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# The K20 survey. V The evolution of the near-IR Luminosity Function Based on observations made at the European Southern Observatory, Chile (ESO LP 164.O-0560).

## 1 Introduction

Over the past few years, a wealth of observations from deep surveys of optically-selected high-redshift galaxies (e.g. Madau et al. 1996, Steidel et al. 1999), complemented by observations in the far-IR/sub-mm (Hughes et al. 1998, Barger et al. 1999), allowed significant progress in our understanding of the evolution of galaxies from the present-epoch back to $`z4`$ and beyond (Steidel et al 1999; Madau, Pozzetti, & Dickinson 1998). However, since these samples of high-$`z`$ galaxies were all selected at optical or far-IR/sub-mm wavelengths, they are dominated by objects with on-going star formation. Therefore, such studies placed constraints more on the evolution of the star birth rate activity than on the formation and assembly of stellar systems through cosmic time.

The study of faint galaxy samples selected in the near-infrared represents an important and complementary possibility to address the still open questions on how the formation and evolution of massive systems evolved with time compared to the predictions of the different theoretical scenarios (Broadhurst et al. 1992). Another advantage of the near-IR selection (in particular in the $`K`$-band) is that the k–corrections are relatively insensitive to galaxy type and fairly small also at high redshift (Cowie et al. 1994), and the dust extinction effects are less severe than in optical samples.

Since the rest-frame near-IR light is a relatively good tracer of the galaxy stellar mass (Gavazzi et al. 1996; Madau, Pozzetti & Dickinson 1998) the near-IR galaxy Luminosity Function (LF) can provide a reasonable estimate of the Galaxy Stellar Mass Function (GSMF). Only recently the 2MASS (Jarrett et al. 2000) surveys allowed accurate determinations of the local near-IR luminosity and of the Galaxy Stellar-mass functions (Cole et al. 2001, Kochanek et al. 2001), while only few attempts have been made to reconstruct their evolution with redshift using deep surveys of near-IR selected samples (i.e. Cowie et al. 1996; Cohen et al. 1999, Cohen 2002).

In order to address the above questions, we performed a new spectroscopic survey of a complete sample of galaxies selected with $`K_s<20`$ (the K20 survey; http://www.arcetri.astro.it/$``$ k20/). The survey and the sample are described in detail in Cimatti et al. (2002b, hereafter Paper III), while the spectral and clustering properties of the Extremely Red Objects (EROs) are discussed in Cimatti et al. (2002a, Paper I) and Daddi et al. (2002, Paper II), respectively. The redshift distribution for the whole sample of $`K_s`$-band selected galaxies is given in Cimatti et al. (2002c, Paper IV). Here we recall that the K20 sample includes 546 objects to $`K_s<20`$ (Vega system), selected from a 32.2 arcmin2 area of the Chandra Deep Field South (CDFS; Giacconi et al. 2001) and from a 19.8 arcmin2 field centered at 0055-269. The total area of the two fields is 52 arcmin2. Optical multi-object spectroscopy was mainly obtained with the ESO VLT + FORS1 and FORS2, while a small fraction ($`4\%`$) of the objects was observed with near-IR spectroscopy using the VLT + ISAAC. We have imaged the 0055-269 field over 10 bands ($`UBGVRR_wIzJK_s`$), obtained with the ESO NTT + SUSI2 ($`UBGVR_wI`$) and SOFI ($`JK_s`$), and VLT + FORS1 ($`R`$ and $`z`$), for a total of about 45 hours of integration. In the CDFS field, we used a combination of public EIS NTT data ($`UK_s`$) and deep FORS1 images ($`BVRIz`$, courtesy of P. Rosati & M. Nonino). The spectroscopic redshift completeness is 94% and 87% for $`K_s<19`$ and $`K_s<20`$, respectively, and it increases to 98% if we include the photometric redshifts obtained with the deep multi-band imaging for the spectroscopically unidentified or unobserved objects (Cimatti et al. 2002b). The K20 sample is the largest and most complete spectroscopic sample of galaxies with $`K_s<20`$ available to date.

In this paper, we investigate the evolution of the near-IR luminosity function up to $`z1.5`$ based on the K20 survey sample. Thanks to the higher statistical significance and completeness of our sample, it is possible to use the LF evolution to place new and more stringent constraints on the formation and evolution of massive galaxies than was possible from previous surveys (Cowie et al. 1996, Cohen et al. 1999, Cohen 2002). In particular our survey has the advantage to include a complete sample of EROs, partially with spectroscopic identifications, which usually were not included in previous spectroscopic surveys (e.g. Cohen 2002) because of their selection. Finally, we compare the LF evolution with the predictions of two competitive scenarios of galaxy evolution: the Pure Luminosity Evolution (PLE) and the Hierarchical Merging Models (HMM). We adopt $`H_0=70`$ km s-1 Mpc-1, $`\mathrm{\Omega }_m=0.3,\mathrm{\Omega }_\mathrm{\Lambda }=0.7`$.

## 2 The K20 spectroscopic sample

From the total K20 sample of $`546`$ objects with $`K_s20`$ we have extracted a sample of $`489`$ galaxies, after excluding objects classified as stars and AGN on the basis of their spectra. In addition to spectroscopic redshifts, photometric redshifts have been derived (Cimatti et al. 2002b) with very high accuracy ($`z_{spe}z_{phot}=\mathrm{\Delta }z=0.012`$ and $`\sigma _{\mathrm{\Delta }z}=0.089(1+z_{spe})`$). Such an accuracy, made possible by the numerous photometric bands and the precision of the magnitude measurements, is consistent with previous results on the HDF-N data set (Fontana et al 2000) and with simulations made by Bolzonella et al. (2000) at high redshift ($`1<z<2`$), where our sample is the largest to date. The magnitude–redshift distribution of selected galaxies is shown in Fig. 1. Thanks to the depth and completeness of our sample, the coverage of the $`K_s`$ – redshift plane is such that the near-IR LF can be derived with good accuracy and over a relatively large range of magnitudes at least up to $`z1`$, still sampling with relatively good statistics the high luminosity part of the LF up to $`z2`$. Since the sample spans a wide range in luminosity, redshift and look-back time, it is therefore well suited to study the evolution of the near-IR Luminosity Function within the sample itself and in comparison to the local population.

## 3 The estimate of the rest-frame near-IR luminosities

The small variance of k-corrections in the $`K_s`$-band (Cowie et al. 1994, Mannucci et al. 2001) greatly simplifies the analysis with respect to optically-selected samples of galaxies. Moreover, we take advantage of the fact that at $`z0.8`$ the observed $`K_s`$-band corresponds to rest-frame $`J`$-band. In order to compute the near-IR luminosity function, we derive the rest-frame $`J`$\- and $`K_s`$-band absolute magnitudes ($`M_J`$ and $`M_{K_s}`$) according to the following relations:

$$M_J=K_s5log(d_L(z)/10pc)+(J_{rest}K_s)(z)$$
(1)
$$M_{K_s}=K_s5log(d_L(z)/10pc)+(K_{s,rest}K_s)(z),$$
(2)
where $`K_s`$ is the total apparent magnitude measured with SExtractor (see Cimatti et al. 2002b, Paper III, for more details), $`d_L(z)`$ is the luminosity distance at redshift $`z`$ and ($`J_{rest}K_s`$) and ($`K_{s,rest}K_s`$) are the “k-correction colors”, i.e. the difference between rest frame and observed magnitude which includes also the $`2.5log(1+z)`$ term (see also Lilly et al. 1995). It should be noted that in Eq. (1) the last term can be written as a conventional k-correction for the $`K_s`$-band (as in Eq. 2) plus a rest-frame (J-$`K_s`$) color. The k-correction colors as a function of redshift are plotted in Fig. 2. This figure clearly shows the small variation of the k-corrections for different spectral types over most of the redshift range covered by our data (for a comparison with a similar plot in the optical bands see Lilly et al. 1995).

These k-corrections for different spectral types are computed using the Bruzual & Charlot (1993) models (GISSEL 2000 version), in order to reproduce spectra, and k-corrections of local galaxies (E, S0, Sa, Sb, Sc, Im) at low redshift (cf. Pozzetti et al. 1996, Mannucci et al. 2001) and the color-redshift diagram ($`RK_s`$ vs. $`z`$) observed in our sample (Fig. 3). In order to take into account the dusty star-forming population, we introduce an additional spectral type dominated by star formation and strong dust extinction consistently describing the SED of red emission line objects and reproducing the sub-class of emission line EROs with $`RK_s>5`$ (cf. Paper I). We have adopted an exponentially declining star formation history ($`SFRexp(t/\tau )`$), with $`\tau =0.3,1,2,4,\mathrm{}`$ Gyrs (E, S0, Sa, Sb, Sc galaxies, respectively), the Salpeter (1955) Initial Mass Function (IMF) and an age of 12.5 Gyrs at $`z=0`$ (i.e. a formation redshift $`z_f=5.7`$). A model with an age of 1 Gyr at all redshifts is adopted for Im galaxies, while a constant SFR and $`E(BV)=0.5`$ has been assumed for the dusty star-forming galaxies (cf. Paper I). We have then assigned a spectral model to each galaxy according to their $`RK_s`$ color and spectral type.

We tested that different assumptions on the k-corrections, i.e. by varying model parameters or using the fitting of multi-band photometry when available, did not affect significantly our results. For example, the k-correction estimates which make use of multi-band fitting of the SED are in excellent agreement with our estimates from $`RK_s`$ colors alone, with no systematic shifts in magnitude and a dispersion of about 0.08 in the $`J`$-band and 0.13 in the K-band up to $`z1.5`$. Varying parameters in the synthetic spectral models, i.e. the IMF (Salpeter 1955, Scalo 1986 and Kennicutt 1983) and the formation redshift ($`z_f=2,3,6`$), the systematic shifts and dispersions at $`z<2`$ are always less than 0.05 magnitudes. We note that magnitudes derived using the k-corrections estimated from observed spectra of local galaxies (Mannucci et al. 2001, Cowie et al. 1994) would be brighter by about 0.1 magnitudes at $`z>0.7`$, and could be considered upper limits due to the possible evolutionary effect on the galaxy spectrum. We are therefore confident that the derived luminosities are robust with respect to varying this set of assumptions. The resulting effects on the Luminosity Functions induced by changes in our assumptions are all comparable with or smaller than the statistical errors (see Sect. 5).

Fig. 4 shows the absolute magnitudes of all galaxies in the spectroscopic sample to $`K_s<20`$ as derived according to our adopted recipes. For the unidentified or unobserved galaxies we have adopted the photometric redshift $`z_{phot}`$. The photometric threshold of the survey, $`K_s<20`$, is clearly visible in the data and translates into different luminosity limits as a function of redshift, varying from less than $`0.1L^{}`$ at $`z<0.5`$ to about $`0.4L^{}`$ at $`z1`$, assuming $`M_J^{}=23.13+5`$log$`h_{70}`$ and $`M_{K_s}^{}=24.21+5`$log$`h_{70}`$ (horizontal lines in Fig. 4) for the local LF (Cole et al. 2001). Adopting the mean stellar mass-to-light ratio and representative stellar mass ($`_{stars}/L_K=1.32`$ in solar unit and $`_{stars}^{}=1.44\times 10^{11}h_{70}^2M_{}`$ for the Salpeter IMF) in the local universe (Cole et al. 2001), the limits in luminosities correspond to $`0.1`$$`0.5_{stars}^{}`$ or even smaller stellar masses since the $`_{stars}/L_K`$ increases as the stellar population ages (Madau, Pozzetti, & Dickinson 1998).

## 4 The estimate of the near-IR Luminosity Function

After the estimate of the rest-frame near-IR luminosities, we compute the $`J`$\- and $`K_s`$-band Luminosity Functions in the following redshift bins: (a) $`0.2<z<0.65`$ ($`z_{mean}0.5`$), (b) $`0.75<z<1.3`$ ($`z_{mean}1.0`$) and (c) $`1.3<z<1.9`$ ($`z_{mean}1.5`$). The redshift bin 0.65$`<`$z$`<`$0.75 has been excluded from this analysis because dominated by two groups/clusters (see Fig. 1 and Paper III for details). The first two redshift bins include respectively 132 and 170 galaxies, of which only few objects (2 and 21 respectively) do not have a spectroscopic redshift. The highest redshift bin includes a smaller number of galaxies (42) with a high fraction of photometric redshifts (60%).

The Luminosity Functions in each redshift bin are estimated using both the $`1/V_{max}`$ formalism (Schmidt 1968, Felten 1976) and the maximum likelihood method STY (Sandage, Tammann & Yahil 1979), in order to represent our data with a Schechter (1976) parameterization. In the $`1/V_{max}`$ analysis, for any given redshift bin ($`z_1,z_2`$) a maximum volume is assigned to each object. This volume is calculated between $`z_1`$ and $`z_{up}`$, the latter being the minimum between $`z_2`$ and $`z_{max}`$, i.e. the maximum redshift at which this galaxy would have satisfied the magnitude limit ($`K_s<20`$) of the survey. We use the model tracks in order to compute $`z_{max}`$. Since the STY method determines the shape of the LF but not its overall normalization, we have normalized the STY LF by matching the galaxy number counts observed in each redshift bin. We have checked and tested the reliability of our results with the independent softwares developed by Zucca et al. (1997) and by Poli et al. (2001), always finding a good agreement between the different methods.

Because of the relatively small number of objects in each redshift bin and only a part of the luminosity function can be recovered, the Schechter parameters ($`\alpha `$, $`M^{}`$ and $`\varphi ^{}`$) derived from our STY analysis are not very well constrained by our data. In particular, the uncertainty on the faint end slope $`\alpha `$ increases with redshift because of the increase with redshift of the minimum observable luminosity. A sample reaching $`K_s21.0`$$`21.5`$ would be needed to better constrain this parameter at $`z>1`$. The results will be discussed in Section 5.

### 4.1 The treatment of the unidentified objects

The treatment of the unobserved or spectroscopically unidentified sources is not a major problem because of the high spectroscopic redshift completeness in our survey. Moreover, as discussed in Sect. 2, tested and reliable photometric redshifts were derived for most of the faint unidentified or unobserved objects, leading to an almost negligible number of objects (9 in total) without any redshift information (see Paper III).

The small uncertainty introduced by the unobserved or unidentified objects has been addressed in two different ways.

We first use only the spectroscopic sample and take into account the remaining redshift incompleteness (72 galaxies) by applying weights to each galaxy with spectroscopic redshift both in the $`V_{max}`$ analysis (Avni & Bahcall 1980) and in the standard STY formulation (Heyl et al. 1997, cf. also Zucca, Pozzetti & Zamorani 1994). The weighting corrections are computed on the basis of the fraction of galaxies with spectroscopic redshift in different regions of the $`(RK_s)K_s`$ plane. This weighting scheme assumes that unidentified objects have the same redshift distribution as the spectroscopically identified with similar $`K_s`$ magnitudes and $`RK_s`$ colors. While this scheme can be reasonably applied over most of the $`(RK_s)K_s`$ plane, the weights are highly uncertain for the optically faintest and reddest galaxies, most of which do not have a spectroscopic redshift. Since the photometric redshifts of these objects are statistically higher than those sampled by the measured spectra, this method would not allow to correctly estimate the luminosity function in the highest redshift bin.

As a second approach, we therefore base the “best” estimate of the luminosity function on the sample of galaxies with spectroscopic plus photometric redshifts. In this case, the 9 objects without any redshift information (because of the absence of the extended multi-band photometry) have an almost negligible effect. To account for them we correct the STY normalization (from 1% to 8% in the 3 redshift bins) according to the fraction of such objects in each bin. The results from the two methods (Fig. 5 and 6) are completely consistent with each other in the first two redshift bins, while some discrepancies are present in the highest redshift bin because, as mentioned above, the weighting correction function is unable to properly take into account the optically faintest and reddest galaxies. Furthermore we tested that the uncertainties in the photometric redshifts did not affect significantly our results. We extracted random samples from the original photometric redshift catalog using the measured dispersion. The derived fluctuations in each magnitude bin of the LFs resulted smaller than Poisson errors and in general the simulated LFs are consistent with the “best” estimate also in the higher redshift bin with no significant systematic effects. In the following sections we will discuss the “best” LFs derived using spectroscopic plus photometric redshifts.

## 5 The cosmic evolution of the near-IR Luminosity Function

Thanks to the high statistical significance and completeness of our sample it is possible to investigate the evolution of the near-IR LF over a wide range of cosmic time. Figs. 5 and 6 show the $`1/V_{max}`$ and the maximum likelihood (STY) results for the LFs in the selected redshift bins and in the $`J`$\- and $`K_s`$-bands, respectively.

We find that the luminosity functions are fairly well fitted by Schechter functions in the first two redshift bins. The magnitude ranges and the best-fit Schechter parameters are summarized in Table 1, with the uncertainties derived from the projection of the 68% confidence ellipse. In the highest redshift bin, due to the bright and limited range in magnitude, our data are well fitted with a single power law ($`\alpha 2.7_{0.7}^{+0.5}`$). This does not mean that a Schechter function can not be a good representation of the luminosity function also in this redshift bin. This is shown by the thin solid lines in the lower panels of Figs. 5 and 6, which represent fits with a Schecther function obtained by fixing the faint end slope $`\alpha `$ at the local value. However, because of the bright limit in absolute magnitude at these redshifts, which reduces significantly the range of sampled luminosities, the Schechter parameters are very poorly determined by these data. For this reason the Schechter parameters for this redshift bin are not reported in Table 1. We point out that a direct comparison of the Schechter parameters could be quite misleading because the parameters are correlated.

In order to trace the evolution down to $`z0`$, we compared the observed LFs as derived from our sample to the Local Luminosity Function (LLF) by Cole et al. (2001) in the $`J`$ and $`K_s`$ bands (Figs. 5, 6) and by Kochanek et al. (2001) in the $`K_s`$-band. We then explored two possible evolutionary scenarios: luminosity or density evolution.

Our analysis (both $`V_{max}`$ and STY) shows that the data (Figs. 5 and 6) are consistent with a mild evolution from $`z=0`$ to $`z1.5`$ both in $`J`$\- and $`K_s`$-bands. In particular the faint-end of the LFs ($`L<L^{}`$) is consistent with the local estimates, with no statistically significant evidence for a change either in the slope or normalization up to $`z<1.3`$ (consistently with Cohen 2002). At higher redshift this part of the luminosity function is not well sampled by our data, but also in this bin a Schechter function with local faint-end slope is consistent with the data (Figs. 5 and 6). Viceversa, it is interesting to note that the density of luminous galaxies (e.g. $`M_{K_s}5`$ log$`h_{70}<25.5`$) is significantly higher than locally.

Because of the statistical correlation between the Schechter parameters ($`\alpha `$, $`M^{}`$ and $`\mathrm{\Phi }^{}`$), in order to estimate the luminosity and/or density evolution within our sample and in comparison with the local LFs, we have fixed the $`\alpha `$ parameters of our LFs to the same values observed locally (Cole et al. 2001), $`\alpha _J=0.93`$ and $`\alpha _{K_s}=0.96`$ (thin solid lines in Figs. 5, 6). We are allowed to do this because all our best fit $`\alpha `$ values are consistent with the local ones (see Table 1). Assuming local $`M_J^{}=23.13+5`$log$`h_{70}`$ and $`M_{K_s}^{}=24.21+5`$log$`h_{70}`$ from Cole et al. (2001) we find a luminosity evolution at $`z1`$ of the order of $`\mathrm{\Delta }M_J0.69\pm 0.12`$ and $`\mathrm{\Delta }M_K0.54\pm 0.12`$ with the normalizations ($`\varphi ^{}`$) in the first two redshift bins consistent with the local values, within from 3 to 20%. At $`z>1.3`$ there is an indication of an even higher luminosity evolution ($`\mathrm{\Delta }M_J1.17`$, $`\mathrm{\Delta }M_K1.07`$), while the $`\varphi ^{}`$ values decrease by a factor $`4`$$`5`$ with respect to the local value. This last result should be taken with caution because of the lower statistics in the highest redshift bin and the smaller range in luminosity covered.

The luminosity evolution estimated from STY analysis are summarized in Table 2 with the formal statistical $`1\sigma `$ confidence limits. The uncertainties introduced by the k-correction, discussed in Section 3, are always less than the statistical errors, and less than 0.03 and 0.10 magnitudes at $`z<1.3`$ and $`z1.5`$, respectively.

We recall here that Cimatti et al. (2002b) discussed the photometric selection effects present in the K20 sample and showed that, on average, the total flux of spirals and ellipticals with $`LL^{}`$ are underestimated by 0.1 and 0.25 magnitudes respectively, while at higher $`L`$ the flux lost for elliptical galaxies could be even higher. For this reason we are confident that our estimate of a positive luminosity evolution is quite conservative. The above estimates of the luminosity evolution could increase on average by about $`0.2`$ magnitudes if we take into account this underestimate of the total flux.

## 6 The Luminosity Function by spectral or color type

In order to investigate the role of different galaxy populations, we divide the K20 sample in two subsamples on the basis of the spectroscopic classification, i.e. early type galaxies without strong emission lines and late type galaxies with emission lines, and study the near-IR LF for the different populations in the two redshift bins at $`z_{mean}0.5`$ and $`1`$. The high fraction of photometric redshifts without any spectroscopic information does not allow us to extend such studies to the highest redshift bin. We take into account the spectral incompleteness using two weighting functions (see Sect. 4.1) derived for each spectral type and correcting the overall normalization in the STY method using the color information of unclassified objects.

The results are shown in Fig. 7. Our analysis indicates that the faint-end slope of the LFs at these redshifts shows the same general dependence on galaxy spectral type as that found in numerous studies of the local LF. Specifically, the faint-end slope is much steeper for late/emission line galaxies than for early type galaxies. A similar result has been found by Cohen (2002) in the HDF–north. More important, we find, for the first time, that at $`z_{mean}0.5`$, early type galaxies clearly dominate the bright-end of the Luminosity Function, in agreement with local observations (Kochanek et al. 2001). A similar result is also visible at $`z_{mean}1.0`$. Some of the previous surveys, selected in the optical bands with follow-up $`K`$-band observations (e.g. Cohen 2002), present a bias against identifying red early type galaxies at high redshift because of substantial incompleteness of EROs in the samples.

The overall density of early type galaxies at $`z0.5`$ is consistent with the local estimate (Kochanek et al. 2001), while at $`z1`$, their number density shows at most a small decrease ($`<30\%`$), consistent with recent results from Im et al. (2002). This decrement could be due both to the existence of a population of galaxies morphologically classified as early-type but with blue colors due to some recent episodes of star formation (Menanteau, Abraham & Ellis 2001, Im et al. 2001) and to our spectral incompleteness, more severe for red/early type galaxies.

Similar results are obtained if we divide the galaxies in two samples according to their $`RK_s`$ colors (we adopt the color of Sa galaxies to divide the sample in red and blue).

We conclude that red and early type galaxies dominate the bright-end of the Luminosity Function already at early epoch and that their number density shows at most a small decrease ($`<30\%`$) up to $`z1`$.

Fig. 8 shows the optical/near-IR colors versus near-IR luminosities in the three redshift bins. While the magnitude limit of the survey, $`K_s<20`$, corresponds to different low luminosity limits in the different redshift bins, there appears to be a correlation of the optical/near-IR colors with near-IR luminosities. In first approximation this correlation can be interpreted as a correlation of age and/or specific star formation rate with stellar mass, with the most “massive” galaxies being “old” and the “low-mass” galaxies being instead dominated by young stellar populations. This is now well established for local galaxies (Gavazzi et al. 1996, Boselli et al. 2001, Kauffmann et al. 2002) and we extend it to $`z1.5`$. Fig. 8 (see empty and filled circles representing galaxies with $`z<z_{mean}`$ and $`zz_{mean}`$) shows that the observed correlation is not induced by a redshift effect within the bins. In Sect. 8 we compare the observed correlation with HMM predictions.

## 7 The near-IR luminosity density evolution

Tracing the cosmic emission history of the galaxies at different wavelengths offers the prospect of an empirical determination of the global evolution of the galaxy population. Indeed, it is independent of the details of galaxy evolution and depends mainly on the star formation history of the universe (Lilly et al. 1996, Madau, Pozzetti & Dickinson 1998). Various attempts to reconstruct the cosmic evolution of the comoving luminosity density have been made previously mainly in the UV and optical bands (Lilly et al. 1996, Cowie et al. 1999). Our survey offers the possibility to investigate it in the near-IR using a LF extended over a wide range in luminosity.

We estimate the comoving luminosity density directly from observed sources using the $`V_{max}`$ formalism (see for details Lilly et al. 1996). The major source of uncertainty is the contribution from galaxies fainter than the magnitude limit $`K_s<20`$. We have therefore estimated also the “LF-corrected” luminosity density using the best-fit LF from STY method and extending it to fainter luminosity (we adopt $`0.02L^{}(z)`$ as our lower limit in luminosity for this extrapolation). A formal uncertainty in this procedure was estimated by considering the range of acceptable Schechter parameters values (see Table 1).

Fig. 9 shows luminosity densities derived in $`J`$\- and $`K_s`$-band as a function of redshift. Up to $`z<1.3`$ the uncertainties due to faint galaxies and LF parameters are small. At higher redshift the uncertainties in the LF parameters do not allow to constrain the luminosity density values. We could therefore only estimate a lower limit to the luminosity density using the observed value.

We find a slow evolution with redshift of the observed near-IR luminosity density, consistent with the results by Cohen (2002) in the HDF-north, even if she had to apply a large correction to her data because of the disappearance of absorption galaxies at high redshift in her sample as they became EROs. Using the observed local luminosity densities derived from Cole et al. (2001), the luminosity density evolution up to $`z1.3`$ is well represented by a power law, $`\rho _\lambda (z)=\rho _\lambda (z=0)(1+z)^{\beta (\lambda )}`$. We find $`\beta (J)0.70`$ and $`\beta (K_s)0.37`$ (Fig. 9).

The near-IR luminosity density evolution is much slower than that found in the UV and optical bands ($`\beta =3.9`$$`2.7`$ from 0.28 to 0.44 $`\mu `$m by Lilly et al. 1996 and $`\beta =1.5`$ at 0.15, 0.28 $`\mu `$m by Cowie et al. 1999, for $`\mathrm{\Omega }_m=1`$). Indeed, while the optical luminosity density evolution is mainly related to the star formation history, the evolution of the near-IR luminosity density is more closely related to the stellar-mass density. The local stellar mass density, derived by Cole et al. (2001) is $`\mathrm{\Omega }_{stars}=(3.7\pm 0.6)\times 10^3h_{70}^1`$. If we adopt the stellar mass-to-light ratio for the galaxy spectral models which best match colors and spectral types for each galaxy, the mean $`_{stars}/L_K`$ in our sample becomes $`0.63`$ and $`0.54`$ at $`z=0.5`$ and $`1`$, with small variations due to the model parameters adopted (see Sect. 3). With these values of $`_{stars}/L_K`$ we derive $`\mathrm{\Omega }_{stars}=(2.0\pm 0.1)\times 10^3h_{70}^1`$ and $`\mathrm{\Omega }_{stars}=(2.1\pm 0.3)\times 10^3h_{70}^1`$ at $`z=0.5`$ and $`1`$ respectively. This analysis suggests that the evolution of the stellar mass density is relatively slow with redshift, with a decrease of about a factor $`1.8\pm 0.4`$ from $`z=0`$ to $`z1`$, consistently with recent results from Dickinson et al. (2002a).

At $`z>1`$ we can only give a lower limit to the near-IR luminosity density. As discussed by Madau, Pozzetti, Dickinson (1998) (cf. also Pozzetti & Madau 2001), a robust determination of the near-IR luminosity density at $`z>1`$ could be fundamental to disentangle between different cosmic histories of star formation (SFH). In fact, SFHs peaked at intermediate redshift ($`1<z<2`$) predict a decrease in the near-IR luminosity density at $`z>1`$$`2`$, while if 50% of the stars formed at $`z>2`$ (similar to the PLE adopted here), the corresponding near-IR luminosity density flattens at $`z>1`$ without a strong decrease (cf. Fig. 6 in Pozzetti & Madau 2001). A detailed comparison of luminosity and stellar-mass density with model predictions and empirical star formation histories will be further investigated in a forthcoming paper.

## 8 The comparison with model predictions

We have compared our LF with the predictions from two competitive scenarios of galaxy evolution: the Hierarchical Merging Models (HMMs) and the Pure Luminosity Evolution (PLE) (Fig. 10). For the HMMs, we used the predictions by Cole et al. (2000, C00, kindly provided us by C. Baugh), Menci et al. (2002, M02), and GIF (Kauffmann et al. 1999). For the GIF simulations, which combine the large high-resolution N-body simulations with semi-analytical models, we derive the LF at a magnitude above which it can be considered complete in luminosity given the mass limit of the simulated galaxy sample ($`2\times 10^{10}`$ $`h_{70}^1M_{}`$). For the PLE parameterization, we adopted the predictions of Pozzetti et al. (1996, 1998, PPLE) (for details see also Paper IV).

For a more reliable comparison with models, we corrected the observed magnitudes by $`0.2`$ mag, in order to take into account the average loss of total flux in the K20 sample (see Papers III-IV).

As discussed in Paper IV at low-$`z`$ ($`z=0.5`$) the HMMs by Cole et al (2000) and by Menci et al. (2002) predict many more galaxies than observed (cf. Fig. 3 in Paper IV). From the present study (upper panel of Fig. 10) we can therefore conclude that such excess is due to low luminosity, “low-mass“ objects, which dominate the steep faint-end in the HMM LF. At $`z=1`$, the HMMs predict even steeper LFs because low-mass galaxies become more numerous in the hierarchical scenario at higher redshift. This is in contrast with the LF derived from our data at $`z=1`$, which does not show a similar behaviour. These discrepancies are consistent with previous results both in the local universe (cf. Fig. 1 in Baugh et al. 2002) and at high redshift ($`z<1`$ and $`z3`$) for the B and UV rest-frame LF, respectively (Poli et al. 2001, Somerville et al. 2001).

Also at the bright end of the LF the HMMs appear to be in disagreement with our data at $`z1`$, where they underpredict the density of bright ($`M_{K_s}<25.5+5`$log$`h_{70}`$) galaxies with respect to our data. For example, our data at $`M_{K_s}=25.6+5`$log$`h_{70}`$ and $`z1`$ are about a factor 2.6 higher than the HMM predictions and even higher at brighter magnitudes if we consider the STY maximum likelihood fit. In the highest redshift bin the excess over the predictions becomes significant at $`M_{K_s}<26+5`$ log$`h_{70}`$. In comparison, the GIF simulated catalogue at $`z=1`$ underpredicts the K20 LFs at all magnitudes. As discussed by Kauffmann et al. (1999), the GIF model produces a factor $`2`$$`3`$ too few galaxies at magnitudes around $`L^{}`$ already at $`z=0`$, while it produces an excess of bright local galaxies. This problem with respect to the local LF affects also the Cole et al. (2000) model (see Fig. 4 in Baugh et al. 2002). Therefore, as discussed in Sect. 5, while the density of luminous objects ($`M_{K_s}5`$ log$`h_{70}<25.5`$) is quite constant or mildly increasing with $`z`$ within our sample, and higher than the local density, it is rapidly decreasing in the Cole et al. (2000) and GIF models at $`z>0.5`$ (Fig. 11) in clear conflict with our data. The problem of a negative evolution with redshift of luminous objects does not affect instead the Menci HMM model, even if also this model significantly and systematically underpredicts their number density at all redshifts.

In addition to the comparison of the data and predictions for the LF, it is also important to verify whether the bright $`L>L^{}`$ galaxies in the K20 survey have colors consistent with the HMM predictions. Fig. 12 shows the comparison between the $`z=1.05`$ GIF simulated catalogue and data at $`0.75<z<1.3`$ ($`z_{mean}1`$). While the deficiency of simulated blue low-luminosity ($`RK_s<4.2`$, $`M_{K_s}5`$ log $`h_{70}>23.5`$) galaxies is due mainly to the mass limit of the GIF catalogue, a serious discrepancy emerges in the two distributions in the magnitude range where the GIF catalogue is expected to be complete. The GIF simulated catalogue shows an excess of blue high-luminosity galaxies ($`RK_s<4.4`$, $`M_{K_s}5`$ log $`h_{70}<24.5`$) and a deficiency of red luminous galaxies (see also the color distributions of high-luminosity galaxies, $`M_{K_s}5`$ log $`h_{70}<24.5`$, in the right panel of Fig. 12, normalized to the same comoving volume). This result is in agreement with the finding of a deficiency of EROs in the HMMs (Daddi et al. 2000, Firth et al. 2002, Smith et al. 2002), but, since it is based not only on colors but also on the luminosity of the galaxies, it points out in particular a clear deficiency of red luminous galaxies in the HMM predictions. This plot clearly shows that a comparison of LF and colors is much more powerful than that of the colors or LF alone and that the GIF $`K_s`$-band LF at $`z=1`$ is obtained with a radically different mix of galaxies compared to the observed one. While the bright end of the HMM LF at $`z=1`$ is dominated by actively starforming galaxies, in the K20 sample it is dominated by the passively evolving galaxies. Given that blue galaxies suggest younger stellar population and lower $`_{stars}/L_K`$ ratios, we expect that the failure of this model in reproducing our LF (see Fig. 10) should be even stronger in term of density of “massive” galaxies at $`z1`$ (cf. also the luminosity and stellar-mass functions in Baugh et al. 2002).

The right panels of Fig. 10 show the comparison of our data with the PLE predictions, computed with two different IMF (Scalo and Salpeter). The overall agreement is much better than with the HMM predictions even if some discrepancies, but at much lower level of significance, are present. In particular, in the highest redshift bin the parameterization with the Salpeter IMF overpredicts the total number of galaxies (see also Paper IV), while the Scalo IMF (dominated by low/intermediate mass stars, which induce a lower luminosity evolution compared to Salpeter at $`z>1`$) fits well the density of galaxies at $`M_{K_s}>26.0+5`$ log$`h_{70}`$, but falls below the data for the brighter galaxies. In Paper IV we found that in the context of PLE models also the observed redshift distribution of K20 galaxies is better fitted assuming an IMF dominated by low/intermediate mass stars (e.g. Scalo IMF) than a Salpeter IMF (see also Pozzetti et al. 1996 and Broadhurst & Bouwens 2000). PLE models with a flatter IMF (i.e. Salpeter-like) can be made consistent with the data (redshift distribution and LF) only if the rapid evolution induced by massive stars is sufficiently suppressed by dust attenuation (Totani et al. 2001, see Paper IV). Indeed, such a dusty phase is predicted by many models for the formation of high redshift spheroids and could be associated to high redshift SCUBA sources.

## 9 Summary and discussion

The cosmic evolution of the $`K_s`$-band selected field galaxy population has been studied over the redshift interval $`0.2<z<1.9`$ using about 500 galaxies from the K20 spectroscopic survey. The sample spans a wide range in redshift and look-back time and allows to study the evolution of the near-IR Luminosity Function both within the sample and in comparison to the local population.

We take advantage of the near-IR selection (in particular in the $`K`$-band), in which the k-corrections are relatively invariant to galaxy type and relatively small also at high redshift (Cowie et al. 1994), and the dust extinction effects are less severe than in optical samples.

We derived the near-IR luminosity function in the rest-frame $`J`$ and $`K_s`$-band in three redshift bins ($`z_{mean}0.5,1.0,1.5`$). The detailed analysis of the observed LF at different redshifts and the comparison with the local LF and with the predictions of galaxy formation models provided the following results:

1- A mild evolution is observed both in the $`J`$ and $`K_s`$ Luminosity Functions to $`z1.5`$, in agreement with previous indications by Cowie et al. (1996), Cohen (2002) and Feulner et al. (2003). There is no evidence of a steepening of the faint-end LFs up to $`z1.3`$. In particular, the faint-end ($`L<L^{}`$) is consistent with the local estimates up to $`z<1.3`$, while at the bright end the data show a luminosity evolution of about $`\mathrm{\Delta }M_J0.69\pm 0.12`$ and $`\mathrm{\Delta }M_K0.54\pm 0.12`$ at $`z1`$. The density of luminous galaxies ($`M_{K_s}5`$ log$`h_{70}<25.5`$) is relatively constant or mildly increasing with redshift within our sample and higher than locally at all redshifts.

2- Pure density evolution cannot reproduce the observed LF at $`z1.3`$.

3- Red and early-type galaxies clearly dominate the bright-end of the Luminosity Function at $`z0.5`$ and a similar trend is also visible at $`z1`$, showing that such systems were already in place and fully assembled at that cosmic epoch. Their number density shows at most a small ($`<30\%`$) decrease up to $`z1`$.

4- The evolution of the rest-frame near-IR comoving luminosity densities up to $`z1`$ can be described by power laws, $`\rho _\lambda (z)=\rho _\lambda (z=0)(1+z)^{\beta (\lambda )}`$, with $`\beta (J)0.70`$ and $`\beta (K_s)0.37`$. Such an evolution is much slower than those observed in the UV and optical bands.

5- The hierarchical merging models overpredict the LF at low luminosity at all redshifts, whereas they underpredict the density of high-luminosity galaxies at $`z>1`$. HMMs by Kauffman et al. (1999) and Cole et al. (2000) overpredict high luminosity galaxies at $`z=0`$, and predict a negative density evolution of the bright end of the LF at $`z>0.5`$ which is not observed.

6- The PLE predictions are in rather good agreement with the mild luminosity evolution observed up to $`z1.5`$.

7- There appears to be a clear correlation of the optical/near-IR colors, i.e. in first approximation the specific star formation rate and ages, with near-IR luminosities, i.e. the stellar mass. This correlation suggests that the most “massive” galaxies are “old”, while the “low-mass” galaxies are instead dominated by young stellar populations. The GIF model shows instead a clear deficiency of red luminous galaxies at $`z1`$ compared to the observations.

From the analysis of the LF and of the comoving near-IR luminosity density, we can derive some indications on the evolution of the Galaxy Stellar-Mass Function (GSMF). A detailed analysis will be presented by Fontana et al. (2003). The present analysis suggests that the evolution of the GSMF and of the stellar mass density is slow with redshift up to $`z1.5`$, in contrast with the rapid evolution of the Galaxy Stellar Mass Function expected in the hierarchical models at $`z<2`$ (cf. Baugh et al. 2002). In our sample, using galaxy spectral models which match colors and spectral types, we found that $`\mathrm{\Omega }_{stars}`$ decreases by a factor about $`1.8\pm 0.4`$ from $`z=0`$ to $`z1`$, mainly due to the decrease in the mass-to-light ratio, which is however slower than in HMMs models. In at least one of these models (GIF) the small adopted M/L ratio corresponds to a color distribution of galaxies at $`z1`$ clearly inconsistent with data (see Fig. 12).

Moreover, the fact that the bright-end of the Luminosity Function is dominated by red/early type galaxies and that the mean spectra of early type EROs at $`z1`$ are consistent with an old stellar population (see Paper I), suggest that old and massive elliptical galaxies were already in place at $`z1`$ (see also Paper I) and, therefore, they should have formed their stars and assembled their mass at higher redshift. These results are in contrast with the current renditions of hierarchical models in which the bulk of massive elliptical galaxies forms through merging at low redshift ($`z<1`$$`2`$) and suggest that most of the merging which form elliptical galaxies in the hierarchical models should occur at higher redshift (say, $`z>2`$$`3`$), followed by a pure “luminosity-like” evolution. On the other hand, HMMs overpredict the density of low-luminosity, low mass, galaxies at $`z<1`$, as previously noted in the local universe (cf. Fig. 1 in Baugh et al. 2002) and in the B and UV rest frame bands at $`z1`$ (Poli et al. 2001, Somerville et al. 2001, Poli et al. 2003).

Our results show the importance of sampling the faint-end of the LF in even deeper near-IR selected samples. In addition, to derive the LF at $`z1`$ in a wider but shallow sample (say $`K<18.5`$) will be essential to trace the evolution of the most massive galaxies with higher statistical significance. In the near future direct measurements of rest-frame $`K`$-band magnitude for high redshift galaxies will be possible with space-based infrared surveys, in particular the SIRTF (Space Infrared Telescope Facility) Legacy Science project GOODS (Great Observatories Origins Deep Survey, P.I. M. Dickinson). Our data allow to directly estimate the number densities of $`z<2`$ galaxies at the different SIRTF-GOODS wavelengths, $`\lambda =3.6,4.5,5.8\mu `$m, which sample the rest-frame $`K_s`$-band at $`z0.7,1.1,1.7`$ respectively, similar to the $`z_{mean}`$ adopted for the K20 LFs. We have converted the absolute $`M_{K_s}`$ magnitudes, derived here for the K20 sample, to SIRTF+IRAC fluxes using the galaxy spectral models described in Sect. 3 for normal galaxies and the spectral model for M82 (Silva et al. 1998) for the dusty star forming galaxies. The expected number densities for objects with $`z<2`$ are shown in Fig. 13. At the expected depth of GOODS (see Dickinson et al. 2002b), SIRTF will detect about 5000 galaxies at $`z<2`$ within 330 arcmin2. GOODS SIRTF Legacy Program, sampling the rest frame near-IR luminosities directly, will allow to derive the $`K`$-band Luminosity Function along with the stellar mass distribution well below the K20 limit (see Fig. 13) and with higher statistical significance. With these data the stellar mass assembly history of galaxies will be measured over a wide range of redshifts and cosmic time.

We make publicy available the $`1/V_{max}`$ estimates at http://www.arcetri.astro.it/ k20/releases/index.html.

###### Acknowledgements.

Part of this work was supported by the MURST (Cofin 2000-2001), ASI and by the European Community Research and Training Network “The physics of the intergalactic medium”. We are in debt with Carlton Baugh for providing the HMM predictions.


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# Adsorption and Depletion of Polyelectrolytes from Charged Surfaces

## I Introduction

The phenomenon of adsorption of charged polymer chains (polyelectrolytes) to surfaces has generated a great deal of interest due to its numerous industrial applications and relevance to biological systems. The theoretical treatment is not yet well established because of the multitude of length scales involved, arising from different interactions: electrostatic interactions between monomers and counter-ions, excluded volume interactions and entropic considerations. Furthermore, when salt is added to the solution, the interplay between polyelectrolytes (PEs) and salt ions as well as the ion entropy has to be taken into account.

The adsorption of PE chains onto charged surfaces has been addressed theoretically in several models in the past. They include among others: solutions of linearized mean-field equations Varoqui ; Varoquietal ; Chatellier ; Joanny ; Manghi ; Wiegel ; Muthukumar , numerical solutions of full mean-field equations Itamar ; Itamar1 ; Itamar2 , various scaling theories for single-chain adsorption Borisov ; Dobrynin , and formulation of a phenomenological criterion describing the adsorption–depletion transition from charged surfaces NetzJoanny ; review ; review1 . Other approaches employed multi-Stern layer models vanderSchee ; vandestig ; Bohmer , where a discrete lattice is used and each lattice site can be occupied by either a monomer, a solvent or a small ion. The electrostatic potential can then be calculated self-consistently together with the concentrations of the monomers and counterions.

In this article we re-examine the mean-field equations describing the PE adsorption and their numerical solutions, with specific emphasis on the adsorption–depletion transition. The present paper can be regarded as an extension of Ref. Itamar . It agrees with the previously obtained low-salt adsorption regime but proposes a different interpretation of the high-salt regime. We find that the high-salt adsorption regime of Ref. Itamar  is pre-empted by an adsorption–depletion transition, in analogy with single-chain results. The mean-field equations and their numerical solutions are formulated in Sec. II, some simple scaling relationships in Sec. III, and the adsorption–depletion transition in Sec. IV. A general discussion and comparison with other models are presented in Sec. V.

## II The Mean Field Equations and Their Numerical Solution

Consider an aqueous solution of infinitely long PEs, together with their counterions and an added amount of salt. Throughout this paper we assume that both the salt ions and counterions are monovalent. Let $`\varphi (𝐫)=\sqrt{c(𝐫)}`$ be the square root of $`c(𝐫)`$, the local monomer concentration, $`a`$ the monomer size and $`f`$ the charge fraction on each PE chain. Also let $`\varphi _\mathrm{b}=\sqrt{c_\mathrm{b}}`$ be the square root of the bulk monomer concentration $`c_\mathrm{b}`$, and $`\psi (𝐫)`$ the electrostatic potential. The mean-field free energy can be obtained either from phenomenological or field theoretical approaches:

$$F=d𝐫\left(f_{\mathrm{pol}}+f_{\mathrm{ion}}+f_{\mathrm{el}}\right)$$
(1)
$`f_{\mathrm{pol}}=k_\mathrm{B}T\left({\displaystyle \frac{a^2}{6}}\left|\varphi \right|^2+{\displaystyle \frac{1}{2}}v\left(\varphi ^4\varphi _\mathrm{b}^4\right)\mu \left(\varphi ^2\varphi _\mathrm{b}^2\right)\right)`$ (2)
$`f_{\mathrm{ion}}=k_\mathrm{B}T{\displaystyle \underset{i=+,}{}}\left[c^i\mathrm{ln}c^ic^i\mu ^i\left(c^ic_\mathrm{b}^i\right)\right]`$ (3)
$`f_{\mathrm{el}}=\left(c^+c^{}+f\varphi ^2\right)e\psi {\displaystyle \frac{ϵ}{8\pi }}\left|\psi \right|^2.`$ (4)
While the full details can be found in Refs. Itamar ; Itamar1 ; Itamar2 , here we just briefly explain each of the terms. The first term of $`f_{\mathrm{pol}}`$ accounts for chain elasticity, the second describes the excluded volume interaction between monomers, where $`v`$ is the second virial coefficient. The third accounts for the coupling with a reservoir with bulk polymer concentration $`\varphi _\mathrm{b}^2=c_\mathrm{b}`$ and chemical potential $`\mu `$. The $`f_{\mathrm{ion}}`$ contribution to the free energy takes into account the entropy of small ions and their chemical potential $`\mu ^\pm `$. Lastly, $`f_{\mathrm{el}}`$ is the electrostatic free energy. Its first term is the interaction energy between the electrostatic potential and the charged objects; namely, the small ions and monomers. The last term is the self-energy of the electric field $`\frac{\epsilon }{8\pi }d𝐫\left|\psi \right|^2`$.

Minimizing the free energy with respect to $`\psi `$, $`\varphi `$, $`c^+`$, $`c^{}`$, and using the bulk boundary conditions: $`\psi \left(x\mathrm{}\right)=0`$, $`\varphi \left(x\mathrm{}\right)=\varphi _\mathrm{b}`$, $`c_\mathrm{b}^{}=c_{\mathrm{salt}}+f\varphi _\mathrm{b}^2`$ and $`c_\mathrm{b}^+=c_{\mathrm{salt}}`$, the profile equations of Ref. Itamar  are reproduced:

$$c^{}=\left(c_{\mathrm{salt}}+f\varphi _\mathrm{b}^2\right)\mathrm{e}^{\beta e\psi }$$
(5)
$$c^+=c_{\mathrm{salt}}\mathrm{e}^{\beta e\psi }$$
(6)
$$^2\psi =\frac{8\pi ec_{\mathrm{salt}}}{\epsilon }\mathrm{sinh}\beta e\psi +\frac{4\pi e}{\epsilon }\left(\varphi _\mathrm{b}^2f\mathrm{e}^{\beta e\psi }f\varphi ^2\right)$$
(7)
$$\frac{a^2}{6}^2\varphi =v\left(\varphi ^3\varphi _\mathrm{b}^2\varphi \right)+\beta fe\psi \varphi ,$$
(8)
where $`\beta =1/k_\mathrm{B}T`$ is the inverse of the thermal energy $`k_BT`$. Equations (5) and (6) show that the small ions obey Boltzmann statistics, while Eq. (7) is the Poisson equation where the salt ions, counterions and monomers can be regarded as the sources of the electrostatic potential. Equation (8) is the mean-field (Edwards) equation for the polymer order parameter $`\varphi (𝐫)`$, taking into account the excluded volume interaction and external electrostatic potential $`\psi (𝐫)`$.

The adsorption onto a flat, homogeneous and charged surface placed at $`x=0`$ depends only on the distance $`x`$ from the surface. In this case the above equations can be reduced to two coupled ordinary differential equations. Defining dimensionless variables $`\eta \varphi /\varphi _\mathrm{b}`$ and $`y\beta e\psi `$, Eqs. (7) and (8) then read:

$$\frac{\mathrm{d}^2y}{\mathrm{d}x^2}=\kappa ^2\mathrm{sinh}y+k_m^2\left(\mathrm{e}^y\eta ^2\right)$$
(9)
$$\frac{a^2}{6}\frac{\mathrm{d}^2\eta }{\mathrm{d}x^2}=v\varphi _\mathrm{b}^2\left(\eta ^3\eta \right)+fy\eta ,$$
(10)
where $`\kappa ^1=\left(8\pi l_\mathrm{B}c_{\mathrm{salt}}\right)^{1/2}`$ is the Debye-Hückel screening length, determining the exponential decay of the potential due to the added salt. Similarly, $`k_m^1=\left(4\pi l_\mathrm{B}\varphi _\mathrm{b}^2f\right)^{1/2}`$ determines the exponential decay due to the counterions. The Bjerrum length is defined as $`l_\mathrm{B}=e^2/\epsilon k_\mathrm{B}T`$. For water with dielectric constant $`\epsilon =80`$, at room temperature, $`l_\mathrm{B}`$ is equal to about $`7`$Å. Note that the actual decay of the electrostatic potential is determined by a combination of salt, counterions, and polymer screening effects.

The solution of Eqs. (9) and (10) requires four boundary conditions. Two of them are the boundary values in the bulk, $`x\mathrm{}`$: $`\eta \left(x\mathrm{}\right)=1`$ and $`y\left(x\mathrm{}\right)=0`$, while the other two are the boundary conditions on the $`x=0`$ surface. In this article we use either constant surface charge density (Neumann boundary conditions) or constant surface potential (Dirichlet boundary conditions). For the former, $`\mathrm{d}y/\mathrm{d}x|_{x=0}=4\pi \sigma e/\epsilon k_\mathrm{B}T=4\pi (\sigma /e)l_\mathrm{B}`$, where $`\sigma `$ is the surface charge density. For the latter, the surface potential is held fixed with a value: $`y\left(0\right)=y_s`$. The other boundary condition for the polymer concentration $`\varphi `$ is taken as a non-adsorbing surface. Namely, $`\varphi \left(0\right)=0`$. Note that far from the surface, $`x\mathrm{}`$, Eqs. (9) and (10) already satisfy the boundary condition: $`y=0`$ and $`\varphi =\varphi _\mathrm{b}`$ (or $`\eta =1`$).

Equations (9) and (10) are two coupled non-linear differential equations that do not have a known analytical solution. The numerical solutions of these equations for low salt conditions were presented in Ref. Itamar  and are reproduced here on Figs. 1 and 2, using a different numerical scheme. The numerical results have been obtained using the relaxation method NR  based on a linearization procedure done on a discrete one-dimensional grid. Then, the equations are transformed to a set of algebraic equations for each grid point. The sum of the absolute difference between RHS and LHS over all grid points is minimized iteratively until convergence of the numerical procedure is achieved.

In calculating the numerical profiles of Figs. 1 and 2 we assume positively charged polymers and a constant negative surface potential. In Fig. 1a the reduced electrical potential $`y=\beta e\psi `$ profile is shown as a function of the distance from the $`x=0`$ surface. Similarly, in Fig. 2a the monomer rescaled concentration profile $`c(x)/c_\mathrm{b}`$, is shown. In both figures a constant surface potential boundary condition is imposed. The different curves correspond to different surface potentials $`y_s`$, monomer charge fractions $`f`$ and monomer size $`a`$. From the numerical profiles of the electrostatic potential and monomer concentration it can be clearly seen that there is a distinct peak in both profiles. Although they do not occur exactly at the same distance from the surface, the corresponding peaks in Fig. 1 and 2 vary in a similar fashion with system parameters. The peak in the concentration (Fig. 2) marks a PE accumulation at the surface and is regarded as a signature of adsorption. The peak in the potential (Fig. 1) marks an over-compensation of surface charges. At the peak of $`\psi (x)`$, the electric field vanishes, $`E=\mathrm{d}\psi /\mathrm{d}x=0`$, meaning that the integrated charge density from the surface up to this distance exactly balances the surface charge.

## III Scaling Estimate of the Adsorption Layer: Counterion only Case

So far numerical solutions within mean-field theory, Eqs. (9) and (10), have been described. We proceed by presenting simplified scaling arguments, which are in agreement with the numerical mean-field results. Note that the treatment here does not capture any correlation effect which goes beyond mean-field. The concept of polymer “blobs” can be useful in order to describe PE adsorption, where such polymer blob can be regarded as a macro-ion adsorbing on a charge surface. The blob size is determined by taking into account the polymer connectivity and entropy as well as the interaction with the charged surface. A single layer of adsorbing blobs is assumed instead of the full continuous PE profile as obtained from the mean-field equations. Therefore, the blob size characterizes the adsorption layer thickness.

### III.1 Fixed Surface Charge Density

The two largest contributions to the PE adsorption free energy are the electrostatic attraction with the surface and the chain entropy loss due to blob formation.

For simplicity, the electrostatic attraction of the monomers with the surface is assumed to be larger than the monomer excluded volume and monomer-monomer electrostatic repulsion. With this assumption the chain has a Gaussian behavior inside each surface blob, $`Dag^{1/2}`$, where $`g`$ is the number of monomers in a blob of size $`D`$, as is shown schematically in Fig. 3. The entropy loss of the chain balances the surface-monomer attraction. As a result the blob attraction with the surface is of order $`k_BT`$. It is now easy to get an estimate of the blob size $`D`$:

$`fg{\displaystyle \frac{\stackrel{~}{\sigma }}{\epsilon }}e^2Dk_\mathrm{B}T`$ (11)
$`Dag^{1/2}\left({\displaystyle \frac{a^2}{l_\mathrm{B}f\stackrel{~}{\sigma }}}\right)^{1/3}`$ (12)
$`g\left(l_\mathrm{B}fa\stackrel{~}{\sigma }\right)^{2/3},`$ (13)
using a rescaled surface density $`\stackrel{~}{\sigma }\left|\sigma /e\right|`$. These results are in agreement with those describing the statistics of single-chain adsorption Wiegel ; Borisov .

The assumption that the electrostatic attraction to the surface is larger than the monomer-monomer electrostatic repulsion and excluded volume can now be checked self-consistently, yielding two conditions: $`\stackrel{~}{\sigma }fa^2`$ and $`fv^3/(a^{10}\stackrel{~}{\sigma }l_B)`$.

The average monomer concentration (per unit volume) in the adsorption layer $`c_m`$, is the blob concentration in the adsorption layer $`n_0`$, times the number of monomers per blob $`g`$, yielding $`c_m=n_0g`$. It is now possible to get an estimate of the blob concentration per unit volume in the adsorption layer, $`n_0`$, by assuming that the adsorbed layer neutralizes the surface charges up to a numerical prefactor of order unity. Hence, $`n_0\stackrel{~}{\sigma }/Dfg`$. This assumption, which is in agreement with our numerical solutions, leads to

$`n_0`$ $``$ $`l_\mathrm{B}\stackrel{~}{\sigma }^2`$ (14)
$`c_m`$ $`=`$ $`n_0g(l_\mathrm{B}a^2f^2\stackrel{~}{\sigma }^4)^{1/3}\stackrel{~}{\sigma }^{4/3}f^{2/3}.`$ (15)
Equation (14) is just the Graham equation Israelachvili  relating the surface charge density with the counterion density at the surface vicinity. The only difference is that the counterions are replaced by the charged polymer blobs. Furthermore, Eq. (15) is in accord with the results of Ref review .

The total amount of PEs in the adsorption layer is $`\mathrm{\Gamma }c_mD=\stackrel{~}{\sigma }/f`$. In other words, the overall polymer charge in the adsorption layer (up to a numerical prefactor) is $`f\mathrm{\Gamma }\stackrel{~}{\sigma }`$. This is just another way to phrase the charge neutralization by the PEs mentioned above.

### III.2 Fixed Surface Potential

Using the boundary condition of a fixed surface potential $`\psi =\psi _s`$, the scaling laws for $`D`$ and $`g`$ can be obtained in a similar fashion as was done in Sec. III.1. Alternatively, one can (in the absence of salt) relate the surface potential to the surface charge density by $`\psi _s\sigma D/\epsilon `$.

The adsorption energy of a blob of charge $`gfe`$ onto a surface held at potential $`\psi _s`$ is just $`gfe\psi _s`$. Requiring that this energy is of order of $`k_BT`$ we obtain in analogy to Eqs. (11)-(13):

$`gfe\left|\psi _s\right|k_\mathrm{B}T`$ (16)
$`Dag^{\frac{1}{2}}{\displaystyle \frac{a}{\sqrt{f\left|y_s\right|}}}`$ (17)
$`g{\displaystyle \frac{1}{f\left|y_s\right|}}`$ (18)
Together with the neutralization condition $`n_0\stackrel{~}{\sigma }/(Dfg)`$ it yields:

$`n_0{\displaystyle \frac{f\left|y_s\right|^3}{l_\mathrm{B}a^2}}`$ (19)
$`c_m=n_0g{\displaystyle \frac{\left|y_s\right|^2}{l_\mathrm{B}a^2}}.`$ (20)
Note that the above results are in accord with the ones previously derived in Ref. Itamar .

Just like in Sec. III.A the self-consistent check can be repeated here for the dominance of the surface-monomer interactions, yielding $`\left|y_s\right|f^{1/3}l_B^{2/3}a^{2/3}`$ and $`fv^\mathit{2}/a^6\left|y_s\right|`$. This condition has been verified, in addition, by examining numerically the mean-field adsorbing profiles.

The overall charge of the polymer in the adsorbed layer is then:

$`\mathrm{\Gamma }c_mD\left|y_s\right|^{3/2}f^{1/2}l_\mathrm{B}^1a^1\left|y_s\right|^{3/2}f^{1/2}`$ (21)
$`f\mathrm{\Gamma }\left|y_s\right|^{3/2}f^{1/2}l_\mathrm{B}^1a^1{\displaystyle \frac{\left|y_s\right|}{l_\mathrm{B}D}}\left|{\displaystyle \frac{d\psi }{dx}}\right|_{x=0}\stackrel{~}{\sigma }`$ (22)
which again verifies that the adsorbed amount scales like the surface charge.

The numerical results of the mean-field equations for constant surface potential $`y_s`$ condition and in the low salt regime ($`c_{\mathrm{salt}}=0.1`$mM) are consistent with this scaling picture, as can be seen in Figs. 1 and 2. In Fig. 1b the rescaled potential $`y/|y_s|`$ is plotted in terms of a rescaled distance: $`x/D`$, with $`D`$ taken from Eq. (17). In Fig. 2b the concentration profile is rescaled by $`c_m`$, Eq. (20), and plotted in terms of the same rescaled distance $`x/D`$. The figures show clearly data collapse of the two profiles, indicating that the characteristic adsorption length $`D`$ is indeed given by the scaling predictions. Note that the agreement with the scaling argument occurs as long as the system stays in the low salt limit. The other limit of high salt is discussed next.

## IV The Adsorption – Depletion Transition in presence of Added Salt

The same numerical procedure outlined in Sec. II, is used to find when the chains stop adsorbing and instead will deplete from the surface. This is not a sharp transition but rather a crossover which is seen by calculating numerically the PE surface excess, as depicted in Fig. 4. The profiles were obtained by solving numerically the differential equations for several values of $`f`$ near the adsorption–depletion transition using a fixed surface potential boundary condition. For salt concentration of about $`c_{\mathrm{salt}}^{}0.16\left|y_s\right|f/(l_\mathrm{B}a^2)`$ (solid line in Fig. 4), the figure show the disappearance of the concentration peak. Namely, a depletion–adsorption crossover.

The dependence of $`\mathrm{\Gamma }=_0^{\mathrm{}}dx\left(\varphi ^2\varphi _b^2\right)`$ on $`c_{\mathrm{salt}}`$ and $`f`$ for constant surface potential is presented in Fig. 5. The place where $`\mathrm{\Gamma }=0`$ indicates an adsorption–depletion transition, separating positive $`\mathrm{\Gamma }`$ in the adsorption regime from negative ones in the depletion regime. In Fig. 5a the dependence of $`\mathrm{\Gamma }`$ on $`f`$ is shown for several salt concentrations ranging from low- to high-salt conditions. For low enough $`f`$, $`\mathrm{\Gamma }<0`$ indicates depletion. As $`f`$ increases, a crossover to the adsorption region, $`\mathrm{\Gamma }>0`$, is seen. In the adsorption region, a peak in $`\mathrm{\Gamma }(f)`$ signals the maximum adsorption amount at constant $`c_{\mathrm{salt}}`$. As $`f`$ increases further, beyond the peak, $`\mathrm{\Gamma }`$ decreases as $`1/\sqrt{f}`$. Looking at the variation of $`\mathrm{\Gamma }`$ with salt, as $`c_{\mathrm{salt}}`$ increases, the peak in $`\mathrm{\Gamma }(f)`$ decreases and shifts to higher values of $`f`$. For very large amount of salt, e.g., $`c_{\mathrm{salt}}=0.5`$ M, the peak occurs in the limit $`f1`$. In Fig. 5b, we plot $`\mathrm{\Gamma }(c_{\mathrm{salt}})`$ for several $`f`$ values. The adsorption regime crosses over to depletion quite sharply as $`c_{\mathrm{salt}}`$ increases, signaling the adsorption-depletion transition. The salt concentration at the transition, $`c_{\mathrm{salt}}^{}`$, increases with the charge fraction $`f`$. The dependence of $`\mathrm{\Gamma }`$ on $`c_{\mathrm{salt}}`$ and $`f`$ for constant surface charge density is plotted in Fig. 6. Both salt and $`f`$ dependences show a similar behaviour to those shown in Fig. 5 for constant surface potential.

The numerical phase diagrams supporting the adsorption–depletion transition are presented in Fig. 7 for constant surface charge conditions. The phase diagrams were obtained by solving numerically the mean-field equations. We scanned the $`(f,c_{\mathrm{salt}})`$ parameter plane for 50 values of $`f`$ between $`0.01<f<1`$ (Fig. 7a) and the $`(\stackrel{~}{\sigma },c_{\mathrm{salt}})`$ plane for 50 values of $`\stackrel{~}{\sigma }=|\sigma /e|`$ between $`10^5`$ \[Å-2\] $`<\stackrel{~}{\sigma }<10^4`$ \[Å-2\] (Fig. 7b). From the log-log plots it can be seen that the adsorption–depletion transition is described extremely well by a line of slope $`2/3`$ in both Fig. 7a and 7b. Namely, at the transition $`c_{\mathrm{salt}}^{}f^{2/3}`$ for fixed $`\stackrel{~}{\sigma }`$ and $`c_{\mathrm{salt}}^{}\stackrel{~}{\sigma }^{2/3}`$ for fixed $`f`$.

To complete the picture, the adsorption–depletion transition is also presented in Fig. 8 for constant surface potential. The phase diagrams are obtained by solving numerically the differential equations. We scanned the $`(f,c_{\mathrm{salt}})`$ parameter plane for 50 values of $`f`$ between $`0.01<f<1`$ (Fig. 8a) and the $`(\left|y_s\right|,c_{\mathrm{salt}})`$ plane for 50 values of $`\left|y_s\right|`$ between $`0.1<\left|y_s\right|<1.0`$ (Fig. 8b). From the figure it is apparent that the adsorption–depletion transition line fits quite well a line of slope 1.0 in both Fig. 8a and 8b plotted on a log-log scale. Namely, $`c_{\mathrm{salt}}^{}f`$ for fixed $`y_\mathrm{s}`$, and $`c_{\mathrm{salt}}^{}y_\mathrm{s}`$ for fixed $`f`$.

These scaling forms of $`c_{\mathrm{salt}}^{}`$ at the transition can be explained using the simplified scaling arguments introduced in Sec. III.

### IV.1 Scaling for Fixed Surface Charge

If the blobs are taken as charged spheres, the mere existence of an adsorption process requires that the attraction of the monomers to the surface persists for all charges up to distances $`D`$ from the charged surface. For high ionic strength solutions, the electrostatic potential at distance $`x`$ for a charged surface can be approximated by the linearized Debye-Hückel potential:

$$y\left(x\right)=4\pi \stackrel{~}{\sigma }l_\mathrm{B}\kappa ^1\mathrm{e}^{\kappa x}.$$
(23)
This is valid as long as the potential is low enough, $`y1`$. The adsorption picture requires that the exponential decay of the potential will not vary substantially inside a region of size $`D`$ comparable to the size of surface blobs, $`y(D)y_s`$. Then, the exponential decay in Eq. (23) yields

$$\kappa D<1.$$
(24)
Namely, the Debye-Hückel screening length is smaller than the adsorption layer thickness, $`D`$. Using Eq. (12) this yields:

$$c_{\mathrm{salt}}<\stackrel{~}{\sigma }^{2/3}f^{2/3}l_\mathrm{B}^{1/3}a^{4/3}$$
(25)
The crossover between adsorption and depletion will occur when $`c_{\mathrm{salt}}^{}(\stackrel{~}{\sigma }^2f^2l_\mathrm{B}^1a^4)^{1/3}`$, in accord with Refs. Wiegel ; Muthukumar ; Dobrynin , and with the numerical results discussed above and presented in Fig. 7.

### IV.2 Scaling for Fixed Surface Potential

For the boundary condition, $`\psi =\psi _s`$, the potential decay from the surface can be approximated to be:

$$y\left(x\right)=y_s\mathrm{e}^{\kappa x}$$
(26)
and the same consideration as in Eq. (24) and (25) gives:

$$c_{\mathrm{salt}}<\frac{\left|y_s\right|f}{l_\mathrm{B}a^2}.$$
(27)
Namely, we expect an adsorption–depletion transition to occur for $`c_{\mathrm{salt}}^{}\left|y_s\right|f/(l_\mathrm{B}a^2)`$, in the case of a fixed surface potential. This supports the numerical results as presented in Fig. 8.

## V Discussion

We have presented numerical calculations of the mean-field equations describing the adsorption of PE chains onto charged surfaces, including multi-chain interactions. The main finding is the existence of an adsorption–depletion transition in presence of added salt or weakly charged chains. The numerical results are discussed in terms of simple scaling arguments describing the adsorption of PEs. The salt concentration at the adsorption–depletion transition scales like $`c_{\mathrm{salt}}^{}f\left|y_s\right|`$ for fixed surface potential and $`c_{\mathrm{salt}}^{}\left(f\stackrel{~}{\sigma }\right)^{2/3}`$ for fixed surface charge density. Within the scaling picture, the condition for depletion is the same as for a single chain, in agreement with our mean-field solutions.

We briefly summarize the main approximations of our mean-field and scaling results. A non-adsorbing surface is used as the polymer boundary condition. However, if the surface has a strong non-electrostatic affinity for the PE chains, the electrostatic contribution does not have to be the dominant one. The method also assumes Gaussian blobs within mean-field theory. In a more refined theory, excluded volume interactions as well as lateral correlation in the blob-blob interactions will alter the adsorption behavior. When the surface charge (or potential) is high enough, the blob size $`D`$ can become comparable with the monomer size $`a`$, and the PE chains will lay flat on the surface. Further investigations might be necessary to address in more detail the above points. It will also be interesting to extend our results to geometries other than the planar charged surface.

Several authors have addressed the problem of adsorption onto surfaces either of a single chain Borisov  or multiple chains Dobrynin  using similar arguments of blobs. In another approach, a Flory-like free energy Itamar  was introduced using the assumption of a single characteristic length scale. The latter gave adsorption-layer scaling laws as in Eqs. (17) and (20), but did not find the depletion criterion. Instead, an adsorption length scale and a characteristic concentration were predicted for the high-salt regime. We show here, using both numerical calculations and scaling arguments, that the high-salt regime does not exist because it is preempted by a PE depletion.

Acknowledgments.  It is a pleasure to thank G. Ariel, I. Borukhov, Y. Burak, E. Katzav and H. Orland for useful discussions and comments. DA acknowledges support from the Israel Science Foundation under grant No. 210/02 and the Alexander von Humboldt Foundation. RRN acknowledges support from the Deutsche Forschungsgemeinschaft (DFG, German-French Network) and the Fonds der Chemischen Industrie.

## Figure Captions

* (a) Numerical profiles of the rescaled electrostatic potential $`y=\beta e\psi `$ as function of the distance from the surface $`x`$ using Eqs. (9) and (10), and constant surface potential. The solid line is for $`a=5`$Å, $`f=1,y_s=1.0`$, the dotted line for $`a=5`$Å, $`f=1,y_s=0.5`$, the dashed line is for $`a=10`$Å, $`f=1,y_s=0.5`$, and the dash-dot line for $`a=5`$Å, $`f=0.1,y_s=0.5`$. All profiles have $`c_{\mathrm{salt}}=0.1`$ mM, $`\varphi _\mathrm{b}^2=10^6`$ Å-3, $`v=50`$Å3, $`\epsilon =80,T=300`$ K. The profiles reproduce those of Ref. Itamar  using a different numerical scheme. (b) Same profiles as in part (a) but in rescaled variables: $`x/D`$ and $`y/\left|y_s\right|`$.
* (a) The concentration profile $`c(x)/c_b=\varphi ^2(x)/\varphi _\mathrm{b}^2`$ for the numerical calculations specified in Fig. 1. The profiles reproduce those of Ref. Itamar . (b) Same as in part (a) but in rescaled variables: $`x/D`$ and $`c(x)/c_m`$.
* A schematic drawing of polyelectrolyte adsorption onto flat surfaces and formation of Gaussian surface blobs each of size $`D`$ and having $`g`$ monomers. The monomer size is $`a`$.
* Numerical polyelectrolyte concentration profiles exhibiting the transition from adsorption to depletion. The dashed line corresponds to $`f=0.12`$, the dot–dash line to $`f=0.1`$, the solid line to $`f=0.09`$, and the dotted line to $`f=0.08`$. All profiles have $`\left|y_s\right|=0.5`$, $`\varphi _b^2=10^6`$ Å-3, $`v=50`$ Å3, $`a=5`$ Å, $`c_{\mathrm{salt}}=70`$mM. The adsorption–depletion transition is found to occur for $`f=0.09`$, corresponding to $`c_{\mathrm{salt}}^{}0.16\left|y_s\right|f/l_Ba^2`$.
* (a) Surface excess of PE adsorption, $`\mathrm{\Gamma }`$, as function of the chain charged fraction $`f`$, for several salt concentrations: 1.0 mM (solid line), 10 mM (dashed line), 0.1 M (dash-dot line), 0.5 M (dots), and for constant surface potential. As the salt concentration increases, the peak in $`\mathrm{\Gamma }`$ shifts to higher $`f`$ values and disappears for $`c_{\mathrm{salt}}=0.5`$ M. The depletion-adsorption transition occurs for $`\mathrm{\Gamma }=0`$. (b) Surface excess as function of salt concentration, $`c_{\mathrm{salt}}`$, for several $`f`$ values: f=0.03 (dots), 0.1 (dashes), 0.3 (dot-dash), 1.0 (solid line). $`\mathrm{\Gamma }`$ is almost independent of $`c_{\mathrm{salt}}`$ for low salt concentrations in the adsorption region. It is then followed by a steep descent into a depletion region at a threshold value. Other parameters used are: $`y_s=1.0`$, $`v=50`$Å3, $`\varphi _b^2=10^6`$Å-3, $`a=5`$Å, $`T=300`$K and $`\epsilon =80`$.
* (a) Surface excess of PE adsorption, $`\mathrm{\Gamma }`$, as function of the chain charged fraction $`f`$, for several salt concentrations: 4.0 mM (solid line), 8.0 mM (dashed line), 21 mM (dash-dot line), 63 mM (dots), and for constant surface charge density. As the salt concentration increases, the peak in $`\mathrm{\Gamma }`$ shifts to higher $`f`$ values and disappears for $`c_{\mathrm{salt}}=63`$ mM. The depletion-adsorption transition occurs for $`\mathrm{\Gamma }=0`$. (b) Surface excess as function of salt concentration, $`c_{\mathrm{salt}}`$, for several $`f`$ values: f=0.1 (dots), 0.2 (dashes), 0.45 (dot-dash), 1.0 (solid line). $`\mathrm{\Gamma }`$ is almost independent of $`c_{\mathrm{salt}}`$ for low salt concentrations in the adsorption region. It is then followed by a steep descent into a depletion region at a threshold value. Other parameters used are: $`\sigma /e=10^4`$Å-2, $`v=50`$Å3, $`\varphi _b^2=10^6`$Å-3, $`a=5`$Å, $`T=300`$K and $`\epsilon =80`$.
* Numerically calculated adsorption–depletion crossover diagram for constant surface charge condition. In (a) the $`(f,c_{\mathrm{salt}})`$ parameter plane on a log-log scale while $`\stackrel{~}{\sigma }=|\sigma /e|`$ is held constant at $`\stackrel{~}{\sigma }=10^3`$ Å-2. The full squares represent the lowest salt concentration for which depletion is detected. The least-mean-square fit to the data points gives a straight line with slope of $`0.69\pm 0.02`$. The figure shows that the numerical results agree with a $`2/3`$ power law as predicted in Sec. IV.A, $`c_{\mathrm{salt}}^{}f^{2/3}`$. In (b) the crossover diagram in calculated numerically in the $`(|\sigma /e|,c_{\mathrm{salt}})`$ parameter plane on a log-log scale, while $`f`$ is fixed to be $`f=0.1`$ The least-mean-square line has a slope of $`0.71\pm 0.02`$, showing that the numerical results agree with a $`2/3`$ power law as predicted in Sec. IV.A, $`c_{\mathrm{salt}}^{}\sigma ^{2/3}`$.
* Numerically calculated crossover diagram on a log-log scale for constant surface potential conditions. Notations and symbols are the same as in Fig. 6. In (a) the $`(f,c_{\mathrm{salt}})`$ parameter plane is presented for constant $`y_\mathrm{s}=1.0`$. The least-mean-square fit has a slope of $`1.00\pm 0.02`$, in excellent agreement with the scaling arguments, $`c_{\mathrm{salt}}^{}f`$. In (b) the $`(\left|y_s\right|,c_{\mathrm{salt}})`$ parameter plane is presented, for constant $`f=0.1`$. The least-mean-square fit has a slope of $`1.04\pm 0.02`$, in agreement with scaling arguments, $`c_{\mathrm{salt}}^{}\left|y_s\right|`$.

Fig. 1, Shafir et al

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