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# One-dimensional Surface Bound States in d-wave Superconductors

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## Abstract

We present an exact quantum theory for the bound states in the vicinity of an edge or a line of impurities in a $`d_{x^2y^2}`$ superconductor. For a $`(110)`$-surface we show that a finite dispersion of the one dimensional band of bound states leads to a two peak structure in the density of states (DOS). We study the effect of an applied magnetic field and a subdominant $`id_{xy}`$ order parameter on the DOS and discuss the implications of our results for tunneling experiments.

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The existence of a zero bias conductance peak (ZBCP), observed by in-plane tunneling spectroscopy on YBa2Cu3O7 (YBCO) thin films  has been interpreted as a signature of unconventional superconductivity. In the framework of the quasiclassical approximation, it was first shown by Hu , and subsequently studied in more details in Refs. , that in superconductors with $`d_{x^2y^2}`$ symmetry the ZBCP arises from a one-dimensional dispersionless band of surface bound states. Recently Covington et al. discovered the splitting of the ZBCP into two peaks not only in the presence of an applied field, $`H`$, but also for $`H=0`$ below $`T_s=8`$ K . Within the quasiclassical approach, the splitting for $`H=0`$ was ascribed to a spontaneously broken time reversal symmetry (BTRS) on the surface of YBCO and the generation of a subleading superconducting order parameter with $`id_{xy}`$ or $`is`$ symmetry . While in conventional superconductors corrections to the bound state energy beyond the quasiclassical approximation are too small to be observed experimentally, the corrections in high temperature superconductors (HTSC) are of the order of $`\mathrm{\Delta }_0^2/E_F3`$ meV and thus comparable to the experimentally observed peak splitting. This necessitates a fully microscopic treatment of the problem before a conclusion about the nature of the splitting for $`H=0`$ can be reached.

In this Letter we present a microscopic theory which goes beyond the quasiclassical approximation and allows us to capture properties of the ZBCP that eluded earlier investigations. By developing a scattering matrix formalism for one-dimensional (1D) defects, appropriate to describe surfaces or lines of impurities, we show that the band of bound states has a finite dispersion that leads to a two-peak structure in the density of states (DOS), even in the absence of a BTRS. We predict the existence of Friedel oscillations associated with the bound states and show that their spatial dependence varies strongly with the so-called acceptance angle of the measurements. In the presence of a supercurrent or magnetic field the DOS exhibits a four-peak structure for small acceptance angles, but only two peaks with increased frequency splitting for large acceptance angles. We show that the onset of a subdominant order parameter with $`id_{xy}`$ symmetry leads to a sharpening of the two-peak structure in the DOS, but does not induce any qualitatively new features. Finally, we compare our results with the in-plane tunneling experiments on YBCO  and comment on the extensions of our formalism to treat surface bound states in systems with other non-trivial order parameters.

We begin by presenting an exact scattering theory which describes the emergence of a bound state in the vicinity of an interface, e.g., a line of impurities or a surface along the $`(1m0)`$ direction, in a $`d_{x^2y^2}`$ superconductor. The scattering of the electrons off the interface is described by $`U(𝐫)=U_{𝐑_i}\delta (𝐫𝐑_i)`$, where the sum runs over all $`𝐑_i=(x,mx)`$. The Green’s function in the presence of this potential is given by

$`\widehat{G}(𝐫,𝐫^{},\omega )`$ $`=`$ $`\widehat{G}_0(𝐫𝐫,\omega )+`$ (2)
$`{\displaystyle \underset{𝐬𝐬^{}}{}}\widehat{G}_0(𝐫𝐬,\omega )\widehat{T}(𝐬,𝐬^{},\omega )\widehat{G}_0(𝐬^{}𝐫^{},\omega ),`$
where the fourier transform of the scattering $`\widehat{T}`$-matrix only depends on the momentum parallel to the line, $`q_{}`$,

$$\widehat{T}(q_{},\omega )=[1U\widehat{\tau }_3^{}\frac{d𝐩}{2\pi }\widehat{G}_0(𝐩,\omega )]^1U\widehat{\tau }_3.$$
(3)
$`\widehat{\tau }_\alpha `$ are the Pauli matrices, and the prime restricts the integration to those momenta in the first Brillouin zone (BZ) for which $`p_x+mp_yq_{}=2\pi n`$, with $`n`$ integer. For the Green’s function of the clean system one has

$$\widehat{G}_0(𝐤,\omega )=[\omega \widehat{\tau }_0ϵ_𝐤\widehat{\tau }_3\mathrm{\Delta }_𝐤^{(0)}\widehat{\tau }_1]^1,$$
(4)
where $`\mathrm{\Delta }_𝐤^{(0)}=\mathrm{\Delta }_0(\mathrm{cos}k_x\mathrm{cos}k_y)/2`$ is the $`d_{x^2y^2}`$ superconducting gap . For the normal state we use a quasi-particle dispersion, representative for the HTSC

$$ϵ_𝐤=2t(\mathrm{cos}k_x+\mathrm{cos}k_y)4t^{}\mathrm{cos}k_x\mathrm{cos}k_y\mu $$
(5)
with $`t=300`$ meV, $`t^{}/t=0.3`$, $`\mu /t=0.99`$ and $`\mathrm{\Delta }_0=25`$ meV .

In the following we consider for definiteness a surface along the $`(110)`$ direction (with $`U=\mathrm{}`$). The induced surface bound states represent quasiparticles that are localized in the direction perpendicular to the surface, but have a well defined momentum parallel to it. The dispersion, $`\omega _s(q_{})`$, of these bound states is determined by the poles of the $`\widehat{T}`$-matrix and thus follows from the condition

$$^{}𝑑𝐩\frac{ϵ_p}{\omega _s^2ϵ_p^2\mathrm{\Delta }_p^2}=\pm ^{}𝑑𝐩\frac{\omega _s}{\omega _s^2ϵ_p^2\mathrm{\Delta }_p^2}.$$
(6)
For a $`(110)`$-surface, the integration is restricted to a line of momenta parallel to the $`(1\overline{1}0)`$-direction (dashed line in the inset of Fig. 1).

For small $`q_{}`$ the integrals in Eq.(6) can be expanded by standard means, and one finds that the dispersion is quadratic in $`q_{}`$ if the Fermi surface (FS) is particle-hole symmetric and linear in $`q_{}`$ when this symmetry is absent (as is the case for the FS shown in Fig. 1). In Fig. 1 we present the dispersion of the bound states, obtained from the full numerical solution of Eq.(6), together with the gap edge of the particle-hole continuum. The sharp drop of the bound state energy at $`q_{}^0`$ occurs when the line of integration crosses the FS at $`𝐤_c`$ (see inset). Just below this crossing, i.e., for $`q_{}q_{}^0`$, the poles of the $`\widehat{T}`$-matrix lie within the particle-hole continuum, and the surface states are damped resonant state.

The DOS, renormalized by the defect/surface scattering, at a distance $`r_{}=(r_xr_y)/\sqrt{2}`$ from the surface is given by $`N(\omega ,r_{})=\mathrm{Im}[\widehat{G}_0(𝐫,𝐫,\omega )+\delta \widehat{G}(𝐫,𝐫,\omega )]_{\mathrm{\hspace{0.17em}11}}`$, where

$`\delta \widehat{G}(r_{},\omega )`$ $`=`$ $`{\displaystyle _\mathrm{\Lambda }^\mathrm{\Lambda }}{\displaystyle \frac{dq_{}}{2\pi }}\widehat{G}_0^{\prime \prime }(\omega ,q_{},𝐫)\widehat{T}(q_{},\omega )\widehat{G}_0^{}(\omega ,q_{},𝐫)`$ (8)
$`\widehat{G}_0^{(\prime \prime )}(\omega ,q_{},𝐫)={\displaystyle ^{(\prime \prime )}}{\displaystyle \frac{d𝐩}{2\pi }}e^{i\mathrm{𝐩𝐫}}\widehat{G}_0(\omega ,𝐩),`$
and the double prime restricts the integration to all momenta in the first BZ with $`p_x+mp_yq_{}=0`$. Summation over all $`q_{}`$ in Eq.(8) corresponds to $`\mathrm{\Lambda }=\sqrt{2}\pi `$. However, in the analysis of tunneling experiments it is in general assumed that $`\mathrm{\Lambda }<\sqrt{2}\pi `$ due to the finite acceptance angle of the experiments ; in what follows we therefore consider two different values of $`\mathrm{\Lambda }`$ in our calculations of the DOS. Note that the above expression for $`\delta \widehat{G}`$ is similar to the one for a single impurity problem .

In Fig. 2 we plot $`N(r_{},\omega )`$ obtained numerically for $`\mathrm{\Lambda }=1/\sqrt{2}`$ and $`\sqrt{2}\pi `$.

In both cases, the DOS exhibits a two-peak structure and Friedel oscillations (FO) whose spatial dependence is described by $`N(r_{},\omega )e^{ik_0r_{}}e^{r_{}/\xi }`$. Both $`k_0`$ and $`\xi `$ vary with frequency and through $`\omega _s(q_{})`$ implicitly depend on $`q_{}`$. For $`\mathrm{\Lambda }=1/\sqrt{2}`$, there exist only two bound states with wave-vector $`\pm q_{}`$ for any frequency $`\omega \omega _s(\mathrm{\Lambda })`$ and one has $`k_0(\omega _s)=2k_{F,}(\omega _s)=\sqrt{2}(k_F^xk_F^y)`$ (see Fig. 1). Moreover, since $`k_0`$ increases with increasing $`|q_{}|`$, the wavelength of the FO decreases with increasing $`|\omega |`$, as can clearly be seen in Fig. 2a. The lengthscale, $`\xi `$, for the exponential decay of the FO into the bulk is set by $`\xi =v_{F,}/\sqrt{\overline{\mathrm{\Delta }}^2\omega _s^2}1`$, where $`\overline{\mathrm{\Delta }}`$ is the superconducting gap at the respective FS crossing. For $`\mathrm{\Lambda }=\sqrt{2}\pi `$, where we integrate over all $`q_{}`$, the FO below and above 4 meV are qualitatively different. For $`\omega 4`$ meV there exist four bound states, two close to $`q_{}=0`$ and $`q_{}=\pi `$ (see Fig. 1), whose superposition leads to the rapid decay of the FO at low frequencies. In contrast, for $`\omega 4`$ meV, only two bound states exist for a given frequency and the DOS again exhibits well defined FO. While a particle-hole symmetry is absent in the DOS for a given $`r_{}`$, it is recovered after averaging over $`r_{}`$.

We next study the effects of an applied magnetic field on the DOS. To avoid the problems arising from the presence of vortices and a spatial variation of the supercurrent, we consider for simplicity an average supercurrent with momentum $`𝐩_s`$; our results are thus exact for the case when a uniform supercurrent is applied to the sample. For $`𝐩_s0`$ the electronic spectrum experiences a Doppler-shift  $`E_𝐤=\sqrt{ϵ_𝐤^2+|\mathrm{\Delta }_𝐤|^2}+𝐯_F(𝐤)𝐩_s`$, where $`𝐯_F(𝐤)=ϵ_𝐤/𝐤`$. Thus, by making the substitution $`\omega \omega 𝐯_F(𝐤)𝐩_s`$ in Eq.(2), we obtain $`N(\omega ,r_{})`$ which we plot in Fig. 3 for a supercurrent along the $`(110)`$-direction with $`p_s=0.015`$.

The bound state energy is now shifted to $`\overline{\omega }_s(q_{})=\omega _s(q_{})+𝐯_F𝐩_s`$, where for $`\pm q_{}`$, $`𝐯_F`$ is the Fermi velocity at the respective FS crossing. This shift leads to a four-peak structure in the DOS, as can be seen in Fig. 3a for $`\mathrm{\Lambda }=1/\sqrt{2}`$. Since the energy shift depends on $`q_{}`$ through $`𝐯_F`$, the peaks which are shifted towards $`\omega =0`$ are sharpened, but still possess the same spectral weight as the apparently weaker peaks shifted to larger $`|\omega |`$. In contrast, for $`\mathrm{\Lambda }=\sqrt{2}\pi `$ (Fig. 3b), the Doppler-shift varies much more strongly along the lines of integration which preserves the two-peak structure in the DOS, increases the frequency splitting between the two peaks, and leads to a filling-in of the gap between the peaks. Thus, we predict that only for small acceptance angles can a four-peak structure be resolved.

We now turn to the effect of a subdominant order parameter with $`d_{xy}`$ symmetry and gap $`\mathrm{\Delta }_𝐤^{(1)}=\mathrm{\Delta }_1\mathrm{sin}k_x\mathrm{sin}k_y`$ on the DOS. In Fig. 4 we plot $`N(\omega ,r_{})`$ for a superconducting gap with $`d_{x^2y^2}`$ (solid line) and $`d_{x^2y^2}+id_{xy}`$ symmetry (dashed line). For the latter, we assume that the total superconducting gap is given by $`\mathrm{\Delta }_𝐤^{(0)}+i\mathrm{\Delta }_𝐤^{(1)}`$ with $`\mathrm{\Delta }_1/\mathrm{\Delta }_0=0.1`$ .

The DOS at small $`\omega `$ increases linearly with energy for the $`d_{x^2y^2}`$ case and exhibits as expected a gap for the $`d_{x^2y^2}+id_{xy}`$ case. Note, that the the onset of an $`id_{xy}`$ component shifts the two peaks to only slightly higher frequencies.

We next comment on the differences between our scattering matrix approach and earlier quasiclassical approaches within the Bogolyubov-deGennes formalism. In the latter, one considers only quasiparticles with a well defined momentum on the Fermi surface, such that for a $`(110)`$-surface the incident and reflected quasiparticles experience a superconducting gap of equal magnitude and opposite sign, which leads to a zero energy bound states for all $`q_{}`$ . This result is exact for $`q_{}=0`$, since here $`\mathrm{\Delta }(𝐤)0`$, but for any finite $`q_{}`$, the scattering between states away from the FS introduces corrections to the quasiclassical energy. Hence, within our scattering matrix formalism, the quasiclassical results are recovered by restricting the integration in Eq.(6) to the Fermi surface which yields $`\omega _s=0`$ for all $`q_{}`$. The appearance of a dispersing band of bound states is thus a pure quantum effect , which cannot be obtained by a quasiclassical approximation.

Experiments of  on YBCO materials show a single peak above $`T_s=8\mathrm{K}T_c`$, and the emergence of a two-peak structure at lower temperatures. This and the small increase in the overall width of the ZBCP was attributed to the appearance of a subleading order parameter ($`id_{xy}`$ or $`is`$) below $`T_s`$. However, the observed broadening of the ZBCP below $`T_s`$ is much smaller than the splitting between the peaks. This is expected if the peak splitting arises not from the appearance of a BTRS, but from the finite bound state dispersion discussed above. A subleading order parameter may sharpen the two-peak structure at lower temperatures and suppress the low energy part of the spectrum but is not predominantly responsible for the peak splitting. Moreover, recent experiments on Bi2Sr2Ca2O8+δ , which find that the width of the ZBCP does not increase with the emergence of a two-peak structure in the DOS, are difficult to explain within the BTRS scenario. Currently, experiments using electron-spin resonance  and phase sensitive measurements  are under way to determine whether a BTRS exists on the surface of HTSC. In addition, detailed measurements of the low energy part of the DOS also provide important information since the DOS for a $`d_{x^2y^2}`$ superconductor is linear at low frequencies, whereas that for $`d+id`$ or $`d+is`$ order parameters is fully gapped. Another interesting feature of the experiments  is that only two peaks are observed in an applied magnetic field, which shift to higher energies with increasing field. One possible explanation of this result is that the acceptance angle of the experiment (see Fig. 3b) is large, in which case the regime of smaller acceptance angles can be accessed in tunneling experiments by using stronger barriers between the superconducting and normal materials. In this limit, we predict that an applied magnetic field induces a four-peak structure in the DOS (Fig. 3a). An alternative explanation is that the acceptance angle is small but that the magnetic field generates a large $`id`$ (or $`is`$) component at the boundary that pushes the peaks to higher energies (Fig. 4). Each of the original peaks should then be split into two, however such splitting may be too small to be observed experimentally. The latter scenario is consistent with a strong decrease in the DOS at zero energy with increasing magnetic field .

Finally, the bound states discussed above provide an interesting new class of one dimensional fermions whose dispersion can be changed continuously by applying a magnetic field (or supercurrent), with the possibility of making all fermions chiral . Moreover, the formalism presented above can be generalized to study surface bound states in systems with other non-trivial order parameters, such as $`d`$-density or spin density wave states suggested recently . We find that a zero energy bound states also exists for a $`d`$-density wave state in the vicinity of a $`(110)`$ surface. This bound state can be observed in tunneling experiments and may thus prove to be an important feature of the underdoped cuprates; an account of our results will appear elsewhere .

In summary we present an exact scattering theory for bound states which are induced close to lines of impurities or surfaces in a $`d_{x^2y^2}`$ superconductors. We find that these bound states disperse linearly with momentum $`q_{}`$, a dispersion that gives rise to a two-peak structure in the density of states. For small acceptance angles, we predict that an applied magnetic field leads to a splitting of the two peaks into four, while for a large acceptance angle, there exist only two peaks. Our results are consistent with recent in-plane tunneling experiments on YBCO and provide important insight into their interpretation. We present detailed predictions for the spatial dependence of the Friedel oscillations in the DOS that may be measured by the STM experiments near the surfaces, grain boundaries, or lines of impurities.

We thank L. H. Greene, D. Van Harlingen, and L. Marinelli for stimulating discussions. DM acknowledges support by the Department of Energy. ED is supported by the Harvard Society of Fellows and the Milton Fund.


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# How can an electron interact with itself?

The self-energy of an electron is an old problem of classical electrodynamics. It assumes an interaction of an electron with the field that the electron produces. The quantum theory of electron has been developed with the discovery of positron, putting the problem of self-energy in a critical state. I would like to discuss its causal effect that can be assumed in the modern repetition of the old problem.

The quantum theory of electron began with the Dirac equation, which allows for electrons having equally either positive or negative energy as solutions . Dirac assumed in the vacuum the negative energy states completely filled with electrons. Later, it was assumed that a vacated negative energy state appears as a positive energy electron of charge $`|e|`$. According to Dirac, an electron-positron pair production could be explained as due to the transition from a negative to a positive energy state of an electron. Feynman, and earlier Stueckelberg, proposed an interpretation of the positron as a negative energy electron moving backward in time . An electron-positron pair production and annihilation could thus be visualized as a closed loop by a positive and a negative energy electrons, characterizing the vacuum polarization.

Weisskopf wrote in retrospect, Pauli asked me to calculate the self-energy of an electron according to the positron theory . Weisskopf calculated the difference between the energy of the vacuum and the energy of an electron in the vacuum . As noted by Furry, the calculation results in a logarithmic divergence of self-energy. In the positron theory, an electron in the vacuum causes a considerable change in the distribution of the vacuum electrons, and the broadening of the charge distribution makes the electrostatic self-energy to diverge logarithmically.

Feynman put forward an intelligible method of using diagrams . It provides an intuitive way of arriving at the correct result with the aid of a convergence factor

$$\frac{1}{q^2}\frac{1}{q^2}\left(\frac{\mathrm{\Lambda }^2}{q^2\mathrm{\Lambda }^2}\right)\text{or}\frac{1}{q^2}\frac{1}{q^2\mathrm{\Lambda }^2}.$$
(1)
The convergence factor is adopted only to define the formally divergent solution. Its physical meaning remains unexplained . The Feynman diagram itself is also unnatural. In the classical theory, the self-force is the reaction back on the electron of its own radiation field. This is taken over into the Feynman diagram, representing the self-energy due to the emission and absorption of a virtual transverse photon. The Feynman diagram for the self-energy is no more than a quantum theoretical description of the static self-force. Note in the diagram a complete neglect of the velocity of propagation.

The following conclusion can be drawn from the qualitative argument of Weisskopf’s calculation: The self-interaction is an effect on the electron of static polarization induced in the vacuum electrons due to the presence of an electron. If the photon virtually disintegrates into an electron-positron pair and annihilates again into a photon for a certain fraction of time, the electron closed loop gives an additional correction to the photon propagator through which an electron interacts with itself. The modification of the photon propagator is then the replacement

$$\frac{1}{q^2}\frac{1}{q^2}[\mathrm{\Pi }_{\mu \nu }(q)]\frac{1}{q^2}.$$
(2)
The polarization tensor $`\mathrm{\Pi }_{\mu \nu }(q)`$ is written as the sum of a constant term $`\mathrm{\Pi }(0)`$ and additional terms. The leading term is a positive constant that depends quadratically on $`\mathrm{\Lambda }`$. Using the operator relation, approximately, we write the replacement in the form

$$\frac{1}{q^2}\frac{1}{q^2}\frac{1}{q^2\mathrm{\Pi }(0)}.$$
(3)
It becomes evident that the vacuum polarization effect gives rise to a modification of the photon propagator corresponding to the convergence factor. By including the electron closed loop in the photon propagator, moreover, the Feynman diagram for self-energy can be put into accord with the positron theory. Thus, the conclusion can also be drawn from the diagrammatic argument of Feynman’s calculation. An electron may interact with itself through the vacuum polarization induced in the vacuum electrons due to the electron.

The vacuum polarization is calculated to diverge quadratically. Feynman has used a convergence procedure found by Bethe, and Pauli and Villars . It takes a difference between the closed loops for electrons of mass $`m`$ and of mass $`(m^2+\lambda ^2)^{1/2}`$, and integrates over $`\lambda `$ to $`\mathrm{\Lambda }`$. In the form of expression, it is just like the convergence factor for photon in terms of the electron closed loop. When viewed from the present point, therefore, the procedure is identified with the replacement

$$\mathrm{\Pi }_{\mu \nu }(q)\frac{1}{q^2}[\mathrm{\Pi }_{\mu \nu }(q)]\frac{1}{q^2},\text{so}\frac{1}{q^2}\frac{1}{q^2\mathrm{\Pi }_{\mu \nu }(q)}.$$
(4)
This shows the vacuum polarization that starts and ends with photon. In the explicit form, it suggests to calculate the vacuum polarization in the production and annihilation, or in the cause and effect, rather than the vacuum polarization itself. The integration over $`\lambda `$ can be considered as that for the negative energy states. The convergence procedure may be explained from this point of view.


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# Evolution of globular cluster systems in elliptical galaxies. II: power-law initial mass function

## 1 Introduction

In a recent paper (Vesperini 2000) we have investigated the evolution of the main properties of globular clusters systems (hereafter GCS) in elliptical galaxies starting with a log-normal GCS initial mass function. The choice of such a functional form for the initial mass function was motivated by the fact that all the globular cluster system mass functions (hereafter GCMF; we will indicate a globular cluster system luminosity function by GCLF) observed so far are well fitted by a log-normal distribution; in particular, a log-normal GCMF fits well the observed GCMF of clusters located in the external regions of galaxies where evolutionary processes are unlikely to have significantly altered the initial properties of clusters.

In Vesperini (2000) it was shown that the main final GCS properties resulting from the evolution of GCS with a log-normal initial GCMF and the relations between GCS properties and those of the host galaxies are in very good agreement with those reported by a number of observational analyses.

In this paper we study the evolution of GCS starting with a power-law initial GCMF. The motivation for considering this functional form for the initial GCMF comes both from some theoretical investigations of globular clusters formation (see e.g. Elmegreen & Efremov 1997, Harris & Pudritz 1994) which predict this shape for the initial GCMF and from several observational studies of young cluster systems in interacting and merging galaxies (see e.g. Schweizer et al. 1996, Miller et al. 1997, Johnson et al. 1999, Zepf et al. 1999; see also Whitmore 1999 for a review and references therein) showing that these systems are characterized by a power-law luminosity function. In fact, whether the observed power-law luminosity function indeed corresponds to an underlying power-law mass function or it results from the age spread of clusters with a log-normal mass function is matter of debate (Fritze-von Alvensleben 1998, 1999, Carlson et al. 1999, Zhang & Fall 1999); moreover a recent analysis of the GCLF of young clusters in the Antennae system seems to show a turnover in the LF which would be therefore better fitted by a two-index power-law (Whitmore et al. 1999).

Most observational analyses, on the basis of the high luminosities and compact sizes observed, support the idea that the young clusters found in interacting galaxies are globular clusters which will eventually evolve into systems similar to old globular clusters (see e.g. the results of Ho & Filippenko 1996a, 1996b which strongly suggest that at least the brightest clusters must indeed be globular clusters; see also Carlson et al. 1998, 1999) but this point has been questioned too: van den Bergh (1995), on the basis of the shape of the GCLF, has claimed that these objects would be more properly classified as young open clusters rather than as young globular clusters.

Several theoretical investigations have shown that evolutionary processes can lead to the disruption of a significant number of clusters and alter the parameters and shape of the initial GCMF (Fall & Rees 1977, Fall & Malkan 1978, Caputo & Castellani 1984, Chernoff, Kochanek & Shapiro 1986, Chernoff & Shapiro 1987, Aguilar, Hut & Ostriker 1988, Vesperini, 1994, 1997, 1998, Okazaki & Tosa 1995, Capuzzo Dolcetta & Tesseri 1997, Gnedin & Ostriker 1997, Murali & Weinberg 1997a, 1997b, Ostriker & Gnedin 1997, Baumgardt 1998); in particular a power-law initial GCMF can be turned by evolutionary processes into a log-normal GCMF (or in general into a bell shaped GCMF). On the other hand it is not clear whether evolutionary processes, acting with different efficiency in galaxies with different structures, can turn an initial power-law into a log-normal GCMF with approximately universal parameters and with a weak radial variation of the GCMF parameters within individual galaxies as found in most current observational studies.

In Vesperini (2000) it has been shown that, for a log-normal initial GCMF, the galaxy-to-galaxy variation of the GCMF parameters resulting from theoretical calculations is perfectly consistent with the observed trends and that a considerable disruption of clusters does not necessarily give rise to a radial gradient of the mean mass of clusters inconsistent with observations. The goal of this paper is that of determining if the same conclusions hold for the case of GCS with a power-law initial GCMF.

The layout of the paper is the following. In §2 we briefly sketch the method used for the investigation and the initial conditions adopted; in §3 we describe the general results while in §4 we discuss in detail the implications of our results for galaxies for which observational data are available. We summarize our conclusions in §5.

## 2 Method and initial conditions

The method adopted to follow the evolution of the masses of individual globular clusters is the same used in Vesperini (2000; see also Vesperini 1998) and we refer to that paper for further details. The evolutionary processes included are mass loss due to stellar evolution, two-body relaxation, the presence of the tidal field of the host galaxy and dynamical friction; the effects of the time-variation of the tidal field for clusters on non-circular orbits (see e.g. Weinberg 1994a, 1994b, 1994c, Gnedin, Hernquist & Ostriker 1999) were not included in the N-body simulations by Vesperini & Heggie (1997) and are not considered here. The analytical expression used to determine the mass of a cluster located at distance $`R_g`$ from the center of its host galaxy at time $`t`$ is based on the N-body simulations carried out by Vesperini & Heggie (1997) and is given by

$$\frac{M(t)}{M_i}=1\frac{\mathrm{\Delta }M_{st.ev.}}{M_i}\frac{0.828}{F_{CW}}t.$$
(1)
$`t`$ is time measured in Myr, $`\frac{\mathrm{\Delta }M_{st.ev.}}{M_i}`$ is the mass loss due to stellar evolution (see eq.10 in Vesperini & Heggie 1997); $`F_{CW}`$ is a parameter introduced by Chernoff & Weinberg (1990), which is proportional to the initial relaxation time of the cluster and is defined as

$$F_{CW}=\frac{M_i}{M_{}}\frac{R_g}{\text{kpc}}\frac{1}{\mathrm{ln}N}\frac{220\text{km s}^1}{v_c},$$
(2)
where $`N`$ is the total initial number of stars in the cluster and $`v_c`$ is the circular velocity around the host galaxy. For the host galaxy we will adopt a simple isothermal model with constant circular velocity. The effects of dynamical friction at any time $`t`$ are included by removing, at that time, all clusters with time-scales of orbital decay (see e.g. Binney & Tremaine 1987) smaller than $`t`$.

The values of the effective masses, $`M_e`$, and effective radii, $`R_e`$, of the host galaxies considered are the same studied in Vesperini (2000) and they are plotted in Fig. 1.

Each GCS investigated initially contains 20000 clusters with a GCMF given by

$$dN(M)=AM^\alpha dM\text{for}10^4M_{}<M<10^7M_{};$$
(3)
the values of $`\alpha `$ considered are $`\alpha =1.5,1.8,2.0`$ which are close to those determined from observation of the GCLF of young cluster systems in merging and interacting galaxies. Clusters are initially distributed inside the host galaxy between $`R_g=0.16R_e`$ and $`R_g=5R_e`$ with a number of clusters per cubic kpc proportional to $`R_g^{3.5}`$ which is similar to that observed for Galactic halo clusters (see also Murali & Weinberg 1997a where a similar slope for the initial radial distribution is derived for the M87 GCS).

The evolution of each GCS is followed for 15 Gyr.

## 3 General results

Fig. 2 shows the contour plots of the final mean mass and dispersion of the GCMF, $`\overline{\mathrm{log}M}_f`$ and $`\sigma _f`$, in the plane $`\mathrm{log}M_e\mathrm{log}R_e`$ for the three values of $`\alpha `$ considered. The flatter the initial GCMF, the larger $`\overline{\mathrm{log}M}_f`$ is for a given model of the host galaxy. We will discuss below in section 4 the implications of our results for host galaxies with values of $`M_e`$ and $`R_e`$ equal to those determined by observations but we note here that the range of values spanned by $`\overline{\mathrm{log}M}_f`$ is significantly larger than that obtained in Vesperini (2000) for a log-normal initial GCMF (compare Fig.2a of Vesperini 2000 with the upper panels of Fig. 2).

Fig. 3 shows the contour plots of the fraction of the total initial number of clusters surviving after 15 Gyr, $`N_f/N_i`$, and of the ratio of the total mass of the survived clusters to the total initial mass of all clusters, $`M_{GCS,f}/M_{GCS,i}`$, in the plane $`\mathrm{log}M_e\mathrm{log}R_e`$. For host galaxies where evaporation by internal relaxation is the dominant disruption process, the fraction of surviving clusters is smaller for steeper initial GCMF (in which the fraction of low-mass clusters is larger); on the other hand, in galaxies where dynamical friction is more important, the fraction of surviving clusters decreases for initial GCMF with smaller values of $`\alpha `$ which initially contain a larger fraction of high-mass clusters.

The left panel of Fig. 4 shows the contour plot of the difference between the final mean mass of inner clusters ($`R_g<R_e`$) and outer clusters ($`R_g>R_e`$) for $`\alpha =1.8`$ (hereafter we will focus our attention on this value of $`\alpha `$ which is equal to that found in several young GCS in merging and interacting galaxies): for a large number of different host galaxies evolutionary processes lead to a significant radial gradient of the mean mass.

In general, GCS with initial GCMF containing a large fraction of low-mass clusters, such as the power-law considered here or a log-normal GCMF with a small initial value of $`\overline{\mathrm{log}M}`$ (see Vesperini 1998), are more prone to the formation of stronger radial gradients of $`\overline{\mathrm{log}M}`$ which are inconsistent with the very weak (if any) radial trends reported by observational analyses.

The right panel of Fig. 4 shows that, as it happens for a log-normal initial GCMF (see Fig.4 in Vesperini 2000), a small value of $`\mathrm{\Delta }\overline{\mathrm{log}M}_{innout}`$ does not necessarily imply a negligible disruption of clusters; the difference in the range of values of $`\mathrm{\Delta }\overline{\mathrm{log}M}_{innout}`$ between GCS with a power-law initial GCMF considered here and those with an initial log-normal GCMF studied in Vesperini (2000) is not due to a difference in the fraction of disrupted clusters (though, in general, GCS with a power-law GCMF tend to have a smaller fraction of surviving clusters) but rather to the different mass distribution of disrupted clusters.

## 4 Implications

In this section we discuss the implications of our results for a sample of galaxies for which effective masses and radii have been determined using observational data by Burstein et al. (1997) (we adopted $`H_0=75\text{km}\text{s}^1\text{Mpc}^1`$). We will focus our attention on the results obtained for $`\alpha =1.8`$ but the general trends found are common to the other values of $`\alpha `$ we have studied.

### 4.1 Mean mass of clusters and fraction of surviving clusters

Fig. 5 shows the contour plot of $`\overline{\mathrm{log}M}_f`$ already shown in Fig. 2 and discussed in §3 with the points corresponding to the observational values of $`\mathrm{log}M_e`$ and $`\mathrm{log}R_e`$ superimposed.

Figs 6a-c show $`\overline{\mathrm{log}M}_f`$, $`N_f/N_i`$, $`M_{GCS,f}/M_{GCS,i}`$ versus the observational values of $`\mathrm{log}M_e`$.

A recent observational analysis by Harris (2000) reports, for giant ellipticals, a mean turnover magnitude $`M_V^0=7.33`$ with a galaxy-to-galaxy rms dispersion of 0.15 (corresponding, for $`M/L_V=2`$, to $`\overline{\mathrm{log}M}_f5.16`$; the galaxy-to-galaxy rms dispersion of $`\overline{\mathrm{log}M}_f`$ is 0.06).

For $`10\text{ }<\text{ }\mathrm{log}M_e\text{ }<\text{ }12`$, Figs 5 and 6a show instead a large spread of values of $`\overline{\mathrm{log}M}_f`$ ($`4.2<\overline{\mathrm{log}M}_f<5.0`$) and a general trend for $`\overline{\mathrm{log}M}_f`$ to increase as $`M_e`$ decreases.

The inconsistency between the observational result of Harris (2000) and the final properties of GCS starting with an initial power-law with $`\alpha =1.8`$ is further illustrated by Fig.7: this figure shows the distribution of theoretical values of $`\overline{\mathrm{log}M}_f`$ for globular cluster systems located in host galaxies with values of $`\mathrm{log}R_e`$ and $`\mathrm{log}M_e`$ equal to the observational values reported by Burstein et al. (1997) for galaxies with $`\mathrm{log}M_e>10.5`$.

The four panels of Fig. 9 show the distribution of $`\overline{\mathrm{log}M}_f`$ for low- ($`\mathrm{log}M_e<9.5`$), intermediate- ($`9.5<\mathrm{log}M_e<10.5`$) and high-mass ($`\mathrm{log}M_e>10.5`$) ellipticals at $`t=2,5,10,15`$ Gyr; the values of $`\mathrm{log}R_e`$ and $`\mathrm{log}M_e`$ considered for these plots are those shown in Fig. 8. The region of the $`\mathrm{log}M_e\mathrm{log}R_e`$ plane shown in Fig. 8 is that where most observational data fall.

As shown in the observational analysis by Harris (2000) (see also Whitmore 1997), clusters in dwarf galaxies tend to have a mean mass lower than clusters in giant galaxies and a larger galaxy-to-galaxy dispersion (in dwarf galaxies, for $`M/L_V=2`$, $`\overline{\mathrm{log}M}_f=4.99`$ with a galaxy-to-galaxy dispersion equal to 0.24).

It is clear from Fig.9 that, adopting a power-law initial GCMF, the final values of $`\overline{\mathrm{log}M}_f`$, the galaxy-to-galaxy dispersion of $`\overline{\mathrm{log}M}_f`$ for different classes of galaxies, and the difference between the distribution of $`\overline{\mathrm{log}M}_f`$ for dwarf and giant ellipticals are not consistent with the current observational results. The large scatter in the distribution of $`\overline{\mathrm{log}M}_f`$ for different classes of galaxies, shown in Fig.9, is a consequence of the strong dependence of the evolution of the GCMF on the structure of the host galaxy when a power-law initial GCMF is adopted.

### 4.2 Radial dependence of the GCMF

For four fiducial systems with values of $`\mathrm{log}R_e`$ and $`\mathrm{log}M_e`$ shown as filled dots in Fig. 8 we have studied in larger detail the radial variation of $`\overline{\mathrm{log}M}_f`$ and of $`N_f/N_i`$.

Fig. 10 shows $`\overline{\mathrm{log}M}_f`$ and $`N_f/N_i`$ vs $`R_g/R_e`$. For all the four host galaxies considered, the fraction of disrupted clusters is large also beyond $`R_e`$; only for the most massive galaxy there is no disruption beyond $`R_g=2R_e`$ while for all the others disruption is significant at any galactocentric distance. As shown in the upper panel of Fig.10, $`\overline{\mathrm{log}M}_f`$ varies significantly with the galactocentric distance: the variation of $`\overline{\mathrm{log}M}_f`$ with $`R_g`$ depends on the structure of the host galaxy and it is not necessarily monotonic. For the two most massive host galaxies considered, the mean mass of the innermost clusters and that of the outermost clusters differ by approximately one order of magnitude or slightly less.

Since in external galaxies only projected distances can be determined, to ease the comparison with observations, the upper panel of Fig.10 shows also the variation of $`\overline{\mathrm{log}M}_f`$ with the projected galactocentric distance. It is clear from Fig.10 that the radial gradient of $`\overline{\mathrm{log}M}_f`$ is too large to be consistent with that reported by observational studies.

It is interesting to note the contrast between the results shown in Fig. 10 and those obtained in Vesperini (2000) for GCS with a log-normal initial GCMF (see Figs 12a and 12b in Vesperini 2000): with a log-normal initial GCMF, although a significant fraction of clusters is disrupted, the radial gradient of $`\overline{\mathrm{log}M}_f`$ is, in most cases, weak and consistent with observations.

### 4.3 Dependence of the results on the slope of the initial GCMF

In the previous two subsections we have shown that the final properties of GCS with a power-law initial GCMF with a value of $`\alpha `$ similar to that observed in several young cluster systems are not consistent with the observational properties of old cluster systems. In particular the values of $`\overline{\mathrm{log}M}_f`$ for high-mass host galaxies have been found to be smaller than those observed and the galaxy-to-galaxy dispersion much larger than that observed.

Although values of $`\alpha `$ too different from that adopted above have not received any support either by theoretical studies of clusters formation or by observational analyses of young cluster systems, it is interesting to study the dependence of our results on $`\alpha `$ and explore the evolution of GCS with initial values of $`\alpha `$ outside the range considered in the previous sections.

We focus our attention on high-mass galaxies with $`\mathrm{log}M_e>10.5`$ and consider the following values of ($`\mathrm{log}M_e,\mathrm{log}R_e`$):(12,1.4), (11.75,1.18), (11.5,1), (11.25,0.8), (11.0,0.64), (10.75,0.52), (10.5,0.4); these values span the entire strip of the $`\mathrm{log}M_e\mathrm{log}R_e`$ plane covered by real galaxies with $`\mathrm{log}M_e>10.5`$. Figs 11a-c show $`\overline{\mathrm{log}M}_f`$, $`N_f/N_i`$ and $`M_{GCS,f}/M_{GCS,i}`$ versus $`\alpha `$. As expected, the smaller $`\alpha `$, the larger the fraction of surviving clusters (but note that the disruption is never negligible) and the larger the final values of $`\overline{\mathrm{log}M}_f`$. Values of $`\overline{\mathrm{log}M}_f`$ consistent with those observed can result only from initial GCMF with values of $`\alpha `$ ($`\alpha 1.21.3`$) significantly flatter than those observed in young cluster systems.

## 5 Summary and conclusions

We have investigated the evolution of the main properties of GCS in elliptical galaxies starting with an initial power-law GCMF similar to that of young cluster systems observed in merging galaxies.

We have considered a large set of different host galaxies and we have shown the dependence of the final parameters of the GCMF, of the fraction of surviving clusters and of the ratio of the final total mass in clusters to the total initial mass of clusters on the effective radius and effective mass of the host galaxy (see Figs 2, 3, and 4). Three different values (close to those determined observationally from the GCLF of young cluster systems) of the index of the initial power-law GCMF have been explored ($`\alpha =1.5,1.8,2.0`$).

While evolutionary processes can easily turn a GCMF with an initial power-law shape into a GCMF with a log-normal shape like that observed in old cluster systems, our investigation reveals several inconsistencies between the observed properties of old GCS in elliptical galaxies and the theoretical results obtained adopting a power-law initial GCMF. In particular, studying the evolution of GCS in a sample of giant, normal and dwarf elliptical galaxies with effective radii and effective masses equal to those determined observationally, we have shown that:

* the theoretical values of $`\overline{\mathrm{log}M}_f`$ are in general smaller than those observed;
* the range spanned by $`\overline{\mathrm{log}M}_f`$ is significantly larger than that reported by observational studies; in particular, for galaxies with $`\mathrm{log}M_e>10.5`$, we have shown that starting with a power-law initial GCMF with $`\alpha =1.8`$, $`\overline{\mathrm{log}M}_f`$ ranges from 4.2 to 5.0 whereas observations show an approximately universal value of $`\overline{\mathrm{log}M}_f`$ ($`\overline{\mathrm{log}M}_f5.16`$ for $`M/L_V=2`$) with a very small galaxy-to-galaxy dispersion ($`0.06`$);
* $`\overline{\mathrm{log}M}_f`$ varies significantly with the effective mass of the host galaxy; specifically $`\overline{\mathrm{log}M}_f`$ tends to increase with decreasing values of $`\mathrm{log}M_e`$ for $`\mathrm{log}M_e>10`$, it reaches a peak and then decreases again for dwarf galaxies; this does not agree with observations which show that for giant galaxies, $`\overline{\mathrm{log}M}_f`$ is approximately constant and larger than $`\overline{\mathrm{log}M}_f`$ of clusters in dwarf galaxies.
* adopting a power-law initial GCMF, a significant dependence of $`\overline{\mathrm{log}M}_f`$ on the galactocentric distance is produced by the effects of evolutionary processes; this is in contrast with several observational studies which fail to find a significant radial gradient of $`\overline{\mathrm{log}M}_f`$ within individual galaxies.
* Starting with an initial power-law GCMF, values of $`\overline{\mathrm{log}M}_f`$ consistent with those observed in massive galaxies can be obtained only with values of $`\alpha `$ smaller ($`\alpha 1.21.3`$) than those observed in young cluster systems.

In Vesperini (2000) it has been shown that the final properties of GCS obtained starting with a log-normal initial GCMF similar to that observed in the external regions of some elliptical galaxies (where evolutionary processes are unlikely to have significantly altered the initial conditions of clusters) are in general good agreement with the observed properties of old cluster systems. In this paper we have shown that, starting with a power-law initial GCMF, the final GCS properties present several discrepancies from those observed in old GCS; this would seem to rule out the possibility that old cluster systems were formed with a power-law initial GCMF similar to that observed in young cluster systems of merging galaxies and to strongly favour a log-normal initial GCMF.

One can not exclude the existence of differences in the process of globular cluster formation at the current epoch and at the time of formation of currently old clusters leading to different initial GCMF. While individual young clusters could indeed be young globular clusters and those which survive could evolve into systems similar to old globular clusters, the future global properties of these young cluster systems could differ from those of currently old cluster systems.

## ACKNOWLEDGMENTS

I wish to thank an anonymous referee for useful comments on the paper. Support from a Five College Astronomy Department fellowship is acknowledged.

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text:
# Soft Interaction Between Dissolved Dendrimers: Theory and Experiment

## I Introduction

Dendrimers are synthetic branched macromolecules with defined structure Vogtle:99 . Starting from a trifunctional flexible monomer (generation 0), subsequent shells of trifunctional units are attached in a well-defined manner. Fig. 1 displays a dendrimer of 4th generation with attached end groups at the ends of the units constituting the last generation. Thus, a tree-like structure is generated, which can be viewed as an interesting intermediate between colloids and polymers: dendrimers of low generations exhibit enough degrees of conformational freedom and will thus present fluctuating structures in solution. Hence, these structures will greatly resemble star polymers or lightly branched polymers. If, on the other hand, the number of generations is increased, steric interactions between the groups located at the periphery of the molecule must result. In this case, significant back-folding of these groups must occur and these structures will exhibit a more homogeneous segmental density. Hence, dendrimers of higher generation will resemble dense colloidal structures.

The average radial density distribution $`T(r)`$ of dendrimers is still a matter of debate. Here, the question arises, whether dissolved dendrimers exhibit their maximum segment density in the center or at the periphery of the molecule. The first theoretical analysis of the radial density distribution by Hervet and de Gennes came to the conclusion that dendrimers have a dense shell and hence a minimum of $`T(r)`$ at the center of the molecule Hervet:83 . Subsequent theoretical studies, however, showed that dendrimers exhibit their maximum segment density at the center of the molecule Muthu:90 ; Mansf:93 ; Murat:96 ; Rub:96 ; Muthu:98 ; Lue:00 . Only if electrostatic repulsion operates between the segments of the dendrimer, a dense shell structure is to be expected Muthu:98 .

Small-angle scattering methods, such as small-angle X-ray scattering (SAXS) Feigin:87  and small-angle neutron scattering (SANS) Higgins:94  are suitable to investigate the radial structure of dissolved dendrimers. Up to now, however, SANS- and SAXS-studies of dendrimers in solution did not yet come to a final conclusion regarding the average radial density distribution $`T(r)`$. A survey of literature may be found in a recent review B:00 . A recent study of a dendrimer of 7th generation concluded that the internal structure of the molecule is rather uniform, with the end groups being preferably located at the periphery of the molecule Topp:99 . This result is in contradiction to the theoretical studies discussed above Muthu:90 ; Mansf:93 ; Murat:96 ; Rub:96 ; Muthu:98 ; Lue:00 . SANS-studies of dendrimers of lower generation, however, showed that the molecules under consideration have approximately a Gaussian density distribution ballauff:99 ; Potschke:99 . The chemical structure of the dendrimers investigated in Refs. Topp:99  and ballauff:99 ; Potschke:99 , differ with regard to the number of generations and the nature of the end groups. The results can therefore only be compared with caution. In this respect, we also mention the simulation results of Ref. Lue:00  where it was found that the conformation of dendritic molecules drastically depends on the generation number, with a soft, Gaussian-like profile resulting for small generations and a “collapsed core” with soft tails for larger generations. Nevertheless, it must be concluded that the question of the overall structure of dissolved dendrimers has not yet found a generally accepted answer (see the discussion of this point in Ref. B:00 .)

Small-angle scattering conducted at different particle concentrations may be useful for further elucidation of this problem. Neglecting incoherent contributions, the measured scattering intensity $`I(q)`$ ($`q`$: magnitude of scattering vector q; $`q=(4\pi /\lambda )\mathrm{sin}(\theta /2)`$; $`\lambda `$: wavelength of radiation; $`\theta `$: scattering angle) may be rendered as Feigin:87 ; Higgins:94

$$I(q)=\rho _\mathrm{d}\left(\overline{\rho }\rho _\mathrm{m}\right)^2I_\mathrm{S}(q)S(q).$$
(1)
In eq. (1) above, $`\rho _\mathrm{d}=N_\mathrm{d}/V`$ is the number density of $`N_\mathrm{d}`$ dissolved dendrimers in the sample volume $`V`$. The difference $`\overline{\rho }\rho _\mathrm{m}`$ is the contrast of the scatterer towards the solvent, whereby $`\overline{\rho }`$ is the average scattering length density of the scatterer and $`\rho _\mathrm{m}`$ that of the solvent. $`I_\mathrm{S}(q)`$ is the form factor of the object, a quantity directly related to the mass distribution of scattering centers within the macromolecular aggregate, as will explained below. Finally, the structure factor $`S(q)`$ accounts for all interparticle correlations arising from the interactions between those.

The effective interaction between dendrimer centers is formally defined as follows lowen:madden:hansen:93 : the centers of mass of the dendrimers are kept fixed at prescribed positions and a canonical trace is carried out over all monomer degrees of freedom. This procedure yields a constrained free energy, depending on the instantaneous configuration of the dendrimers’ centers of mass. Then, the effective interaction energy between the dendrimers is $`k_BT`$ times the logarithm of this partition function, where $`k_B`$ is Boltzmann’s constant and $`T`$ is the absolute temperature. When averaging over the dendrimers’ positions by employing the so-defined effective Hamiltonian, the thermodynamics of the system remains invariant. In general, this procedure generates two-, three- and higher-order interactions between the centers of mass of the dendrimers. However, we will follow usual practice and limit our considerations to two-body potentials only, that is, we will make the usual pair-potential approximation, introducing an effective pair interaction $`V_{\mathrm{eff}}(R)`$ between the centers of mass of two dendrimers separated by the distance $`R`$. We comment on the accuracy of the pair potential approximation in section III. Since we are dealing with particles which have an overall spherical shape, this effective interaction is spherically symmetric and depends only on the magnitude of the vector connecting the two centers.

The structure factor $`S(q)`$ is directly related to the pair correlation function $`g(R)`$ and hence to the total interaction potential of the solute molecules Hansen:86 . Once $`V_{\mathrm{eff}}(R)`$ is known, the calculation of $`g(R)`$ and $`S(q)`$ follows from the solution of any of the rich variety of so-called liquid integral equation theories Hansen:86 . For infinite dilution $`S(q)=1`$. Hence, from an experimental point of view, eq. (1) shows that $`I_\mathrm{S}(q)`$ may be obtained from SANS- or SAXS-data which have been suitably extrapolated to vanishing concentration Higgins:94 .

The structure factor $`S(q)`$ gives direct information on the steepness of the repulsion of the dissolved particles: in the case of hard spheres, a pronounced structuring of the solution will occur, which leads to a marked maximum of $`S(q)`$ Hansen:86 . If the dissolved particles interact via soft repulsion, the maximum of $`S(q)`$ is decreased. Recently, the problem of $`S(q)`$ of star polymers has been addressed Jus:99 ; anom . Here, it could be shown that star polymers may be looked upon as ultrasoft colloidal particles. The predictions of theory have met with gratifying success when compared to SANS-data measured for concentrated solutions of star polymers Lik:98 ; Lik:00 .

Up to now, only a few experimental studies have addressed the problem of the structure factor of dissolved dendrimers. Ramzi et al. Ram:98  studied concentrated solutions of dendrimers by SANS. In the case of uncharged dendrimers, these workers found a marked depression of the peak of $`S(q)`$ despite the strong decrease of the structure factor at low $`q`$. They concluded that the absence of a peak of $`S(q)`$ is related to the softness of interaction, which results from the high internal flexibility of the dendritic structures. If charges are added to the segments of the dissolved dendrimers, a strong peak of $`S(q)`$ is generated which is clearly traced back to the screened Coulombic interactions of the now charged species (cf. also Ref. Mic:98 .) A SANS-study by Topp et al. Amis:99 , showed that the dendrimers under consideration exhibited only a weak maximum of $`S(q)`$, in particular at lower generation. At high concentrations the evaluation of data according to eq. (1) did not lead to meaningful results, which indicates a considerable change of the internal structure of the dendrimers in this regime. The dilute regime has been studied in Refs. ballauff:99 ; Potschke:99 . The data of $`S(q)`$ have been interpreted in terms of a simplified model, treating the dendrimers as effective hard spheres. It is hence evident that the problem of $`S(q)`$ of dissolved dendrimers is not yet understood quantitatively.

In this work, we wish to apply a simple theory which allows us to calculate the effective interaction between dendrimer centers using the measured density profile of an isolated dendrimer as a starting point. It turns out that the interaction has a Gaussian form. Subsequently, we employ it to calculate theoretically the structure factor $`S(q)`$ of dissolved dendrimers at various concentrations using the hypernetted chain (HNC) approximation. The consequences of the internal flexibility on the measured structure factor $`S(q)`$ will be discussed explicitly. Moreover, a quantitative comparison with the experimental data presented in Ref. Potschke:99  will be given, showing excellent agreement. It will be demonstrated that the radial density distribution $`T(r)`$ derived from scattering experiments may directly be used to calculate $`S(q)`$.

## II Theory

The starting point for the theory is the monomer density profile $`\rho (r)`$ around the center of mass of an isolated dendrimer. The experiments of Ref. ballauff:99 ; Potschke:99  offer a direct access to this quantity, through the so-called shape function $`T(r)`$. The scattering intensity $`I_\mathrm{S}(q)`$ from a solution of dendrimers at infinite dilution has been written as (see eq. (18) in Ref. ballauff:99 ):

$$I_\mathrm{S}(q)=T^2(q),$$
(2)
meaning that $`T^2(q)`$ is the form factor of the dendrimer and hence $`T(q)`$ the Fourier transform of $`T(r)`$. Hence, as already pointed out in Ref. ballauff:99 , $`T(r)`$ is a “shape function” that describes the way in which $`\rho (r)`$ varies in space. This shape function is dimensionless, hence we may write:

$$\rho (r)=\rho _0T(r),$$
(3)
where $`\rho _0`$ is a constant having dimensions of density (length<sup>-3</sup>) and which will be specified now. Eq. (3) above, together with eq. (2) of Ref. ballauff:99  imply:

$$𝑑𝐫\rho (r)=\rho _0V_p,$$
(4)
where $`V_p`$ is the measured partial volume of the solute molecule. On the other hand, the integral of $`\rho (r)`$ has to yield the total number of monomers $`N`$ within the dendrimer and this fact together with eq. (4) imply:

$$\rho (r)=\frac{N}{V_p}T(r).$$
(5)
The shape function $`T(r)`$ is determined by an inverse Fourier transform of $`T(q)`$, the latter being given by eq. (20) of Ref. ballauff:99 . Ignoring the ‘tail’ $`(aq^2+bq)\mathrm{exp}(dq^2)`$ there, we have:

$$T^2(q)=V_p^2\mathrm{exp}(q^2R_g^2/3).$$
(6)
From eq. (6) and after an inverse Fourier transformation, we readily obtain:

$$T(r)=V_p\left(\frac{3}{2\pi R_g^2}\right)^{3/2}\mathrm{exp}\left(\frac{3r^2}{2R_g^2}\right).$$
(7)
It can be easily seen that $`𝑑𝐫T(r)=V_p`$, in agreement with eq. (2) of Ref. ballauff:99 .

From eqs. (5) and (7) we obtain the monomer density as:

$$\rho (r)=N\left(\frac{3}{2\pi R_g^2}\right)^{3/2}\mathrm{exp}\left(\frac{3r^2}{2R_g^2}\right).$$
(8)
We now assume that two such dendrimers are kept with their centers of mass at a separation $`𝐑`$ apart and wish to calculate the ensuing interaction potential. Let us assume that the monomer-monomer interaction potential is given by some function $`v(𝐫_1𝐫_2)`$ where $`𝐫_1`$ and $`𝐫_2`$ are the positions of the two monomers. In the mean-field approximation, i.e., ignoring the correlations and possible deformations of the dendrimers, the total interaction potential $`V_{\mathrm{eff}}(𝐑)`$ can be approximated by a double integral over the unperturbed density profiles times the monomer-monomer interaction kernel graf:lowen:98 . This approximation should hold when the dendrimers are not too deeply interpenetrating and reads as:

$$V_{\mathrm{eff}}(𝐑)=𝑑𝐫_1𝑑𝐫_2\rho (𝐫_1)\rho (𝐫_2𝐑)v(𝐫_1𝐫_2).$$
(9)
We now make the simplest possible assumption and model the monomer-monomer interaction by a delta function (contact repulsion):

$$v(𝐫_1𝐫_2)=v_0k_BT\delta (𝐫_1𝐫_2),$$
(10)
introducing the excluded volume parameter $`v_0`$. Eqs. (9) and (10) then yield:

$$V_{\mathrm{eff}}(𝐑)=v_0k_BT𝑑𝐫\rho (𝐫)\rho (𝐫𝐑).$$
(11)
In this approximation, the interaction is proportional to the convolution of the monomer density of a single dendrimer with itself. But each density profile has the form $`N(\alpha /\pi )^{3/2}\mathrm{exp}(\alpha r^2)`$, i.e., $`N`$ times a normalized Gaussian with width parameter $`\alpha `$. It is known that the convolution of a normalized Gaussian having width $`\alpha `$ with itself is again a normalized Gaussian, but with width $`\alpha /2`$. Hence, eqs. (8) and (11) yield the final result:

$$V_{\mathrm{eff}}(R)=N^2\left(\frac{3}{4\pi R_g^2}\right)^{3/2}v_0k_BT\mathrm{exp}\left(\frac{3R^2}{4R_g^2}\right).$$
(12)
The effective potential depends only on the magnitude $`R=|𝐑|`$ of the center-to-center separation, because of rotational symmetry. Note that the interaction potential of eq. (12) above, is identical to the Flory-Krigbaum effective interaction potential between the centers of mass of two polymer chains flory:krigbaum:50 . The fact that we are dealing with dendrimers enters into the relation between $`N`$ and $`R_g`$. For long, self-avoiding chains, $`R_gN^{3/5}`$ holds; in the present study this is not the case and we determine both quantities from experiment.

The important feature is that the resulting interaction has a Gaussian form:

$$V_{\mathrm{eff}}(R)=\epsilon \mathrm{exp}\left(\frac{R^2}{\sigma ^2}\right),$$
(13)
with

$$\epsilon =N^2\left(\frac{3}{4\pi R_g^2}\right)^{3/2}v_0k_BT$$
(14)
and

$$\sigma =\sqrt{\frac{4}{3}}R_g.$$
(15)
The task is now to calculate $`\epsilon `$ from the experimental data. The number of monomers per dendrimer, is $`N=94`$, (see Fig. 1) where the aromatic end-groups are also included in the counting as “single monomers”.

Next we need an estimate for the excluded volume parameter $`v_0`$. For this, we set $`v_0=l_0^3`$, where $`l_0`$ is the monomer length. Taking the realistic value $`l_0=0.4\mathrm{nm}`$ for the latter quantity, we obtain:

$$v_0=0.064\mathrm{nm}^3.$$
(16)
The above values, together with the experimentally determined gyration radius $`R_g=1.85`$ nm yield:

$$\epsilon =10.42k_BT.$$
(17)
The corresponding value for linear chains is about $`2k_BT`$ ard1:00 . Hence, the energy barrier for the dendrimers at hand is about five times higher as that for linear chains, a result that is physically reasonable as dendrimers are more compact objects than chains. A general study of the structural and thermodynamic properties of a system of particles interacting by a Gaussian potential (the “Gaussian core model”, GCM), has been presented recently lang:etal:gcm . The GCM shows no freezing for $`\epsilon 100`$ lang:etal:gcm , hence we conclude that the system of dendrimers at hand will remain fluid at all concentrations.

Next, we express the density of dendrimers in units that are more convenient. Since there are $`N_\mathrm{d}`$ dendrimers in the volume $`V`$, the density $`\rho _\mathrm{d}`$ of dendrimers is $`N_\mathrm{d}/V`$. In Ref. ballauff:99 , the volume fraction $`\varphi `$ was used which is related to $`\rho _\mathrm{d}`$ by

$$\varphi =\rho _\mathrm{d}V_p.$$
(18)
In order to suppress the dependence on $`V_p`$, it is natural to use as the unit of length the parameter $`\sigma `$ of the pair potential and to introduce a dimensionless measure of the density, namely:

$$\eta =\frac{\pi }{6}\rho _\mathrm{d}\sigma ^3,$$
(19)
which may be regarded as an effective volume fraction of the dissolved dendrimers. From eqs. (15), (18) and (19) we obtain:

$`\eta `$ $`=`$ $`{\displaystyle \frac{\pi }{6}}\left({\displaystyle \frac{4}{3}}\right)^{3/2}{\displaystyle \frac{R_g^3}{V_p}}\varphi =0.338\varphi ,`$ (20)
where the known values $`R_g=1.85\mathrm{nm}`$ and $`V_p=15.1\mathrm{nm}^3`$ have been used ballauff:99 .

For every value of $`\eta `$, the Hypernetted Chain (HNC) equation Hansen:86  for a system interacting via $`\beta v(r)=10.42\mathrm{exp}(r^2/\sigma ^2)`$ was solved and the structure factor $`S(q)`$ was obtained as a function of $`q\sigma `$. Using eq. (15) we obtain $`\sigma =2.136\mathrm{nm}`$. This is in close agreement with the effective radius of 2.4 nm estimated in Ref. ballauff:99  by a simple model valid only for dilute solutions. In what is to follow the $`q`$-scale was reexpressed in $`\mathrm{nm}^1`$ units.

## III Results and Discussion

As can be seen from Fig. 2, the Gaussian interaction potential yields excellent agreement between theory and experiment at all three concentrations measured. Moreover, this is achieved without the use of free fit parameters and it is physically reasonable that soft, interpenetrable objects such as dendrimers interact by means of a correspondingly soft interaction. The boundedness of the effective interaction at zero separations between the dendrimer centers is also physically correct: configurations where the centers of mass of two dendrimers coincide are possible, without violation of excluded-volume conditions, hence the effective potential does not diverge at the origin. This is quite analogous to the case of polymer chains, where the effective interaction is known to be Gaussian ard1:00 .

The precise numerical value $`\epsilon =10.42k_BT`$ of the energy barrier, eq. (17), yields an optimal agreement with the experimental data. However, small deviations from this value can also be tolerated and by comparing with the SANS data we have established the limits in which this parameter can vary as $`8.0\epsilon 12.0`$, yielding a corresponding tolerance interval $`0.370\mathrm{nm}l_00.425\mathrm{nm}`$ for the “effective monomer length” $`l_0`$.

A prominent characteristic of the Gaussian potential at the reduced temperatures considered here (and also at higher ones), is its property to yield structure factors which do not show any pronounced peak with increasing density, in direct contradistinction with hard, diverging interactions such as the hard sphere (HS) potential lang:etal:gcm . In order to demonstrate this point, we have also attempted to fit the experimental data using a hypothetical HS interaction between the dendrimers, with the HS diameter $`\sigma _{\mathrm{HS}}`$ as a fit parameter. The results are shown in Fig. 3. The best fit at the lowest concentration is obtained by the choice $`\sigma _{\mathrm{HS}}=1.95R_g`$, which is thereafter kept constant. It can be seen that the fit quality worsens with increasing density, as the HS interaction yields a too high peak as well as a structure factor at low $`q`$-values which lies below the experimental data. However, as we are in the very dilute regime, the strong differences between the structure factors produced by these two interactions (Gaussian and HS) are not very pronounced. These differences become evident only if one looks at higher densities. The result found here is therefore in agreement with the findings of Ref. ballauff:99 . There it has been found that modeling the structure factor in terms of a simple hard-sphere ansatz leads to a satisfactory description of the data in the region of lowest volume fractions.

It is therefore evident that a more stringent test of theory can only be achieved by SANS-studies conducted at much higher concentrations. Experiments using the G4 and G5 dendrimer used in Ref. ballauff:99 ; Potschke:99  are under way. Here we present further evidence for the validity of the proposed interaction by comparing with and by offering a theoretical explanation for data already existing in the literature Ram:98 ; Amis:99 .

In Fig. 5 of Ref. Ram:98 , Ramzi et al. display the experimentally determined structure factor for a very wide concentration range of dendrimers, ranging from dilute to above the overlap concentration. It is seen that $`S(q)`$ is deprived of any significant structure; it has a weak peak of height $`1.1`$ at intermediate concentrations and thereafter the peak disappears and $`S(q)`$ becomes a monotonic function of $`q`$. At the same time, this phenomenon is accompanied by a monotonic reduction of the osmotic compressibility of the solution, the latter being proportional to the $`q0`$ limit of $`S(q)`$. This is precisely the behavior of $`S(q)`$ of the Gaussian core model lang:etal:gcm . The latter has a freezing and reentrant melting transition with increasing density at energies $`\epsilon 100k_BT`$, meaning that the liquid $`S(q)`$ has an anomalous dependence on the density: the height of its principal maximum grows up to a certain density and then it diminishes again. As the temperature is increased, the anomaly in $`S(q)`$ remains, but the height of the principal peak becomes smaller. In order to provide a semi-quantitative comparison with the data of Ref. Ram:98 , we show in Fig. 4 the evolution of $`S(q)`$ of the GCM with density for an energy barrier $`\epsilon =10k_BT`$ and packing fractions $`\eta =0.012.00`$, corresponding to $`\varphi 0.67`$. A striking similarity with the results of Ref. Ram:98  can be easily seen.

Similar conclusions hold when we compare our predictions with the scattering data of Topp et al., Figs. 7 and 8 in Ref. Amis:99 . There, the $`S(q)`$’s from samples of two different dendrimers are displayed; the same anomalous dependence of $`S(q)`$ on the concentration is seen, with the additional feature that the $`S(q)`$’s from the dendrimers with the larger generation number have higher peaks than their counterparts from the smaller dendrimers at the same concentration. In our language, a larger generation number, which implies a larger monomer number $`N`$, corresponds to a higher energy barrier $`\epsilon `$, see eq. (14). This automatically causes $`S(q)`$ to develop stronger peaks for larger generation numbers.

Of particular interest is the shape of $`S(q)`$ for very high concentrations which, as can be seen in Refs. Ram:98  and Amis:99  is a monotonic function of $`q`$. This behavior can be fully understood in the framework of the Gaussian interaction potential. It has been recently shown that bounded potentials in general, show at high densities a particular ‘mean-field behavior’ lang:etal:gcm ; likos:00 ; ard2:00 . The direct correlation function $`c(r)`$ in this limit becomes equal to $`\beta v(r)`$, where $`v(r)`$ is the interaction potential at hand and $`\beta =\left(k_BT\right)^1`$. For the case of the Gaussian potential, this implies that the structure factor at the high density limit takes the form lang:etal:gcm ; ard2:00 :

$$S(q)=\frac{1}{1+\pi ^{3/2}\beta \epsilon \rho \sigma ^3\mathrm{exp}\left[\left(Q\sigma /2\right)^2\right]},$$
(21)
or, more generally for any bounded potential $`v(r)`$ likos:00 ; ard2:00 :

$$S(q)=\frac{1}{1+\beta \rho \stackrel{~}{v}(q)},$$
(22)
where $`\stackrel{~}{v}(q)`$ is the Fourier transform of $`v(r)`$. Eq. (21) shows that, for the GCM, $`S(q)`$ has the form of a “smoothed out” step function. It is small at low $`q`$’s and approaches unity at high $`q`$’s, as $`\stackrel{~}{v}(q)0`$ there. The same conclusion holds, actually, for any bounded potential whose Fourier transform is a monotonically decaying, nonnegative function of $`q`$ likos:00 , as can be seen from eq. (22).

The anomalous behavior of the peak heights of the structure factor would be impossible if the assumed interaction between dendrimers were diverging at the origin as any power law. Indeed, power-law systems are known to undergo a freezing transition, this implying that the corresponding $`S(q)`$ develops stronger and stronger peaks with increasing density until, ultimately, freezing occurs when the principal peak reaches the quasi-universal Hansen-Verlet value $`2.85`$ hansen:verlet:69 . Hence, effective dendrimer-dendrimer interactions with such kinds of divergence at the origin can be immediately ruled out. This argument, however, does not rule out all diverging interactions. Indeed, the peak-height anomaly has also been observed in the framework of a theoretical treatment of star polymers anom , whose effective interaction is diverging logarithmically at the origin. This behavior, which has also been experimentally seen olaf:phd:95 , is again intimately related to the reentrant melting behavior of these systems watzlawek:etal:prl:99 ; martin:phd:00 . In fact, it has already been suggested Amis:99  that dendrimers may resemble star polymers below the critical arm number $`f_\mathrm{c}=34`$ at which crystallization is marginally possible watzlawek:etal:prl:99 ; martin:phd:00 ; witten:86 . However, at variance with the Gaussian interaction, the star-star effective potential Lik:98  does not have a mean-field high density limit and the structure factor of stars never becomes a monotonic function of $`q`$, even at extremely high densities anom , a feature which appears for bounded interactions only. In this respect, there is a difference between the effective interaction between the central monomers of two dendrites or two stars (which diverges) and that between their centers of mass (which does not).

On purely theoretical grounds, the underlying assumptions leading to the derivation of the logarithmic interaction between star polymers do not hold for dendrimers. Unlike stars, dendrimers do not obey a power-law dependence of the density profile around the center; they show no self-similarity, captured in the Daoud-Cotton blob model of the stars Daoud:CottonL82:1 ; and they are at least one order of magnitude smaller than star polymers, with the implication that many of the notions of polymer physics, based on long chains and universality cannot be automatically carried over to dendrimers.

We conclude this section with a remark on the accuracy of the pair potential approximation. Though many-body forces between the dendrimers are necessarily present in the solution, there are good reasons to believe that their effect can be neglected to a very good approximation. This belief is based on the one hand on the corresponding findings on star polymers triplet:00 . By a direct measurement of the triplet forces, it was established there that these have a very small effect on the total force on a star center, and this only shows up at concentrations considerably beyond the overlap value. On the other hand, a recent simulational work by Louis et al. ard1:00 , reached a similar conclusion for single chains. There, it was found that the pair potential yielding the correct thermodynamics of the system remains density-independent up to the overlap concentration and displays only a very weak density dependence above the latter. This density dependence is, of course, just another way to formulate the many-body effects. Once more, they were found to be of minor significance. Barring any dramatic alterations in the conformations of single dendrimers upon increasing density (such as collapsing), we expect the Gaussian pair potential picture to capture the salient characteristics of the behavior of this system at all concentrations.

## IV Summary and conclusions

By using the density profile of an isolated dendrimer and the experimentally determined characteristics of the macromolecules as input, we derived an effective interaction between the dendrimers’ centers of mass which is Gaussian in form. By direct comparison with experimental data at dilute solutions, we show that this interaction provides an excellent description of the measured structure factor. Moreover, it reproduces correctly the as of now unexplained trends and features of experimental structure factors at higher densities. A direct comparison with SANS data at high concentrations is, evidently, of crucial importance for further putting the proposed theory into a strong test. Work along these lines is currently in progress.

###### Acknowledgements.

The authors gratefully acknowledge financial support by the Deutsche Forschungsgemeinschaft and by the Bundesministerium für Forschung und Technologie.