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# The XMM-Newton Serendipitous Survey Based on observations obtained with XMM-Newton, an ESA science mission with instruments and contributions directly funded by ESA Member States and the USA (NASA)

## 1 Introduction

In contrast with all-sky X-ray surveys which typically provide relatively shallow coverage, serendipitous surveys provide much deeper observations, albeit restricted to smaller sky areas. Serendipitous X-ray sky surveys, taking advantage of the relatively wide field of view afforded by typical X-ray instrumentation, have been pursued with most X-ray astronomy satellites since the Einstein Observatory. The resultant serendipitous source catalogues (e.g. EMSS \[835 sources\] Gioia et al. gioia (1990), Stocke et al., stocke (1991); WGACAT \[$`62000`$ unique sources\] White, Giommi & Angelini, WGA (1994); ROSAT 2RXP & ROSAT 1RXH \[$`95000`$ & $`11000`$ sources respectively\] the ROSAT Consortium, 2000) have been the basis for numerous studies and have made a significant contribution to our knowledge of the X-ray sky and our understanding of the nature of the various Galactic and extragalactic source populations.

The XMM-Newton Observatory (Jansen et al., jansen (2001)), launched in December 1999, provides unrivaled capabilities for serendipitous X-ray surveys by virtue of the large field of view of the X-ray telescopes with the EPIC X-ray cameras (Turner et al., turner (2001); Strüder et al., struder (2001)), and the high throughput afforded by the heavily nested telescope modules. This capability guarantees that each XMM-Newton observation provides a significant harvest of serendipitous X-ray sources in addition to data on the original target. This potential is now starting to be realised, as is described below.

## 2 The role of the XMM-Newton Survey Science Centre (SSC)

In recognition of the importance of the XMM-Newton serendipitous science ESA solicited proposals for an XMM-Newton Survey Scientist in 1995. The role of the Survey Scientist centres on providing a coordinated approach to XMM-Newton serendipitous data to ensure that the whole scientific community can exploit this valuable resource. In fact the role of the Survey Scientist required by ESA was much wider than this, involving the substantial additional tasks of making a major contribution to the development of the scientific processing and analysis software for XMM-Newton, the routine “pipeline” processing of all the observations and the compilation of the XMM-Newton Serendipitous Source Catalogue.

The XMM-Newton Survey Science Centre (SSC) consortium was selected by ESA in early 1996. The SSC is an international collaboration involving a consortium of 8 institutions in the UK, France and Germany, together with 7 Associate Scientists. The SSC’s role in facilitating the exploitation of the XMM-Newton serendipitous survey is the main subject of this paper, but here we emphasise the other contributions that the SSC is making to the project. Since 1996 the SSC has been working closely with ESA’s Science Operations Centre (SOC) staff in the development of the scientific analysis software required for the XMM-Newton project. This is the software that both carries out the initial pre-processing of the XMM-Newton scientific data and permits the detailed scientific analysis of the observations: the modules can be used in a fixed configuration for the routine processing of the XMM-Newton data, and can be used in an interactive configuration by XMM-Newton observers to carry out custom analysis of their data. For documentation of the XMM-Newton science analysis software, a collection of software tools now known as the XMM-Newton “SAS”, see http://xmm.vilspa.esa.es/sas/. At the time of writing version 5.0 of the SAS is undergoing final testing with a planned full public release of the system before the end of 2000.

In parallel with the software developments, the SSC has developed the infrastructure required to carry out, on behalf of ESA, the routine “pipeline” processing of all the XMM-Newton observations from each of the three instruments. The aim here is to provide a set of data products which will be of immediate value for the XMM-Newton observer as well as for the science archive where they will also be stored for eventual public release. The XMM-Newton data products include calibrated, “cleaned” event lists which are intended to provide the starting point for most interactive analysis of the data as well as a number of secondary high-level products such as sky images, source lists, cross-correlations with archival catalogues, source spectra and time series. These provide a useful overview of the observation for the XMM-Newton observer as well as constituting key archival resources and the starting point for the compilation of the Serendipitous Source Catalogue.

The XMM-Newton Serendipitous Source Catalogue will be based on the EPIC source lists111OM results will also be incorporated. from the pipe-line processing, but will also contain comprehensive archival catalogue data, and results from the SSC (and other) follow-up programme(s) described below. The SSC will emphasize the reliability, uniformity and usability of the catalogue paying particular attention to the external catalogue correlations and identification information. The provision of ancillary information such as sky-coverage and sensitivity estimates is planned to ensure the scientific usefulness of the catalogue.

## 3 Performance of XMM-Newton for serendipitous surveys

Observations obtained in the early phases of the XMM-Newton observing programme have been analysed by the project teams in order to establish the in-orbit performance of the Observatory and its instrumentation. Here we concentrate on those aspects of the XMM-Newton performance which are important for serendipitous surveys.

### 3.1 Field of view and image quality

The field of view of the XMM-Newton X-ray telescopes has a radius of $`15`$ arcmin beyond which baffles reduce the out-of-field response to very low levels. The X-ray telescope field of view is completely covered by the EPIC MOS and pn X-ray cameras out to a radius of $`14`$ arcmin. The on-axis point spread functions (PSFs) of the X-ray telescopes, confirmed by in-orbit data (Jansen et al., jansen (2001)), have FWHM values 5-7 arcsec and HEW values $``$14-15 arcsec. The optical design of the X-ray telescopes produces a PSF which shows only a very slow degradation out to a radius of $``$10 arcmin (Jansen et al., jansen (2001)). With appropriate on-board and ground processing (as incorporated into the SAS) to remove hot pixels and noise effects, the EPIC X-ray images are remarkably free from defects with the most noticeable features being the inter-chip gaps in the EPIC pn and EPIC MOS cameras. Fig. 1 shows example EPIC images which illustrate these points.

### 3.2 Positional accuracy for EPIC source detections

The accuracy with which EPIC source detections can be measured depends on the accuracy with which the EPIC camera coordinate system can be related to the celestial astrometric reference frame and the statistical accuracy of the individual position determinations in the camera coordinate system. The transformation between the EPIC camera coordinate system and sky coordinates provided by the XMM-Newton aspect system has a typical accuracy of $``$ 4 arcsec. To improve on this, cross-correlation of EPIC X-ray sources with catalogued optical objects (e.g. the USNO A2.0 catalogue) will be used routinely in the processing pipeline to provide an updated transformation between the EPIC and sky frames with an expected accuracy of $`1`$ arcsec across the whole EPIC field. Using this approach, the EPIC source positions, even for faint sources close to the detection limit, have typical 90% confidence radii of only $`25`$ arcsec, limited by statistical accuracy of the measurements. An illustration of the positional accuracy already achieved is given in Fig. 2 which shows the X-ray - optical position residuals for a typical XMM-Newton observation.

### 3.3 Survey sensitivity

The major uncertainty in predicting the EPIC sensitivity pre-launch was the background levels which would be encountered in-orbit. The actual in-orbit background levels measured in the first part of the Lockman Hole observation are $`(2.1,2.9)\times 10^3\mathrm{ct}\mathrm{s}^1\mathrm{arcmin}^2`$ for the EPIC pn camera in the soft (0.5-2 keV) and hard (2-10 keV) bands respectively. Very similar values: $`(2.0,2.6)\times 10^3\mathrm{ct}\mathrm{s}^1\mathrm{arcmin}^2`$ are found for the two EPIC MOS cameras combined. A significant fraction of this background, particularly at hard X-ray energies, is due to residual particle background with contributions from both high energy particles interacting with the body of the EPIC detectors and from soft protons scattered into the focal plane by the X-ray mirrors. These background levels correspond to the nominal quiescent background detected outside of background flares at high galactic latitudes and appear to be relatively stable and reproducible over the first 9 months of science operations.222The soft band (0.5-2 keV) background levels of course show a factor of few change over the sky due to intrinsic variations in the Galactic foreground, cf. ROSAT studies. The hard band background shows much smaller variation, except at very low Galactic latitudes. During background flares the background can increase by large factors ($`>10`$ is not uncommon) and portions of these data are of limited use for faint source detection or the mapping of low surface brightness emission.

Using the nominal quiescent background values together with the measured XMM-Newton PSF we have computed an updated EPIC point source sensitivity based on a simple 5$`\sigma `$ source detection criterion against assumed purely Poissonian background fluctuations, as shown in Fig. 3.333The 5$`\sigma `$ value represents a relatively conservative limit which crudely takes into account the fact that there are additional systematic background effects which have yet to be characterised in detail. For the effective beam area of XMM-Newton, the appropriate limit for purely Poissonian background fluctuations to yield $`1`$ spurious source per field is $`3.54\sigma `$. Empirical data from analysis of several XMM-Newton fields using the source detection software developed by the SSC for the SAS are broadly consistent with these plots. The actual background in an observation depends critically on the fraction of background flares removed, i.e. the trade-off between net background levels and net exposure time. An investigation of a few example fields demonstrates that the effective sensitivity of typical observations is within a factor 2 of the values plotted in Fig. 3. A few observations are affected by enhanced background throughout; here the average background can be several times higher than the nominal values even after the removal of the largest flares.

At very faint fluxes the effective sensitivity is limited by confusion effects. Although a detailed study of source confusion has not yet been carried out, the long XMM-Newton observations of the Lockman Hole (Hasinger et al., hasinger01 (2001)) demonstrate that source confusion is not a significant problem in either the soft (0.5-2 keV) or hard (2-10 keV) X-ray bands for an observation duration of $`100`$ ksec which reaches flux limits $`f_X0.31`$ and $`1.4\times 10^{15}\mathrm{erg}\mathrm{cm}^2\mathrm{s}^1`$ in the soft and hard bands respectively.

## 4 The XMM-Newton Serendipitous Survey

### 4.1 Scope and scientific potential

The high throughput, large field of view and good imaging capabilities of XMM-Newton mean that it detects significant numbers of serendipitous X-ray sources in each pointing, as is illustrated in Fig. 1. To quantify the serendipitous source numbers expected from XMM-Newton observations we note that for the typical exposure time of 20 ksec, XMM-Newton will detect sources down to $`10^{15}\mathrm{erg}\mathrm{cm}^2\mathrm{s}^1`$ in the 0.5-2 keV band, and $`10^{14}\mathrm{erg}\mathrm{cm}^2\mathrm{s}^1`$ in the 2-10 keV band, these values referring to a 5$`\sigma `$ detection in the combined EPIC pn and MOS cameras (cf. Fig. 3). The X-ray source density at these flux levels in the high latitude sky is already established from ROSAT studies in the soft band (Hasinger et al., hasinger98 (1998)) and has now been extended to harder energies by recent Chandra and XMM-Newton studies (Mushotzky et al. mushotzky00 (2000); Giacconi et al., giacconi00 (2000); Hasinger et al., hasinger01 (2001)). Taking into account the telescope vignetting which reduces the sensitivity off-axis and the distribution of exposure times yields an expected $`50100`$ sources per typical EPIC field (over the whole field, i.e. in a sky area $`0.2`$ sq.deg.). Around 30–40% of these are expected to be detected in the hard band, smaller than might have been expected from the higher sky density at higher energies, this fraction reflecting the lower effective hard-band sensitivity in flux terms.

The extent to which these expectations are matched by the real data is illustrated by the images in Fig. 1 which show three typical XMM-Newton EPIC observations of calibration and performance verification fields covering a range of Galactic latitudes and exposure times. The source content of these fields is summarised in Table 1 (note that the numbers are given for off-axis angles $`12`$ arcmin., i.e. an area of $`0.125`$ sq.deg.; the full field numbers are 25–30% higher). The source numbers in the high latitude and mid-latitude fields are in general accord with our expectations (predicted numbers in Table 1 are for the Hasinger et al., hasinger98 (1998) & Giacconi et al., giacconi00 (2000) source counts and the sensitivities given in Fig. 3 with an approximate correction for the sensitivity decrease off-axis due to telescope vignetting; these predicted numbers are only accurate to 10–20%). The G21.5$``$0.9 field, at low Galactic latitude and with a high column density ($`N_{HI}+N_{HII}10^{23}\mathrm{cm}^2`$), samples a rather different source population as shown by the somewhat lower source density and the fact that there is little correspondence between the soft and hard band detections. In the soft band the detections in this field are likely to be dominated by foreground objects, most of which will be active stars (see section 5). In the hard band the faint source population revealed is likely to be dominated by a mixture of background extragalactic sources seen through the Galactic disk and distant (and hence similarly absorbed) luminous Galactic objects which may include cataclysmic variables and other low luminosity accreting systems. The approximate calculation of the expected extragalactic source numbers in the G21.5$``$0.9 field given in Table 1 (sensitive to the column density distribution) indicates that a significant fraction, but not all, of the hard band sources maybe background objects.

With the current operational efficiency, XMM-Newton makes of the order 500-800 observations per year, covering $`100`$ sq.deg. of the sky. The XMM-Newton serendipitous X-ray catalogue will thus grow at a rate of $`50000`$ sources per year, i.e. the annual rate will be comparable in size to the complete ROSAT All Sky Survey, but will go to fluxes 2-3 orders of magnitude fainter. The catalogue will thus constitute a deep, large area sky survey which will represent a major resource for a wide range of programmes. The extended energy range of XMM-Newton, compared with previous imaging X-ray missions such as ROSAT and the Einstein Observatory, will mean that XMM-Newton is expected to detect significant numbers of obscured and hard-spectrum objects (e.g. obscured AGNs, heavily absorbed Galactic binaries) which are absent from earlier studies. This will provide an important extra dimension to the serendipitous catalogue.

Chandra observations will also provide a serendipitous sky survey comparable in many ways to what XMM-Newton can offer. Nevertheless a number of factors, in particular the smaller field of view with good imaging quality and the fact that the full ACIS array is not always selected by the observer, contribute to producing a significantly smaller sky coverage (by a factor 5-10) for the Chandra serendipitous sky survey. XMM-Newton also has a very significant advantage at photon energies above 4-5 keV: at low energies the ratio of EPIC/ACIS effective areas is 3-4 but this increases to $`6`$ at 5 keV and $`>10`$ at 7 keV. The XMM-Newton serendipitous sky survey is thus likely to contain much larger samples of highly obscured sources, an important factor for the study of the objects currently believed to make up the bulk of the X-ray background (cf. Lockman Hole study of the 5-10 keV source counts, Hasinger et al., hasinger01 (2001)).

X-ray selection of samples provides a well-proven and extremely efficient means of finding some of the most astrophysically interesting objects, many of which have their peak luminosity in the X-ray band. XMM-Newton, with its broad-band and high sensitivity will provide less biased samples than those based on previous soft X-ray missions. It is clear that the XMM-Newton serendipitous source catalogue will prove to be a major resource in many areas of scientific investigation. Examples include:

* the importance of obscuration in the faint AGN population
* the evolution of the quasar luminosity function with redshift
* the nature of faint X-ray galaxies - their contribution to the X-ray background
* the evolution and luminosity function of clusters of galaxies and the nature of density fluctuations in the early Universe
* the coronal activity in stars and its dependence on luminosity, spectral type, stellar rotation and age
* the space density of accreting binary systems.

### 4.2 Need for follow-up studies

In order to exploit the full potential of the XMM-Newton serendipitous survey in the context of a wide range of scientific programmes, the key initial step will be the ‘identification’ of the X-ray sources, i.e. a knowledge of the likely classification into different object types. For the XMM-Newton serendipitous sources, the X-ray observations themselves will provide the basic parameters of each object: the celestial position, X-ray flux for all sources and information on the X-ray spectrum, spatial extent and temporal variability for the brighter objects detected. This information alone may, in some cases, be sufficient to provide a clear indication of the type of object, but for the vast majority of sources, additional information will be required before a confident classification of the object can be made. Some of this information will come from existing astronomical catalogues, or from existing or planned large-scale optical, IR and radio surveys (e.g. SDSS, 2MASS, Denis, FIRST/NVSS), but it is clear that the full exploitation of the XMM-Newton serendipitous survey will require a substantial programme of new observations, primarily in the optical and IR using ground-based facilities.

### 4.3 The SSC Follow-up (XID) Programme

The overall aim of the SSC Follow-up Programme, for simplicity the ‘XID Programme’, is to ensure that the potential of the XMM-Newton serendipitous survey can be fully exploited by the astronomical community. The XID Programme is thus designed to maximise its value for a wide range of potential scientific uses of the serendipitous data. In order to ensure the optimum utility of the programme, the results from the SSC XID Programme will enter the public XMM-Newton Science Archive.444The SSC XID Programme is restricted to XMM-Newton data which is in the public domain, i.e. outside the 1-year proprietary period, except for observations where the XMM-Newton observer has given explicit permission for the SSC to commence follow-up work in the proposal for XMM-Newton observations. The value of building a ‘statistically’ identified catalogue of EPIC sources and delivering it to the community is that it will provide large homogeneous samples for studying class properties and to search for rare objects.

The approach planned by the SSC is a programme which brings together the XMM-Newton data themselves, existing catalogue and archival material and new ground-based observational data in an integrated fashion. The main new observational elements, the ‘Core Programme’ and the ‘Imaging Programme’, are outlined below.

### 4.4 The XID Core Programme

The aim of the Core Programme is to obtain the identifications for a well-defined sample of X-ray sources drawn from selected XMM-Newton fields, primarily using optical/IR imaging and spectroscopy. Imaging is required both to locate potential candidates accurately and reveal their morphology, whilst the optical spectroscopy provides the diagnostics needed both for object classification and for determining basic object parameters such as redshift and spectral slope. The principal objective is to obtain a completely identified sample which can be used to characterise the XMM-Newton source population overall sufficiently well that we can use the basic X-ray and optical parameters to assign a ‘statistical’ identification for a large fraction of all the sources in the XMM-Newton serendipitous source catalogue.

The strategy involves two samples: one for the high and one for the low galactic latitude sky. The high galactic latitude sample consists of three subsamples, each containing $`1000`$ X-ray sources in three broad flux ranges: $`f_x>10^{15}`$ ; $`f_x>10^{14}`$; $`f_x>10^{13}\mathrm{erg}\mathrm{cm}^2\mathrm{s}^1`$ in the 0.5-4.5 keV band (see Table 2). The size of the subsamples is dictated by the need to identify enough objects to reveal minority populations. Studying sources at a range of X-ray fluxes is necessary because we already know that the importance of different source populations changes with X-ray flux level. A parallel study is planned for the low galactic latitude sample. Taking into account the difficulty of obtaining completely identified samples close to the Galactic plane, here we aim to identify a sample of $`1000`$ sources above a flux level of $`5\times 10^{15}\mathrm{erg}\mathrm{cm}^2\mathrm{s}^1`$(0.5-4.5 keV), from target fields covering a range of galactic latitudes and longitudes (Table 2). In our programme we also need to minimise bias against any particular X-ray spectral form by recognising flux limits in different X-ray bands. To achieve this, additional soft and hard X-ray selected samples will be included in the programme.

The requirements for the Core Programme are summarised in Table 2. The median optical magnitudes in Table 2 (and the size of the subsamples) illustrate that this is a very demanding programme. For example spectroscopy of the counterparts to the faintest X-ray sources will require access to multi-object spectrographs on 8-10 m class telescopes, and indeed a substantial fraction of counterparts will be inaccessible, whilst even for the sources in the ‘medium’ flux sample access to 4-8 m class telescopes will be needed. For the ‘bright’ sample the situation will be somewhat different in that a large fraction of counterparts will be on existing optical sky survey material (e.g. POSS), and a significant fraction may have likely identifications with catalogued objects, leading to reduced requirements for spectroscopic follow-up.

Taking into account the fact that reaching the faint sample depth requires long XMM-Newton exposures, and that most of these observations are being pursued for surveys by the observation PIs, the current emphasis in the SSC XID programme is on the medium flux sample (and later as the observations become available, on the bright sample) which, although ambitious, is feasible provided access to the necessary ground-based observing facilities is possible.

### 4.5 The Imaging Programme

Whilst the Core Programme focuses on the identification of a selected subsample of XMM-Newton serendipitous sources, the complementary Imaging Programme aims to obtain optical/IR photometry and colours for a large number of XMM-Newton fields. The programme rationale is based on the fact that a combination of X-ray flux & X-ray colours (from the XMM-Newton data) and optical magnitude and optical colours (e.g. from new ground-based observations) will provide the key parameters which make possible an accurate ‘statistical’ identification of the XMM-Newton sources. This will be possible using the results from the Core Programme which characterise the XMM-Newton source populations, thus providing the link, in a statistical sense, between the source identification and these basic parameters.

Multi-colour optical imaging provides good discrimination between object types (e.g. AGN-star separation) as well as photometric redshifts, whilst IR imaging has an important role to play as the counterparts to obscured X-ray sources are expected to also show significant reddening.

The Imaging Programme will primarily be pursued using new optical/IR imaging. To reach R$`2325^\mathrm{m}`$, and K$`20^\mathrm{m}`$, the typical values required for the serendipitous survey follow-up, is within the range of 2-4m class telescopes.555Imaging from the XMM-Newton OM (Mason et al., mason (2001)) will in many cases provide valuable data for the Imaging Programme, in particular by extending the coverage to the UV. Availability of appropriate OM data cannot be guaranteed however, because the choice of OM readout modes, filters etc. are selected by the observation PI.

## 5 XID Programme implementation and first results

The SSC XID Programme started in April 2000 with initial optical and IR imaging and the first spectroscopic data were taken in June 2000. As noted above, the current emphasis of the programme is on the medium flux sample (cf. Table 2). A substantial fraction of the observing time for the current programme was awarded within the Canary Islands International Time Programme (ITP) to a project, known as “AXIS” (An XMM-Newton International Survey, http://www.ifca.unican.es/$``$xray/AXIS) which focuses on the follow-up of the medium flux XID sample and the nature of the hard X-ray source population.

Optical imaging has been obtained for more than 30 XMM-Newton fields using the INT Wide Field Camera and the ESO-MPG 2.2m Wide Field Imager. The Sloan u,g,r,i,z bands have been chosen for optical imaging as these provide significant advantages for the determination of spectroscopic redshifts. Near-IR imaging of a few fields has already been obtained with the INT 2.5m and the CIRSI IR camera in the H band (CIRSI does not offer the K band). For spectroscopy, three short runs have already been completed using the WHT 4.2m with the WYFFOS multi-object spectrograph, the WHT with the ISIS dual-beam spectrograph and with the NOT 2.5m with the ALFOSC spectrograph. The WHT spectroscopy with WYFFOS can reach R$`21^\mathrm{m}`$ and $`22^\mathrm{m}`$ with ISIS. The NOT/ALFOSC spectroscopy concentrated on objects with R$`<18^\mathrm{m}`$.

We have already obtained spectroscopic identifications for $`40`$ XMM-Newton sources in the first few fields studied. These fields include the Mkn 205 field (cf. Fig. 1 and Table 1, we used detections from the combined data of the two exposures), three of the five G21.5$``$0.9 calibration observations (these cover $`0.5`$ sq.deg; cf. Fig. 1 and Table 1 which relate to one of the five observations), and two Guaranteed Time (GT) fields at high galactic latitude. Fig. 4 shows the finding charts and optical spectra of three example identifications made in these fields:

* A $`z=0.33`$ galaxy in the Mkn 205 field showing H$`\beta `$ and \[OIII\] narrow emission lines at $`\lambda \lambda 6466,5803,6595`$Å. Judging by its X-ray luminosity ($`L_X10^{43}\mathrm{erg}\mathrm{s}^1`$) and line ratios this galaxy probably hosts an active nucleus.
* An object at $`z=1.82`$ in a GT field666A field for which SSC follow-up permission was granted by the observation PI. which shows broad emission lines (notably Si IV, C IV, CIII\] & Mg II at $`\lambda \lambda 3939,4365,5381,7890`$Å) with broad blue-shifted absorption troughs to the CIV & CIII\] lines (arrowed in Fig. 4). This thus appears to be a broad absorption line (BAL) quasar. If confirmed this would be one of the first X-ray selected BAL objects so far, such objects being extremely faint at soft X-ray energies (Green & Mathur, green (1996)).
* An object at $`z=2.26`$, in the same field, showing the typical broad emission lines of a quasar. The strongest lines are Ly$`\alpha `$, CIV & CIII\] at $`\lambda \lambda 3959,5040,6212`$Å.

Although it is premature to discuss the results in any detail at this stage, as our programme has yet to accumulate statistically useful samples of identifications, we can nevertheless make some general remarks. In the high galactic latitude fields for which we have spectroscopic data so far, broad-line AGN (15 objects) dominate the total number of identified sources. The other identified objects include 4 narrow emission line galaxies (NELGs; in this context this means extragalactic objects with no obviously broad lines), 1 “normal” galaxy and 3 stars (2 of which are dMe).

As found in previous ROSAT surveys, e.g. Lehmann et al., (lehmann (2000)), all the NELGs are at $`z<0.5`$. Some of these NELGs may actually be obscured AGN, but more thorough analysis and better quality spectra are required to confirm this. Our programme has not yet found an example of a high redshift type II AGN, but this is as expected because we have concentrated on the X-ray and optically brighter objects so far.

In the one low latitude region for which we have spectroscopy so far (the three overlapping G21.5$``$0.9 fields), initial problems in establishing good astrometry for the field led to poorer X-ray source positions. Because of the high star density at low latitudes, this exacerbated the difficulty of selecting optical counterparts. Accordingly our observations to date have concentrated on the brighter optical counterparts. Of the 27 sources observed to date, 11 show clear stellar spectra. Only 3 of these show clear spectroscopic evidence of being active at the current spectroscopic resolution; this highlights the fact that XMM-Newton can detect stars with lower activity. Analysis of the data for the other objects observed is still in progress. Given the current emphasis on the brighter counterparts, it is not surprising that our study has not yet revealed other classes of object, e.g. distant, faint cataclysmic variables or even background AGN which will be both faint and highly reddened.

The XID programme is in the early stages of what is a long-term project. We look forward to realising the potential of the XMM-Newton serendipitous survey over the coming years in what seems likely to be a rich and rewarding programme.

###### Acknowledgements.

It is a pleasure to acknowledge the efforts and dedication of the large team of people who have been essential in developing the SSC, not all of whom are represented as co-authors of this paper. We gratefully acknowledge allocations of telescope time for the public XID programme by ESO, PATT and the CCI for the AXIS project. Mat Page and Ismael Perez-Fournon are thanked for their contribution to the AXIS programme observing. The INT and the WHT are operated on the island of La Palma by the Isaac Newton Group in the Spanish Observatorio del Roque de Los Muchachos of the Instituto de Astrofisíca de Canarias. Support for the SSC project provided by the following agencies: Deutsches Zentrum für Luft- und Raumfahrt (DLR) under grant numbers 50 OR 9908 0 & 50 OX 9701 5; PPARC (UK); CNES (France) and NASA (via the HEASARC). TM thanks the Italian Space Agency (ASI) for financial support. The referee, Thierry Courvoisier, is thanked for his constructive suggestions for improvements to this paper.


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# Polyelectrolyte adsorption

## I Introduction

Polymers are often used as chemical additives to control the stability or tune the viscoelastic properties of colloidal suspensions. In these applications the interaction between polymers and colloidal particles in solution plays a major role. Neutral polymers are mostly used in organic solvents. Their interaction with colloidal particles has been studied in great details, both theoretically and experimentally, and their adsorption behavior is rather well understood . Because polymer additives are often charged in aqueous solvents, it is of great importance to understand quantitatively their interaction with colloidal particles.

In this short review we try to give an overview of the adsorption behavior of charged polymers (polyelectrolytes) on colloidal particles. We focus on the limit where the polymer size is much smaller than the particle size. Hence, it is sufficient to study the adsorption of polyelectrolyte chains on flat surfaces. Although no complete description of polyelectrolyte adsorption exists at present, some important results have recently been obtained using mean-field theory and other approximations. These theoretical results seem to be in good agreement with the experimental observations. One of the points that we would like to highlight is the possibility of surface charge inversion. A charged polymer adsorbing on an oppositely charged surface can overcompensate the original surface charge. Because the polyelectrolyte creates a thin adsorbing layer adjacent to the surface, the overall charge of the surface combined with the adsorbing polymer can have an opposite sign than the original surface charge.

Let us start by considering single chain behavior in a dilute aqueous solution of polyelectrolytes . At this low concentration limit, the polyelectrolyte chains only weakly interact with one another and can be considered as isolated chains dispersed in solution. For simplicity we consider as a reference only neutral polymers in a $`\theta `$ solvent, where the chain conformation obeys Gaussian statistics. The typical radius of a neutral chain of $`N`$ monomers is $`R_0^2=2Nal_0`$ where $`a`$ is the monomer size and $`l_0`$ the persistence length. Charged chains are highly stretched as compared to neutral chains with the same chemical composition but with no dissociated charged groups. The repulsive interaction energy between two charged monomers at a distance $`r`$ can be written as $`v(r)=e^2/4\pi \epsilon r=k_\mathrm{B}Tl_\mathrm{B}/r`$ where $`l_\mathrm{B}=e^2/4\pi \epsilon k_\mathrm{B}T`$ is the Bjerrum length, $`\epsilon `$ is the dielectric constant of the aqueous medium, and $`k_\mathrm{B}T`$ the thermal energy. For water with $`\epsilon 80\epsilon _0`$ and at room temperature, $`ł_\mathrm{B}7`$Å. When salt (electrolyte) is added to the solution, the electrostatic interaction is screened over the Debye length $`\kappa ^1=(8\pi nl_\mathrm{B})^{1/2}`$ where $`n`$ is the salt concentration.

Let us now consider two types of polyelectrolytes: flexible and semi-rigid chains. If the polymer backbone is semi-rigid or if the polymer is highly charged, the main effect of the electrostatic interaction is to increase the persistence length . The effective persistence length due to electrostatic interaction is $`l_\tau =l_0+(\tau ^2l_\mathrm{B})/(4\kappa ^2)`$ where $`\tau =f/a`$ is the charge density per unit length and $`0f1`$ is the fraction of charged monomers on the chain. In the limit of low ionic strength the polymer becomes very stiff and behaves as a rigid rod ($`R=Na`$).

If the polymer backbone is flexible, or the polymer is only weakly charged, the statistics of polymer conformation is Gaussian at small length scales but the chain is stretched at larger length scales. A simple way to describe the chain conformation is shown in Fig. 1 and uses the so-called “electrostatic blob” model . The chain can be viewed as a fully stretched chain of Gaussian subunits (called the electrostatic blobs) of size $`\xi _{\mathrm{el}}a(a/f^2l_\mathrm{B})^{1/3}`$ and each containing $`g`$ monomers. Within each blob the chain segment obeys Gaussian statistics, $`g(\xi _{\mathrm{el}}/a)^2`$. The blob size $`\xi _{\mathrm{el}}`$ is obtained by equating the electrostatic interaction of $`fg`$ charged monomers inside the blob with the thermal energy $`k_\mathrm{B}T`$. The size of the entire chain is then $`RNa^{2/3}(f^2l_\mathrm{B})^{1/3}`$. The crossover between the rigid and the flexible polyelectrolyte behaviors occurs when $`a^2>f^2l_\mathrm{B}l_0`$.

In the remaining of the paper we review the adsorption of flexible and semi-rigid polyelectrolyte chains on planar surfaces. We discuss the adsorption of a single polyelectrolyte chain on a charged surface of opposite charge. Section 3 is devoted to the mean-field theory of multi-chain polyelectrolyte adsorption on a charged surface. We first summarize the results obtained analytically by asymptotic methods and then present some scaling arguments based on numerical studies of the mean-field equations. In section 4, we comment on correlation effects of semi-rigid (rod-like) and charged polymers. The last section is devoted to two specific examples: (i) interactions between surfaces coated by an adsorbed polyelectrolyte layer, and (ii) polyelectrolyte multilayers.

## II Single chain adsorption

In this section we discuss the adsorption of an isolated polymer chain on an oppositely charged surface. First we consider flexible and weakly charged chains and then semi-rigid chains.

### A Flexible and weakly charged chains

When a flexible polyelectrolyte is attracted by an oppositely charged surface with surface charge density (in units of number per unit area) $`\sigma `$, the polymer adsorbs and forms a thin layer of thickness $`\delta `$ adjacent to the surface. This is shown schematically on Fig. 2. The chain thickness results from a balance between the attractive electrostatic interaction and the repulsive confinement force due to the Gaussian chain entropic elasticity . The thickness resulting from the minimization of the adsorbed chain free energy is:

$$\delta =(a^2/f\sigma l_\mathrm{B})^{1/3}$$
(1)
This result is valid at sufficiently large $`\sigma `$ where the thickness $`\delta `$ is smaller than the Gaussian radius $`R_0`$. At lower values of $`\sigma `$, the chain of blobs retains its conformation upon adsorption and is only weakly adsorbed (see Ref.  for more details). Another polymer-surface interaction originates from the dielectric discontinuity between the surface and the aqueous solution. The dielectric discontinuity can be understood in terms of repulsive image charges that cause repulsive interaction at surfaces having a dielectric constant lower than that of the bulk solution. This interaction competes with the adsorption mechanism but is rather weak for moderately high $`\sigma `$ and can be ignored in most situations.

When salt is added to the aqueous solution the electrostatic interaction close to the surface is screened. The conformation of the adsorbed chain does not change as long as the Debye screening length is larger than the thickness, $`\kappa ^1>\delta `$. If the screening length becomes shorter than $`\delta `$, the chain no longer adsorbs . This gives the criterion for adsorption: $`\sigma >\kappa ^3a^2/(f\sigma l_\mathrm{B})`$. The last result can be understood also by considering the screening effect on the free energy of the adsorbing chain.

### B Semi-rigid chains

Using similar arguments it is possible to describe the adsorption of semi-rigid chains on planar surfaces. The force that opposes confinement does not originate from the Gaussian chain elasticity but is due to bending fluctuations of semi-rigid chains . The thickness of the adsorbed chain is

$$\delta =(l_\mathrm{B}\sigma \tau l_{\mathrm{eff}}^{1/3})^{3/5}$$
(2)
The effective persistence length of the chain $`l_{\mathrm{eff}}`$ includes both the electrostatic and the bare bending contributions. The electrostatic contribution to the persistence length does not reduce here to the contribution calculated by Odijk  because the length scales involved in the adsorption can be shorter than the screening length. This is the reason why we introduce here an effective persistence length . This has been discussed in detail in Ref. . When image charge effects are taken into account, the relevant persistence length is always the bare persistence length $`l_0`$. When salt is added, a semi-rigid chain also desorbs when the screening length is of the order of the chain thickness i.e., if $`\sigma <\kappa ^{5/3}/(\tau l_{\mathrm{eff}}^{1/3}l_\mathrm{B})`$.

Although it is difficult to perform experiments for very dilute polyelectrolyte solutions in the bulk, single chain manipulations are possible at surfaces. Conformations of individual adsorbed chains can be probed by pulling a single chain off the surface with the tip of an atomic force microscope (AFM). These experiments measure the interplay between the chain elasticity and the surface-chain electrostatic interaction . The signature of the electrostatic interaction is an increase of the force with the distance from the surface up to distances comparable to the Debye screening length. For larger distances the force profile reaches a plateau.

### C Counterion release

When a strongly charged polyelectrolyte adsorbs on an oppositely charged surface, the counterions that neutralize the chain charges play an important role. Above a critical charge per unit length, $`\tau _c=1/l_\mathrm{B}`$, some of the counterions condense on the polymer and the polyelectrolyte together with the condensed counterions has an effective charge (per unit length) $`\tau _{\mathrm{eff}}`$ lower than its nominal $`\tau `$ value and approximately equal to the critical condensation charge $`\tau _{\mathrm{eff}}\tau _c=1/l_\mathrm{B}`$. This phenomenon is known as counterion or Manning condensation .

When the chain is adsorbing on an oppositely charged surface, the condensed counterions can be released into the solution, because their release leads to a big increase in counterion translational entropy. The corresponding free energy gain can be as large as the direct electrostatic interaction and, thus, is a major driving force for the adsorption. For a semi-rigid polyelectrolytes adsorbing on a flat surface, counterion release has recently been studied . The main result is that a complete counterion release occurs only for very large surface charges.

## III Mean-field theory of polyelectrolyte adsorption

### A The adsorption profile equation

The simplest approach to study the adsorption of a multi-chain polyelectrolyte solution on a solid surface is to use a mean-field theory in analogy to what has been done for the adsorption of neutral polymers . The polymer conformation is calculated in a mean-field potential due to the interactions with the surface and the other polymer chains, $`U(z)`$, and is described by $`\varphi `$, the so-called order parameter. This order parameter is related to the local concentration $`c(z)`$ at a distance $`z`$ from the surface by $`\varphi (z)=\sqrt{c(z)}`$. Next, for long enough chain, $`N1`$, it is possible to employ the ground state dominant approximation. Corrections beyond the ground state dominance are important if the chain tails have important contribution to the adsorption energetics. These corrections are not important when the adsorbing layer is thin and dense, as is the case for polyelectrolytes. The equation governing the order parameter is the standard Edwards equation

$$\frac{a^2}{6}\frac{d^2\varphi }{dz^2}+(U(z)+E)\varphi =0$$
(3)
where $`E`$ is the ground state free energy and can be calculated by equating the polymer chemical potential in the adsorbed layer and in the bulk. The mean-field potential $`U`$ includes both the local electrostatic potential and the excluded volume interaction with the other monomers. For simplicity, we consider here only the case of a $`\theta `$ solvent where the 2nd virial coefficient exactly vanishes $`v=0`$, and write $`U(z)=f\psi (z)+w^2c^2(z)/2`$ where $`w^2`$ is the 3rd virial coefficient for the (repulsive) interactions between monomers, $`c=\varphi ^2`$ is the monomer concentration and $`\psi `$ the rescaled electrostatic potential (in units of $`e/k_\mathrm{B}T`$). We choose the zero of electrostatic potential so that far from the surface, $`\psi =0`$, and discuss the case where the polymer is negatively charged and the surface is positive. The electrostatic potential $`\psi `$ satisfies the Poisson-Boltzmann equation

$$\frac{d^2\psi }{dz^2}=\kappa ^2\mathrm{sinh}\psi +4\pi l_\mathrm{B}f\varphi ^2$$
(4)
The above equation is the Poisson equation relating the Laplacian of the electric potential to the total charge in the system, which is the sum of the small ionic charges (satisfying the Boltzmann distribution) and the polymer charges. In addition, we need to specify the boundary conditions for $`\psi `$ and $`\varphi `$. The electrostatic boundary condition is $`d\psi /dz|_0=4\pi l_\mathrm{B}\sigma `$ because the surface charge density is fixed, and the $`\varphi `$ boundary condition can be expressed in terms of the short range non-electrostatic interactions between the polymer and the surface $`\varphi ^1d\varphi /dz|_0=1/d`$. We note that this boundary condition is often used in problems of polymer adsorption. It conveniently depends only on one parameter $`d`$. The extrapolation length $`d`$ is inversely proportional to the short range interaction between the polymer and the surface. It is positive and of the order of a molecular size if the polymer-surface interaction is attractive and of order $`k_\mathrm{B}T`$ per monomer. The length $`d`$ is negative if the chains are repelled by the surface and it vanishes for an impenetrable surface (a hard wall) where $`\varphi (0)=0`$. We will also consider an indifferent surface for which $`1/d`$ vanishes; it is a surface at the transition between adsorption and depletion (ignoring electrostatic effects).

This set of equations (3)-(4) can be used to calculate the mean field adsorption profiles. The profile equations have been solved either numerically  or using asymptotic analysis. We summarize below the main findings, starting with the case of adsorption on non-charged surfaces.

### B Adsorption on electrically neutral surfaces

We first consider an electrically neutral surface in the limit of very small ionic strength ($`\kappa ^10`$). For example, this can be the case of polyelectrolyte adsorption at liquid-air or liquid-liquid interfaces. The polymer chains are attracted to the surface by non-electrostatic interactions as is parameterized by the length $`d`$, and form a thin layer on the surface. Only a small fraction of the counterions are localized in this layer as can be checked a posteriori. To a good approximation, the electrostatic problem can be solved by considering the dense adsorbed polymer layer by itself as a charged surface with a charge density $`\sigma =f\mathrm{\Gamma }`$, where $`\mathrm{\Gamma }`$ is the monomer surface coverage (per unit area):

$$\mathrm{\Gamma }=[c(z)c_{\mathrm{bulk}}]𝑑z$$
(5)
The electrostatic potential is obtained by solving the standard Gouy-Chapman problem for the counterion charge density in presence of a charged surface. At length scales smaller or comparable with the adsorbed layer thickness, the electrostatic potential $`\psi =2\mathrm{log}(\kappa \lambda _{\mathrm{GC}})/2`$ is constant, where the Gouy-Chapman length is defined as $`\lambda _{\mathrm{GC}}=1/(2\pi l_\mathrm{B}\sigma )=1/(2\pi l_\mathrm{B}f\mathrm{\Gamma })`$.

Close to the surface, the excluded volume interaction dominates and the monomer concentration decays as a power law

$$c(z)1/(z+d/2)$$
(6)
The electrostatic potential creates a strong barrier against adsorption that starves the adsorbed layer and reduces the adsorption when the charge of the polymer increases. At large distances (though smaller than $`\lambda _{\mathrm{GC}}`$), the concentration decays exponentially $`c(z)\mathrm{exp}(2z/\delta _n)`$ where the layer thickness is $`\delta _n=a/\sqrt{6f\psi }`$. Because $`\mathrm{\Gamma }a^2`$, the thickness is indeed much smaller than the Gouy-Chapman length and the counterions are not localized inside the adsorbed polymer layer in consistent with our assumptions. The strong adsorption limit requires that $`\delta _n>d`$. This indeed fixes the minimum strength of the attractive short range potential. Note also that the adsorption on a charged surface having the same sign as the polymer charge can be treated in a similar way, but then the effective charge of the surface is $`f\mathrm{\Gamma }+\sigma `$.

### C Adsorption on oppositely charged surfaces: charge inversion

When the polymer adsorbed on a charged surface with an opposite charge, and in the limit of low ionic strength, the polymer essentially neutralizes the charge of the surface or even slightly overcompensates it. The effective charge of the surface coated by the adsorbed polymer layer is low and, as a first approximation, the Poisson-Boltzmann equation can be linearized. The polymer forms a very thin and dense adsorbing layer on the surface almost free of counterions. An asymptotic expansion of the mean-field equations can be carried out  ignoring the role of the counterions in the adsorbed layer. If the surface charge is low, excluded volume interactions are negligible and the thickness of the adsorbed layer remains comparable with the thickness of a single adsorbed chain, $`\delta `$, given by eq. 1. The polymer charge always overcompensates the surface charge by a small amount, $`\mathrm{\Delta }\sigma /\sigma \kappa \delta (1+\delta ^2/\xi _{\mathrm{el}}^2)`$, where the overcharging is defined as $`\mathrm{\Delta }\sigma =f\mathrm{\Gamma }\sigma `$.

At higher values of the surface charge, $`\sigma >\sigma _cf`$, excluded volume becomes important and the thickness $`\delta _{\mathrm{ev}}`$ of the adsorbed layer increases with the surface charge $`\delta _{ev}\xi _{\mathrm{el}}^2/\delta `$. In this regime as well, the surface charge is weakly overcompensated. In the limit of high ionic strength, the electrostatic interaction is short range and essentially contributes to the excluded volume interaction. The properties of the adsorbed layer strongly depend on the short range interaction between the polymer and the surface. If the adsorbing surface is an ideal impenetrable surface (with no other interactions), there is no adsorption just like the case for a single chain. If the surface is indifferent, i.e., if the short range attraction exactly compensates the impenetrable surface repulsion yielding $`1/d=0`$, the overcompensation can be quite large, $`\mathrm{\Delta }\sigma =2\sigma `$.

Numerical studies of the mean-field equation allow an explicit calculation of the polymer concentration profiles. In Ref.  polyelectrolyte adsorption is investigated using different boundary conditions from the one discussed above. The results are interpreted in terms of scaling laws. The polymer concentration was fixed to be zero on the surface, which effectively means that the adsorption length $`d`$ vanishes. The electrostatic boundary condition is chosen to be either a fixed surface potential $`\psi _s=const`$ or a fixed surface charge $`\sigma =const`$. The numerical results  for different surface boundaries, different monomer size and polymer charge indicate that, to a good approximation, the adsorption can be characterized by a single adsorption length scale, $`D`$.

For low salt concentration, $`D\kappa ^1`$ and for a constant $`\psi _s`$,

$$Df^{1/2}\psi _s^{1/2}$$
(7)
In this limit, $`\psi _s\sigma Dl_B`$, and these results are in agreement with the asymptotic analysis discussed above, $`D\delta `$. The polymer surface excess $`\mathrm{\Gamma }`$ can also be obtained by scaling arguments and is equal to

$$\mathrm{\Gamma }\psi _s^{3/2}f^{1/2}\sigma f^1$$
(8)
The asymptotic analysis predicts in this case a weak charge inversion, which is consistent with this scaling result. The overcompensation is observed numerically by calculating the electrostatic potential which is non monotonic. Namely, at some distance from the surface the electric field is zero: $`d\psi /dz=0`$.

In high salt conditions, the salt screens all electrostatic interactions including the repulsive monomer-monomer interactions and the attractive surface-monomer interactions. The characteristic size of the adsorbed polyelectrolyte layer $`D`$ now depends on $`\kappa `$,

$$D\frac{\kappa }{f\psi _s}$$
(9)
Using the appropriate relation between $`\psi _s`$ and $`\sigma `$: $`\psi _s\sigma l_B/\kappa `$, the scaling with $`\sigma `$ is

$$D\frac{\kappa ^2}{f\sigma }$$
(10)
Because of the Debye screening, the electrostatic interaction generates an electrostatic contribution to the 2nd virial coefficient $`v_{\mathrm{elec}}f^2\kappa ^2`$ even when the solvent is a $`\theta `$ solvent. For large enough values of the polymer charge $`f`$, the surface excess is

$$\mathrm{\Gamma }\frac{\kappa \psi _s}{f}\frac{\sigma }{f}$$
(11)
At high salts, the overcompensation is not universal and strongly depends on the system parameters such as $`d`$. It is thus difficult to compare the numerical results to the asymptotic results presented above in very specific conditions. One of the ways to cause overcompensation is to change the solvent quality. For a polymer in a good solvent, the overcompensation increases with the excluded volume parameter $`v`$ (the 2nd virial coefficient). For $`vv_{\mathrm{elec}}`$ a strong overcompensation is expected. This indeed was obtained in Ref.  from the numerical solution of the profile mean-field equations.

### D Adsorption from dense solutions

The structure of an adsorbed polyelectrolyte layer strongly depends on the concentration of the bulk solution. The main feature of semi-dilute or dense solutions is that the structure factor $`S(q)`$ has a strong peak at a wavenumber $`q^{}>0`$ indicating that concentration fluctuations decay in an oscillatory manner. Any perturbation of the otherwise homogeneous solution creates a spatial modulation in the polymer concentration profile with a period $`2\pi /q^{}`$. This phenomenon also manifests itself for adsorbing polyelectrolytes. Damped oscillations of the concentration profile have been explicitly calculated in  using a Debye-Hückel (linearized) theory and treating the adsorbing surface as a perturbation. The modulations exist at weak ionic strength, while the concentration profile becomes monotonically decreasing for large ionic strength, ($`\kappa >q^{}`$). It is conceivable to assume that these damped oscillations occur also beyond the validity of the linear Debye-Hückel regime. They can be related to oscillatory forces measured in thin film balance with soap films containing polyelectrolytes .

## IV Adsorption of semi-rigid polyelectrolytes: correlation effects

The main assumption of mean-field theory is that only the average concentration is treated while neglecting concentration fluctuations. Because electrostatic interactions between adsorbed chains are very strong, they can lead to pronounced correlations. In particular, it is important to consider concentration fluctuations in the direction parallel to an adsorbing surface. A general treatment of concentration fluctuations is not yet available for flexible chains. For semi-rigid polymers, a rough approximation is to assume that semi-rigid polyelectrolytes adsorbed on a surface of opposite charge form a perfect two-dimensional smectic phase where the all the rods are parallel to one of the surface directions and equally spaced in the other direction . A large charge overcompensation is found under certain ionic strength conditions. The total adsorbed polymer charge is $`f\mathrm{\Gamma }=\tau \kappa /\mathrm{log}(\tau \sigma ^1\kappa )`$. Charge inversion is thus found at large enough ionic strength for $`\tau \kappa >\sigma `$. This model has been extended to highly charged polymers taking into account counterion condensation by Shklovskii and collaborators .

For weakly charged polyelectrolytes, concentration fluctuations certainly play an important role and the chains adsorbed on the surface can similarly show a smectic or nematic order. A model where the flexible polymers are treated as rods formed by blobs of chains is presented in Ref. . The main result is a strong charge overcompensation obtained in the intermediate ionic strength regime.

## V concluding remarks

We have described in this short review some of the basic properties of polyelectrolytes adsorbing on planar surfaces at thermodynamic equilibrium. Assuming that the system is in thermodynamic equilibrium is certainly a strong assumption. The electrostatic interaction between chains is strong and the relaxation towards the equilibrium state may be very slow in certain experiments. The adsorbed polyelectrolyte layer can then be trapped in a metastable state. A non equilibrium theory taking into account adsorption kinetics is needed to understand these experiments. We hope that it will be addressed in future works.

Because polyelectrolyte adsorption is of great importance in more complex situations, we would like to briefly discuss two types of experimental setups. In the first the interactions between surfaces (or large colloidal particles) is mediated by polyelectrolytes, whereas in the second a multilayered adsorption of alternating positive and negative polyelectrolytes is considered.

### A Polyelectrolyte adsorption and inter-colloidal forces

The interactions between two planar surfaces coated by polyelectrolytes have been studied using a mean-field approach and scaling arguments by Borukhov et al. . Within mean-field theory, a general contact theorem can be obtained and leads to an expression for the inter-surface force in this system. The force is calculated numerically from polyelectrolyte profiles and analytically, in some limits. The principal result shows that overcompensation of surface charges by the polyelectrolyte can lead to effective attraction between two equally charged surfaces.

At low salt concentration, depicted on Fig. 3, strong repulsion between the two surfaces results from depletion of the polyelectrolyte from the inter-surface gap at short separations. At larger separations when the two polyelectrolyte adsorbing layers on each of the surface have a strong overlap, the inter-surface force becomes attractive. The magnitude of this attraction scales as $`f^{1/2}`$ and its characteristic length scale scales as $`l_0/f^{1/2}`$. At large inter-surface separations the two surfaces interact only via weak electrostatic repulsion.

At high salt concentration and for highly charged polyelectrolyte $`f1`$, the polymer contribution to the attraction at short distances scales as $`f/\kappa `$ and the characteristic length scale is $`\kappa l_0^2/f`$. An example is shown on Fig. 4. In the other limit of weakly charged polyelectrolytes, $`f1`$, the interaction is repulsive for all surface separations and decays exponentially with a decay length equal to $`\kappa ^1`$.

It is worth mentioning that irreversible effects play an important role on inter-surface forces because of very slow kinetics in the process of polyelectrolyte adsorption. In many situations it is a good approximation to consider that the surface excess of adsorbed polyelectrolytes remains constant as the distance between the two plates is varied. In Ref.  it was shown that attractive forces can be obtained for irreversible adsorption and that their magnitude is larger than the ones corresponding to equilibrium processes.

### B Polyelectrolyte multilayers

Polyelectrolyte multilayers are obtained by consecutive adsorption of positively and negatively polyelectrolytes either on a flat surface or on a colloidal particle . If the process is initiated from a charged planar surface, the surface charge can be inverted by adsorption of the first polyelectrolyte layer (of opposite charge) as discussed in the previous sections. The second polyelectrolyte layer is bound to the first layer by polyelectrolyte complexation. A simple Debye-Hückel model has recently been proposed in Ref. . This model predicts charge inversion after adsorption of the second layer, and allows the built-up of alternating positively and negatively charged polyelectrolyte layers by successive complexations. The Debye-Hückel approach is a high temperature approximation which ignores strong association between ions. An alternative approach considering explicitly the formation of ion pairs has recently been proposed by Zeldovich and Khokhlov .

###### Acknowledgements.

One of us (DA) would like to acknowledge financial support from the Israel Science Foundation founded by the Israel Academy of Sciences and Humanities — centers of Excellence Program and the US–Israel Binational Science Foundation (BSF) under grant no. 98-00429.

## FIGURE CAPTIONS

* Fig. 1 A polyelectrolyte is represented as a rod-like chain of electrostatic blobs. Inside each blob of size $`\xi `$, the chain obeys Gaussian statistics. The chain length is $`R`$.
* Fig. 2 A chain adsorbed on a flat solid surface is schematically drawn. The adsorption length is $`\delta `$.
* Fig. 3 Inter-surface interactions for a polyelectrolyte solution between two surfaces held at a constant potential, $`\psi _s=2`$, and in low salt condition, $`n=10^6`$ M. (a) The surface free energy $`2\pi \mathrm{\Delta }F`$ as a function of the inter-surface separation $`w`$. (b) The force per unit area $`\mathrm{\Pi }=\mathrm{\Delta }F/w`$ between the two surfaces as a function of the separation $`w`$. The different curves correspond to different polymer charge: $`f=1`$ (solid curve) and $`f=0.2`$ (dashed curve). Adapted from Ref. .
* Fig. 4 Inter-surface interactions for highly charged polyelectrolytes ($`f=1`$) at high salt concentration. (a) The surface free energy $`2\pi \mathrm{\Delta }F`$ as a function of the inter-surface separation $`w`$. (b) The force per unit area $`\mathrm{\Pi }=\mathrm{\Delta }F/w`$ between the two surfaces as a function of the separation $`w`$. The salt concentration is $`n=0.1`$ M (solid curve) and $`n=1`$ M (dashed curve). The inset shows the mid-plane values of the electrostatic potential $`y(0)=\psi (w/2)`$ as a function of $`w`$. Adapted from Ref. .


text:
# Oxygen line formation in 3D hydrodynamical model atmospheres

## 1. Introduction

Besides being relatively common, oxygen has attracted a great deal of attention due to its special role in galactic and stellar evolution. The ratio \[O/Fe\] at different cosmic epochs give important insight to the formation and evolution of the Galaxy, as well as constraining the physics of supernovae. Oxygen can also significantly influence stellar evolution and is crucial for the production of the light elements Li, Be and B through cosmic ray spallation. Following the first indication of an oxygen over-abundance relative to iron in metal-poor stars, a great number of studies have been devoted to quantifying this enhancement but with little concordance. The forbidden \[O i\] line at 630.0 nm in metal-poor giants suggest a nearly flat plateau at \[O/Fe\] $`0.5`$ for \[Fe/H\] $`<1.0`$ while the O i triplet at 777 nm in dwarfs tend to imply systematically higher values, often with a monotonic increase towards lower metallicities. Recently, Israelian et al. (1998) and Boesgaard et al. (1999) have analysed the UV OH lines down to \[Fe/H\] $`3.3`$ and have found a linear trend in \[O/Fe\] vs \[Fe/H\] with a slope of about -0.4, in stark conflict with the \[O i\] results. All oxygen criteria have their pros and cons, which influence the conclusions. Of particular interest is the possible systematic errors introduced by the inherent assumptions behind the 1D model atmospheres employed in the analyses of the various O diagnostics. Significant progress in this respect has recently been accomplished with the construction of 3D stellar convection simulations (e.g. Stein & Nordlund 1998; Asplund et al. 1999, 2000a). The aim of the present investigation is to study the impact of such improved models on oxygen line formation.

## 2. 3D hydrodynamical model atmospheres and line formation

Realistic ab-initio 3D, time-dependent simulations of stellar surface convection form the foundation for the present study. The same incompressible radiative hydrodynamical code which previously has been applied successfully to studies of solar and stellar granulation (e.g. Stein & Nordlund 1998; Asplund et al. 1999, 2000a) have here been used to construct sequences of 3D model atmospheres. Special care have been taken to include the most appropriate input physics in terms of equation-of-state, opacities and line-blanketing. Further details on the numerical procedures may be found in the above-mentioned references.

The 3D model atmospheres differ from classical 1D models both in their average photospheric structures and through the presence of temperature inhomogeneities and convective flows, which all influence the spectral line formation (e.g. Asplund et al. 2000a,b). In particular for metal-poor stars, the 3D simulations differ radically from 1D model atmospheres (Asplund et al. 1999). Due to the dominance of adiabatic cooling over radiative heating in the optically thin layers, very low temperatures are encountered in the metal-poor simulations compared with the 1D radiative equilibrium expectations. As a result, the 3D models have a profound impact on the line formation of in particular low-excitation lines of minority species and molecular lines, such as Li i and OH.

## 3. Impact on O abundances in metal-poor stars

Since essentially all of O is in the ground state of O i and the \[O i\] line formation is very well described by LTE, the influence of 3D models on the \[O i\] line is minor. As a consequence, the \[O/Fe\] plateau appears robust, provided high $`S/N`$ spectra and Fe ii lines are employed (Fig. 1 and Nissen et al., in preparation).

Kiselman (these proceedings) has given convincing arguments that the O i triplet suffers from departures from LTE. The O i line formation has therefore been investigated through detailed 3D non-LTE calculations for the Sun and HD 140283 (\[Fe/H\] $`=2.5`$) using multi3d (Botnen 1997) and an extensive 23-level O model atom. Very similar non-LTE abundance corrections to the 1D non-LTE results (Kiselman 1993) are found, typically 0.2 dex with only a minor metallicity dependence. Thus, 3D models will unlikely provide a mean to bring down the \[O/Fe\] trend to plateau-like values (Fig. 2).

The low atmospheric temperatures in the metal-poor 3D models become very apparent in the OH line strengths. Since molecular formation is extremely temperature sensitive ($`N_{\mathrm{OH}}T^{12\mathrm{}14}`$), 1D model atmospheres are bound to severely underestimate the OH line strengths, and consequently overestimate the O abundances at low metallicities (Fig. 2). The here presented 3D LTE OH analysis therefore casts doubts on recent claims of large O over-abundances in metal-poor stars. The OH line formation is studied further in Asplund & García Pérez (2000).

## 4. Conclusions

The new generation of 3D hydrodynamical model atmospheres has a dramatic impact on in particular the OH line formation in metal-poor stars. Caution must, however, be exercised in interpreting these 3D findings in terms of galactic cosmic evolution until detailed 3D non-LTE calculations for the OH molecular formation and line formation have been performed.

### Acknowledgments.

The author greatly appreciates very stimulating collaborations with among others M. Carlsson, A.E. García Pérez, D. Kiselman, D.L. Lambert, P.E. Nissen, Å. Nordlund and F. Primas.

## References

Asplund M., et al., 1999, A&A 346, L17

Asplund M., et al., 2000a, A&A 359, 729

Asplund M., et al., 2000b, A&A 359, 743

Asplund M., García Pérez A.E., 2000, submitted to A&A

Boesgaard A.M., et al., 1999 AJ 117, 492

Botnen A.V., 1997, Cand. Sci. thesis, University of Oslo

Israelian G., et al., 1998, ApJ 507, 805

Stein R.F., Nordlund Å., 1998, ApJ 499, 914


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# John Bell’s Observations on the Chiral Anomaly and Some Properties of Its Descendants

## 1 John Bell and the Chiral Anomaly

I expect that most everyone in this audience knows that John Bell codiscovered the mechanism of anomalous symmetry breaking in quantum field theory. Indeed, our paper on this subject  is his (and my) most-cited work. The symmetry breaking in question is a quantum phenomenon that violates the correspondence principle; it arises from the necessary infinities of quantum field theory. Over the years it has become evident that theoretical/mathematical physicists are not the only ones to acknowledge this effect. Nature makes fundamental use of the anomaly in at least two ways: the neutral pion’s decay into two photons is controlled by the anomaly  and elementary fermions (quarks and leptons) arrange themselves in patterns such that the anomaly cancels in those channels to which gauge bosons – photon, W, Z – couple . (There are also phenomenological applications of the anomaly to collective, as opposed to fundamental, physics – for example, to edge states in the quantum Hall effect.) Beyond physics, in mathematics one finds closely related structures, such as Atiyah-Singer index theory, zero modes of Dirac operators, Chern-Pontryagin characteristics of gauge fields, Chern-Simons secondary characteristics. The mathematical ideas were developed at nearly the same time as the physical ones, and this unexpected conjunction between physics and mathematics seeded joint activity that flourishes to this day.

Once it was appreciated that the anomaly is not merely an obscure pathology of quantum field theory, but reflects an as-yet-to-be-understood wrinkle in the field-theoretic description of Nature, many people wrote many papers providing various and alternative derivations of the result. But not John Bell. It seems that all he had to say on the subject was contained in our first joint paper. He did follow the subsequent developments and elaborations, and he commented on them to me whenever we met in Geneva or Cambridge.

In his characteristically diffident manner, he did not always support the various fancy elaborations, and he remained skeptical about their value. On the contrary, he insisted on one statement, which already appeared in our original paper, but which perhaps had not been forcefully enunciated, so I want to call attention to it here.

Our original analysis concerns the correlation function for three currents – one axial vector and two vector currents – which is given in lowest order by the fermionic triangle graph. With massless fermions, this correlation function should be transverse in all three channels, the axial vector and both vectors, as a consequence of various symmetries in the theory. The anomaly manifests itself in that any evaluation of the relevant diagram is ambiguous up to a local term, owing to the underlying infinities of the quantum field theory. Moreover, no matter how one fixes the ambiguity, the transversality conditions fail – the calculated amplitude is not transverse in all three channels. Thus the full extent of symmetry, which would ensure full transversality, is broken. While specific choices for resolving the ambiguity allow transversality in some (but not all three) channels, John Bell always insisted that there is no intrinsic way to select a “correct” result. And this opinion informed his criticism of alternative derivations of the anomaly, which usually preserve vector transversality at the expense of axial vector transversality. Whenever we discussed yet another new approach to the anomaly, he always wanted to verify that there remained the possibility of obtaining a variety of results. If this freedom were not present, he would dismiss the rederivation as too restrictive.

One alternative viewpoint did appeal to John Bell. The lack of transversality in a particular channel can be ascribed to an anomalous nonconservation of the appropriate “symmetry” current, with the nonvanishing anomalous current divergence determined by the gauge fields with which the fermions interact. But from another perspective, one could state that transversality fails because the commutators between the relevant current operators differ from the corresponding Poisson brackets of their classical antecedents – the commutators contain additional, quantal (anomalous) contributions. (Indeed, this is the point of view one must adopt in the interaction picture, where operator equations do not see the interaction.) The form for the anomalous commutators is uniquely determined by the triangle graph, yet the transversality conditions retain their ambiguity, because they continue to reflect the arbitrariness in the local contribution to the graph. This gives an appealing algebraic characterization of the anomaly . Either point of view signals absence of the expected symmetries and exposes a breakdown of the correspondence principle.

John Bell’s insistence that the triangle graph supports a variety of anomalies is not merely a pedantic nicety. In fact it has a physical realization in Gerard ’t Hooft’s calculation of fermion-number nonconservation in the standard model , where the vectorial fermion number current in the triangle graph carries the anomaly, and the chiral current is anomaly free .

## 2 Descendants of the Anomaly

The axial anomaly, that is, the departure of transversality of the 3-fermion current correlation function, involves $`{}_{}{}^{}FF`$, an expression constructed from the gauge fields to which the fermions couple. Specifically, in the Abelian case one encounters

$${}_{}{}^{}F_{}^{\mu \nu }F_{\mu \nu }=\frac{1}{2}\epsilon ^{\mu \nu \alpha \beta }F_{\mu \nu }F_{\alpha \beta }=4𝑬𝑩$$
(1)
where $`F_{\mu \nu }`$ is the covariant electromagnetic tensor

$$F_{\mu \nu }=_\mu A_\nu _\mu A_\nu $$
(2a)
while $`𝑬`$ and $`𝑩`$ are the electric and magnetic fields
$$E^i=F^{io},B^i=\frac{1}{2}\epsilon ^{ijk}F_{jk}.$$
(2b)
The non-Abelian generalization reads

$${}_{}{}^{}F_{}^{\mu \nu a}F_{\mu \nu }^a=\frac{1}{2}\epsilon ^{\mu \nu \alpha \beta }F_{\mu \nu }^aF_{\alpha \beta }^a$$
(3)
where $`F_{\mu \nu }^a`$ is Yang-Mills gauge field strength

$$F_{\mu \nu }^a=_\mu A_\nu ^a_\nu A_\mu ^a+f^{abc}A_\mu ^bA_\nu ^c$$
(4)
and $`a`$ labels the components of the gauge group, whose structure constants are $`f^{abc}`$.

The quantity $`{}_{}{}^{}FF`$ is topologically interesting. Its integral over 4-space is quantized, and measures the topological class (labeled by integers) to which the vector potential $`A`$ belongs. Consequently, the 4-volume integral of $`{}_{}{}^{}FF`$ is a topological invariant and we expect that, as befits a topological invariant, it should be possible to present $`{}_{}{}^{}FF`$ as a total derivative, so that its 4-volume integral becomes converted by Gauss’ law into a surface integral, sensitive only to long distance, global properties of the gauge fields. That the total derivative form for $`{}_{}{}^{}FF`$ holds is seen when $`F_{\mu \nu }`$ is expressed in terms of potentials. In the Abelian case, we use (2a) and find immediately

$$\frac{1}{2}{}_{}{}^{}F_{}^{\mu \nu }F_{\mu \nu }=_\mu \left(\epsilon ^{\mu \alpha \beta \gamma }A_\alpha _\beta A_\gamma \right).$$
(5)
For the non-Abelian fields, (4) establishes the desired result:

$$\frac{1}{2}{}_{}{}^{}F_{}^{\mu \nu a}F_{\mu \nu }^a=_\mu \epsilon ^{\mu \alpha \beta \gamma }\left(A_\alpha ^a_\beta A_\gamma ^a+\frac{1}{3}f^{abc}A_\alpha ^aA_\beta ^bA_\gamma ^c\right).$$
(6)
The quantities whose divergence gives $`{}_{}{}^{}FF`$ are called Chern-Simons terms. By suppressing one dimension they become naturally defined on a 3-dimensional manifold (they are 3-forms), and we are thus led to consider the Chern-Simons terms in their own right :

$`\mathrm{CS}(A)`$ $`=\epsilon ^{ijk}A_i_jA_k`$ (Abelian) (7)
$`\mathrm{CS}(A)`$ $`=\epsilon ^{ijk}\left(A_i^a_jA_k^a+\frac{1}{3}f^{abc}A_i^aA_j^bA_k^c\right)`$ (non-Abelian). (8)
The 3-dimensional integral of these quantities is again topologically interesting. When the non-Abelian Chern-Simons term is evaluated on a pure gauge, non-Abelian vector potential

$$A_i=g^1_ig$$
(9)
the 3-dimensional volume integral of $`\mathrm{CS}(g^1g)`$ measures the topological class (labeled by integers) to which $`g`$ belongs. The integral in the Abelian case – the case of electrodynamics – is called the magnetic helicity $`\mathrm{d}^3r𝑨𝑩`$, $`𝑩=\mathbf{}\times 𝑨`$, and measures the linkage of magnetic flux lines. An analogous quantity arises in fluid mechanics, with the local fluid velocity $`𝒗`$ replacing $`𝑨`$, and the vorticity $`𝝎=\mathbf{}\times 𝒗`$ replacing $`𝑩`$. Then the integral $`\mathrm{d}^3r𝒗𝝎`$ is called kinetic helicity .

I shall not review here the many uses to which the Chern-Simons terms, Abelian and non-Abelian, introduced in , have been put. The applications range from the mathematical characterization of knots to the physical description of electrons in the quantum Hall effect , vivid evidence for the deep significance of the Chern-Simons structure and of its antecedent, the chiral anomaly.

Instead I pose the following question: Can one write the Chern-Simons term as a total derivative, so that (as befits a topological quantity) the spatial volume integral becomes a surface integral. An argument that this should be possible is the following: The Chern-Simons term is a 3-form on 3-space, hence it is maximal and its exterior derivative vanishes because there are no 4-forms on 3-space. This establishes that on 3-space the Chern-Simons term is closed, so one can expect that it is also exact, at least locally, that is, it can be written as a total derivative. Of course, such a representation for the Chern-Simons term requires expressing the potentials in terms of “pre-potentials”, since the formulas (7), (8) show no evidence of derivative structure. \[Recall that the total derivative formulas (5), (6) for the axial anomaly also require using potentials to express $`F`$.\]

There is a physical, practical reason for wanting the Abelian Chern-Simons term to be a total derivative. It is known in fluid mechanics that there exists an obstruction to constructing a Lagrangian for Euler’s fluid equations, and this obstruction is just the kinetic helicity $`\mathrm{d}^3r𝒗𝝎`$, that is, the volume integral of the Abelian Chern-Simons term, constructed from the velocity 3-vector $`𝒗`$. This obstruction is removed when the integrand is a total derivative, because then the kinetic helicity volume integral is converted to a surface integral by Gauss’ theorem. When the integral obtains contributions only from a surface, the obstruction disappears from the 3-volume, where the fluid equation acts .

It is easy to show that the Abelian Chern-Simons term can be presented as a total derivative. We use the Clebsch parameterization for a 3-vector

$$𝑨=\mathbf{}\theta +\alpha \mathbf{}\beta .$$
(10)
This nineteenth-century parameterization of the a 3-vector $`𝑨`$ in terms of the prepotentials ($`\theta `$, $`\alpha `$, $`\beta `$) is an alternative to the usual transverse/longitudinal parameterization. In modern language it is a statement of Darboux’s theorem that the 1-form $`A_i\mathrm{d}r^i`$ can be written as $`\mathrm{d}\theta +\alpha \mathrm{d}\beta `$ . With this parameterization for $`𝑨`$, one sees that the Abelian Chern-Simons term is indeed a total derivative:

$`\mathrm{CS}(A)`$ $`=\epsilon ^{ijk}A_i_jA_k`$ (11)
$`=\epsilon ^{ijk}_i\theta _j\alpha _k\beta `$
$`=_i\left(\epsilon ^{ijk}\theta _j\alpha _k\beta \right).`$
When the Clebsch parameterization is employed for $`𝒗`$ in the fluid dynamical context, the situation is analogous to the force law in electrodynamics. While the Lorentz equation is written in terms of field strengths, a Lagrangian formulation needs potentials from which the field strengths are reconstructed. Similarly, Euler’s equation involves the velocity vector $`𝒗`$, but in a Lagrangian for this equation the velocity must be parameterized in terms of the prepotentials $`\theta `$, $`\alpha `$, and $`\beta `$.

In a natural generalization of the above, one asks whether a non-Abelian vector potential can also be parameterized in such a way that the non-Abelian Chern-Simons term (8) becomes a total derivative. We have answered this question affirmatively and we have found appropriate prepotentials that do the job , but the details of the construction are too technical to be presented here. We hope that our non-Abelian generalization of the Clebsch parameterization will be as interesting and useful as the Abelian one.


text:
# Detection of Excess Hard X-ray Emission from the Group of Galaxies HCG62

## 1. Introduction

Clusters of galaxies are thought to have released a large amount of dynamical energy in their initial collapse phase. During their subsequent evolution, starburst-driven winds, cluster mergers, radio galaxies, and random galaxy motions may have supplied additional heating energy to the intracluster space. Presumably, these processes have generated energetic particles (e.g. Kang et al. (1996); Takizawa (2000)), as evidenced by diffuse synchrotron radio emission from some clusters.

Such energetic particles are expected to produce nonthermal X-rays as well, by Compton-boosting cosmic microwave background (CMB) photons. Long searches for such effects among galaxy clusters have recently revealed two candidates; the excess soft X-ray emission detected with EUVE (Lieu et al., 1996; Mittaz et al., 1998; Bowyer & Berghofer, 1998), and the spectral hard X-ray tail observed with BeppoSAX (Fusco-Femiano et al., 1999; Kaastra et al., 1999). However, the exact nature of these emission components remain unclear.

Groups of galaxies are the poorest class of galaxy clusters. Their thermal emission is limited to energies below $`5`$ keV, because the temperature of their hot intragroup medium is about 1 keV (e.g. Mulchaey et al. (1996); Fukazawa et al. (1996)). Therefore, they allow us to search for nonthermal X-ray emission, even with instruments operating below an energy of $`10`$ keV. Here we report the detection of excess hard X-ray emission from the group of galaxies HCG62 with the ASCA GIS (Ohashi et al., 1996; Makishima et al., 1996). We employ 90% confidence limits throughout this paper, and use the Hubble constant of 50 km s-1 Mpc-1. Solar abundances refer to Anders & Grevesse (1989).

## 2. Observations and Data Reduction

With a redshift of 0.0137 (Hickson et al., 1988), HCG62 is one of the nearest Hickson compact galaxy groups. It was observed twice with ASCA ; on 1994 January 14–15 in a single pointing, and on 1998 January 13–17 in 4 pointings to cover the whole group region. The GIS was operated in PH mode, and the SIS in 2CCD FAINT mode in 1994. We do not use the SIS data taken in 1998, because of the insufficient field of view of 1 CCD mode employed at that time. After an appropriate gain correction, we co-added all the available data from different sensors, chips, and pointings, separately for the GIS and the SIS. The livetime is $`30`$ ksec for the 1994 observation, and $`20`$ ksec for each of the 4 pointings of the 1998 observation. The total GIS livetime thus amounts to 110 ksec.

For our purpose, it is important to accurately subtract the GIS background, which consists of cosmic X-ray background (CXB) and intrinsic detector background (IDB). We first summed data of the ASCA Large Sky Survey (Ueda et al., 1999), conducted in 1993 December and 1994 June over blank sky fields, with a total exposure time of 233 ksec. Then, after Ikebe (1995), we excluded regions in the GIS images where count rate exceeds those from surrounding regions by $``$2.5$`\sigma `$. This eliminates faint sources with the 2–10 keV flux $`>8\times 10^{14}`$ erg s-1 cm-2.

We next corrected the IDB level of each pointing individually for its gradual increase by 2–3% per year, and for its random day-by-day fluctuation by 6–8% (Ishisaki et al., 1997). For this purpose, we derived three GIS spectra, denoted $`S(E)`$, $`B(E)`$, and $`N(E)`$, from the on-source data, the blank sky data prepared as above, and night earth data, respectively. They were accumulated over an annulus of radius $`13^{}25^{}`$ from the GIS field center and in the 6–10 keV energy range, to ensure that $`S(E)`$ is free from the HCG62 emission, and that the CXB is relatively minor compared to the IDB in $`S(E)`$ and $`B(E)`$. Then, assuming that the IDB spectrum and its radial profile are both constant, we fitted $`S(E)`$ with a linear combination $`B(E)+fN(E)`$; here $`f`$ is a free parameter, and $`fN(E)`$ represents the secular IDB change between the two epochs when $`S(E)`$ and $`B(E)`$ were acquired. We have obtained $`f=0.00`$ and $`f=0.080.12`$ for the 1994 data and those of 1998, respectively, in agreement with the IDB long-term increase (Ishisaki et al., 1997). By analyzing various ASCA data, we also confirmed that this method can reproduce, to within 5%, the GIS background spectra and its radial profiles acquired at any epoch over 1993–1999.

The SIS has a lower efficiency in the hard X-ray band, a shorter exposure time, and a smaller field of view, than the GIS. We therefore utilize the SIS spectrum only to determine the soft thermal emission from the intragroup medium. We subtract the SIS background in a conventional way, utilizing the archival SIS background set.

## 3. Results

To avoid the diffuse thermal emission with a typical plasma temperature of $`kT1.0`$ keV (Ponman et al., 1993; Fukazawa et al., 1998; Davis et al., 1999), we produced the GIS image of HCG62 in the hard 4.5–8 keV band, as shown in figure 1. There, we overlaid the 1.0–2.4 keV image as a measure of the thermal emission, of which the brightness peak coincides in position with the group center to within $`1^{}`$. The image reveals a hard X-ray emission, which apparently extends up to $`10^{}`$ from the group center.

Figure 2 shows the radial GIS count-rate profile in the energy band of 4.5–8 keV, centered on the soft X-ray brightness peak. Also shown are the instrumental point-spread function (PSF), and the profile of the estimated background. Thus, the background level is well reproduced at larger radii within 5%, and the hard X-ray emission is more extended than the PSF, detectable up to $`10^{}`$ from the group center. As shown in the inset to figure 2, the hard X-ray surface brightness is higher in the north region than in the south region. Such a feature cannot be explained as a spill-over from the 1 keV thermal emission. The hard X-ray brightness is not correlated with the galaxy distribution, either, including emission line galaxies (Carvalho et al., 1997).

The observed hard X-ray emission, though apparently extended, could simply be a result of several hard point sources, such as active galaxies, either related or unrelated to HCG62. To answer this issue, we examined the archival ROSAT image of HCG62, and found four point sources with 0.1–2 keV fluxes of $`(48)\times 10^{14}`$ erg s-1 cm-2 (shown in figure 1 as open squares) at the locations where the hard-band GIS image actually exhibits possible enhancements with the implied 2–10 keV fluxes of $`10^{13}`$ erg s-1 cm-2. The flux ratio between ASCA and ROSAT indicates that the source spectra have a power-law shape of photon index $`1.5`$. We have accordingly excluded photons falling within $`2.5^{}`$ of these four sources. In addition, in order to remove possible point-like sources at the central region of HCG62, we excluded photons within $`3^{}`$ of the group center. Then, the 4.5–8 keV GIS2+GIS3 flux from the on-source data has become $`3772\pm 61`$ photons over the radius of $`3^{}15^{}`$, compared to $`3351\pm 20`$ expected from the background count rate. The excess, $`421\pm 65`$ counts, well exceeds the $``$60 counts expected for the 1 keV thermal emission. Thus, the presence of the extended excess hard X-ray emission is significant from the GIS imagery even after excluding possible point-source contamination.

In order to examine the excess hard X-ray emission through spectroscopy, we have produced spectra over the radius of $`3^{}15^{}`$, by utilizing all the available data from the GIS and only the first pointing data from the SIS. The regions within 2.5 of the four point-like sources were again excluded. We discarded the SIS data above 4 keV for the reason described before. The obtained spectra are presented in figure 3. We fitted them simultaneously, by a single temperature plasma emission model (Raymond & Smith, 1977) (R-S model) with solar abundance ratios (Fukazawa et al., 1996, 1998), modified by photoelectric absorption. As shown in table 1 and figure 3, the model successfully reproduced the data in lower energies, and the derived temperature and metallicity are consistent with those of Fukazawa et al. (1998). However, the model is not acceptable due to significant residuals seen in the GIS fit over energies of $`>3`$ keV. When we limit the energy band to $`<2.4`$ keV, the fit becomes acceptable with a reduced chi square of 1.29 and the best-fit temperature of $`0.95\pm 0.05`$ keV. In contrast, when we use only the hard energy band above 2 keV, the best-fit temperature increases to $`2.1\pm 0.3`$ keV; this is inconsistent with that indicated by the soft-band data, and is much higher than the prediction from the galaxy velocity dispersion of $`300`$ km s-1 (Mulchaey et al., 1996). These results reconfirm the presence of excess hard X-ray emission above the prediction of the thermal emission of temperature $`1`$ keV. The results of Finoguenov & Ponman (1999), who reported a high temperature of $`>1.5`$ keV around $`5^{}`$ of the group center, are also consistent with ours.

We refitted the whole-band spectra by adding a Bremsstrahlung or a power-law component, to represent the excess hard X-ray emission. As summarized in table 1, either modeling has given an acceptable joint fit to the ASCA spectra. The Bremsstrahlung temperature has been constrained as $`>6.3`$ keV, while the power-law photon index $`\alpha _{\mathrm{ph}}`$ was found at $`1.5_{0.7}^{+1.2}`$. Although $`\alpha _{\mathrm{ph}}`$ can be as high as 2.7, such a steep power-law forces the R-S component to have an extremely high metallicity. When we fix the metallicity of the R-S component at 0.30 solar which is typically found from clusters of galaxies, the upper limit on $`\alpha _{\mathrm{ph}}`$ becomes 2.2. Below, we utilize this limit instead of the original one. The normalization of the hard component does not change by more than 20%, if we use plasma emission codes other than the R-S code.

The upper limit on narrow Fe-K line features at $`6.6`$ keV is uninteresting, several keV in equivalent width. The absorption column density cannot be constrained in any case, and consistent with the Galactic value of $`2.9\times 10^{20}`$cm-2 (Stark et al., 1992). The 2–10 keV X-ray flux and luminosity of the hard X-ray component are $`(1.0\pm 0.3)\times 10^{12}`$ erg cm-2 s-1 and $`(8.0\pm 2.0)\times 10^{41}`$ erg s-1, respectively, regardless of the choice between the two modelings. This amounts to about 20% of the 0.5–10 keV thermal-component luminosity of $`4.9\times 10^{42}`$ erg s-1 (Fukazawa 1997).

Although we have carefully estimated the background, it is still important to examine to what extent our results are affected by possible background uncertainties. To see this, we intentionally increased the IDB background level by 5%, and found that the 2–10 keV flux and luminosity of the hard component becomes $`(5.58.4)\times 10^{13}`$ erg s-1 cm-2 and $`(4.36.5)\times 10^{41}`$ erg s-1, respectively. Thus, the hard emission remains statistically significant.

## 4. Discussion

From the galaxy group HCG62, we have detected the excess X-ray emission with a very hard spectrum, which extends up to more than 10 from the group center and somewhat enhanced at the north region. Although its surface brightness is only $``$20% of that of the GIS background, we have confirmed its reality through careful analysis. Below, we discuss the origin and nature of this phenomenon.

An immediate possibility is collection of binary X-ray sources in the member galaxies of HCG62. However, based on the total optical luminosity of HCG62 ($`1\times 10^{11}L_{}`$; Carvalho et al. (1997)) and the optical vs. X-ray luminosity correlation among elliptical galaxies (Matsushita, 1997), this contribution is estimated to be at most $`4\times 10^{40}`$ erg s-1, which is an order of magnitude short of the observed luminosity. A second possibility is assembly of faint active galactic nuclei (AGNs) in HCG62. However, the optical evidence for AGNs in HCG62 is moderate (Carvalho et al., 1997), and we have already subtracted such candidates based on the ROSAT image. Any remaining AGNs are estimated to contribute no more than 30–40% of the total hard X-ray emission. Yet another possibility is fluctuation of background faint sources. Utilizing the log$`N`$–log$`S`$ relation in the 2–10 keV band (Ueda et al., 1999), this contribution is estimated to be at most $`2\times 10^{13}`$ erg cm-2 s-1 over the radius of $`3^{}15^{}`$, which is again too low to explain the data. From these considerations, we conclude that the excess hard X-ray emission cannot be explained by assembly of discrete hard X-ray sources, whatever their nature be.

Considering the loose constraint on the Fe-K line, the excess emission might be of thermal origin from very hot plasmas. Actually, Buote (2000) described the ASCA spectra of HCG62, integrated over a radius of $`0^{}`$$`3^{}`$, by a two-temperature plasma model of $`kT=0.7`$ and $`kT=1.5`$ keV. We have independently reconfirmed their results. However, our spectra (Figure 3) that are accumulated over the $`3^{}`$$`15^{}`$ range requires a temperature of $`>6.3`$ keV; the original two-temperature model found by Buote (2000) gives a very poor fit ($`\chi ^2/\nu =1.66`$). Thus, thermal emission with an “ordinary” temperature cannot explain the data. Insignificant detection of excess hard X-rays over a radius of $`0^{}`$$`3^{}`$ might be due to poor photon statistics and complex spectra of thermal components (Fukazawa et al., 1998) at the center region, spectral change of hard components, and so on. There might still be plasmas much hotter than the escape temperature, as is actually found in starburst galaxies (e.g. Ptak et al. (1997)). However, within $`15^{}`$ of HCG62, there is no bright IRAS sources with the 60 $`\mu `$m flux exceeding 2 Jy (SkyView at High Energy Astrophysics Science Archive Research Center). We therefore conclude that the thermal interpretation of the excess hard X-ray emission is unrealistic.

Given the difficulties with the discrete-source and thermal interpretations of the diffuse hard X-ray emission, we regard nonthermal interpretation as most promising. One popular scenario of non-thermal X-ray production is inverse Compton scattering of the CMB photons by relativistic electrons with Lorentz factor $`\gamma 10^{34}`$, as has been invoked to explain the excess hard X-ray emission from rich clusters (e.g. Fusco-Femiano et al. (1999)). However, we cannot constrain the intragroup magnetic field in HCG62 due to lack of information on the diffuse radio flux. If we assume a representative magnetic field intensity of 1 $`\mu `$G, we would observe synchrotron radio emission with a flux density of $``$0.3 Jy. Since such a strong radio emission is not seen from HCG62 (SkyView; NVSS VLA image), the inverse-Compton interpretation holds for HCG62 only if its magnetic field is much weaker than 1 $`\mu `$G. The reality of such a weak magnetic field is an open question, and in an apparent contradiction to the generally accepted inter-galactic field strengths of $`1\mu `$G (Kronberg, 1994), even though such a condition is suggested by the BeppoSAX and RXTE observations of some rich clusters of galaxies (Valinia et al., 1999; Fusco-Femiano et al., 1999).

An alternative interpretation is nonthermal Bremsstrahlung between the thermal gas and subrelativistic particles, as proposed for the hard X-ray emission from Abell 2199, of which diffuse radio flux is quite weak (Kempner & Sarazin, 2000) like in the case of HCG62. Let us assume for simplicity that the nonthermal electrons have typical energies of 10–100 keV, and their spatial density distribution is similar to that of the thermal intragroup gas. Then, the nonthermal to thermal luminosity ratio in the 0.5–10 keV band becomes $`\sqrt{10}\alpha `$, where $`\alpha `$ is the density ratio of the nonthermal electrons to the thermal ones. The observed luminosity ratio of $`0.2`$ implies $`\alpha `$0.06, indicating that the energy density of nonthermal electrons is 0.6–6 times as high as that of thermal electrons (depending on the spectrum). If this is the case, the mechanism of such particle acceleration becomes an important issue. In addition, the non-thermal pressure associated with such a particle population would considerably increase the total mass of HCG62, and hence its dark-matter content, estimated from the X-ray data.

The diffuse hard X-ray emission has been observed with ASCA from some other galaxy groups as well (Fukazawa, 1999). However, its prominence relative to the thermal X-ray emission appears to scatter from object to object like rich clusters (Molendi et al., 1999), with HCG62 one of the strongest case. Although it is yet to be studied what makes such variety, the hard X-ray emission might be related with transient phenomena such as mergers.

The authors are grateful to Dr. Takizawa for helpful discussions, and to an anonymous referee for helpful comments. This research was supported in part by the Grants-in-Aid for the Center-of-Excellence (COE) Research of the Ministry of Education, Science, and Culture in Japan (07CE2002).