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# Soft X-ray properties of a high redshift sample of QSOs observed with ROSAT

## 1 Introduction

QSOs or quasars represent the high luminosity end of a class of objects known as active galactic nuclei (AGNs). They are the most luminous continuously emitting objects in the universe and emit over the entire range of electromagnetic waves. It is widely believed that high energy emission (X-rays and $`\gamma `$-rays) from an AGN originates in the innermost region of accretion disk around a super-massive black hole (SMBH) and much of the low energy emission e.g., infrared, optical, ultraviolet, is due to the reprocessing of high energy photons in a medium surrounding the accretion disk. While the atomic line emission in the optical, UV, and X-ray probe the circumnuclear medium surrounding the SMBH, the shape of the X-ray spectrum described by photon index ($`\mathrm{\Gamma }_X`$) is a critical parameter to constrain competing models for the mechanisms of X-ray continuum emission.

The increased sensitivity of the position sensitive proportional counter (PSPC) on-board ROSAT compared to earlier missions allowed a significant improvement in the study of the soft X-ray emission of AGNs. The X-ray spectral shape of quasars has been studied extensively using earlier missions such as HEAO-I, Einstein, EXOSAT, and Ginga (e.g., Mushotzky 1984; Wilkes & Elvis 1987; Canizares & White 1989; Comastri et al. 1992; Lawson et al. 1992; Williams et al. 1992). Some of these missions were not sensitive below $`2\mathrm{keV}`$. These earlier studies suggested that the X-ray emission of quasars is well described by a power-law with photon index $`\mathrm{\Gamma }_X1.5`$ for radio-loud quasars and $`2.0`$ for radio quiet quasars. Large samples of AGNs have been studied by Walter & Fink (1993), Wang, Brinkmann & Bergeron (1996), and by Rush et al. (1996) using the ROSAT PSPC. However, most of the objects studied in the above papers are nearby and intrinsically bright AGNs. Also the AGN samples studied in the above papers are not complete and the derived results may be biased by selection effects. Laor et al. (1994, 1997) studied X-ray spectra of a complete sample of 23 quasars from the Bright Quasar Survey (BQS) with $`z0.4`$ and $`\mathrm{N}_\mathrm{H}\text{ }<1.9\times 10^{20}\mathrm{cm}^2`$. They found an average photon index of $`2.63\pm 0.07`$ for their complete sample. Reeves & Turner (2000) studied a larger sample of 62 quasars with redshift in the range 0.06 – 4.3 and $`\mathrm{M}_\mathrm{V}<23`$. They found an average photon index, $`\mathrm{\Gamma }_X=1.66\pm 0.04`$ for 35 radio-loud quasars and $`\mathrm{\Gamma }_X=1.89\pm 0.05`$ for 27 radio-quiet quasars in their sample. Although the sample of Laor et al. (1997) is complete, it is confined to the nearby universe. The sample of Reeves & Turner (2000) includes some high redshift quasars but most of the quasars are nearby and the sample is not complete.

We present the results of a detailed spectral and timing analysis of a nearly complete sample of 22 type 1 QSOs obtained from the ROSAT PSPC deep survey of McHardy et al. (1998). The basic parameters of the QSOs are listed in Table 1. We will refer to all the objects as QSO, independent of their luminosity, but note that some have low X-ray luminosity (see Table 4). The aims are to extend the study of soft X-ray properties of QSOs at higher redshifts and to investigate whether QSOs at high redshifts have excess soft X-ray emission similar to that seen in the narrow-line Seyfert 1 galaxies. The outline of the paper is as follows. In $`\mathrm{\S }2`$ we describe the sample; in $`\mathrm{\S }3`$ we describe the X-ray observations and analysis. Section 4 deals with optical spectroscopy. In $`\mathrm{\S }5`$, we compare our results with other studies and discuss some of the implications. Finally, we conclude our study in $`\mathrm{\S }6`$.

Throughout the paper, luminosities are calculated assuming isotropic emission, a Hubble constant of $`H_0=75\mathrm{km}\mathrm{s}^1\mathrm{Mpc}^1`$ and a deceleration parameter of $`q_0=0`$ unless otherwise specified.

## 2 The QSO sample

The QSOs were selected from the second deepest ROSAT PSPC survey of McHardy et al. (1998) which covers a circular region of radius $`15\mathrm{arcmin}`$ of the sky towards the direction where the Galactic $`\mathrm{N}_\mathrm{H}`$ is low ($`7.9\times 10^{19}\mathrm{cm}^2`$). The ROSAT survey consists of two observations with PSPC and one observation with HRI (see below). There are 32 QSOs identified to a flux limit of $`2\times 10^{15}\mathrm{erg}\mathrm{cm}^2\mathrm{s}^1`$ in the energy band of 0.5–2.0 keV (see Jones et al. 1997; McHardy et al. 1998). In order to be able to derive the shape of the soft X-ray spectrum of the individual QSOs from the single observation with the longest exposure and thus to avoid any effect due to the variation of soft X-ray emission over long time scales, we have selected 22 QSOs and excluded the faintest 10 QSOs which are not detected above $`5\sigma `$ level in any of the two PSPC observations. The soft X-ray selected sample of 22 QSOs (type 1) is nearly complete to a flux limit of $`1.4\times 10^{14}\mathrm{erg}\mathrm{cm}^2\mathrm{s}^1`$ in the energy band of 0.1$``$2.0 keV (corresponding to $`5\times 10^{15}\mathrm{erg}\mathrm{cm}^2\mathrm{s}^1`$ in the $`0.52\mathrm{keV}`$ energy band). There are two X-ray sources, MJM 9 and MJM 54 brighter than the above flux limit but the optical nature of these objects is not known (McHardy et al. 1998) due to either lack of an optical counterpart or ambiguity in the identification. The ROSAT HRI image of the circular region of radius $`15\mathrm{arcmin}`$ is shown in Figure 1. The HRI image was binned by $`16\mathrm{pixels}`$ ($`8\mathrm{arcsec}`$) and then smoothed by convolving with a Gaussian of $`\sigma =2\mathrm{pixels}`$. All the 22 QSOs are marked in Fig. 1. The centres of the small circles are the optical positions of the QSOs as identified by McHardy et al. (1998). X-ray sources shown in Fig. 1, were classified as QSOs based on their optical spectra. All the 22 QSOs show broad (full width at half maximum (FWHM) $`>1000\mathrm{km}\mathrm{s}^1`$) permitted emission lines (Jones et al. 1997; McHardy et al. 1998). The hardness ratio ($`HR`$), defined as $`HR=\frac{HS}{H+S}`$, where H and S are the count rates in the 0.5–2.0 keV and 0.1–0.5 keV bands, of the QSOs spans a range of $`0.141.78`$. In Figure 2, we show the distribution of the QSOs in the sample as a function of redshift and R mag. The number of QSOs increases with magnitude up to $`R=20.5\mathrm{mag}`$ and falls at fainter magnitudes (see Fig. 2). The QSO sample is optically complete at $`R<21`$ but it is likely that a few fainter QSOs have not been detected (McHardy et al. 1998). The redshift of the QSOs ranges from $`0.26`$ to $`3.43`$.

## 3 X-ray observations and analysis

### 3.1 X-ray Observations

The region of the sky containing the QSOs was observed twice with the ROSAT (Trümper 1983) Position Sensitive Proportional Counter (PSPC) during 1991–1993, and once with the High Resolution Imager (HRI) (Pfeffermann et al. 1987) in 1997 June 19–July 16. The two PSPC observations carried out during 1991 June 23–26, and 1993 June–July together comprise the second deepest ROSAT PSPC survey. These observations were targeted at $`\alpha (2000)=13^h34^m37.0^s`$, $`\delta (2000)=+37\mathrm{°}54\mathrm{}44\mathrm{}`$ in the sky with an extremely low obscuration due to matter in our Galaxy ($`\mathrm{N}_\mathrm{H}\text{ }=7.9\times 10^{19}\mathrm{cm}^2`$). The PSPC deep survey data has already been reported by McHardy et al. (1998). The HRI observation was also a deep survey (exposure time = 201513 s) and was carried out in the same region of sky as the PSPC deep surveys. The details of the ROSAT observations are given in Table 2. All the QSOs lie within $`15\mathrm{}`$ from the field centre.

### 3.2 Optical Identification

The X-ray sources, presented here, were optically identified with QSOs using ROSAT PSPC and optical images, and optical spectra by McHardy et al. (1998). Here we have confirmed their identification using high resolution HRI X-ray images(central full width half maximum of $`4\mathrm{}`$). The analysis of HRI X-ray images has been carried out using the PROS111The PROS software package provided by the ROSAT Science Data Center at Smithsonian Astrophysical Observatory. software package. X-ray images were extracted from the observations listed in Table 2 and were smoothed by convolving with a Gaussian of $`\sigma `$=$`2\mathrm{}`$. We have overlaid the contours of the smoothed HRI image of each QSO onto the corresponding optical image. The optical R band images the QSOs were obtained from the 2.5-m Isaac Newton Telescope (INT) using the wide-field camera on the night of 1999 April 19. The pixel scale is 0.333 arcsec per pixel and the seeing (FWHM) was $`1.3\mathrm{}`$. The overlays of X-ray contours onto the R-band images are shown in Figure 3. The QSO MJM 61 was not detected in the HRI observation, therefore it is not shown in Fig. 3. The overlays reveal that X-ray emission from some of the QSOs is contaminated with that due to neighbouring sources. In particular, the X-ray emission from the QSOs MJM 18, 20, 23, and 24 may be contaminated significantly, however, the dominant X-ray emission is that due to QSOs. In the following, we have attributed the X-ray emission seen with the PSPC to the individual QSOs due to the difficulty in separating out the small contribution of neighbouring sources in the lower resolution (FWHM $`25\mathrm{arcsec}`$) PSPC images.

The HEASOFT v5.0.1 package was used to analyze the PSPC X-ray data of all QSOs. We have estimated the X-ray count rates for all the QSOs in our sample from the PSPC observations of 1991 and 1993. The total source counts for each QSO were obtained in the energy band of 0.1–2.0 keV from the unsmoothed PSPC images using a circular region centered on the peak positions, and after subtracting the background estimated from 3-4 nearby circular regions. Note that for a few objects e.g., MJM 2, MJM 15 the centres of the circular region were shifted by a few arcsec in order to avoid the contamination from the neighboring objects. The radii of circles, used to extract the source counts, vary from $`4590\mathrm{arcsec}`$. This was necessitated due to the different off-axis position of individual QSOs and to avoid contamination with the nearby X-ray sources. The background counts were estimated separately for individual objects using 3-4 nearby circular regions of radii $`1.52.5\mathrm{arcmin}`$ in order to avoid any spatial variation of the background intensity. Net source counts were derived by subtracting appropriately scaled background counts. The count rates of all the QSOs, derived from the observations of 1991 and 1993, are listed in Table 3. Also listed in Table 3 are the hardness ratio (HR) values where HR is defined as the ratio of the source counts in the energy band of 0.5–2.0 keV to that in the energy band 0.1–0.5 keV. The QSOs MJM 31, 56, and 63, are not detected during the observation of 1993.

### 3.3 X-ray Light Curves

In order to investigate the time variability of soft X-ray emission from the QSOs, we have extracted light curves from the ROSAT PSPC observations. The light curves for the source and the background were extracted using the ‘xselect’ package with time bins of 2000 s and in the PSPC energy band of 0.1–2.0 keV containing all the X-ray photons falling within “good time intervals”. The source regions and the background regions were the same as described above. It was found that the background was variable by a factor of $`23`$ during the observation of 1993 June 19. Therefore, the light curves obtained from the 1993 observation are not suitable for variability studies. During the observation of 1991 June 23, the background was reasonably constant. The background subtractions were carried out after appropriately scaling the background light curve to have the same area as the source extraction area. In order to test the constancy of the background light curves and soft X-ray variability of the QSOs, we have fitted constant count rates to the background light curves and source light curves. From the best-fit minimum $`\chi ^2`$ values, it was found that background count rates obtained separately for each QSO are reasonably constant. It was also found that all QSOs, except MJM 10, do not show significant short-term variability during the observation of 1993 June-July. The soft X-ray variability characteristics of the QSO MJM 10 has been discussed by Dewangan et al. (2001).

A comparison of count rates during the observations 1991 and 1993 (see Table 3) reveals that 9 out of 22 QSOs show long term (time scale $`2\mathrm{yr}`$) variability. The QSOs MJM 2, 15, 17, and 48 varied by a factor of 2 within 2 yr while the QSOs MJM 7, 21, and, 30 varied by factor of $`3`$, $`1.5`$, and $`1.8`$, respectively. The two QSOs MJM 56, and MJM 63, which are not detected above $`3\sigma `$ level during the observation of 1993, varied by factor of more than 3.6 and 1.3, respectively.

### 3.4 X-ray Spectral Analysis

Photon energy spectra of all the QSOs in our sample were accumulated from their PSPC observation of 1991. The same regions for the source and the background, as described above ($`\mathrm{\S }4.1`$), were used. To improve the statistics, the ROSAT PSPC pulse height data obtained in 256 pulse height channels for each QSO were appropriately re-grouped to have at least 20 counts in each channel. As examples, X-ray spectra of two QSOs thus obtained from the observation of 1991 are shown in Figure 4111Rest of the X-ray spectra can be made available on request to G. C. Dewangan (email: gulab@tifr.res.in).

We used the XSPEC (Version 11.0) spectral analysis package to fit the data with spectral models. An appropriate response matrix and an auxiliary response file of the effective area of the telescope were used to define the energy response of the PSPC. The ROSAT PSPC spectra of QSOs shown in Fig. 4, were used for fitting spectral models. The X-ray spectrum of each QSO in the sample was first fitted with a redshifted power-law model with photon index, $`\mathrm{\Gamma }_X`$, and absorption due to an intervening medium (Model A) with the absorption cross-sections as given by Balucinska-Church & McCammon (1992) and using the method of $`\chi ^2`$-minimization. The results of this fitting and the best-fit spectral model parameters are shown in Table 4. The errors quoted were calculated at the $`90\%`$ confidence level based on $`\chi _{\mathrm{min}}^2`$+2.71. This simple model is a good fit to all the individual QSO spectra as evidenced by the minimum reduced $`\chi ^2`$ values. The absorbing column densities derived by fitting the power-law model to the spectra of MJM 2, MJM 3, MJM 11, MJM 13, MJM 17, MJM 18, MJM 20, MJM 21, MJM 23, MJM 24, MJM 31, MJM 37, MJM 56, MJM 57, and MJM 61 are similar within errors to that due to our own Galaxy measured from 21-cm radio observations along the line of sight to the source (Dickey & Lockman 1990), however, the error bars in the derived $`\mathrm{N}_\mathrm{H}`$ are quite large for some objects. To better constrain the photon indices for these QSOs, we next fixed the absorbing column density to the Galactic value and fitted the power-law model (Model B) to each QSO. The results of this fitting are also given in Table 4.

The absorbing column densities, $`20.7_{9.7}^{+13.6}\times 10^{19}\mathrm{cm}^2`$, $`18.1_{4.7}^{+6.0}\times 10^{19}\mathrm{cm}^2`$, $`18.7_{7.4}^{+9.8}\times 10^{19}\mathrm{cm}^2`$, derived for the QSOs MJM 7, MJM 10, and MJM 15 by fitting absorbed power-law model are in excess of the Galactic value ($`7.9\times 10^{19}\mathrm{cm}^2`$) measured along their line of sight. This indicates that all the X-ray absorption may not be only due to matter in our own Galaxy but also due to matter local to the source. In order to verify the presence of excess absorption, we fixed the neutral hydrogen column density to the Galactic value and fitted the absorbed power-law model (Model B). In each case, although the fit is acceptable, there is an increase in the value of $`\chi ^2`$ ($`\mathrm{\Delta }\chi ^2=5.33`$ for 23 dof in case of MJM 7; $`\mathrm{\Delta }\chi ^2=16.46`$ for 25 dof in case of MJM 10; $`\mathrm{\Delta }\chi ^2=6.648`$ for 15 dof in case of MJM 15). To estimate the excess absorption local to each of the three QSOs, we introduced an additional component for absorption local to the source in our model B (Model C – redshifted power-law modified with Galactic as well as intrinsic absorption local to the source) and fitted to PSPC spectrum of the each of the three QSOs. The derived excess absorption, $`\mathrm{\Delta }N_H`$, are $`9.7_{8.1}^{+12.0}\times 10^{20}\mathrm{cm}^2`$ for MJM 7, $`2.8_{0.8}^{+1.7}\times 10^{20}\mathrm{cm}^2`$ for MJM 10, and $`9.5_{7.4}^{+10.0}\times 10^{20}\mathrm{cm}^2`$ for MJM 15. The best-fit photon indices ($`\mathrm{\Gamma }_X`$) are $`3.1_{0.6}^{+0.8}`$, $`3.7_{0.3}^{+0.3}`$, and $`3.3_{0.5}^{+0.7}`$ for MJM 7, MJM 10, and MJM 15, respectively. We measure the statistical significance of the reduction in the best-fit $`\chi ^2`$ with addition of an intrinsic absorption component, described by $`\mathrm{N}_\mathrm{H}`$ as a free parameter, using the F-test (Bevington 1969). The calculated values of F-statistic values and the corresponding probabilities are given in Table 5 for the QSOs MJM 7, 10, and 15. The F-statistics probability is the probability that the reduction in $`\chi ^2`$ is not statistically significant. As can be seen the Table 5, at $`95\%`$ level, the presence of additional absorption component local to the source is significant for the QSOs MJM 7, MJM 10 and MJM 15.

For the QSOs MJM 29, MJM 30, MJM 48, MJM 61, and MJM 63, the amount of the absorbing column derived from the power-law fitting is unphysically small compared to the Galactic values of absorbing columns along their respective lines of sight. In order to constrain the photon indices, we fixed the absorbing column density to the Galactic value along the respective sight lines of individual QSOs and carried out the power-law model fitting to the PSPC spectra of the above QSOs. The PSPC spectra of the QSOs are well described by a power-law modified with absorbing column in our own Galaxy, as evidenced by the reduced $`\chi _{min}^2`$ values (see Table 4).

In order to investigate any change in the soft X-ray spectral shape and flux, we have also analyzed the PSPC spectra of the QSOs observed in 1993. The PSPC spectra of the QSOs and the corresponding background spectra were extracted from the observation of 1993 using the similar extraction regions as for the observation of 1991. The same spectral models, namely redshifted and absorbed power-law model with $`\mathrm{N}_\mathrm{H}`$ as a free parameter and $`\mathrm{N}_\mathrm{H}`$ fixed to the Galactic, as described above were fitted to the PSPC spectra obtained in 1993. The power-law model with $`\mathrm{N}_\mathrm{H}`$ as a free parameter is a good description to the observed PSPC spectra of individual QSOs. Except for the QSOs MJM 7 and MJM 10, the Galactic $`\mathrm{N}_\mathrm{H}`$ along the line of sight of each QSO was found to be well within the range of derived $`\mathrm{N}_\mathrm{H}`$ . Therefore, the power-law model with $`\mathrm{N}_\mathrm{H}`$ fixed to the Galactic value was fitted to the spectrum of each QSO. The best-fit parameters derived are given in Table 6.

The PSPC spectrum of the QSO MJM 7 is well described by a power-law of $`\mathrm{\Gamma }=3.91_{0.58}^{+1.38}`$, and $`\mathrm{N}_\mathrm{H}\text{ }=3.24_{1.19}^{+1.70}\times 10^{20}\mathrm{cm}^2`$ (reduced $`\chi _{min}^2=1.262`$ for 17 dof). The best-fit value of $`\mathrm{N}_\mathrm{H}`$ is much higher than the Galactic value ($`N_H^{Gal}=7.9\times 10^{19}\mathrm{cm}^2`$) suggesting excess absorption. The power-law fit with $`\mathrm{N}_\mathrm{H}`$ fixed to the Galactic value is not acceptable (reduced $`\chi _{min}^2=2.123`$ for 18 dof). Addition of an absorbing component, apart from the Galactic absorption component, local to the QSO gives an acceptable fit (reduced $`\chi _{min}^2=1.344`$ for 17 dof) The best-fit parameters are $`\mathrm{\Gamma }_X=4.74_{1.11}^{+1.69}`$, and $`\mathrm{\Delta }\mathrm{N}_\mathrm{H}\text{ }=2.86_{1.57}^{+2.48}\times 10^{21}\mathrm{cm}^2`$. The F-statistic value for the addition of the intrinsic absorption component to the power-law with $`\mathrm{N}_\mathrm{H}`$ fixed at the Galactic value is 11.4 and the F-statistic probability is $`3.55\times 10^3`$. Thus the addition of an excess absorption at the QSO redshift to the power-law model with fixed $`\mathrm{N}_\mathrm{H}`$ is a significant improvement at $`99.4\%`$ level.

The power-law model with $`\mathrm{N}_\mathrm{H}`$ as a free parameter is an acceptable fit (reduced $`\chi _{min}^2=0.83`$ for 11 dof) to the PSPC spectrum of MJM 10. The best-fit parameters are $`\mathrm{N}_\mathrm{H}\text{ }=16.0_{6.4}^{+9.1}\times 10^{19}\mathrm{cm}^2`$ and $`\mathrm{\Gamma }_X=3.7_{0.4}^{+0.5}`$. The best-fit value of $`\mathrm{N}_\mathrm{H}`$ is significantly higher than the Galactic value ($`N_H^{Gal}=7.9\times 10^{19}\mathrm{cm}^2`$) indicating excess absorption. The best-fit power-law model with $`\mathrm{N}_\mathrm{H}`$ fixed to the Galactic value is also an acceptable fit (reduced $`\chi _{min}^2=1.11`$ for 12 dof) although the fit is becomes poor again indicating excess absorption. Next, we introduced an additional absorbing component local to the source and carried out the model fitting. The fit is an acceptable fit (reduced $`\chi _{min}^2=0.82`$ for 11 dof). The F-statistic value for the addition of new component to the power-law model with fixed $`\mathrm{N}_\mathrm{H}`$ is 5.24 and the corresponding F-statistic probability is $`4.28\times 10^2`$. Hence the power-law model modified by Galactic absorption and intrinsic absorption is a significant improvement at $`90\%`$ level but not a significant improvement at $`95\%`$ level over the power-law model with Galactic absorption. In the case of MJM 15, an excess absorption is not inferred from the 1993 observations. This discrepancy could be due to the low S/N and poor spectral resolution of the PSPC spectra of MJM 15.

### 3.5 Optical Spectroscopy

Optical spectra of 12 of the 22 QSOs were obtained on the night of 1994 April 7 with the Multi Object Spectrograph (MOS) on the 3.6-m Canada France Hawaii Telescope (CFHT) as a part of a program to identify X-ray sources (McHardy et al. 1998). A $`300\mathrm{l}\mathrm{mm}^1`$ grism in the first order with a Lorel3 CCD detector was used to cover a wavelength range of $`4000\mathrm{\AA }`$$`9000\mathrm{\AA }`$ with $`15\mathrm{\AA }`$ resolution.

Optical spectra of the 12 QSOs were reduced using IRAF (v2.11.3). For details of the reduction see McHardy et al (1998). The flux calibration is somewhat uncertain because the slitlets were not aligned at the parallactic angle. The flux calibrated spectra were corrected for Galactic extinction by adopting the extinction law in Cardelli et al. (1989). Color excess $`E_{BV}`$ due to Galactic reddening along the line of sight of each QSO was calculated from the neutral hydrogen column density $`\mathrm{N}_\mathrm{H}`$  using the relation

$$\mathrm{N}_\mathrm{H}\text{ }=4.93\times 10^{21}\times E_{BV}\mathrm{cm}^2$$
(1)
(Diplas & Savage 1994). The dereddened spectra were then deredshifted by dividing the starting wavelength and the pixel width in Angstrom by (1+z). The final spectra of 12 QSOs are shown in Figure 5. For each of the 12 objects, relative flux against the rest wavelength in $`\mathrm{\AA }`$ has been plotted. Strong emission lines have been marked in the figure.

The analysis of the emission lines of MJM 10 has been discussed by Dewangan et al. (2001). Emission lines of other QSOs were modeled by Gaussian profiles using the IRAF task ngaussfit. As a first step, we fitted a single Gaussian profile to the strong emission lines. Most of the emission lines are described by a single Gaussian profiles, however, the broad wings of the Mg II lines in the spectra of the QSOs MJM 3, 7, and 20 are not well fitted by a single Gaussian profile. Therefore, the Mg II line in the spectra of the above QSOs were modeled by two Gaussian which gave satisfactory fit to the line core as well as to the wings. The two component fitting to the Mg II line revealed that the broad component is blue shifted with respect to the narrow component (see Table 7). The broad components of the Mg II line is blue shifted by $`1180`$, $`790`$, and $`1080\mathrm{km}\mathrm{s}^1`$ in the spectra of MJM 3, 7, and 20, respectively. In the rest of the QSO spectra only one component is detected. This could be due to the low S/N ratios of the optical spectra.

## 4 Discussion

### 4.1 The soft X-ray spectral shape

The deep $`ROSAT`$ PSPC observations together with improved sensitivity and energy resolution, compared with earlier instruments, allows us to determine the shape of the soft X-ray continua of QSOs of redshifts up to 3.43. There are three QSO namely MJM 7, MJM 10, and MJM 15 which show steeper soft X-ray continua ($`\mathrm{\Gamma }_X>3.0`$). The QSO MJM 10 is known to be a narrow-line QSO (NLQSO) – high luminosity version of narrow-line Seyfert 1 galaxies (NLS1s) (Dewangan et al. 2001). The average photon index of the QSOs is $`2.40\pm 0.09`$ with a dispersion of $`0.57`$. 10 QSOs with $`z>1.6`$ have mean photon index of $`2.12\pm 0.10`$ (with dispersion about mean of $`0.39`$) and 12 QSO with $`z<1.6`$ have mean photon index of $`2.62\pm 0.15`$ with a dispersion of $`0.61`$. The average photon index of the QSOs with $`z>1.6`$ in our sample appears to be flatter than the average photon index of QSOs at low redshifts. Walter & Fink (1993) analyzed the PSPC spectra of 58 AGNs observed in the $`ROSAT`$ All Sky Survey (RASS) which contains a subsample of 24 QSOs with mean photon index, $`\mathrm{\Gamma }_X=2.57\pm 0.06`$ (Laor et al. 1997). A similar average photon index of $`2.65\pm 0.07`$ was found by Schartel et al. (1996) for 72 QSOs from the LBQS sample detected in the RASS. Laor et al. (1997) studied the $`ROSAT`$ PSPC spectra of a complete sample of 23 optically selected QSOs with $`z0.4`$ and found average photon index of $`2.62\pm 0.09`$ for their sample.

In order to further explore the redshift dependence of soft X-ray spectral slope of QSOs, we formed average spectra of QSOs in four redshift bins – $`z=0.251.0`$ (5 QSOs), $`z=1.01.6`$ (7 QSOs), $`z=1.62.0`$ (7 QSOs), and $`z=2.03.43`$ (3 QSOs). The average spectra were then fitted by simple power-law modified by the Galactic absorption only. In Figure 6, we have plotted the average photon index as a function of redshift for the QSOs in our sample. Also plotted in Fig. 6 is the average photon index of 23 Quasars from the Bright Quasar Survey (BQS) sample of Laor et al. (1997). The average photon index flattens at higher redshifts e.g., $`<\mathrm{\Gamma }_X>=2.62\pm 0.09`$ at $`z0.4`$ and $`<\mathrm{\Gamma }_X>=2.17_{0.08}^{+0.09}`$ at $`1.6z2.0`$.

Blair et al. (2000) studied soft X-ray spectral evolution with redshift using a large sample of 165 QSOs observed with ROSAT and found the $`0.12\mathrm{keV}`$ average spectra in 5 redshift bins harden from $`\mathrm{\Gamma }_X2.6`$ at $`z=0.4`$ to $`\mathrm{\Gamma }_X2.1`$ at $`z=2.4`$. This result is similar to that found here. Blair et al. (2000) also noted that the spectra in $`0.52\mathrm{keV}`$ band show no significant variation in spectral index with redshift suggesting the presence of a spectral upturn below $`0.5\mathrm{keV}`$. While Blair et al. (2000) found that at lower redshifts spectra need a soft excess component in addition to a power-law and inclusion of a blackbody component ($`kT100\mathrm{eV}`$) for the soft excess results in a significant improvement over a single power-law, Laor et al. (1997) did not require such a soft excess component. The discrepancy could be due to the fact that Laor et al. (1997) added $`1\%`$ systematic errors in quadrature to the statistical errors. The difference between the average spectral slopes of QSOs at low and high redshifts can be understood in terms of mean X-ray spectrum consisting of a power-law of $`\mathrm{\Gamma }_X1.9`$ and a soft excess below $`0.5\mathrm{keV}`$ in the rest frame. At higher redshifts ($`z2`$) the rest frame soft excess component below $`0.5\mathrm{keV}`$ is not covered in the observed $`0.12\mathrm{keV}`$ band, the observed spectrum is a power-law with $`\mathrm{\Gamma }_X1.9`$. While at lower redshifts, the observed spectrum, consisting of both soft excess and power-law component, is steeper when fitted with a single power-law and similar to that of $`z2`$ QSOs when the soft excess component below $`0.5\mathrm{keV}`$ is excluded from the fit. This could also be the reason why Reeves & Turner (2000) found mean photon index of $`1.9`$ in the $`0.610\mathrm{keV}`$ ASCA band for their sample of 27 radio quiet quasars.

### 4.2 Intrinsic Absorption

Due to the low signal-to-noise of the PSPC spectra of the QSOs in our sample, we are not able to determine the consistency of HI columns derived from the 21 cm radio observations (Dickey & Lockman 1990) and HI columns derived from the absorbed power-law model fits to the observed PSPC spectra. Laor et al. (1997) have shown that the two columns agree to a level of about $`5\%9\%`$ at high Galactic latitudes. There are indications that some broad-line AGNs show intrinsic absorption (e.g., Page et al. 2001; Akiyama et al. 2000). The power-law models modified by the Galactic absorption provide acceptable fits to the PSPC spectra of all QSOs except MJM 7, MJM 10, and MJM 15 (see Tables 4,& 5). Thus most of the QSOs in our sample lack intrinsic absorption. Only three QSOs, MJM 7, MJM 10, and MJM 15, out of 22 show indications for the presence of intrinsic absorption. The amount of intrinsic absorption inferred from the best-fit absorbed power-law models, $`10^{21}\mathrm{cm}^2`$ for MJM 7, is quite high and may cause the QSO to be redder than others in the sample. The ratio of soft X-ray to optical R band flux can be written as

$$log(\frac{f_X}{f_R})=log(f_X)+\frac{m_R}{2.5}+3.5$$
(2)
where $`f_X`$ and $`f_R`$ are X-ray and optical R band fluxes, and $`m_R`$ is the R band magnitude. For MJM 7, the ratio of observed X-ray and optical flux ($`\frac{f_X}{f_R}`$) is calculated to be $`2.95\times 10^3`$ while the ratio is 0.0160 for MJM 15 which is located at the same redshift (z=1.14) as MJM 7. In order to investigate whether the lack of soft X-ray emission of MJM 7 is only due to intrinsic absorption or the QSO is intrinsically X-ray weak, we calculated the ratio of unabsorbed soft X-ray flux and observed R band flux for MJM 7 and MJM 15. The ratio ($`\frac{f_X}{f_R}`$) is 0.017 for MJM 7 and 0.072 for MJM 15. Thus, the low observed X-ray flux of MJM 7 may not be entirely due to absorption and MJM 7 could be intrinsically weaker. The amount of intrinsic HI column in MJM 10 is small ($`2.8_{0.8}^{+1.7}\times 10^{20}\mathrm{cm}^2`$) and is similar to that observed in some NLS1 galaxies (Grupe et al. 1998).

### 4.3 Optical Spectra

Optical spectra of the 12 QSOs, except MJM 10, are typical of QSOs. The optical spectra of MJM 10 is typical of NLS1 galaxies or NLQSOs and has been discussed in detail by Dewangan et al. (2001). The other 11 QSOs show broad permitted lines in the ultra-violet region. The Mg II lines in the spectra of the QSOs MJM 3, 7, and 20 have been decomposed into a narrow and a broad component. The broad component is found to be blueshifted by $`1180`$, $`790`$, and $`1080\mathrm{km}\mathrm{s}^1`$ with respect to the narrow component in the spectra of MJM 3, 7, and 20. The Mg II lines in the spectra of the QSOs MJM 3, 7, and 20 have been decomposed into a narrow and a broad component. The broad component is found to be blueshifted by $`1180`$, $`790`$, and $`1080\mathrm{km}\mathrm{s}^1`$ with respect to the narrow component in the spectra of MJM 3, 7, and 20. This suggests that either the red wings of the Mg II lines of MJM 3, 7, and 20 are affected by absorption features more strongly than the blue wings or the broad components of the Mg II lines originate in the outflowing winds.

## 5 Conclusions

We have derived soft X-ray spectral shapes and light curves of a nearly complete sample of 22 QSOs. We also presented optical spectra of 12 QSOs from our sample. Our main results are as follows.
(i) About $`33\%`$ of the QSOs show a long term ($`2\mathrm{yr}`$) soft X-ray variability while only one QSO MJM 10 shows rapid variability.
(ii) Only three QSOs, MJM 7, 10, and 15 out of 22 QSOs ($`7\%`$) show indications for the presence of significant intrinsic absorption. The former two QSOs show excess absorption during both the observations of 1991 and 1993, while MJM 15 does not show excess absorption during the observation 1993.
(iii) The soft X-ray photon index of the QSOs in our sample ranges from 1.4 to 3.7. The average photon index of the sample is $`2.40\pm 0.09`$ with a dispersion of $`0.57`$.
(iv) The average photon index of the QSOs is found to flatten at higher redshift. This can be understood in terms of the redshift effect of mean intrinsic QSO spectra consisting two components – a soft excess component and a power-law.
(v) Only one QSO MJM 10 out of 22 has been found to be an NLQSO.
(vi) The broad component of the Mg II line in the spectra of MJM 3, 7, and 20 are found to be blueshifted by $`1180`$, $`790`$, and $`1080\mathrm{km}\mathrm{s}^1`$, respectively.


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# Bending rigidity of stiff polyelectrolyte chains: a single chain and a bundle of multichains

## I Introduction

Like-charged polyelectrolytes (PEs) such as DNA and F-actin undergo a dramatic compaction to highly ordered structures in the presence of multivalent counterions bloomfield ; kremer ; winkler ; pincus ; janmey ; janmey2 ; amis ; klein ; ha.2rods ; ha.bundle ; ha.pre ; ha.angle ; Lee ; jensen ; marcelja ; joanny ; podgornik ; oosawa ; manning ; oosawa.book ; raspaud . Theoretical description of the phases of highly charged PE condensates is complicated due to the interplay between the chain deformations and counterion-mediated interactions. This complex interplay is often not treated adequately. In the classical work on stiff PEs osf , the effect of the condensed counterions is simply to renormalize the backbone charge density. More recently, Park et al. park  and Ubbink and Odijk uo  have considered the bending rigidity of DNA strands that can form bundles. The underlying assumption in these calculations is that total bending energy can be written as a sum over all bending energies from individual chains. It is, however, not obvious when this is valid, since electrostatic interactions are long-ranged and the counterion-mediated attractions are not pairwise additive. In a previous study, we considered charge fluctuation effects on the bending rigidity of randomly charged polymers ha.thirum . Notably we have shown that charge fluctuations along the polymer chains give rise to a reduction in the bending rigidity as compared to the corresponding uncharged cases. Several other authors kardar ; andelman ; hansen ; nguyen  have also considered a similar problem of the bending rigidity of a single stiff PE. All the existing approaches, however, do not provide much insight into a more realistic case, namely bundles of PE chains, since they do not take inter-chain coupling into account. Note that the attraction that softens PEs also induces interchain collapse. In fact, counterion-induced interactions are not pairwise additive and thus the result for a single chain can easily be invalidated by the interchain coupling. The key to understanding the bending rigidity of PE condensates lies in a consistent treatment of both interchain and intrachain couplings.

In this paper, we present a theoretical model for describing the bending rigidity of highly charged stiff PEs, both a single chain and many chains which form bundles. Throughout this paper, the bending rigidity is estimated in terms of the persistence length, which is a length scale over which the chain does not change its direction appreciably. The persistence length is simply the bending rigidity divided by $`k_BT`$, where $`k_B`$ is the Boltzmann factor and $`T`$ is the temperature. In particular, we study the interplay between preferential adsorption of multivalent counterions and charge correlations in determining the bending rigidity of PE chains. We begin by first considering a single chain case. We show that, below a certain critical value of the electrostatic strength, the PE chain becomes stiffer with the increasing interaction strength. Above the critical value, the chain becomes softer as the interaction strength increases. Thus a simple scaling function does not describe the bending rigidity. At first glance, this is quite surprising because our results imply that the bending rigidity of condensates can be reduced by increasing the backbone charge density. The bending rigidity also varies nonmonotonically with the concentration of multivalent counterions, $`n_2`$. For sufficiently highly charged PEs, the electrostatic bending rigidity drops to a large negative value (signalling the collapse of the PE) upon a small increase in $`n_2`$ from zero, while it decreases in magnitude with increasing $`n_2`$ beyond a certain value of $`n_2`$. In other words, these exists an optimal value of $`n_2`$ at which the PE is most efficiently softened. In contrast to the previous work ha.thirum ; kardar , we consider a bundle of multichains as well. In some cases, a long single PE chain can fold back on itself (in a rodlike bundle) or wind around itself (in a toroidal bundle) to form a bundle. In the case of rodlike bundles, there is extra complexity arising from hairpin turns of the chain at both ends of the bundle, while, in toroidal bundles, non-parallel portions of the chain complicate the problem park . Here we ignore these comlexities; in the resulting picture, the distinction between rodlike bundles and toroidal bundles becomes minor. With this simplification, we consider toroidal bundles without a loss of generality. Whether a bundle is formed by a single chain or many different chains, we can consider the bundle to be formed by many loops; each loop in a toroidal bundle corresponds to one complete turn (wind) of the chain. As a result, all monomers in a loop can be considered as interacting with each other through intra-chain (or intra-loop) interactions, since any portions of the loop do not wind around each other. We then discuss the effect of coupling between loops in the bundle on the bending rigidity. Our theory implies that, the bending free energy of each loop in the bundle cannot be added up to give the total bending free energy. We also show that the bending free energy cannot be computed by summing up the interactions over all pairs of loops. The theory rather suggests that the inter-loop coupling further softens the condensate. This is due to the many-body nature of electrostatic interactions induced by counterions. As a result, the bending free energy of the condensate varies linearly with the number of loops.

## II Model and Bending Rigidity

### II.1 general formalism

Our calculations are based on a model adopted in Ref. ha.thirum ; kardar ; andelman . The PEs are uniformly charged chains, forming a bundle of $`N`$ loops. Each loop is assumed to consist of $`M`$ monomers of length $`b`$, and each monomer carries either a negative charge of $`e`$ or 0. In reality, different loops can have different numbers of monomers, but this polydispersity will not influence the persistence length as long as the loop size is somewhat larger than the screening length $`\kappa ^1`$, as assumed here. If $`f_0`$ is the fraction of charged monomers, then each monomer is asigned a charge $`ef_0`$ on average. Besides monovalent salts, there are $`(Z:1)`$ multivalent salts as well in the solution. Counterions are divided into two classes, “condensed” (ı.e., they are bound to the PE chain) and “free” (ı.e., they move freely in the solution) oosawa ; manning . The charge on loop $`j`$ of monomer $`s`$ (in units of electronic charge $`e`$) can assume the values

$$q_j(s)=f_0^j+m_1^j+m_2^jZ,$$
(1)
where $`m_1^j,m_2^j=0,1,2,3,\mathrm{}`$ are, respectively, the numbers of monovalent and multivalent condensed counterions at the site. Due to condensed counterions, the charge distribution along the chain is heterogeneous. The resulting charge destribution is characterized not only by the average charge per each site, $`\overline{q}_j=\overline{q_j(s)}=f_0+f_1^j+Zf_2^j`$, but also by the variance in the charge per site $`\overline{\mathrm{\Delta }}_j=\overline{\left[q_j(s)\right]^2}\left[\overline{q_j(s)}\right]^2=\left(f_1^j+Z^2f_2^j\right)`$ remark . Note here that $`\overline{\left(\mathrm{}\right)}`$ is an average over all realizations of the charge distribution, and $`f_1^j`$ and $`f_2^j`$ are the average numbers of the monovalent and multivalent condensed counterions on loop $`j`$ per site, respectively. The electrostatic interaction Hamiltonian can be expressed in terms of $`q_j(s)`$:

$$\frac{_{\mathrm{elec}}}{k_BT}=\frac{\mathrm{}_B}{2}\underset{jj^{}=1}{\overset{N}{}}\underset{ss^{}=1}{\overset{M}{}}q_j(s)q_j^{}(s^{})\frac{\mathrm{e}^{\kappa |𝐫_j(s)𝐫_j^{}(s^{})|}}{|𝐫_j(s)𝐫_j^{}(s^{})|},$$
(2)
where $`𝐫_j(s)`$ describes conformations of PE chains in the bundle. The Bjerrum length $`\mathrm{}_B=e^2/4\pi \epsilon k_BT`$ is the distance at which the electrostatic interaction between two elementary charges $`e`$ is equal to the thermal energy $`k_BT`$, and $`\epsilon `$ is the dielectric constant of the solution. The Debye screening parameter is $`\kappa ^2=8\pi \mathrm{}_BI`$ where $`I`$ is the ionic strength.

The partition function is a sum over all charge variables and conformations. We treat the free ions within the three dimensional Debye-Hückel (DH) theory, and consider backbone charges together with their condensed counterions as forming one-dimensional Debye-Hückel (DH) systems ha.2rods ; ha.bundle . Thus our approach should be contrasted with the approach of Nguyen et al. nguyen , which is based on a strongly correlated liquid (SCL) model of condensed counterions. In Appendix A, we argue that the major contribution to the electrostatic bending rigidity can arise from long-wavelength charge fluctuations as captured by our DH approach, even when the condensed counterions are strongly correlated. This is because small bending is more efficiently felt by long-wavelength fluctuations, even when counterion ordering is mainly driven by short-wavelength fluctuations. However, aspects of SCL picture will become more pronounced at low temperatures.

For a given conformation of a PE described by $`[𝐫_j(s)]`$, we can trace over the charge variables. If we define the following block matrix $`𝑸[𝐫_j(s)]`$ whose element $`𝑸_{jj^{}}[𝐫_j(s)]`$ is

$`𝑸_{jj^{}ss^{}}[𝐫_j(s)]=\overline{\mathrm{\Delta }}_{j}^{}{}_{}{}^{1}\delta _{jj^{}}\delta _{ss^{}}+\mathrm{}_B{\displaystyle \frac{\mathrm{e}^{\kappa |𝐫_j(s)𝐫_j^{}(s^{})|}}{|𝐫_j(s)𝐫_j^{}(s^{})|}},`$ (3)
then the electrostatic free energy functional becomes

$`{\displaystyle \frac{_{\mathrm{elec}}[𝐫_j(s)]}{k_BT}}`$ $`=`$ $`{\displaystyle \frac{1}{2}}{\displaystyle \underset{jj^{}=1}{\overset{N}{}}}{\displaystyle \underset{ss^{}}{\overset{M}{}}}\overline{q}_j\overline{q}_j^{}\{\overline{\mathrm{\Delta }}_j^1\delta _{jj^{}}\delta _{ss^{}}`$ (4)
$`\overline{\mathrm{\Delta }}_j^1\overline{\mathrm{\Delta }}_j^{}^1𝑸_{jj^{}ss^{}}^1[𝐫_j(s)]\}`$
$`+\frac{1}{2}\mathrm{log}\left\{\mathrm{det}\overline{\mathrm{\Delta }}_j𝑸[𝐫_j(s)]\right\}`$
$`+\text{self-energy}.`$
Note that the derivation of this result is analogous to the derivation of the free energy of bundles of rodlike PE chains which have been studied extensively ha.2rods ; ha.bundle ; ha.pre ; ha.angle ; ha.interface . This result can readily be obtained by performing standard Gaussian integrals. So the intermediate steps that lead to this result are omitted. The first term in eq 4 corresponds to the screened repulsion, while the second term comes from charge fluctuations. The last term comes from $`j=j^{}`$ and $`s=s^{}`$, and is a self energy that should be subtracted from the free energy in eq 4. Note here that the self energy does not contribute to the persistence length, which measures a free energy cost for bending or the free energy of the PE chain with reference to a rodlike conformation. This is because the self-energy is the same for all chain conformations.

When PEs are near the rod limit, it is reasonable to assume that they are bent uniformly. The central axis of PEs can then be parameterized by $`𝐫_j(s)`$ as $`\vartheta _j(s)=s/R`$, where $`R`$ is the radius of curvature. Note that this parametrization amounts to adopting a ground state dominance approximation in the chain conformations. With this parameterization, the free energy with respect to the reference rod conformation can be obtained. To this end, we write

$`𝑸_{jj^{}ss^{}}`$ $``$ $`𝑸_{jj^{}ss^{}}[\vartheta _j(s)]`$ (5)
$``$ $`\overline{\mathrm{\Delta }}_j^1\delta _{jj^{}}\delta (R\vartheta )+{\displaystyle \frac{\mathrm{}_B}{\sqrt{R^2\vartheta ^2+R_{jj^{}}^2}}}`$
$`\times \mathrm{e}^{\kappa \sqrt{R^2\vartheta ^2+R_{jj^{}}^2}}+\underset{¯}{{\displaystyle \frac{\mathrm{}_B}{24}}\mathrm{e}^{\kappa \sqrt{R^2\vartheta ^2+R_{jj^{}}^2}}}`$
$`\times \underset{¯}{\left({\displaystyle \frac{R^2\vartheta ^4}{(R^2\vartheta ^2+R_{jj^{}}^2)^{3/2}}}+{\displaystyle \frac{\kappa R^2\vartheta ^4}{R^2\vartheta ^2+R_{jj^{}}^2}}\right)},`$
where $`R_{jj^{}}`$ is the distance between chains $`j`$ and $`j^{}`$. Note that this equation is similar to eq 5.2b in Ref ha.thirum , except that the coupling between loops is included in this case. It can be shown that the underlined term in eq 5 is much smaller than the first two terms near the rod limit, ı.e., $`\kappa R1`$, by the factor of $`1/R^2`$. If we denote $`𝑸_0`$ to be the corresponding matrix for the rod-like case, ı.e., the first two terms in eq 5, then we can thus write $`𝑸[\vartheta (s)]=𝑸_0\left\{1+\left[𝑸_0^1\left(𝑸[\vartheta (s)]𝑸_0\right)\right]\right\}`$ and consider the term in $`[]`$ as an expansion parameter. Convergence of the expansion is assured if $`\kappa R1`$. Both $`𝑸^1[\vartheta ]`$ and $`det𝑸[\vartheta ]`$ can be computed in powers of $`1/R^2`$.

When PE chains form a bundle of $`N`$ loops, charges on one loop correlate not only with others on the same loop but also with charges on different loops. In other words, the intra-loop and inter-loop charge fluctuations are coupled with each other. Consistent treatment of intra- and inter-loop correlations is hard even when all loops are perfectly rigid and parallel (in the absence of conformational deformations) ha.bundle . In the following subsection, we will provide explicit solutions for the case of $`N=1`$. The effects of loop-loop interactions on the bending rigidity of PE condensates, namely bundles of PE chains, is discussed in Subsection C. The electrostatic contribution to the bending free energy of a bundle, ı.e., the change in the electrostatic free energy due to bending is approximated as

$`{\displaystyle \frac{\mathrm{\Delta }_{\mathrm{elec}}}{k_BT}}`$ $``$ $`{\displaystyle \frac{1}{2}}{\displaystyle \underset{jj^{}}{}}{\displaystyle \underset{ss^{}\vartheta }{}}{\displaystyle \frac{\overline{q}_j\overline{q}_j^{}}{\overline{\mathrm{\Delta }}_j\overline{\mathrm{\Delta }}_j^{}}}\left[𝑸_0^1(𝑸𝑸_0)𝑸_0^1\right]_{jj^{}ss^{}}`$ (6)
$`+{\displaystyle \frac{1}{2}}{\displaystyle \underset{j}{}}{\displaystyle \underset{s\vartheta }{}}\left[\left(𝑸_0^1\overline{\mathrm{\Delta }}_j\right)(𝑸𝑸_0)\right]_{jjss},`$
where the subscripts $`j`$ and $`j^{}`$ run over loops. Here, the first term comes from the repulsion between charges, which is screened by both condensed counterions and added salt. The second term, which vanishes as $`\overline{\mathrm{\Delta }}_j0`$, represents the attraction due to charge fluctuations in the monomeric charges. It should be noted here that the two terms in eq 6 are put on an equal footing. What is suppressed here is non-Gaussian fluctuations which are responsible for short-wavelength charge correlations. We argue in the appendix that Gaussian fluctuations can easily dominate the $`\mathrm{\Delta }_{elec}`$ as long as $`\kappa b`$ is small. This justifies our neglect of non-Gausian fluctuations in the computation of $`\mathrm{\Delta }_{elec}`$ (thus the persistence length).

When $`\kappa ^1`$ is somewhat smaller than the loop size, then the matrix element $`\left(𝑸_0^1\right)_{jj^{}ss^{}}`$ in eq 6, for example, depends on $`|ss^{}|`$ for given $`j`$ and $`j^{}`$. This enables us to further simplify the bending free energy in eq 6 by summing it with respect to $`s`$. To this end, let us define matrices $`D(s)`$ and $`{}_{}{}^{0}D`$ as

$`{}_{}{}^{0}D_{jj^{}}^{}`$ $`=`$ $`{\displaystyle \frac{\xi }{12}}{\displaystyle _0^{\mathrm{}}}𝑑ss^4\mathrm{e}^{\kappa \sqrt{s^2+R_{jj^{}}^2}}`$
$`\times \left({\displaystyle \frac{1}{(s^2+R_{jj^{}}^2)^{3/2}}}+{\displaystyle \frac{\kappa }{s^2+R_{jj^{}}^2}}\right)`$
$`D_{jj^{}}(s)`$ $`=`$ $`{\displaystyle \frac{\xi }{12}}s^4\mathrm{e}^{\kappa \sqrt{s^2+R_{jj^{}}^2}}`$ (7)
$`\times \left({\displaystyle \frac{1}{(s^2+R_{jj^{}}^2)^{3/2}}}+{\displaystyle \frac{\kappa }{s^2+R_{jj^{}}^2}}\right),`$
and $`{}_{}{}^{0}`$ and $`(k)`$ as

$`{}_{}{}^{0}_{jj^{}}^{}`$ $`=`$ $`\overline{\mathrm{\Delta }}_j^1\delta _{jj^{}}+2\xi K_0(\kappa R_{jj^{}})`$
$`_{jj^{}}(k)`$ $`=`$ $`\overline{\mathrm{\Delta }}_j^1\delta _{jj^{}}+2\xi K_0(R_{jj^{}}\sqrt{\kappa ^2+k^2}),`$ (8)
where $`\xi \mathrm{}_B/b`$ and $`K_0(x)`$ is the zeroth-order modified Bessel function of the second kind. In terms of $`{}_{}{}^{0}D,D(s),{}_{}{}^{0}`$, and $`(k)`$, the bending free energy can be partly diagonalized. In other words, the free energy can be Fourier transformed from $`s`$ to its Fourier conjugate $`k`$. To order $`1/R^2`$, we obtain

$$\frac{\mathrm{\Delta }_{\mathrm{elec}}}{k_BT}\frac{L}{2R^2}\mathrm{}_{elec},$$
(9)
where

$`\mathrm{}_{elec}`$ $``$ $`{\displaystyle \frac{1}{b}}{\displaystyle \underset{jj^{}}{}}{\displaystyle \frac{\overline{q}_j\overline{q}_j^{}}{\overline{\mathrm{\Delta }}_j\overline{\mathrm{\Delta }}_j^{}}}\left[\left({}_{}{}^{0}\right)^1{}_{}{}^{0}D\left({}_{}{}^{0}\right)^1\right]_{jj^{}}`$ (10)
$`+{\displaystyle \underset{jj^{}=1}{\overset{N}{}}}{\displaystyle _0^{\mathrm{}}}𝑑sD_{jj^{}}(s){\displaystyle \frac{dk}{2\pi }[^1(k)\overline{\mathrm{\Delta }}]_{jj^{}}}`$
$`\times \mathrm{cos}ks,`$
where $`\overline{\mathrm{\Delta }}_{jj^{}}=\overline{\mathrm{\Delta }}_j\delta _{jj^{}}`$. Despite its apparent complexity, the expression in eq 10 can readily be derived in the same spirit as the bundle free energy ha.bundle ; ha.pre ; ha.interface . In Appendix B, we outline the detailed intermediate mathematical steps that lead to eq 10. Note that the bending free energy cannot be written as a sum of two-body interactions over all pairs of loops. This is consistent with the earlier finding that rod-rod interactions in polyelectrolyte solutions are not pairwise additive ha.bundle ; ha.pre . It is not surprising to see that the breakdown of pairwise additivity is also manifested in the bending free energy.

### II.2 single-loop cases: $`N=1`$

For $`N=1`$, the bending free energy given in eq 10 can be further simplified:

$`\mathrm{}_{elec}`$ $``$ $`{\displaystyle \frac{\mathrm{}_{\mathrm{OSF}}}{\left[1+2\xi \overline{\mathrm{\Delta }}K_0(\kappa b)\right]^2}}{\displaystyle \frac{(\xi \overline{\mathrm{\Delta }})^2}{12}}{\displaystyle 𝑑s(s^2+s^3\kappa )\frac{\mathrm{e}^{\kappa s}}{s}}`$ (11)
$`\times {\displaystyle }{\displaystyle \frac{dk}{2\pi }}{\displaystyle \frac{2K_0(b\sqrt{k^2+\kappa ^2})}{1+2\xi \overline{\mathrm{\Delta }}K_0(b\sqrt{k^2+\kappa ^2})}}\mathrm{cos}ks.`$
In this equation and in what follows we drop the subscript 1 in $`\mathrm{\Delta }_1`$ if it refers to a single-loop case. This expression should be compared with the OSF result, ı.e., $`\mathrm{}_{\mathrm{OSF}}=\mathrm{}_B\overline{q}^2/4b^2\kappa ^2`$, where $`e\overline{q}`$ is the “renormalized” charge per site and, in our notation, is $`\overline{q}=(f_0+f_1+Zf_2)`$. In OSF theory, the effect of condensed counterions is simply to reduce uniformly the backbone charge density. In contrast to OSF result, the effects of condensation cannot be described in terms of a single renormalized parameter $`\overline{q}`$. The first term in eq 11, arising from the net charge repulsion, tends to stiffen the chain, while the second term, originating from charge fluctuations, softens the chain and is responsible for the chain collapse at low temperatures kremer ; pincus ; klein .

In the limit of small $`\kappa b`$, the persistence length is dominated by large-scale charge fluctuations, corresponding to small-$`k`$ contributions. This leads to the following asymptotic expression for the persistence length

$$\mathrm{}_{elec}\frac{\mathrm{}_{\mathrm{OSF}}}{(1+2\xi \overline{\mathrm{\Delta }}K_0(\kappa b))^2}\frac{\xi ^2\overline{\mathrm{\Delta }}^2}{16}\frac{\kappa ^1}{1+2\xi \overline{\mathrm{\Delta }}K_0(\kappa b)}.$$
(12)
Note that the charge correlation contribution, ı.e., the second term, does not exhibit simple scaling behavior as a function of $`x\overline{\mathrm{\Delta }}\xi `$. For small $`x`$, it varies quadratically with $`x`$, but it crosses over to one that scales as $`x`$ for large $`x`$.

The OSF result is valid for $`\overline{\mathrm{\Delta }}\xi 1`$ (Cf. Fig. 1). Thus when the charge fluctuations are important, OSF result is not accurate and the fluctuation correction should be incorporated properly, as will also be detailed later. Our results in eq 11 should be compared with those for polyampholyte chains reported before ha.thirum . In the former case, we sum up all multipole expansions remark'' , while in the latter case the free energy is expanded in powers of $`\overline{q}`$ and $`\overline{\mathrm{\Delta }}`$. Inclusion of all multipole terms ha.bundle ; ha.pre  is crucial in the present case. This is because the counterion-mediated attraction becomes important when the chain is highly charged, ı.e., for large values of $`f_0`$. In this case, the multipole expansion diverges ha.bundle ; ha.pre . On the other hand, $`q`$ and $`\overline{\mathrm{\Delta }}`$ can be adjusted independently in the case of polyampholytes, and there can be finite ranges of parameters where the perturbative description is valid. The convergence of the expansion is ensured for the screened cases if $`\overline{\mathrm{\Delta }}`$ is small enough, as is the case for the problem discussed in Ref ha.thirum . More recently, Golestanian et al. kardar  and Ariel and Andelman andelman  have also considered a similar problem of the bending rigidity of a stiff polyelectrolyte. In contrast to the theory presented here, they only consider single-loop cases. At a low salt limit, our attractive bending rigidity scales as $`\kappa ^1\mathrm{log}(1/\kappa b)`$, which is in agreement with their result. On the other hand, our result in eq 12 differs from the one in Ref. nguyen , which is based on a SCL model of condensed counterions. If our result includes charge correlations driven by long-wavelength fluctuations, then the SCL approach captures short-wavelength charge correlations. Note that these two kinds of charge correlations should contribute to $`\mathrm{}_{elec}`$. More precisely the competition between the two will essentially determine the leading behavior of the persistence length. In Appendix A, we provide a heuristic argument to study this competition. We find that the persistence length can be mainly determined by long-wavelength correlations as captured by our approach, even when the charge correlation between counterions is dominated by short-wavelength correlations. This is because small bending is more efficiently felt by long-wavelength charge correlations. In other words, the mode of charge correlations that dominates $`\mathrm{}_{elec}`$ also depends on the mode of chain deformation, not just on counterion ordering.

The electrostatic free energy in eq 4 depends on the average number of the condensed counterions per monomer, $`f_\alpha `$ $`(\alpha =1,2)`$. To solve for $`f_\alpha `$ self-consistently, we equate the chemical potentials of condensed and free ions oosawa.book . In the following derivation, the subscript $`\alpha =1`$ and 2 refer to monovalent and multivalent ions, respectively. The chemical potential of free ions is mainly associated with the configurational entropy of mixing and is approximately given by $`\mu _\alpha ^{free}/k_BT\mathrm{log}n_\alpha v_0`$, where $`n_\alpha `$ is the bulk ion concentration and $`v_0`$ is the volume of ions. The chemical potential of condensed counterions arises from the attraction of counterions to PE chains and the entropic penalty for confinement remark3 :

$$\frac{\mu _\alpha ^{cond}}{k_BT}Z_\alpha \xi \overline{q}K_0(b\kappa )+\mathrm{log}f_\alpha +\frac{\mu _\alpha ^{fluc}}{k_BT},\alpha =1,2,$$
(13)
where $`\mu _\alpha ^{fluc}`$ is the charge fluctuation contribution to the chemical potential given by

$`{\displaystyle \frac{\mu _\alpha ^{fluc}}{k_BT}}=\left({\displaystyle \frac{}{f_\alpha }}\right)\{b{\displaystyle _0^{\mathrm{}}}{\displaystyle \frac{dk}{2\pi }}[\mathrm{log}(1+2\overline{\mathrm{\Delta }}\xi `$
$`\times K_0(b\sqrt{\kappa ^2+k^2}))2\overline{\mathrm{\Delta }}\xi K_0(b\sqrt{\kappa ^2+k^2})]\}.`$ (14)
Note that the term in $`\{\mathrm{}\}`$ is a standard charge fluctuation free energy of an one-dimensional Debye-Hückel system immersed in a three dimensional ionic fluid ha.bundle . Strictly speaking, our expression for $`\mu _\alpha ^{cond}`$ is valid for a rodlike chain conformation. In principle, the effect of chain deformation can be included; $`\mu _\alpha ^{cond}`$ can also be expanded in powers of $`1/R`$. The leading-order behavior of $`\mathrm{}_{elec}`$, however, is not influenced by the chain deformation correction to $`\mu _\alpha ^{cond}`$, since it only leads to a subleading correction to $`\mathrm{}_{elec}`$. The equilibrium value of $`f_\alpha `$ can be fixed by requiring $`\mu _\alpha ^{free}=\mu _\alpha ^{cond}`$. Note that $`\mu _\alpha ^{fluc}`$ can be important when $`Z`$ is large and $`\kappa ^1`$ is finite nguyen1 .

To demonstrate the potency of multivalent counterions in softening PE chains, we have solved for $`f_\alpha `$ and the electrostatic persistence length $`\mathrm{}_{elec}`$ simultaneously. We plot $`\mathrm{}_{elec}`$ as a function of $`f_0`$ in Fig. 1. We have chosen the parameters $`n_1=1\mathrm{m}\mathrm{M}`$, $`b=1.7\mathrm{\AA }`$, $`r_c=2\mathrm{\AA }`$, and $`\mathrm{}_B=7.1\mathrm{\AA }`$ (corresponding to $`T=300`$K in water for which $`\epsilon =80`$). First consider the case for which counterions are monovalent (ı.e., $`n_2=0`$) as described by the thin curves. In this case, $`\mathrm{}_{elec}`$ changes non-monotonically as $`f_0`$ increases. Our calculation should be compared with the corresponding OSF result $`\mathrm{}_{OSF}`$, which varies monotonically. Note that the OSF curve does not vary quadratically with $`f_0`$ beyond $`f_00.2`$. This is because condensed counterions start to renormalize the backbone charge density beyond $`f_00.2`$. The discrepancy between OSF result and ours may seem surprising. Our theory predicts that the chain size increases as the strength of Coulomb interaction increases, up to $`f_00.2`$. Beyond this, the chain shrinks its size with the increasing backbone charge fraction. This puzzling behavior can be understood in terms of the competition between the net charge repulsion and counterion-mediated attractions. When $`f_0<0.2`$, the long-ranged repulsion is dominant and the size of chain grows approximately quadratically with $`f_0`$, consistent with OSF result. The OSF behavior crosses over to the attractive regime where the charge fluctuations start to shrink the chain size. For sufficiently large $`f_0`$, $`\mathrm{}_{elec}`$ can become negative. In other words, the bending rigidity of highly charged PE chains is smaller than the corresponding non-ionic chains. The reduction in the bending rigidity is attributed to the charge correlation effect that becomes dominant over the respulsive contribution due to a finite excess charge.

The effect of counterion condensation is far more pronounced in the presence of a small concentration of 0.1mM of trivalent counterions ($`Z=3`$). Both OSF result (the bold dotted line) and our result (the bold solid line) start to deviate from the monovalent case (corresponding to the thin curves) beyond $`f_00.05`$. In other words, the presence of 0.1mM of trivalent counterions is more influential on the bending rigidity of PE chains than that of 1mM of monovalent ions. The result for $`\mathrm{}_{elec}`$ in this case is strikingly different from the corresponding monovalent case; $`\mathrm{}_{elec}`$ is much smaller than in the corresponding monovalent case as long as $`f_0>0.05`$; it is also negative over a wider range of $`f_0`$. Our results clearly demonstrate the efficiency of multivalent counterions in shorterning the persistence length of the PE chain, thus causing the collapse of the PE chain. The efficiency of $`Z=3`$ in reducing $`\mathrm{}_{elec}`$ can be attributed to the interplay between preferential adsorption of multivalent counterions (over monovalent ones) and charge fluctuation effects in determining the persistence length; highly charged macrions can preferentially bind multivalent counterions even when the bulk concentration is dominated by monovalent ions. Thus multivalent counterions are far more efficient on a molar basis in neutralizing the macroion charge jacob . The OSF result in the presence of a tiny concentration of multivalent counterions can strongly deviate from that for monovalent cases. Additionally, the strength of charge fluctuations grows approximately linearly with the valency of counterions, if preferential adsorption is assumed. When these two effects are combined, multivalent counterions can dramatically change the bending rigidity of PE chains as demonstrated in Fig. 1.

To further demonstrate the dramatic effects of multivalent counterions, we have estimated the electrostatic persistence length as a function of the concentration of multivalent counterions $`n_2`$. We have chosen the parameters $`Z=3`$, $`n_1=1\mathrm{m}\mathrm{M}`$, $`b=1.7\mathrm{\AA }`$, $`r_c=2\mathrm{\AA }`$, and $`\mathrm{}_B=7.1\mathrm{\AA }`$. We plot the electrostatic persistence length $`\mathrm{}_{elec}`$ in Fig. 2 as a function of $`n_2`$ for a few different values of $`f_0`$. Our results in the figure are intriguing. For all these cases (ı.e., $`f_0=1,0.75,0.5`$), $`\mathrm{}_{elec}`$ varies non-monotonically with $`n_2`$. It becomes more negative as $`n_2`$ increases from zero up to a certain value of $`n_2`$. Beyond this, it decreases in magnitude with increasing $`n_2`$. This implies that there is an optimal concentration at which $`\mathrm{}_{elec}`$ is most negative. Somehow this optimal value is not sensitive to $`f_0`$; it falls in the range $`0.01\mathrm{mM}n_20.1\mathrm{mM}`$ and hence only a small concentration is needed to soften PE chains. This clearly demonstrates the efficiency of multivalent counterions in softening oppositely charged PE chains. For the entire range of $`n_2`$ adopted in Fig. 2, $`\mathrm{}_{elec}`$ does not show a simple scaling law. When $`n_2`$ is somewhat smaller than the optimal value, $`\mathrm{}_{elec}`$ has weak dependence on $`n_2`$ as shown in the figure. We find that, for all cases (ı.e., $`f_0=1,0.75,0.5`$), $`\mathrm{}_{elec}`$ assumes the simple scaling form: $`\mathrm{}_{elec}c+d\mathrm{log}n_2`$, where $`c`$ and $`d`$ are $`n_2`$-independent negative numbers and the concentration $`n_2`$ is in mM. As evidenced in Fig. 2, $`d`$ (ı.e., the slope of the curves) is insensitive to $`f_0`$; it has been estimated to be close to $`0.2\mathrm{\AA }`$ for all three cases. In contrast, $`c`$ changes linearly with $`f_0`$ and is more negative for larger $`f_0`$; for the chosen parameters, $`c`$ has shown to be approximately given by $`c10f_0`$ (Å). It should be emphasized that both $`c`$ and $`d`$ are non-universal constants that can depend on $`\kappa `$ and $`Z`$ for fixed $`\mathrm{}_B`$ and $`b`$. Also note that this simple scaling behavior can be invalidated by the competitive binding on the one hand and the presence of the opposing effects in determining $`\mathrm{}_{elec}`$ (cf. eq 11) on the other.

The efficiency of multivalent counterions as evidenced by our results in Fig. 2 can also be understood in terms of competitive binding and charge fluctuations. When $`n_2=0`$, only the monovalent counterions bind to the PE chain. When $`n_20`$, however, the PE chain can preferentially bind multivalent counterions, replacing monovalent counterions in its vicinity, thus softening the PE chain, as can be seen by solving the linear equations in eq 13 simultaneously remark1 . For sufficiently highly charged PE chains $`(f_01)`$ at zero concentration, only a tiny concentration of multivalent counterions is needed to replace monovalent counterions. Note that the optimal value of $`n_2`$ at which $`\mathrm{}_{elec}`$ has the minimum value depends not only on $`n_1`$ but also on the concentration of PE chains. Beyond the optimal value, multivalent counterions start to contribute toward screening, weakening the correlation effect and thus leading to the non-monotonic variation of $`\mathrm{}_{elec}`$ with $`n_2`$. Our result in Fig. 2 corresponds to PE chains at zero concentration and thus a direct comparison of our result to experimantal data for PE chains at non-zero concentration should be made with due caution. Finally, computer simulations have explicitly provided evidence for the efficiency of multivalent counterions in inducing collapse of strongly charged polyelectrolytes Lee .

### II.3 Multi-loops

So far we have restricted ourselves to the single-loop case. Due to the breakdown of the pairwise additivity of charge-fluctuation interactions ha.bundle ; ha.pre , it is important to discuss the effects of inter-loop coupling on the bending rigidity. Based on our common intuition, we expect the inter-loop interactions to stiffen the condensate. This is because the net charge repulsion is longer ranged than the attraction ha.2rods . This conjecture is, however, based on the pairwise additivity of the electrostatic interactions between different loops and can easily be invalidated unless the charge fluctuations are small enough ha.bundle ; ha.pre ; ha.interface . For the case of parallel rods, it has been shown that the pairwise additivity is valid only when the interaction is repulsive ha.bundle ; ha.pre . By the same token, it is crucial to include non-pairwise additive interactions or many-body effects thirum  in the description of the bending rigidity of PE condensates. Because the solution of eq 10 in general cases is difficult, we invoke physically motivated simplification. To understand the physical consequences of non-pairwise additive interactions on the bending rigidity, we make some approximations. First we do not explicitely include excluded volume repulsion between loops. To keep different loops from approaching arbitrarily close to each other, we assume that loops in the condensate are arranged on a square lattice with lattice constant $`a`$. The lattice constant $`a`$ can be considered as an equilibrium distance between two neighboring loops, which is determined by the balance of a few competing effects: charge correlation attractions, excluded volume repulsions, etc. We also assume that all loops in the bundle remain parallel with each other, even when they bend, and that $`\overline{\mathrm{\Delta }}_j`$ and $`\overline{q}_j`$ are independent of $`j`$ and taken to be equal to $`\overline{\mathrm{\Delta }}`$ and $`\overline{q}`$, respectively. With this simplification, we can take advantage of this periodicity to recast the problem using discrete Fourier transform. The resulting bending free energy is given by

$`\mathrm{}_{elec}`$ $``$ $`{\displaystyle \frac{\overline{q}^2\left({}_{}{}^{0}\stackrel{~}{D}\right)}{\left[1+2\xi \overline{\mathrm{\Delta }}\left({}_{}{}^{0}\stackrel{~}{K_0}\right)\right]^2}}{\displaystyle \underset{j_1j_2=0}{\overset{\sqrt{N}1}{}}}{\displaystyle 𝑑sD_𝐣_{}(s)}`$ (15)
$`\times {\displaystyle \underset{𝐤_{}}{}}{\displaystyle }{\displaystyle \frac{dk}{2\pi }}{\displaystyle \frac{2\overline{\mathrm{\Delta }}\xi \stackrel{~}{K_0}(𝐤_{},k)}{1+2\overline{\mathrm{\Delta }}\xi \stackrel{~}{K_0}(𝐤_{},k)}}\mathrm{cos}(𝐤_{}𝐣_{})`$
$`\times \mathrm{cos}ks,`$
where $`𝐤_{}`$ is the wave vector conjugate to $`a𝐣_{}`$, where $`𝐣_{}(j_1,j_2)`$ and $`j_1,j_2=0.1,\mathrm{},\sqrt{N}1`$, and is given by $`𝐤_{}=\frac{2\pi }{\sqrt{N}}(n_1,n_2)`$ with $`n_1,n_2=0,1,\mathrm{},\sqrt{N}1`$. We denote the discrete Fourier transform of a function $`g(a|𝐣_{}|\sqrt{\kappa ^2+k^2})`$ as

$$\stackrel{~}{g}(k,𝐤_{})\underset{j_1j_2=0}{\overset{\sqrt{N}1}{}}g(a|𝐣_{}|\sqrt{\kappa ^2+k^2})\mathrm{cos}𝐤_{}𝐣_{}.$$
(16)
Finally, the function $`{}_{}{}^{0}\stackrel{~}{g}`$ is simply $`g(k=0,𝐤_{}=0)`$.

First note that the bending free energy of $`N`$-loop condensates is not simply $`N`$ times that of a single loop. Our theory suggests that each loop in a bundle is further softened due to the inter-loop coupling, as implied by eq 15. We expect that the repulsive bending rigidity per loop $`decreases`$ with $`N`$. This is because coupling between charges on different loops enhances screening in electrostatic repulsions. Similarly, the attractive interaction becomes stronger as $`N`$ increases, due to enhanced charge correlations as will be detailed later. More precisely, inter-loop correlations enhance intra-loop correlations. A similar issue for the case of rigid PEs is discussed by Ha and Liu ha.correlation . The implication of eq 15 is most striking in the limit of $`\kappa b0`$: For sufficiently large $`N`$, the repulsive term in eq 15 scales as $`1/N`$ and becomes vanishingly small as $`N\mathrm{}`$. Thus, only the attraction can modify the bending rigidity in this case. Recently, Ha and Liu ha.interface  have considered two interacting bundles of randomly-charged rods and shown that, as $`\kappa b0`$, the interfacial interaction comes from charge-fluctuation attractions only. This is analogous to the vanishingly small contribution of the repulsion to the bending rigidity in the present case. For the screened case of $`\kappa 0`$, on the other hand, the repulsion also contributes to the bending rigidity.

For sufficiently large $`N`$, we can show that the condensate has a well-defined bulk bending free energy: $`\mathrm{\Delta }_{\mathrm{elec}}V\mathrm{}_{bulk}`$ where $`V`$ is the condensate volume and $`\mathrm{}_{bulk}`$ is $`N`$-independent persistence length. To establish this, we examine the behavior of $`{}_{}{}^{0}K_{0}^{},\stackrel{~}{K_0}(k,𝐤_{})`$, and $`\stackrel{~}{D}(k,𝐤_{})`$ for large $`N`$. For large $`x`$, $`K_0(x)1/\sqrt{x}\mathrm{e}^x`$ and thus $`{}_{}{}^{0}\stackrel{~}{K_0},{}_{}{}^{0}\stackrel{~}{D},\stackrel{~}{K_0}(k,𝐤_{})`$ approach constants as $`N\mathrm{}`$. Similarly, it can be shown that $`{}_{}{}^{0}\stackrel{~}{D},\stackrel{~}{D}(k,𝐤_{})`$ also become constants as $`N\mathrm{}`$. This is trivially true for finite $`\kappa `$. As $`\kappa 0`$, it suffices to establish this asymptotic behavior for the attractive term only, since the repulsive term becomes dominated in this limit. As $`\kappa 0`$, $`D_{ij}(s)`$ in eq II.1 vanishes at least as fast as $`1/R_{ij}^2`$ for large $`|ij|`$. Thus the descrete Fourier transform is convergent. Furthermore, for large $`N`$, we can replace the sum $`_𝐤_{}`$ can be replaced by $`N_0^{2\pi /a}\frac{d𝐤_{}}{(2\pi )^2}`$, up to a correction of order unity. From these arguments, we conclude that the bending free enegy per monomer increases linearly with $`N`$ for sufficiently large $`N`$. This enables us to write the total bending free energy as $`\mathrm{\Delta }F_{elec}/k_BT=\frac{1}{2}\mathrm{}_{bulk}V/R^2a^2`$, where $`\mathrm{}_{bulk}`$ is $`N`$-independent persistence length per loop. An asymptotic behavor of $`\mathrm{}_{bulk}`$ can be obtained replacing the summations by integrals; we found that, for $`\kappa D1`$, $`\mathrm{}_{bulk}`$ varies as

$$\mathrm{}_{bulk}\frac{\kappa ^1}{\mathrm{log}(\kappa ^1/D)},$$
(17)
where $`D`$ is the crosssectional diameter of the bundle, $`D=\sqrt{N}a`$. This should be compared with the corresponding result for a single loop case; the PE chains are further softened by inter-loop couplings by the factor of $`\mathrm{log}(b/D)`$. Park et al. park  have used a similar expression for the bending free energy (Cf. their eq 1) without the benefit of derivation. Here, we have shown that “many-body effects”, ı.e., loop-loop couplings, lead to the bending free energy of PE condensates which grows linearly with $`N`$ for $`N1`$, providing a quantitative basis for the previous work of Park et al. park .

## III Conclusions

In conclusion, we have studied the effect of charge fluctuations on the stiffness of highly charged stiff PE chains. In particular, we have focused on the interplay between competitive binding of counterions to PE chains and charge correlations between condensed counterions in softening the PE chains. We have shown that the bending rigidity of the PE chain, in the presence of counterion condensation, cannot be captured by a simple scaling behavior. The existence of multiple distinct regimes characterizes the conformations of highly charged PEs. This is a consequence of the simultaneous presence of competing interactions, which tends to invalidate a simple scaling analysis. Our theory also illustrates the significance of non-pairwise additivity of counterion-mediated interactions in softening PE chains; we have shown that the inter-loop coupling enhances softening, resulting in a well-defined bulk bending free energy.

Acknowledgements: This work was supported in part by the National Science Foundations through grant number CHE0209340 (DT) and by the Natural Science and Engineering Research Council of Canada (BYH). We are grateful to D. Andelmann for helpful comments.

## Appendix A

In this appendix we argure that the Debye-Hückel (DH) approach may be valid over a much wider parameter space than implied by a simple thermodynamic consideration in Ref. nguyen . In Ref. nguyen , condensed counterions are considered as forming a strongly correlated liquid (SCL) confined to the surface of their binding PE chains. It was then argued that the negative, charge correlation contribution to the persistence length is dominated by these strong charged correlations of the SCL. In this appendix, we argue the thermodynamic argument underestimates the importance of long-wavelength charge fluctuations as compared to SCL correlations, since it ignores the coupling of charge correlations to bending. Recently, it has been shown that, at high temperatures, long-wavelength (LW) charge fluctuations dominate the free energy, while short-wavelength (SW) fluctuations are dominant at low temperatures ha.mode . Even below the freezing temperature, there exists a LW contribution to the free energy. Interestingly the major contribution to the electrostatic bending rigidity of a polyelectrolyte chain can arise from LW charge fluctuations even when the free energy is dominated by SW fluctuations, as long as the chain is near the rod limit. This is because small bending is more effectively felt by the LW charge fluctuations. In this case the DH approach ought to be a good approximation.

To focus on the essential physics of this issue, we here consider a single-loop case where all backbone charges are neutralized by counterions. Near the rod limit, we can write the interaction Hamiltonian as follows: $`=_{\mathrm{rod}}+\mathrm{\Delta }`$ where $`_{\mathrm{rod}}`$ corresponds to the rodlike conformation and $`\mathrm{\Delta }`$ is the change in the interaction due to bending. The free energy cost due to bending is

$$\mathrm{\Delta }=\mathrm{\Delta }=\frac{1}{2}\underset{ss^{}}{}D(s,s^{})q(s)q(s^{})+𝒪\left(R^4\right),$$
$`(A1)`$
where $`\mathrm{}`$ is an average with respect to the Boltzmann factor $`\mathrm{e}^{_{\mathrm{rod}}/k_BT}`$ and $`D(s,s^{})`$ is

$$D(s,s^{})=\frac{\xi }{24}\frac{\mathrm{e}^{\kappa |ss^{}|}}{|ss^{}|}\left(|ss^{}|^2+\kappa |ss^{}|^3\right).$$
$`(A2)`$
The charge correlation contribution to the persistence length can be read off from this expression:

$$\mathrm{}_{corr}=\frac{\xi }{24L}\underset{ss^{}}{}D(s,s^{})q(s)q(s^{}).$$
$`(A3)`$
Now the computation of the persistence length reduces to the computation of the charge correlation function $`q(s)q(s^{})`$. So far our formalism is exact up to $`1/R^2`$.

If we use a Debye-Hückel (DH) approximation, then $`q(s)q(s^{})`$ is simply

$$q(s)q(s^{})_{DH}=Q^1(s,s^{}),$$
$`(A4)`$
where $`Q`$ is a matrix whose matrix element $`Q(s,s^{})`$ is

$$Q(s,s^{})=\overline{\mathrm{\Delta }}^1\delta _{ss^{}}+\mathrm{}_B\frac{\mathrm{e}^{\kappa |ss^{}|}}{|ss^{}|}.$$
$`(A5)`$
As a result, the persistence length in eq $`A3`$ reduces to the one in eq 12. In the limit of $`\kappa 0`$, the DH approximation leads to

$$\mathrm{}_{DH}\frac{\left(\xi \overline{\mathrm{\Delta }}\right)^2}{16}\frac{\kappa ^1}{1+2\xi \overline{\mathrm{\Delta }}\mathrm{log}(1/\kappa b)}.$$
$`(A6)`$
The persistence length in this expression grows linearly with the Debye screening length.

At low temperatures, the backbone charges together with the condensed counterions tend to be strongly correlated. To simplify the problem we assume that $`f_0=1`$ and that counterions are divalent ($`Z=2`$) and form an ionic crystal such that the charge distribution along the chain is represented by a ground state $`(++++)`$. The resulting charge correlation can then be approximated by the following oscillatory function: $`q(s)q(s^{})_{osc}\mathrm{cos}(\pi |ss^{}|/b)`$. If we use this expression in eq $`A3`$, then we have

$$\mathrm{}_{osc}=\frac{\xi }{6}\underset{s=1}{\overset{\mathrm{}}{}}\frac{\mathrm{e}^{\kappa s}}{s}\left(s^2+\kappa s^3\right)\mathrm{cos}\left(\frac{\pi s}{b}\right).$$
$`(A7)`$
In the limit of $`\kappa b0`$, $`\mathrm{}_{osc}`$ approaches

$$\mathrm{}_{osc}=\frac{\mathrm{}_B}{26}.$$
$`(A8)`$
This result can be compared to the one based on the SCL model of polyelectolytes nguyen , $`\mathrm{}_{SCL}=Z^2\mathrm{}_B/96`$. For $`Z=2`$, this leads to $`\mathrm{}_{SCL}=\mathrm{}_B/24`$. Note that $`\mathrm{}_{SCL}`$ is only slightly different from the one in eq $`A8`$. This difference can be attributed to the fact that we treat the charge fluctuations differently from the SCL approach. Note that $`\mathrm{}_{DH}`$ is much larger than $`\mathrm{}_{SCL}`$ for small $`\kappa b`$. This is becase the LW charge fluctuations are much more effectively felt by small bending in this case.

However, neither of $`\mathrm{}_{DH}`$ nor $`\mathrm{}_{OSC}`$ solely describes the bending rigidity of polyelectrolyte chains for a wide range of $`T`$ or $`f_0`$. This is because $`\mathrm{}_{OSC}`$ suppresses fluctuations while $`\mathrm{}_{DH}`$ does not accurately capture strong charge fluctuations. In general both LW and SW charge flcutuations contribute to the persistence length. To study the competition between the two, we use a linear response theory and assume that the free energy of the charge fluctuations on a rod can be written in the Fourier space as

$$\frac{_{\mathrm{rod}}}{k_BT}=\frac{1}{2}\underset{k}{}\delta q(k)S^1(k)\delta q(k),$$
$`(A9)`$
where $`S(k)`$ is the charge structure factor. The probability of the fluctuation $`\delta q(k)`$ is proportional to the factor $`\mathrm{exp}\left[S^1(k)\right]`$. At high temperatures, $`S(k)S_{DH}(k)Q^1(k)`$ while at low temperatures $`S(k)S_{OSC}(k)\delta _{k\frac{\pi }{b}}`$. At intermediate temperatures, we assume that $`S(k)A(T)S_{DH}(k)+B(T)S_{OSC}(k)`$. Within this approximation, the charge correlation persistence length is given by

$$\begin{array}{cc}\hfill \mathrm{}_{corr}& A(T)\mathrm{}_{DH}B(T)\mathrm{}_{OSC}\hfill \\ \hfill & A(T)\frac{\xi \overline{\mathrm{\Delta }}}{32}\frac{\kappa ^1}{\mathrm{log}(1/\kappa b)}B(T)\frac{\mathrm{}_B}{26}\hfill \end{array}.$$
$`(A10)`$
Suppose the free energy is dominated by short-wavelength fluctuations, ı.e., $`A(T)B(T)`$. Even in this case, however, the persistence length can be dominated by long-wavelength fluctuations, ı.e., $`\mathrm{}_{corr}A(T)\mathrm{}_{DH}`$ in the limit of $`\kappa b0`$. This is because small bending is much more effectively felt by the long-wavelength fluctuations in this limit. Unfortunately, the precise form of $`A(T)`$ and $`B(T)`$ for a wide range of $`T`$ are not known to date. Nevertheless it is clear that $`A(T)1`$ is a good approximation at high temperatures, while $`B(T)1`$ as $`T0`$. Near and at the crossover region between $`\mathrm{}_{DH}`$ and $`\mathrm{}_{OSC}`$, however, $`A(T)`$ and $`B(T)`$ may deviate from this asymptotic value, ı.e., 1. If we use this, we would get a simple criterion for the DH approach to be valid:

$$\frac{\kappa ^1}{\mathrm{log}\left(1/\kappa b\right)}>1.$$
$`(A11)`$
Note that this can easily be satisfied at a low salt limit. This implies that the electrostatic persistence length can be mainly determined by $`\mathrm{}_{DH}`$, even when $`A(T)B(T)`$. As a result, our DH approach is valid for a much wider parameter space than implied by Ref. nguyen  which suppressed the interplay between chain deformation and charge correlations in determining the mode of charge correlations that dominates the persistence length.

## IV Appendix B

In this appendix, we outline the derivation of our major result in eq 10. In this appendix we use $`𝑫`$ to denote $`𝑸𝑸_\mathrm{𝟎}`$. First consider the first term of eq 10. To simplify this term, consider

$$\begin{array}{cc}\hfill I& \underset{ss^{}}{}\left[𝑸_0^1𝑫𝑸_0^1\right]_{jj^{}ss^{}}\hfill \\ & =\underset{ss^{}s^{\prime \prime }s^{\prime \prime \prime }}{}\left[\left(𝑸_0^1\right)_{ss^{\prime \prime }}𝑫_{s^{\prime \prime }s^{\prime \prime \prime }}\left(𝑸_0^1\right)_{s^{\prime \prime \prime }s^{}}\right]_{jj^{}}\hfill \end{array}.$$
$`(B1)`$
In this equation and in what follows, $`\left(𝑨_{ss^{}}\right)_{jj^{}}=𝑨_{ss^{}jj^{}}`$, where $`𝑨`$ is a block matrix such as $`𝑸`$. It then follows that $`\left[\left(𝑨𝑩\right)_{ss^{}}\right]_{jj^{}}=\left(_{s^{\prime \prime }}𝑨_{ss^{\prime \prime }}𝑩_{s^{\prime \prime }s^{}}\right)_{jj^{}}=_{j^{\prime \prime }}_{s^{\prime \prime }}𝑨_{jj^{\prime \prime }ss^{\prime \prime }}𝑩_{j^{\prime \prime }j^{}s^{\prime \prime }s^{}}`$, where $`𝑩`$ is also a block matrix of the same rank. Note that $`\left(𝑸_0^1\right)_{jj^{\prime \prime }ss^{\prime \prime }}`$ is a function of $`|ss^{\prime \prime }|`$. It is easy to show that

$$\underset{s}{}\left(𝑸_0^1\right)_{jj^{\prime \prime }ss^{\prime \prime }}=\left[\underset{s}{}\left(𝑸_0^1\right)_{ss^{\prime \prime }}\right]_{jj^{\prime \prime }}={}_{}{}^{0}_{jj^{\prime \prime }}^{1},$$
$`(B2)`$
where $`{}_{}{}^{0}`$ is the same matrix defined in eq 8. Here, the second step follows from

$$\begin{array}{cc}\hfill \left[\underset{s}{}\left(𝑸_0^1\right)_{ss^{\prime \prime }}\right]_{jj^{\prime \prime }}& =\left[\underset{s}{}\left(\frac{1}{\overline{\mathrm{\Delta }}^1+𝑽}\right)_{ss^{\prime \prime }}\right]_{jj^{\prime \prime }}\hfill \\ & =\left[\underset{s}{}\overline{\mathrm{\Delta }}\left(1\overline{\mathrm{\Delta }}𝑽+\overline{\mathrm{\Delta }}^2𝑽^2+\mathrm{}\right)_{ss^{\prime \prime }}\right]_{jj^{\prime \prime }}\hfill \\ & =\frac{1}{b}\left[\overline{\mathrm{\Delta }}\left(1\overline{\mathrm{\Delta }}2\xi K_0+\mathrm{\Delta }^2(2\xi K_0)^2+\mathrm{}\right)\right]_{jj^{\prime \prime }}\hfill \\ & ={}_{}{}^{0}_{jj^{\prime \prime }}^{1}\hfill \end{array},$$
$`(B3)`$
where $`𝑽_{jj^{}ss^{}}=\mathrm{}_B\frac{e^{\kappa |𝐫_j(s)𝐫_j^{}(s^{})|}}{|𝐫_j(s)𝐫_j^{}(s^{})|}`$ and $`\left(K_0\right)_{jj^{}}=K_0(\kappa R_{jj^{}})`$. If we use this in eq $`B1`$, then we have

$$I=\left[{}_{}{}^{0}_{}^{1}\underset{s^{\prime \prime }s^{\prime \prime \prime }}{}𝑫_{s^{\prime \prime }s^{\prime \prime \prime }}{}_{}{}^{0}_{}^{1}\right]_{jj^{}}.$$
$`(B4)`$
This , if combined with eq 6, essentially leads to the first term of eq 10 in the continuum limit.

To simplify the second term of eq 10, consider

$$J\left(𝑸_0^1𝑫\right)_{jjss}=\left[\underset{s^{}}{}\left(𝑸_0^1\right)_{ss^{}}𝑫_{s^{}s}\right]_{jj}.$$
$`(B5)`$
Here $`\left(𝑸_0^1\right)_{ss^{}}`$ can be expanded as follows:

$$\begin{array}{cc}\hfill \left(𝑸_0^1\right)_{ss^{}}& =\left(\frac{1}{\overline{\mathrm{\Delta }}_j^1+𝑽}\right)_{ss^{}}\hfill \\ & =\overline{\mathrm{\Delta }}_j\left(\delta _{ss^{}}\overline{\mathrm{\Delta }}_j𝑽_{ss^{}}+\overline{\mathrm{\Delta }}_j^2\underset{s^{\prime \prime }}{}𝑽_{ss^{\prime \prime }}𝑽_{s^{\prime \prime }s^{}}+\mathrm{}\right)\hfill \end{array}.$$
$`(B6)`$
Using this in eq $`B5`$, we have

$$\begin{array}{cc}\hfill J=& \overline{\mathrm{\Delta }}_j[𝑫_{ss}\underset{s^{}}{}(\overline{\mathrm{\Delta }}_j𝑽_{ss^{}}𝑫_{ss^{}}\hfill \\ & \overline{\mathrm{\Delta }}_j^2\underset{s^{}s^{\prime \prime }}{}𝑽_{ss^{\prime \prime }}𝑽_{s^{\prime \prime }s^{}}𝑫_{s^{}s}\hfill \\ & +\overline{\mathrm{\Delta }}_j^3\underset{s^{}s^{\prime \prime }s^{\prime \prime \prime }}{}𝑽_{ss^{\prime \prime }}𝑽_{s^{\prime \prime }s^{\prime \prime \prime }}𝑽_{s^{\prime \prime \prime }s^{}}𝑫_{s^{}s}+\mathrm{})]_{jj}\hfill \end{array}.$$
$`(B7)`$
Note that the first-order term in $`\overline{\mathrm{\Delta }}_j`$ in this equation will cancel the term containing $`\overline{\mathrm{\Delta }}`$ in the second term of eq 10. As a result, the second term of eq 10 becomes

$$\begin{array}{cc}\hfill \text{2nd term}& =\frac{1}{2}\underset{j}{}\overline{\mathrm{\Delta }}_j[\underset{ss^{}}{}(\overline{\mathrm{\Delta }}_j𝑽_{ss^{}}𝑫_{ss^{}}\hfill \\ & \overline{\mathrm{\Delta }}_j^2\underset{s^{\prime \prime }}{}𝑽_{ss^{\prime \prime }}𝑽_{s^{\prime \prime }s^{}}𝑫_{s^{}s}\hfill \\ & +\overline{\mathrm{\Delta }}_j^3\underset{s^{\prime \prime }s^{\prime \prime \prime }}{}𝑽_{ss^{\prime \prime }}𝑽_{s^{\prime \prime }s^{\prime \prime \prime }}𝑽_{s^{\prime \prime \prime }s^{}}𝑫_{s^{}s}+\mathrm{})]_{jj}\hfill \end{array}.$$
$`(B8)`$
In the Fourier space $`k`$, conjugate to $`ss^{}`$, this equation can be diagonalized with respect to $`s`$ and $`s^{}`$ and resummed:

$$\begin{array}{cc}\hfill \text{2nd term}=& \frac{M}{2}\underset{j}{}\overline{\mathrm{\Delta }}_j[\frac{dk}{2\pi }(\overline{\mathrm{\Delta }}_j𝑽(k)𝑫(k)\hfill \\ & \overline{\mathrm{\Delta }}_j^2𝑽(k)𝑽(k)𝑫(k)\hfill \\ & +\overline{\mathrm{\Delta }}_j^3𝑽(k)𝑽(k)𝑽(k)𝑫(k)+\mathrm{})]_{jj^{}}\hfill \\ & =\frac{M}{2}\underset{j}{}\overline{\mathrm{\Delta }}_j\left[\frac{dk}{2\pi }\frac{\overline{\mathrm{\Delta }}_j𝑽(k)𝑫(k)}{1+\overline{\mathrm{\Delta }}_j𝑽(k)}\right]_{jj}\hfill \end{array},$$
$`(B9)`$
where $`f(k)`$ is a Fourier transform of $`f(s)`$: $`f(k)=_sf(s)\mathrm{cos}ks`$. This essentially leads to the second term of eq 10.


text:
# References

## References

\[T\] A. Tumanov, Extremal discs and the regularity of CR mappings in higher codimension, Amer. J. Math. 123 (2001), 445–473.

Alexander Tumanov, Department of Mathematics, University of Illinois, Urbana, IL 61801. E-mail: tumanov@uiuc.edu