules at the surface of a protein can be structurally different from those in the bulk. A phenomenological theory developed recently proposes to explain the emergence of slow dynamics in terms of a dynamical equilibrium between bound and free water molecules at the surface . Recent atomistic molecular dynamics simulations of an aqueous micellar assembly, the cesium pentadecaflurooctanoate (CsPFO), have shown that the orientational correlation function of the water molecules near the micelle show a dramatic slowing down in its long time decay . Note that micelles are not only of great interest themselves, but they also mimic surfaces of many biological molecules. The presence of a compact hydrophobic core and a hydrophilic surface resembles proteins rather closely.

In this study, we explore the two most important microscopic aspects of water dynamics near the micellar surface – the hydrogen bond lifetime of the water-PHG hydrogen bond and also the distance dependence of the dynamics of the water-water hydrogen bond. The best way to study this dynamics is to investigate the hydrogen bond time correlation functions, $`S_{\mathrm{HB}}(t)`$ and $`C_{\mathrm{HB}}(t)`$ (defined below), introduced originally by Rapaport  and used by Chandler et al  to study pure water and more recently by Chandra  to explore effects of ions in water on the lifetime of the hydrogen bond. The time correlation function $`S_{\mathrm{HB}}^{\mathrm{wPHG}}(t)`$ for the hydrogen bond between the polar head group and the water molecules on the surface is defined by

$$S_{\mathrm{HB}}^{\mathrm{wPHG}}(t)=h_{\mathrm{wPHG}}(0)H_{\mathrm{wPHG}}(t)/h_{\mathrm{wPHG}}$$
(1)
where the population variable $`h_{\mathrm{wPHG}}(t)`$ is unity when a particular tagged hydrogen bond between a water molecule and a polar head group is hydrogen bonded at time $`t`$ according to an adopted definition, and zero, otherwise. On the other hand, $`H_{\mathrm{wPHG}}(t)=1`$ if the tagged polar head group-water hydrogen bond remains continuously hydrogen bonded during the time duration $`t`$ and zero otherwise. Thus, $`S_{\mathrm{HB}}^{\mathrm{wPHG}}(t)`$ describes the lifetime of a tagged pair. The angular brackets denote averaging over initial time values and over all water-PHG pairs. We employed a geometric definition of the $`\mathrm{wPHG}`$ hydrogen bond such that a water molecule was assumed to be hydrogen bonded to a surfactant if the distance between the oxygen of the water molecule and the carbon of the headgroup was less than 4.35Å, and that the oxygen of the water molecule and the oxygen of the headgroup was less than 3.5Å. These distance criteria were obtained from the first minimum in the respective pair correlation functions. For water-water hydrogen bonds, we have used the same criteria as used by Chandra , which were found to hold good for water-water hydrogen bonds near the interface also.

In order to understand the structural relaxation of a tagged hydrogen bond, one also defines the following time correlation function, $`C_{\mathrm{HB}}^{\mathrm{wPHG}}(t)`$,

$$C_{\mathrm{HB}}^{\mathrm{wPHG}}(t)=h_{\mathrm{wPHG}}(0)h_{\mathrm{wPHG}}(t)/h_{\mathrm{wPHG}}$$
(2)
Unlike $`S_{\mathrm{HB}}^{\mathrm{wPHG}}(t)`$, this correlation function is expected to exhibit a longtime tail .

The surfactant in this simulation is pentadecafluorooctanoate, with cesium being the counterion, commonly referred to as CsPFO. The CsPFO-H2O system has been well studied experimentally  and is regarded as a typical binary to exhibit micellization. The amphiphiles form disc shaped micelles, stable over an extensive range of concentration and temperature. Details of our MD simulations have been discussed elsewhere . The molecular dynamics simulation was carried out in the NVT ensemble for an aggregate of 62 CsPFO molecules in 10,562 water molecules. The potential for water molecules is the extended simple point charge (SPC/E) model , the counterions carry a unit positive charge, which is compensated by a $`+0.4e`$ charge on the carbon of the octanoate headgroup and a $`0.7e`$ charge on each of the oxygens of the headgroup . The equations of motion were integrated with the RESPA scheme  using the PINY-MD program  with an outer timestep of 4 fs. The analyses reported here were carried out from different sections of a subsequent 3.5 ns trajectory. The S(t) and C(t) functions were obtained with time resolutions of 12 fs and 1 ps respectively. The results reported here are at a temperature of 300K.

Figure 1 shows the time dependence of the correlation function $`S_{\mathrm{HB}}^{\mathrm{wPHG}}(t)`$, with the inset showing the $`S_{\mathrm{HB}}^{\mathrm{ww}}(t)`$ (i.e., water-water) correlation function in bulk water, for comparison. Note the lengthening of the time scale in the H-bonding with the PHG of the micelle. $`S_{\mathrm{HB}}^{\mathrm{wPHG}}(t)`$ can be fitted to a sum of three exponentials, with the longest time constant being equal to 9 ps which is to be compared with 0.97 ps in pure water. The amplitudes and time constants are given in Table 1 . From these, one can obtain an average time constant of around 6.8 ps, which is thirteen times larger than its value for the water-water hydrogen bond in pure water. It is difficult to pinpoint the reason for the slowdown of $`S_{\mathrm{HB}}(t)`$ at the surface. We found that the water molecules at the surface form bridge hydrogen bonds involving PHGs of the nearest neighbor surfactant molecules which could stabilize the $`\mathrm{wPHG}`$ hydrogen bond.

In figure 2, we show the hydrogen bond time correlation function $`C_{\mathrm{HB}}^{\mathrm{wPHG}}(t)`$. In the inset we show $`C_{\mathrm{HB}}^{\mathrm{ww}}(t)`$ for bulk water. Note again the lengthening of the long time decay. The values of the time constants and the respective amplitudes are given in Table 1. In this case, the long time constant stretches to more than one hundred picoseconds. The reason for this unusual long decay time can be traced back to those trajectories which leave the micellar surface to go to the bulk but return after a long time to get bonded to the same PHG at the surface. This is in line with the explanation of the long time decay of the $`C_{\mathrm{HB}}(t)`$ function in bulk water . In the present problem, the existence of such trajectories indicate presence of correlations in the surface region. The $`S(t)`$ function is thus a more accurate representation of the lifetime dynamics of the hydrogen bond than the $`C(t)`$ function, although the latter contains rich information on the correlated pair diffusion of the water molecules.

Analysis of the trajectories of the individual water molecules at the micellar surface reveals an amazing richness of events. In figure 3, we show representative trajectories over 800 ps, of four arbitrarily chosen water molecules that were hydrogen bonded to the surface at time zero. The plot shows the shortest distance, $`D_{\mathrm{W}\mathrm{PHG}}`$, of each of the water molecules to the micellar surface as a function of time . For example, the water molecule shown in the top left figure, rattles near the surface for about 150 ps, then diffuses into the bulk region, stays there for around 500 ps, and then revisits the micelle surface, presumably to form a new hydrogen bond with a PHG. It should also be noted that the micelle itself is quite fluxional over these time scales. Note also that while the $`S_{\mathrm{HB}}^{\mathrm{wPHG}}(t)`$ and $`C_{\mathrm{HB}}^{\mathrm{wPHG}}(t)`$ functions study the dynamics of a particular wPHG hydrogen bond (with average lifetimes of 6.9 and 43.7ps respectively), the apparently longer lifetime of bound water molecules shown in the trajectories in figure 3 arises from the fact that a water molecule can remain bound to the micellar surface even after its hydrogen bond with a particular PHG is broken.

Such dynamical processes involving water molecules affect the way they form hydrogen bond between themselves. We have explored this aspect by studying the water-water hydrogen bond time correlation functions, for water molecules that belong to different interfacial layers. In figure 4 we show the lifetime correlation functions, $`C_{\mathrm{HB}}^{\mathrm{ww}}(t)`$ and $`S_{\mathrm{HB}}^{\mathrm{ww}}(t)`$ between two water molecules that both exist at several regions away from the surface . This function shows a sharp slow down as the surface is approached closely. The time constant obtained from the $`S_{\mathrm{HB}}`$ function for the water molecules within 6Å from the micellar surface is around 25-30% larger than that for water molecules in the bulk region. The time constant for the same water molecules obtained from the $`C_{\mathrm{HB}}`$ function is about 45% slower than that for bulk water. Again, the $`S_{\mathrm{HB}}`$ function decays much faster than the $`C_{\mathrm{HB}}`$ one.

The simulation results can be combined with a theoretical model to obtain useful information on the micelle-water interaction. The model assumes a dynamical equilibrium between the “bound” and “free” states of water molecules at the micellar surface . The dynamical variable $`h(t)`$ represents the instantaneous population of the bound state and the correlation function, $`C_{\mathrm{HB}}^{\mathrm{wPHG}}`$(t) gives, under the regression hypothesis (or linear response theory) , the decay of an initial (t=0) bound state and its formation at a later time. Therefere, we can set, in the long time, $`C_{\mathrm{HB}}^{\mathrm{wPHG}}`$(t) $``$ e$`^{\frac{t}{\tau _{\mathrm{BF}}}}`$, where $`\tau _{B\mathrm{F}}`$ is the time constant for the bound to free transition. From Table 1, we find the average time constant at 300K to be 43.7ps. We can obtain an activation energy $`E_\mathrm{A}`$, for this transition using transition state theory to express the rate constant ($`\frac{1}{\tau _{\mathrm{BF}}}`$), as,

$$\frac{1}{\tau _{BF}}=\frac{k_BT}{h}e^{\frac{E_A}{k_BT}}$$
(3)
where, $`k_\mathrm{B}`$ is the Boltzmann constant, $`T`$ is temperature, and $`h`$ is the Planck constant. $`E_\mathrm{A}`$ is then found to be 3.34 kcal/mole. A similar analysis of $`C_{\mathrm{HB}}^{\mathrm{wPHG}}`$(t) at 350K (data not shown here) yields a time constant of 18.9ps. Using an Arrhenius dependence of the time constant with temperature, we find that the activation energy is 3.50 kcal/mole, in close agreement with the result of the transition state theory presented above, showing the robustness of the above analysis.

To conclude, we have carried out large scale atomistic molecular dynamics simulations of an aqueous micellar system, with emphasis on understanding the hydrogen bond breaking dynamics at the micellar surface. We find the rather surprising result that the hydrogen bond between the micellar polar head group and a water molecule has a much longer lifetime – almost 13 times larger than that in the bulk between two tagged water molecules. This longer lifetime could originate from the bridge bonds that the surface water molecules form with the PHGs and also from the coupling to the micelle which acts as a bath for HB excitations. Another interesting result is that the lifetime of hydrogen bonds between two tagged water molecules increase only by about 25-30% as one approaches the micellar surface. Although this slowdown is not as dramatic as the slowdown in the orientational relaxation of the water molecules with large residence times near the interface, it is rather sharp. Analysis of the individual trajectories reveal that the quasi-bound water at the micellar surface (immobilized by double or more hydrogen bond bridges) may be partly responsible for the slow dynamics. The activation energy for the transition from a bound to a free state for the water molecules on the micellar surface, estimated from both the transition state theory and from the temperature dependence of the hydrogen bond lifetime, is about 3.5 kcal/mole. The agreement between the rather simple model and the temperature dependent simulation data is remarkable. We believe that the results discussed here are generic to organized assemblies and biological macromolecules that possess a hydrophilic surface or hydrophilic pockets that are accessible to water.

Acknowledgments

It is a pleasure to thank Prof. A. Chandra for helpful comments on an earlier version of this manuscript and for pointing out Ref. . The research reported here was supported in part by grants from the Council of Scientific and Industrial Research (CSIR) and the Department of Science and Technology (DST), Government of India.


text:
# Singularity-Free Electrodynamics for Point Charges and Dipoles:Classical Model for Electron Self-Energy and Spin

## I Introduction

The most elementary problems in classical electrodynamics are likely to involve point charges, point dipoles and other tractable mathematical idealizations of physical reality. But the simplicity of these solutions often obscures a subtle but pervasive conceptual flaw. This appears even in the most elementary formula of electrostatics, Coulomb’s law of force between two point charges $`q_1`$ and $`q_2`$ separated by a distance $`r`$

$$F=\frac{q_1q_2}{r^2}$$
(1)
with the corresponding energy of interaction

$$W=\frac{q_1q_2}{r}$$
(2)
What if we want to know the hypothetical force a point charge would exert on itself? Since we would then have $`r=0`$ in these equations, this force becomes infinitely large, as does the self-energy—the energy of interaction of the point charge with its own electric field. For the most part, these difficulties have been “swept under the rug” since electrically-charged bodies in real life have a finite size. A point charge is perhaps just an abstraction. Still, it would be highly desirable, even for purely aesthetic reasons, to remove this imperfection from the otherwise beautiful and complete edifice of Maxwell’s electrodynamics. Dimensionlesss point charges are in fact the paradigm for representing fundamental particles in quantum mechanics and quantum field theory. And all experimental evidence from high-energy physics appears to support such models. For example, recent high-energy electron-positron scattering experiments imply an upper limit of $`2\times 10^{16}\mathrm{cm}`$ on the radius of the electron.

The strategy we pursue invokes constitutive relations. Usually, these are phenomenological parameters which represent properties of matter, serving as inputs to Maxwell’s equations, not implied by the stucture of electrodynamics itself. In certain favorable instances, these parameters can be determined theoretically from quantum theories of matter. The idea which we will exploit is to attribute constitutive properties to the vacuum. According to quantum field theory, the ultramicroscopic vicinity of an elementary charged particle is a seething maelstrom of virtual electron-positron pairs (and other particles and antiparticles) flashing in and out of existence. To take account of this well-established physical reality, a phenomenological representation for vacuum polarization is introduced within the framework of classical electrodynamics. As we will show, such a model enables a consistent picture of classical point charges with finite electromagnetic self-energy. We must emphasize that the model is intended in a purely classical context and will not necessarily be in agreement with details of quantum electrodynamics. In the same sense, continuum models for dielectric media can be extremely successful without taking account of the underlying atomic nature of matter.

## II Self-Energy of a Point Charge

The energy contained in an electromagnetic field is given by

$$W=\frac{1}{8\pi }\left(𝐄𝐃+𝐁𝐇\right)d^3𝐫$$
(3)
In a rest frame, the field produced by a point charge $`e`$ in vacuum is represented by $`𝐃=𝐄=e\widehat{𝐫}/r^2`$, $`𝐁=𝐇=0`$. For concreteness, let the particle be an electron. The electromagnetic self-energy is then given by

$$W=\frac{1}{8\pi }\frac{e^2}{r^4}\mathrm{\hspace{0.17em}4}\pi r^2𝑑r=\mathrm{}$$
(4)
The result is infinite unless a lower cutoff is introduced—in which case the electron acquires a finite size, as in the models proposed by Thomson, Lorentz, Abraham and others a century ago. With a radius of the order of $`r_0=e^2/mc^22.818\times 10^{13}`$ cm, known as the classical or Thomson radius, the electromagnetic self-energy can be adjusted to equal $`mc^2`$. This is in accord with the original idea of Lorentz and Abraham that the electron’s rest mass is purely electromagnetic in origin. Because of mutual repulsions among the electron’s elements of charge, the whole structure might be expected to blow itself apart. Poincaré postulated the existence of nonelectromagnetic attractive forces—later called Poincaré stresses—to somehow counterbalance the Coulomb repulsion.

It was suggested in the 1930’s by Furry and Oppenheimer that quantum-electrodynamic effects could give the vacuum some characteristics of a polarizable medium, which Weisskopf represented phenomenologically by an inhomogeneous electric permittivity, viz.,

$$𝐃(r)=ϵ(r)𝐄(r)$$
(5)
Thus, assuming the electron’s rest mass is entirely electromagnetic,

$$W=\frac{1}{8\pi }_0^{\mathrm{}}\frac{1}{ϵ(r)}\frac{e^2}{r^4}\mathrm{\hspace{0.17em}4}\pi r^2𝑑r=mc^2$$
(6)
The net charge density $`\rho (r)`$, taking account of the conjectured vacuum polarization, is given by

$$𝐄=\frac{eϵ^{}(r)}{r^2[ϵ(r)]^2}=4\pi \rho (r)$$
(7)
The original point charge is here exactly cancelled by a deltafunction contribution from the polarization charge. A functional form for $`ϵ(r)`$ can be determined if the charge density $`\rho (r)`$ is assumed to be proportional to the electromagnetic energy density, so that

$$\frac{ϵ^{}(r)}{4\pi r^2[ϵ(r)]^2}=\frac{e^2}{8\pi mc^2ϵ(r)r^4}$$
(8)
The result is

$$ϵ(r)=\mathrm{exp}\left(\frac{e^2}{2mc^2r}\right)=\mathrm{exp}\left(\frac{r_0}{2r}\right)$$
(9)
The self-energy then follows from

$$W=\frac{e^2}{2}_0^{\mathrm{}}\frac{e^{r_0/2r}}{r^2}𝑑r=\frac{e^2}{r_0}=mc^2$$
(10)
## III Self-Energy of a Dipole

A point electric dipole $`𝔭`$$`𝔭`$$`𝔭`$ located at the origin and directed along the polar axis produces an axially symmetric field given by

$$𝐃=\frac{2𝔭\mathrm{cos}\theta }{r^3}\widehat{𝐫}+\frac{𝔭\mathrm{sin}\theta }{r^3}\widehat{\theta }\widehat{\theta }\widehat{\theta }$$
(11)
If it is assumed that the permittivity $`ϵ(r)`$ remains spherically symmetrical, the field energy integrated over solid angle is given by

$$\frac{1}{8\pi }_0^{2\pi }_0^\pi 𝐄𝐃\mathrm{sin}\theta d\theta d\varphi =\frac{2𝔭^2}{r^6ϵ(r)}$$
(12)
The charge density analogous to (7) is determined by the proportionality

$$\rho (r)=\frac{1}{4\pi }𝐄\frac{ϵ^{}(r)}{r^3[ϵ(r)]^2}$$
(13)
so that the relation analogous to (8) implies a permittivity of the form

$$ϵ_{\mathrm{dipole}}(r)=\mathrm{exp}(k^2/r^2)$$
(14)
where $`k`$ is a parameter with dimensions of length. For example, a hypothetical electric dipole $`𝔭`$$`𝔭`$$`𝔭`$ with electromagnetic self-energy $`Mc^2`$ would imply

$$k=\left(\frac{𝔭^2\sqrt{\pi }}{4Mc^2}\right)^{1/3}$$

The treatment of a magnetic dipole $`𝔪`$$`𝔪`$$`𝔪`$ is closely analogous. The magnetic field in vacuum is give by

$$𝐇=\frac{2𝔪\mathrm{cos}\theta }{r^3}\widehat{𝐫}+\frac{𝔪\mathrm{sin}\theta }{r^3}\widehat{\theta }\widehat{\theta }\widehat{\theta }$$
(15)
Assuming a spherically-symmetrical magnetic permeability, we have

$$𝐁=\mu (r)𝐇$$
(16)
In analogy with (12), the magnetic field energy integrated over solid angle is given by

$$\frac{1}{8\pi }_0^{2\pi }_0^\pi 𝐁𝐇\mathrm{sin}\theta d\theta d\varphi =\frac{2𝔪^2\mu (r)}{r^6}$$
(17)
The current density of polarized charge can be found from

$$𝐉=\frac{c}{4\pi }\times 𝐁\frac{\mu ^{}(r)}{r^3}$$
(18)
An analogous assumption that the magnetic energy density is proportional to the polarization current density thus implies a magnetic susceptibility of the form

$$\mu (r)=\mathrm{exp}(b^2/r^2)$$
(19)
Since $`ϵ(r)\mathrm{}`$ and $`\mu (r)0`$ as $`r0`$, both $`𝐄𝐃`$ and $`𝐁𝐇`$ vanish at the origin. Thus we need not consider contact contributions of the form $`𝔭𝔭𝔭\delta (𝐫)`$ or $`𝔪𝔪𝔪\delta (𝐫)`$.

## IV Classical Model for the Electron

Let the electron be pictured as a structureless point charge $`e`$ with a magnetic dipole moment $`𝔪=e\mathrm{}/2mc`$. If the energy is entirely electromagnetic, according to Lorentz-Abraham, the intrinsic angular momentum should likewise be electromagnetic. In this way we can sidestep any need to explain how a point particle can have a spin angular momentum. (Alternatively, this might be attributed to the motion of the polarization charge surrounding the electron.) The angular momentum of an electromagnetic field is given by

$$𝐒=\frac{1}{4\pi c}𝐫\times (𝐄\times 𝐇)d^3𝐫$$
(20)
Identifying this with the electron’s spin of one-half, we can write

$$S_z=\frac{1}{4\pi c}r\mathrm{sin}\theta (𝐄\times 𝐇)_\varphi d^3𝐫=\frac{\mathrm{}}{2}$$
(21)
Using the fields

$$𝐃=\frac{e}{r^2}\widehat{𝐫},𝐄=\frac{𝐃}{ϵ(r)},𝐇=\frac{2𝔪\mathrm{cos}\theta }{r^3}\widehat{𝐫}+\frac{𝔪\mathrm{sin}\theta }{r^3}\widehat{\theta }\widehat{\theta }\widehat{\theta }$$
(22)
with

$$𝔪=\frac{e\mathrm{}}{2mc}$$
(23)
and the permittivity parametrized as

$$ϵ(r)=e^{a/r}$$
(24)
Eq (21) is satisfied with

$$a=\frac{2}{3}\frac{e^2}{mc^2}=\frac{2}{3}r_0$$
(25)
The electric-field energy then works out to

$$W\mathrm{elec}=\frac{1}{8\pi }𝐄𝐃d^3𝐫=\frac{3}{4}mc^2$$
(26)
The magnetic contribution must then supply the remaining quarter of the rest energy:

$$W\mathrm{mag}=\frac{1}{8\pi }𝐁𝐇d^3𝐫=\frac{1}{4}mc^2$$
(27)
With the parametrization $`\mu (r)=\mathrm{exp}(b^2/r^2)`$, Eq (27) is satisfied with

$$b=\left(\frac{𝔪^2\sqrt{\pi }}{mc^2}\right)^{1/3}=\frac{\pi ^{1/6}}{2^{2/3}\alpha ^{2/3}}r_0$$
(28)
where $`\alpha =e^2/\mathrm{}c`$, the fine structure constant.

## V Conclusion

We have shown how to accommodate point structures with finite self-energies into classical electrodynamics without altering the equations of Maxwell’s theory. This is in contrast to earlier attempts of Born, Bopp and others, which involved nonlinear reformulations of the fundamental equations. The key to our approach is the introduction of constitutive parameters for the electromagnetic vacuum, which actually has a physical rationale according to quantum field theory. In any event, our results reduce smoothly to conventional electrodynamics for scales large compared to $`10^{13}`$ cm. In particular, $`ϵ(r)`$ and $`\mu (r)`$ both rapidly approach their vacuum values of 1.

The Lorentz-Abraham conjecture, that the electron’s rest mass of 0.511 MeV$`/c^2`$ is entirely electromagnetic, is made more plausible by the model we have described. This is consistent as well with the (nearly, if not exactly) zero rest mass of the electron’s uncharged weak isodoublet partner—the neutrino—which can be regarded as an electron with zero charge. We note also that the neutron-proton mass difference (1.29 MeV/$`c^2`$) is of comparable order of magnitude. The parameters which we have fit to the electron’s mass, angular momentum and magnetic moment imply a $`g`$-factor of 2, consistent with Dirac’s relativistic theory. (We have resisted the temptation to adjust this to 2.0023, to account for QED radiative corrections.)

Of course, the real physical electron must ultimately be described by quantum mechanics or quantum field theory. Still, a fully consistent classical model can provide a useful starting point. And classical results do (usually) represent $`\mathrm{}0`$ limits in quantum theory. Since it is by no means settled that the current formalism of quantum electrodynamics is the final theory of the electron, it is worthwhile to explore the classical limit that some successor theory might also exhibit. Although the infinities associated with transverse radiation fields do remain, we have succeeded in eliminating those of classical origin for a point charge.

REFERENCES

 A definitive review of classical electron theories is given by F. Rohrlich, Classical Charged Particles (Addison-Wesley, Reading, MA, 1990).

 W. Furry and J. R. Oppenheimer, Phys. Rev. 45, 245 (1934).

 V. F. Weisskopf, Det. Kgl. Danske Videnskab. Selskab. Mat.-Fys. Medd. 14, 1 (1936). Reprinted in J. Schwinger, Quantum Electrodynamics (Dover, New York, 1958).

 S. M. Blinder, Repts. Math. Phys. 47, 269 (2001). Online version: http://arXiv.org/find/physics/1/au:+Blinder/0/1/0/past/0/1

 M. Born, Proc. Roy. Soc. A143, 410 (1934); M. Born and L. Infeld, Proc. Roy. Soc. A144, 425 (1934).

 F. Bopp, Ann. Phys. 38, 345 (1940).

 The connection between classical and quantum theories of the electron is discussed by P. Pearle, “Classical electron models,” in Electromagnetism: Paths to Research, ed D. Teplitz (Plenum, New York, 1982) pp. 211-295.