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# Soft X-ray magnetic circular dichroism study of the ferromagnetic Cr1-δTe

## I Introduction

Chromium chalcogenides Cr1-δX (X=S, Se, Te) with metal-deficient NiAs type crystal structures show various magnetic and electronic properties.LB  Among them, chromium tellurides Cr1-δTe are ferromagnets with Curie temperatures of 170-360K. Ipser et al. systematically studied the phase diagram of Cr-Te system and determined the relationship between the phase and crystal structures.Ipser83  The Cr1-δTe with $`\delta <0.1`$ form the hexagonal NiAs crystal structure, while the Cr3Te4($`\delta `$=0.25) and Cr2Te3($`\delta `$=0.33) form the monoclinic and the trigonal crystal structures, where Cr vacancies occupy in every second metal layer. The effective paramagnetic moments described as $`\mu _{\mathrm{eff}}=g\sqrt{J(J+1)}`$ are $`44.9\mu _\mathrm{B}`$ for the hexagonal Cr1-δTe, $``$4.2$`\mu _\mathrm{B}`$ for Cr3Te4 and $``$3.96$`\mu _\mathrm{B}`$ for Cr2Te3, which have been explained by the spin moments $`2\sqrt{S(S+1)}`$ only with $`S=2`$ for $`\delta `$ 0 and with $`S=3/2`$ for $`\delta `$=0.333.Lotgering57 ; Hirone60 ; Ohsawa72 ; Grazhdankina70 ; Hashimoto69 ; Yamaguchi72 ; Andresen63 ; Andresen70 ; Hashimoto71 ; Kanomata00  However, the ordered magnetic moments evaluated from the magnetization measurements show much smaller values such as 2.4-2.7$`\mu _\mathrm{B}`$ for the hexagonal Cr1-δTe, 2.35$`\mu _\mathrm{B}`$ for Cr3Te4($`\delta `$=0.25) and 2.0$`\mu _\mathrm{B}`$ for Cr2Te3($`\delta `$=0.333) than those expected from the ionic model.Lotgering57 ; Hirone60 ; Ohsawa72 ; Grazhdankina70 ; Hashimoto69 ; Yamaguchi72 ; Andresen63 ; Andresen70 ; Hashimoto71 ; Kanomata00 ; Ohta93 ; Kanomata98  According to neutron-diffraction studies, the small value of saturation magnetization is partly explained if we take the spin canting into account for $`\delta =0.125,0.167`$ and $`0.25`$.Andresen70  The magnetic moment induced on the Cr ion for $`\delta `$=0.25 is close to an integral number of Bohr magnetons, suggesting the existence of mixed valence Cr. Andresen70  However for Cr2Te3($`\delta `$=0.33), the ordered magnetic moment of $`2.652.70\mu _B`$, deduced from the neutron diffraction, is much smaller than that calculated using the ionic model, $`3\mu _B`$, suggesting the itinerant nature of the $`d`$ electrons.Andresen70 ; Hamasaki75

The experimental Hall resistivity of Cr0.9Te as a function of applied magnetic field up to 3T in the temperature range of 4.2-340K can be fitted with the ordinary formula containing the normal and anomalous Hall coefficients as for the most ferromagnetic materials.Dijikstra89  The temperature dependent anomalous Hall coefficient $`R_\mathrm{S}`$ can be understood for the collinear ferromagnets.Dijikstra89  The number of carriers, which has been estimated from the normal Hall coefficient $`R_0`$ is +0.9/formula unit, suggesting hole carriers in Cr0.9Te.Dijikstra89  In contrast, the Hall resistivity of Cr3Te4 shows a different behavior from that of Cr0.9Te below $`T`$=100K, which suggests that there exists a complex magnetic structure in the monoclinic Cr3Te4 below $`T`$=100K.Oda01

Remarkable magnetovolume effect of Cr1-δTe has been reported, where the spontaneous magnetization decreases rapidly with increasing pressure as reported for Cr2Te3 and Cr0.92Te.Kanomata98 ; Kanomata00  It has also been reported very recently that the ferromagnetism disappears at 7GPa, and under pressure above 13GPa the structural phase transition occurs from the NiAs type structure to the orthorhombic MnP type structure.Ishizuka01 ; Eto01

Electronic specific heat coefficients $`\gamma `$ are also much dependent on $`\delta `$. The estimated $`\gamma `$ for Cr5Te6($`\delta `$=0.167), Cr3Te4($`\delta `$=0.25) and Cr2Te3($`\delta `$=0.333) are 10, 1 and 4 mJ/atom/K2.Gronvold64  The $`\gamma `$ for Cr3Te4 is quite close to the predicted value 1.0$``$1.4 mJ/atom/K2 using the calculated density of states (DOS) at the Fermi level ($`E_\mathrm{F}`$), while that for Cr2Te3 is much larger than the predicted one, $`\gamma 0.820.96`$ mJ/atom/K2.Dijikstra89 ; Ishida  Such large $`\gamma `$ values suggest that electron correlation effects are also important in Cr5Te6 and Cr2Te3. The electron correlation effects in these ”itinerant ferromagnets” Cr1-δTe has been discussed with the photoemission spectra.Shimada96  It has been pointed out that the spectral weight in $`E_\mathrm{B}`$=2-4eV observed in the photoemission spectra of Cr0.95Te and Cr3Te4 can not be explained by the theoretical band structure calculation, and the intensity at $`E_\mathrm{F}`$ is found to be smaller than the theoretical DOS. On the other hand, the spectral weight in $`E_\mathrm{B}`$=2-4eV has been reproduced with the configuration interaction cluster-model calculation, indicating the importance of the electron correlation effect in Cr1-δTe.Shimada96

It is known that soft X-ray core absorption spectroscopy (core XAS) is a powerful tool to study the element specific valence electronic states of materials. X-ray magnetic circular dichroism (XMCD) in the core XAS spectrum provides us with useful information on the element specific spin and orbital magnetic moments with use of the ”sum rule”.Thole92 ; Carra93 ; Chen95  It is widely known that the spectral shapes of the XAS and XMCD spectra are strongly dependent on the electronic states or the electronic configuration of the derived atom. Besides, these lineshapes can be remarkably affected by the intersite hybridization between the surrounding atoms or by the band structure of the crystal. In other words, the spectra can be a good fingerprint of the electronic states inside the crystals. For example, the valency (or the electron number) can be determined by the XAS and XMCD spectral lineshapes. One can also determine several physical parameters such as the Coulomb repulsion energy, the charge transfer energy as well as the hybridization energy from the analyses of experimental XAS and XMCD spectral lineshapes. In order to understand how the electronic states are related to the $`\delta `$ dependence of the magnetic and electronic properties, we have done Cr $`2p`$ XAS and XMCD study for Cr8Te9($`\delta =0.11`$), Cr5Te6($`\delta =0.17`$), Cr3Te4($`\delta =0.25`$) and Cr2Te3($`\delta =0.33`$).

## II Experimental

Metallographical studies for the Cr-Te system have shown that the existence of stoichiometric ’CrTe’ is ruled out.Ipser83  For example, the stability range of the phase with NiAs-type structure extends from 52.4 to 53.3 at.% Te. Polycrystalline samples were synthesized from mixed powders of constituent elements. They were sealed in evacuated silica tubes, which were heated for a week at 1000$`{}_{}{}^{}C`$. After this, the samples were ground and sealed in silica tubes again and heated for 2 hours at 1450C and then cooled gradually to 1000C and finally quenched into water.Koyama00  The stoichiometry and the homogeneity of Cr1-δTe have been estimated by means of Electron Probe Micro-Analysis (EPMA). X-ray diffraction studies confirmed that all of the samples were in a single phase.

Cr $`2p`$ core absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) spectra were measured at BL25SU of SPring-8 in Japan.Suga01 ; Suga02 ; Saitoh01 ; Saitoh02  Circularly polarized light was supplied from a twin-helical undulator, with which almost 100% polarization was obtained at the peak of the first-harmonic radiation. After having set the two undulators to opposite helicity, helicity reversal was realized by closing one undulator and fully opening the other.Saitoh01  Cr $`2p`$ XAS spectra were measured by means of the total photoelectron yield method by directly detecting the sample current while changing the photon energy $`h\nu `$. The photon energy resolution was set to $`E/\mathrm{\Delta }E=5000`$ for the Cr $`2p`$ core excitation regions. The measurement was performed in the Faraday geometry with both the incident light and the magnetization perpendicular to the sample surface. We used two pairs of permanent dipole magnets with holes for passing the excitation light. The external magnetic field of $`1.4T`$ at the sample position was alternatingly applied by setting one of the two dipole magnets on the optical axis by means of a moter-driven linear feedthrough. The XMCD spectra were taken for a fixed helicity of light by reversing the applied magnetic field at each $`h\nu `$. In the present paper, the XMCD spectrum is defined as $`I_+I_{}`$, where $`I_+`$ and $`I_{}`$ represent the absorption spectra for the direction of magnitization (which is opposite to the direction of the majority spin) parallel and antiparallel to the photon helicity, respectively.Suga01  Clean surfaces were obtained by in situ scraping of the samples with a diamond file under ultra high vacuum condition (3$`\times `$10-8 Pa). The cleanliness of the sample surfaces was first checked by the disappearance of a typical structure related to Cr oxides. We could also check the degree of contamination from the magnitude of the XMCD signal, because its amplitude grew and finally saturated when the sample surface became clean enough. We considered that the unscraped or contaminated surface was covered with antiferromagnetic or paramagnetic compounds such as Cr2O3, which hardly contribute to the XMCD spectrum. It is generally known that the the total photoelectron yield reflects the absorption spectrum in the core-excitation region. The temperatures during the measurement were $``$110K for all of the samples.

## III CI Cluster Model Calculation with Full Multiplets

The CI cluster model calculation has been done with a program code developed by A. Tanaka by means of the recursion method. The detailed procedures are described elsewhere.Tanaka94  Slater integrals have been calculated by Cowan’s code and the calculated values are listed in Table 1. In the calculation, the Slater integrals are scaled down to 80% of the listed values to take into account intra-atomic relaxation effect.

## IV Results and Discussion

The XAS and XMCD spectra in the Cr $`2p`$ core excitation region have been measured for Cr8Te9 ($`\delta =0.11`$), Cr5Te6($`\delta =0.17`$), Cr3Te4($`\delta =0.25`$) and Cr2Te3($`\delta =0.33`$). The Cr $`2p`$ XAS ($`I_+`$ and $`I_{}`$) spectra with both helicities of incident radiation and the XMCD ($`I_+I_{}`$) spectra of Cr5Te6 are shown in Fig.1 (a) and (b). It is found that the $`2p_{3/2}`$ and the $`2p_{1/2}`$ core absorption peaks are located at about 576 and 585 eV, and the broad hump is found around the photon energy of 600-605 eV. Since the core level binding energies ($`E_\mathrm{B}`$) of the Cr $`2p`$ and Te $`3d`$ levels are quite close to each other, one may expect the overlapping of these absorption edges.Fuggle80  We expect much lower Te $`3d5p`$ absorption cross section ($`<`$5%) compared to that of the Mn $`2p3d`$ absorption as observed, i.e., in Te $`4d5p`$ absorption spectrum of MnTe2.Kaznacheyev98  We also expect that the observed Cr $`2p`$ XAS fine structures are almost unaffected by the Te $`3d`$ XAS spectrum because the Te $`3d`$ core absorption is expected to be very broad due to the wide conduction band derived from the strong Cr $`3d`$-Te $`5p`$ hybridization. Therefore one can assume that the Te $`3d`$ core absorption spectrum behaves like a background for the Cr $`2p`$ core absorption structures and the observed XAS spectra in the present photon energy range mostly reflect the Cr $`2p`$ core absorption. However, the broad hump at 600-605 eV can be still assigned to the Te $`3d5p`$ absorption mainly because the observed XMCD asymmetry is negligible in this energy region. It is found that the intensity of $`I_+`$ is larger than that of $`I_{}`$ in the $`2p_{3/2}`$ core absorption region, whereas the intensity of $`I_+`$ is smaller than that of $`I_{}`$ in the $`2p_{1/2}`$ region. Besides, the spectral weight of $`I_+`$ is shifted to lower energy compared to $`I_{}`$ in both $`2p_{3/2}`$ and $`2p_{1/2}`$ regions. This derives the complicated XMCD ($`I_+I_{}`$) structures as shown by the solid line in Fig.1 (b). Here, the spectrum (solid line) shows remarkable XMCD with positive sign at the $`2p_{3/2}`$ core absorption edge ($`h\nu `$=575.5eV) as marked with A, which is followed by the smaller asymmetry with negative sign ($`h\nu `$=578eV) as represented by B. It is noticed that the XMCD signal does not reach zero even in the region between the spin-orbit split $`2p`$ components. There is still finite and negative XMCD on the lower energy side of the $`2p_{1/2}`$ absorption edge ($`h\nu `$=583eV). Then one finds a small positive ($`h\nu `$=584eV) and a large negative ($`h\nu `$=585.5eV) XMCD peaks with increasing $`h\nu `$ as marked with C, D and E in Fig.1 (b). To eliminate the possible instrumental asymmetries, we have taken the spectra by reversing the helicity of the incident radiation. As a result of this procedure, it is found that the observed XMCD signals with opposite helicities of the incident lights are quite symmetric with respect to the zero line as shown by the solid and dashed lines. This means that the observed complicated structures of the XMCD spectrum are intrinsic signals.

In Fig.2, are shown the helicity averaged Cr $`2p`$ XAS spectra represented as $`(I_++I_{})/2`$ of (a)Cr8Te9($`\delta `$=0.11), (b)Cr5Te6($`\delta `$=0.17), (c)Cr3Te4($`\delta `$=0.25) and (d)Cr2Te3($`\delta `$=0.33). In contrast to the spectrum of Cr5Te6 (Fig.2 (b)), one finds a shoulder on the higher $`h\nu `$ side of the $`2p_{3/2}`$ edge in the spectrum of Cr8Te9. One also finds broad and small shoulder on the lower energy side of the $`2p_{1/2}`$ peaks in Cr8Te9. In the cases of the higher $`\delta `$ compounds like Cr5Te6, Cr3Te4 and Cr2Te3, the line width of the $`2p_{3/2}`$ edge is narrower with some tail extending to the higher $`h\nu `$ compared to that of Cr8Te9. Besides, the shoulder on the lower $`h\nu `$ side of the $`2p_{1/2}`$ edge has comparable spectral weight to that of the $`2p_{1/2}`$ main peak in the spectra of Cr5Te6, Cr3Te4 and Cr2Te3. In addition, the broad humps are observed at the same $`h\nu `$ region near 600-605eV in all of the spectra as in the case of Cr5Te6.

The XMCD spectra obtained as $`I_+I_{}`$ of (a)Cr8Te9, (b)Cr5Te6, (c)Cr3Te4 and (d)Cr2Te3 are shown in Fig.3. We find that the overall lineshapes of the present XMCD spectra are similar to each other, in which all of the fundamental structures A-E are observed, but we observe small changes depending on $`\delta `$. In the spectra of Cr3Te4 and Cr2Te3, the shoulder structures are present on the lower energy side of the Cr $`2p_{3/2}`$ absorption edge as denoted by F in Fig.3. In addition, the negative structures on the higher energy side of the $`2p_{3/2}`$ main peak is sharper in the spectra of Cr3Te4 and Cr2Te3 than in those of Cr8Te9 and Cr5Te6.

First, we have tried to evaluate the contribution of the orbital magnetic moment $`m_{\mathrm{orb}}`$ with the use of the following sum ruleThole92 ; Chen95 ,

$$m_{\mathrm{orb}}=\frac{4}{3}\frac{_{L_3+L_2}(I_+I_{})𝑑h\nu }{_{L_3+L_2}(I_++I_{})𝑑h\nu }(10n_d)$$
(1)
, where $`n_d`$ represents $`3d`$ electron number. The estimated $`m_{\mathrm{orb}}`$ value is turned out to be almost negligible, suggesting the quenched Cr $`3d`$ orbital magnetic moment in consistence with the measured $`g`$ value ($`g2`$).Grazhdankina70

Next, in order to evaluate several physical parameters that control the physical properties of Cr1-δTe, we have calculated the Cr $`2p`$ XAS and XMCD spectra by means of a configuration interaction (CI) cluster-model calculation with full multiplets assuming a \[CrTe6\]10- cluster so as to reproduce the experimental spectra of Cr1-δTe. Here, the nominal $`d`$ electron numbers in Cr8Te9($`\delta =`$0.11), Cr5Te6($`\delta =0.17`$), Cr3Te4($`\delta =0.25`$) and Cr2Te3($`\delta =0.33`$) are $``$ 3.75, 3.60, 3.33 and 3.00 per Cr atom, respectively when we assume the Te valence to be $`2`$. Among them, the formal valency of Cr8Te9 is the closest to $`2+`$ ($`3d^4`$), which is the nominal valency of CrTe (mono telluride).

For Cr8Te9, we have assumed the nominal $`d^4`$ configuration and have employed two more charge-transfer states such as $`d^5\underset{¯}{L}`$ and $`d^6\underset{¯}{L}^2`$, where $`\underset{¯}{L}`$ denotes a hole in the Te $`5p`$ orbital. Thus the initial state is expanded by a linear combination of $`d^4`$, $`d^5\underset{¯}{L}`$, $`d^6\underset{¯}{L}^2`$ and the final state is described by a linear combination of $`\underset{¯}{2p}d^5`$, $`\underset{¯}{2p}d^6\underset{¯}{L}`$, $`\underset{¯}{2p}d^7\underset{¯}{L}^2`$, where $`\underset{¯}{2p}`$ denotes a created hole in the $`2p`$ core level in the absorption final state. Slater integrals and spin-orbit coupling constants for $`d^4`$, $`d^5`$ and $`d^6`$ configurations in the initial state and for $`p^5d^5`$, $`p^5d^6`$ and $`p^5d^7`$ in the XAS final states are listed in Table 1. To perform the CI calculation, four adjustable parameters are introduced as follows; the charge-transfer energy $`\mathrm{\Delta }E(d^5\underset{¯}{L})E(d^4)`$, the Coulomb interaction energy $`U_{dd}`$ between the $`3d`$ electrons, the Coulomb energy $`U_{cd}`$ between the $`2p`$ core hole and $`3d`$ electrons, the hybridization energy $`V_{\mathrm{e}_\mathrm{g}}[=\sqrt{3}(pd\sigma )]`$ and the octahedral crystal field splitting $`10Dq`$. We have neglected the hybridiation energy between the anion $`p`$ orbitals.

We have used the $`U_{dd}`$2.3eV, which has been estimated from the Cr $`M_{23}VV`$ Auger-electron spectra and the self-convolution of the Cr $`3d`$-derived spectra.Shimada96  We have also used the same value $`V_{\mathrm{e}_\mathrm{g}}`$=1.3eV, which has been evaluated by using the formula $`(pd\sigma )=\eta _{pd\sigma }{\displaystyle \frac{\mathrm{}^2}{m}}{\displaystyle \frac{r_d^{1.5}}{d^{3.5}}}`$ with $`\eta _{pd\sigma }=2.95`$ and $`r_d`$(Cr)=-0.9Å.Harrison  Here, $`U_{cd}`$ has been fixed to $`U_{dd}/U_{cd}=0.83`$ and the relationship $`(pd\sigma )/(pd\pi )=2.0`$ has been assumed. Consequently, we have adjusted the charge transfer energy $`\mathrm{\Delta }`$ and $`10Dq`$ to fit the experimental XAS and XMCD spectra of Cr8Te9. Fig.4 (b) and (d) show the calculated XAS and XMCD spectra for Cr8Te9, which are broadened by the Lorenzian function with 2$`\mathrm{\Gamma }`$=1eV. It is noticed that the calculated XAS spectrum fits well with the experimental spectrum of Cr8Te9 including the shoulder structure in the $`2p_{1/2}`$ region except for the narrower band width in the calculated $`2p_{3/2}`$ XAS spectrum. The calculated XMCD spectrum reproduces not only the dispersive XMCD feature at the $`2p_{3/2}`$ edge (A and B), but also the structures at $`2p_{1/2}`$ edge including the small positive structure found in the lower $`h\nu `$ region (C, D and E) as shown in Fig.4 (d). It has been clarified that the hybridization effect between the Cr $`3d`$ and Te $`5p`$ states as well as the electron correlation effect of the Cr $`3d`$ electrons is quite important to understand the electronic states of Cr1-δTe. The calculated result also shows that the ground state wave function can be described as $`\mathrm{\Psi }_g=0.27|d^4+0.62|d^5\underset{¯}{L}+0.11|d^6\underset{¯}{L}^2`$. One notices from this result that the weight of the $`d^5\underset{¯}{L}`$ component is more than two times larger than that of the $`d^4`$ and the contribution of the $`d^6\underset{¯}{L}^2`$ is not negligible in the ground state, which has been derived from the strong hybridization between Cr $`3d`$ and Te $`5p`$ orbitals. The averaged $`3d`$ electron number is 4.8, which is much larger than 4 (Cr2+) as shown in Table 2. According to the CI calculation, the estimated $`m_{\mathrm{spin}}`$ and $`m_{\mathrm{orb}}`$ are 4.2$`\mu _\mathrm{B}`$ and -0.04$`\mu _\mathrm{B}`$, respectively. Such a quite small $`m_{\mathrm{orb}}`$ stems from the dominant $`d^5\underset{¯}{L}`$ configuration in the ground state and is consistent with the estimated value with use of the sum rule as mentioned above. The calculated $`m_{\mathrm{spin}}`$=4.2$`\mu _\mathrm{B}`$ is consistent with the formerly calculated result for the valence band photoemission spectrum of Cr0.95Te, but is much larger than the values given by the band-structure calculation 3.3$`\mu _\mathrm{B}`$Dijikstra89  and the observed saturation magnetic moment $``$2.5$`\mu _\mathrm{B}`$. In fact, we have neglected the Cr $`dd`$ overlap along the $`c`$-axis in the CI calculation. This may derive the larger spin magnetic moment in the calculation. The observed discrepancy in the experimental XAS spectrum with the broader width accompanying the higher energy tail compared with the calculated one may also be ascribed to this lack of the $`dd`$ interaction.

We have also applied the cluster model calculation to Cr2Te3, which has the nominal valency of 3+ (3$`d^3`$). We have performed the calculation with the ground state wave function that is expanded by a linear combination of $`d^3`$, $`d^4\underset{¯}{L}`$, $`d^5\underset{¯}{L}^2`$ and $`d^6\underset{¯}{L}^3`$ configurations. In this case, the charge transfer energy can be defined as $`\mathrm{\Delta }E(d^4\underset{¯}{L})E(d^3)`$. We have used the same values of $`U_{dd}`$=2.3eV, $`U_{cd}=(U_{dd}/0.83)`$ and $`V_{\mathrm{e}_\mathrm{g}}`$=1.3eV as used for Cr8Te9. Figs.5 (b) and (d) show the calculated XAS and XMCD spectra with the parameters $`\mathrm{\Delta }`$=-1.5eV and $`10Dq`$=1.0eV. We find a good correspondence between the calculated XAS/XMCD spectra and the experimental ones. We recognize that the calculated XMCD spectrum not only reproduces the observed fundamental structures A-E but also the shoulder F as shown in Figs.5 (c) and (d) It is noted that we have obtained the negative value of $`\mathrm{\Delta }`$ for Cr2Te3, which means that the ground state is not dominated by the $`d^3`$ configuration but by the $`d^4\underset{¯}{L}`$ and $`d^5\underset{¯}{L}^2`$ configurations because the energy differences $`E(d^4\underset{¯}{L})E(d^3)`$ and $`E(d^5\underset{¯}{L}^2)E(d^3)`$ are expressed as $`\mathrm{\Delta }`$(=-1.5eV) and $`2\mathrm{\Delta }+U_{dd}`$(=-0.7eV), respectively when the hybridization ($`V_{\mathrm{e}_\mathrm{g}}`$) is off. That is, the most stable $`d^4\underset{¯}{L}`$ is formed by the charge transfer from the ligand Te $`5p`$ orbitals to the Cr $`3d`$ orbitals. The resultant ground state wave function is $`\mathrm{\Psi }_g=0.11|d^3+0.48|d^4\underset{¯}{L}+0.36|d^5\underset{¯}{L^2}+0.05|d^6\underset{¯}{L}^3`$. From this result, the evaluated average electron number is found to be 4.3 and the calculated $`m_{\mathrm{spin}}`$ and $`m_{\mathrm{orb}}`$ are estimated to be 3.2$`\mu _\mathrm{B}`$ and -0.03$`\mu _\mathrm{B}`$, respectively as listed in Table II. It is recognized that the small $`m_{\mathrm{orb}}`$ is consistent with the XMCD result, while the calculated spin magnetic moment is smaller than that for Cr8Te9 and is larger than the measured values of $``$2.0-2.7$`\mu _\mathrm{B}`$.

Finally we discuss the $`\delta `$ dependence of the electronic structures in Cr1-δTe. We have already found that the XMCD spectral lineshapes are not changed so much with $`\delta `$ as shown in Fig.3. This means that the change in the local Cr $`3d`$ electronic states is very weak when the Cr vacancy is introduced. This interpretation can be supported by the CI cluster-model calculation. As we have obtained in the CI cluster calculation with the parameters $`\mathrm{\Delta }=0.0eV`$ and $`U_{dd}=2.3eV`$ for Cr8Te9, the relationship $`\mathrm{\Delta }<U_{dd}`$ indicates that the Cr8Te9 can be classified in the charge transfer regime in the Zaanen-Zawatzky-Allen diagram.Zaanen85  The early transition metal (Sc-Cr) compounds were originally classified in the Mott-Hubbard regime ($`U_{dd}<\mathrm{\Delta }`$), but recent CI cluster calculation analyses of core-level photoemission spectra have shown that even the Cr oxides such as Cr2O3 and LaCrO3 are reclassified in the intermediate region between the Mott-Hubbard and charge-transfer regimes ($`U\mathrm{\Delta }`$).Bocquet96  It is, therefore, considered that the classification of Cr tellurides in the charge-transfer regime is reasonable if we take into account the much smaller electron negativity of Te compared to oxygen.

Now we take into account the one hole (one electron removal) state that corresponds to the $`3d`$ photoemission final state. To make the story as simple as possible, we describe the ground state wave function as $`\mathrm{\Psi }_g=\alpha |d^4+\beta |d^5\underset{¯}{L}`$. Then the one-hole state can be described as $`\mathrm{\Psi }_f=\alpha ^{}|d^3+\beta ^{}|d^4\underset{¯}{L}`$. Here the energy difference $`E(d^3)E(d^4\underset{¯}{L})`$ can be represented as $`\mathrm{\Delta }U_{dd}`$. According to the relationship $`\mathrm{\Delta }<U_{dd}`$ as discussed above, the $`d^4\underset{¯}{L}`$ state is energetically lower compared to the $`d^3`$ state as shown in Fig.6. In the other expression, if we introduce a hole in the \[CrTe6\]10- cluster, the hole preferably stays in the Te $`5p`$ orbital. The same interpretation can be applicable in the Cr deficient materials, Cr1-δTe. The created holes by the Cr vacancy in Cr1-δTe are likely to be in the Te $`5p`$ orbitals, then the decrease of the $`3d`$ electron number with the increase of $`\delta `$ is weak, which is consistent with the calculated negative $`\mathrm{\Delta }`$ value for Cr2Te3 and the present XMCD results. This is also consistent with the calculated band structure of Cr1-δTe, where the hole pocket derived from the Te $`5p`$ state appears around $`\mathrm{\Gamma }`$ point in the Brillouin zone when the Cr vacancy is introduced in the material.Dijikstra89

## V Conclusion

We have observed the Cr $`2p`$ XAS and XMCD spectra of Cr8Te9($`\delta `$=0.11), Cr5Te6($`\delta `$=0.17), Cr3Te4($`\delta `$=0.25) and Cr2Te3($`\delta `$=0.33). The observed changes with the Cr vacancy in the experimental XMCD spectra of Cr1-δTe are found to be quite small. The experimental XAS and XMCD spectra of Cr8Te9 and Cr2Te3 have been compared with the result of the CI cluster-model calculation. With the best fit parameters, $`\mathrm{\Delta }`$=0eV, $`U_{dd}`$=2.3eV and $`V_{\mathrm{e}_\mathrm{g}}`$=1.3eV, the calculated XAS and XMCD spectra have reproduced well the experimental spectra of Cr8Te9. The obtained parameters show that Cr1-δTe can be classified in the charge transfer type metal and the created holes in this compound should preferably exist in the ligand Te $`5p`$ orbitals, which is consistent with the obtained negative $`\mathrm{\Delta }`$ for Cr2Te3 and the unchanged feature of the XMCD spectral lineshapes by the Cr defect concentration $`\delta `$. These results are supported by the band structure calculation.

###### Acknowledgements.

The authors would like to thank Dr. Y. Saitoh of the Japan Atomic Energy Research Institute for a fine adjustment of the monochromator and Professor A. Fujimori of the University of Tokyo and Professor T. Kanomata of Tohoku Gakuin University for their fruitful discussion. This work was done under the approval of the SPring-8 Advisory Committee (Proposal No. 2000B0439-NS -np). This work was supported by the Ministry of Education, Science, Sports and Culture.


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# Interactions between proteins bound to biomembranes

## I Introduction

A significant proportion of all proteins in a typical eukaryotic cell are membrane proteins. These are found anchored to cell membranes. Many of these carry out tasks such as signal transduction, pore or channel formation, cytoskeletal binding etcalberts . Others are involved in endocytosis and exocytosis. In particular it is now understood that the formation of clathrin coated pits is driven by the controlled geometric aggregation of clathrin which exert corresponding forces on the cell membraneclathrin1 ; clathrin2 . There also exists a less well understood class of membrane invaginations, known as caveolae, that are less morphologically distinct than clathrin coated pits and resemble aspherical invaginations with a typical size of the order of 100nmrothberg . There is good evidence that caveolae are involved in endocytosisfunction1  and play an important role in cell signalingreview1 . Intriguingly they are probably also involved in the sensing of shear-stressshear ; shear2 . Such stresses would be expected to act on the tension $`\gamma `$ of the cell membrane. Thus, the present work may yield predictions for some of the direct physical consequences of surface tension, e.g. on inter-protein forces. In section II we discuss some qualitative effects of surface tension although a quantitative analysis of the effect of shear on membrane tension is beyond the scope of the present work. Recent elegant experiments demonstrate that better control of the surface tension may be achieved via micropipette aspiration facilitating studies of the effects of tension on membrane elasticityrawicz ; albersdorfer ; hackl  and permeability to water olbrich .

It has now been shown that caveolinslisantiJCB94 , a recently discovered class of membrane-bound proteins, are necessary for the formation of caveolae. These caveolins have a short membrane spanning sequence and N- and C-terminus polypeptide “tails”, totalling about 150 amino acids, both found on the cytoplasmic side of the cell membrane. It is thought that these caveolin molecules are typically found in small aggregates of size $`b`$ (a few nm) containing of approximately 15 moleculeslisantiPNAS95 . A crude thermodynamic (entropic) bound on the bending moment would be $`>k__BTb`$, higher for larger aggregates.

Many theoretical studies have sought to calculate the effect of adsorbed polymer on flexible, fluid membranes, see e.g. lipowsky2 ; carlos ; lipowsky1a ; lipowsky1b ; kim . One reason for this approach is that the simplified models available from polymer physics allow for a more or less exact computation of the entropic pressure exerted by the polymer on the membrane. Our work represents a generalization of this approach. An anchored polymer is but one example, or model, of a membrane inclusions that exerts a force on the membrane. Any membrane protein that isn’t perfectly symetrical across the membrane should exert forces, the distribution of which will be dictated by the precise protein configuration. Furthermore, it can be argued that the physical effect of integral membrane protein can also be described by a well chosen force distribution. Hence there is a need for a general theory on the effect of arbitrary force distributions on flexible membrane. Our premier interest are large peripheral membrane protein such as caveolin. Our theory is, however, general enough to be applied to any flexible fluid interface with fixed tension, containing embedded impurities.

Much of the previous work on interaction between membrane-bound objects has focused on membranes with vanishing surface tensionlipowsky2 ; carlos ; lipowsky1a ; lipowsky1b , although there have been exceptions golestanian . This work exists within the context of an extensive literature on membrane mediated interactions on tensionless membranes, see e.g. goulian ; goulianepl ; goulianeplerratum , which focussed mainly on Casimir-like forces originating from membrane fluctuations. It was argued that these could be either attractive or repulsive depending on the temperature and certain details of the model. The interest in tensionless membranes has its origin in the fact that isolated, self-assembled lipid membranes should be tensionless at equilibrium. Importantly this is not the case for many cell membranes. Other studies include tension as a (shape dependent) parameter determined self-consistently for closed membrane surfacesseifert . A study of the behavior of membranes under constant surface tension may shed light on the physics occurring on biological membrane, which are not truly at equilibrium and hence bear substantial tensionssheetz ; lorz . Cells commonly adjust their surface tension to a set value via a mechanism known as Surface-Area-RegulationSAR . Hence membrane phenomena over sufficiently long timescales effectively occur at constant surface tension. Previous studies of the effects of rod-like objects embedded in fluid membranesgolestanian  and impurities at gas-liquid interfacesfournier ; stamou  share certain similarities with this study.

## II Analysis of membrane deformation and membrane mediated interactions

Our aim is to construct a theoretical model for the membrane-mediated interactions between proteins bound to cell membranes. To achieve this we will denote the normal membrane displacement from its average flat state as $`u(𝐫)`$, where $`𝐫`$ is a 2D vector in the plane of the unperturbed membrane. Motivated by a desire to analyze small membrane deviations we employ an expansion of the free energy of the membrane in powers and gradients of $`u`$. The free energy of a deformed fluid membrane, without inclusions, is well approximated bysafran

$$F_{memb}=d^2r\left[\frac{\kappa }{2}(^2u(𝐫))^2+\frac{\gamma }{2}(u(𝐫))^2\right]$$
(1)
Which represents the truncation of an arbitrary expansion at order $`u^2`$ (odd orders are excluded by symmetry) and at the second derivatives of $`u`$. For a planar membrane, with normal in the $`\widehat{z}`$-direction, the gradient operator is $`=\widehat{x}\frac{}{x}+\widehat{y}\frac{}{y}`$. The only two parameters that are needed to describe the physics of the membrane are $`\kappa `$, the elastic bending modulus (typicallyevans  $`20k__BT`$ for biomembranes) and $`\gamma `$ the surface tension (estimated to be sheetz  $`10^1`$ to $`10^2`$pN/nm).

To include the work done by the pressure (normal force per unit area) $`f(𝐫)`$ exerted by one or more inclusions we exploit the fact that, for small deviations, the work done is merely the surface integral of the product of pressure and distance. The displacement has no effect on the pressure field at this order. Thus the total free energy, including the effect of inclusions is

$$F=d^2r\left[\frac{\kappa }{2}(^2u(𝐫))^2+\frac{\gamma }{2}(u(𝐫))^2f(𝐫)u(𝐫)\right]$$
(2)
where the term involving $`f(𝐫)`$ is chosen to have a minus sign to ensure that the membrane displacement has the desired sign. At thermodynamic equilibrium the free energy $`F`$ must reach its minimum value, at which point $`u(𝐫)`$ satisfies the Euler-Lagrange equation

$$_1_2u(𝐫)\frac{f(𝐫)}{\kappa }=0$$
(3)
with $`_1=^2`$, $`_2=^2k^2`$ and $`k^2=\gamma /\kappa `$ indicating an intrinsic length scale $`k^130`$nm (with perhaps $`6\mathrm{n}\mathrm{m}<k^1<100\mathrm{n}\mathrm{m}`$). We solve this under the boundary condition $`lim_𝐫\mathrm{}u(𝐫)=0`$ and that $`lim_{𝐫0}u(𝐫)`$ exists. Since the commutator $`[_1,_2]=0`$ it can be shown that

$$u(𝐫)=\frac{1}{\gamma }\left[G_1(𝐫,𝐫^{})G_2(𝐫,𝐫^{})\right]f(𝐫^{})d^2𝐫^{},$$
(4)
where $`G_1`$ and $`G_2`$ are the Green’s functions corresponding to the self adjoint problems determined by $`_1`$ and $`_2`$ (and their boundary conditions) respectively. We now seek to find the Green’s functions of these self adjoint operators.

For $`_1`$ we solve

$$_1G_1(𝐫,𝐫^{})=^2G_1(𝐫,𝐫^{})=\delta (𝐫𝐫^{})$$
(5)
The only boundary conditions compatible with this equation are Neumann conditions at infinity i.e. $`lim_{𝐫𝐫^{}\mathrm{}}G_1(𝐫𝐫^{})=0`$. This corresponds to the membrane being asymptotically flat and yields the well known Green’s function of Poisson’s equation in 2-D

$$G_1(𝐫,𝐫^{})=\frac{1}{2\pi }\mathrm{log}A|𝐫𝐫^{}|$$
(6)
where $`A`$ is an arbitrary constant with dimensions of (length)-1. We choose $`A=k`$ for convenience, this choice corresponds only to a definition of the zero of the free energy.

For $`_2`$ we must solve

$$\left(^2k^2\right)G_2(𝐫,𝐫^{})=\delta (𝐫𝐫^{}).$$
(7)
subject to the boundary conditions specified above. This self adjoint problem has linearly independent solutions $`K_0(k|𝐫𝐫^{}|)`$ and $`I_0(k|𝐫𝐫^{}|)`$. These are, respectively, the zeroth order modified Bessel functions of the first and second kind. The function $`I_0(x)`$ diverges as $`x\mathrm{}`$ therefore we write the Green’s function as

$$G_2(𝐫𝐫^{})=\frac{1}{2\pi }K_0(k|𝐫𝐫^{}|)$$
(8)
This gives us the solution of equation (3), subject to the stated boundary conditions as

$$u(𝐫)=G(𝐫,𝐫^{})f(𝐫^{})d^2𝐫^{}$$
(9)
with the Greens function

$$G(𝐫,𝐫^{})=\frac{1}{2\pi \gamma }\left[K_0(k|𝐫𝐫^{}|)+\mathrm{log}k|𝐫𝐫^{}|\right]$$
(10)
Equations 9 and 10 represent a solution for the equilibrium membrane displacement $`u(𝐫)`$ due to an arbitrary force distribution. The formal analysis is concluded in the appendix, where we show that this solution is unique.

### Interaction Potential between two proteins

Consider a fluid membrane with two, not necessarily identical, inclusions bound to it. Denote the pressure fields acting on the membrane surface due to each inclusion by $`\psi ^{(1)}`$ and $`\psi ^{(2)}`$. Without loss of generality we may let $`\psi ^{(1)}`$ be centered at the origin and let the vector $`𝐫`$ joining the centers of the pressure distributions lie along the x-axis. Mathematically this means that we write the total pressure distribution as

$$f(𝐫^{})=\psi ^{(1)}(𝐫^{})+\psi ^{(2)}(𝐫^{}𝐫),$$
(11)
where $`\psi ^{(2)}(𝐫^{}𝐫)`$ is the pressure distribution of the second inclusion centered at $`𝐫`$, rather that the origin. Hence the Free Energy at equilibrium is given by $`F=F_{self}^{(1)}+F_{self}^{(2)}+\mathrm{\Phi }(𝐫)`$, where $`F_{self}^{(i)}`$ is the self energy of the ith inclusion and $`\mathrm{\Phi }(𝐫)`$ is the interaction energy. We are interested only in $`\mathrm{\Phi }(𝐫)`$ as this is what determines the physics of interest to us here. By direct analysis or analogy with electrostatics this may be expressed as

$$\mathrm{\Phi }(𝐫)=d^2𝐫^{}d^2𝐫^{\prime \prime }\psi ^{(1)}(𝐫^{})\psi ^{(2)}(𝐫^{\prime \prime })G(𝐫𝐫^{}+𝐫^{\prime \prime })$$
(12)
where $`G(𝐫)`$ is the real space Green’s function.

For the case that we have two inclusions with circular symmetry we are able to determine the interaction potential exactly. Consider two circularly symmetric inclusions i.e. $`\psi ^{(i)}(𝐫^{})=\psi ^{(i)}(|𝐫^{}|)=\psi ^{(i)}(r^{})`$ such that $`\psi ^{(i)}(r^{})=0`$ for $`r^{}>b`$, where $`b`$ is some maximum radius of the inclusion. Also each pressure field is such that no average force acts ($`\psi ^{(i)}(𝐫^{})d^2𝐫^{}=0`$). For inclusions which are not anchored to external structures, such as the cytoskeleton, this condition must be satisfied on general grounds. Indeed Newton’s third law requires that any average force applied to the membrane by an inclusion must be equal and opposite to the reaction force applied by the inclusion to some external structure. If there is no external structure for this reaction force to act against then there can be no average force on the membrane. We assume that the pressure fields do not overlap so that $`r>2b`$. Under these assumptions the logarithmic term in Eq (10) gives a vanishing contribution to the integral Eq (12) due to Gauss’ Theorem. It corresponds to the electric field due to two circularly symmetric charged discs in 2-D, each carrying no average charge and thus with zero field in the region outside both discs. This analogy will be revisited when we discuss non-circularly symmetric inclusions in section IV below. The potential between two circularly symmetric inclusions is therefore given by

$$\mathrm{\Phi }(𝐫)=\frac{1}{2\pi \gamma }_0^br^{}𝑑r^{}_0^br^{\prime \prime }𝑑r^{\prime \prime }\psi ^{(1)}(r^{})\psi ^{(2)}(r^{\prime \prime })_0^{2\pi }𝑑\theta ^{}_0^{2\pi }𝑑\theta ^{\prime \prime }K_0(k|𝐫(𝐫^{}𝐫^{\prime \prime })|),$$
(13)
the upper limits of integration are both $`b`$ since $`\psi (r^{})=0`$ for $`r>b`$. We make use of the identities

$$_0^{2\pi }K_0(k|𝐫(𝐫^{}𝐫^{\prime \prime })|)𝑑\theta ^{\prime \prime }=2\pi K_0(kr)I_0(k|𝐫^{}𝐫^{\prime \prime }|)$$
(14)
valid for $`r>|𝐫^{}𝐫^{\prime \prime }|`$, and

$$_0^{2\pi }I_0(k|𝐫^{}𝐫^{\prime \prime }|)𝑑\theta ^{}=2\pi I_0(kr^{})I_0(kr^{\prime \prime })$$
(15)
valid for $`r^{}r^{\prime \prime }`$. Thus we are able to derive an exact analytical form for the interaction potential between non-overlapping ($`r>2b`$) circularly symmetric inclusions

$$\mathrm{\Phi }(𝐫)=\frac{1}{2\pi \gamma }\zeta ^{(1)}\zeta ^{(2)}K_0(kr)$$
(16)
where $`\zeta ^{(i)}=2\pi _0^{\mathrm{}}r^{}\psi ^{(i)}(r^{})I_0(kr^{})𝑑r^{}`$ characterizes the strength of the ith membrane/inclusion coupling. By employing the expansion of $`I_0(kr^{})`$ the quantity $`\zeta ^{(i)}`$ can be thought of as a series of moments of the force distribution. The radial force is, as usual given by the derivative of the potential $`f_r=\mathrm{\Phi }/r`$. The interaction is everywhere repulsive. Some previous studies have reported attractive interactions between polymer chains grafted on tensionless membraneslipowsky2 ; carlos . In these studies the position $`u(0)`$ of the chain grafting point was fixed, effectively by a Lagrange force which then acted to ensure that there was no average force, although this condition was not identified explicitly by these authors. In the case of vanishing tension it was found that there was no interaction between inclusions unless they “touch”, i.e. their force fields overlap. One can understand this as follows: For tensionless membranes the membrane deformation under the force field is dictated by the minimisation of an energy similar to Eq (2) but with $`\gamma =0`$. The membrane deformation outside the extent of the force field simply minimises the curvature energy, hence has a zero mean curvature and does not contribute to the total energy. As two inclusions approaches each other, the total energy does not change until one force field couples to the membrane deformation directly under the other force field, since the deformation energy of any piece of membrane that it not in direct contact with a force field is zero. There is no characteristic lengthscale $`k^1`$ to give the interactions finite range when $`\gamma =0`$. In consequence, inclusions interact only when the two force fields overlap. in the case of grafted ideal polymer chains, the energy is decreased when the force fields overlap because they both want to deform the membrane in the same direction, resulting in an attraction. We note that the interaction between overlapping membrane inclusions is very sensitive to the direct physical, rather than membrane mediated, interactions between them, unlike Eq (16) which is universal. In the $`\gamma 0`$ limit Eq (16) gives vanishing interactions, entirely consitant with these earlier results for tensionless membranes.

As mentioned in the introduction recent experiments on the effect of shear forces on living cells provide a crude control on membrane tension. In future studies we plan to calculate the precise effect of this on, e.g. surface phase equilibria and budding phenomena.

## III Microphase separation at the surface of caveolar invagination

Membrane-mediated interactions between membrane-bound inclusions have been extensively studied theoretically goulian  with, however, relatively little discussion of how experiments could easily support these predictions. Although presumably long range, these interactions are expected to be quite small, and are probably often dominated by stronger, (bio)chemically specific, short range phenomena. Long range interactions can, however, profoundly influence the phase behaviour of certain membrane proteins even if stronger, short range interactions, are present. As we emphasise below studies of such surface phases might provide an indirect probe of the membrane mediated interactions of interest here. This might be of particular relevance for the study of the phase behaviour of the protein caveolin, which is found at high density on certain membrane invaginations called caveolae (see sec.I).

One peculiar feature of the caveolae bulbs is their texture. Distinct striations are seen at the surface of these budsrothberg  (see also Fig.13.48 in alberts ). These are now thought to correspond with the organization and alignment of caveolin oligomers on the membrane cterm1b . The observation of these surface stripes is intruiging, and the reader may find it interesting that radially symmetrical oligomers can give rise to non-symmetrical surface phases. We discuss this below, arguing that the stripe phase may be a signature of the membrane mediated repulsion between protein aggregates, such as those calculated in section II. Indeed, studying the phase behaviour of membrane inclusions may provide one of the best ways to test theory against experiment in this field. Molecular dissection of the caveolin protein has shown that caveolin oligomers strongly attract each other through contacts of specific protein sequencesreview1  (a short range attraction). It is well known that a solution of particle interacting via hard core repulsion and a short range attraction undergo a gas/liquid phase separation. This results in large dense regions (the liquid) coexisting with less dense regions (the gas). The caveolin oligomer being anchored to the cell membrane, there exists an additional membrane-mediated, longer range repulsion between between them, as demonstrated in section II, which allow for a more complex phase behavior111A number of other factors, including variation in the membrane composition, may influence the phase behavior of these objects. It has been recently argued at the light of computer simulationsgelbart ; searPRE ; searJCP  that a long range repulsion should break the gas and liquid phases into microdomains. The short range attraction still locally drives a gas/liquid phase separation, but large aggregates are costly because of the long range repulsion. The microdomains are circular liquid islands at low density, circular gas regions at high density, and stripes otherwise.

To gain a quantitative understanding of how stripes may form on caveolae we study the stability of an homogenous (2-D) solution of oligomers of area $`s_b=\pi b^2`$ interacting via a potential $`V(𝐫)`$, which include a short range (the particle size $`b`$) attractive exponential interactions and the longer range membrane mediated repulsion of Eq (16): $`V(r)=E_ae^{r/b}+E_rK_0(kr)`$, where $`E_a`$ and $`E_r`$ are respectively the strength of the attraction and the repulsion. We look at small perturbations $`\delta \varphi `$ (with the conservation rule $`𝑑S\delta \varphi (r)=0`$) around the average surface coverage $`\varphi _0`$. The free energy includes the pair interaction and the translation entropy of the inclusions, for which we use the gas-on-a-lattice model. Expanding the free energy:

$`F={\displaystyle \frac{dS}{s_b}\left(\varphi \mathrm{log}\varphi +(1\varphi )\mathrm{log}(1\varphi )\right)}+{\displaystyle \frac{1}{2}}{\displaystyle \frac{dSdS^{}}{s_b^2}\varphi (r)V(|rr^{}|)\varphi (r^{})}`$ (17)
$`\delta F={\displaystyle \frac{dS}{s_b}\frac{\delta \varphi ^2}{2\varphi _0(1\varphi _0)}}+{\displaystyle \frac{1}{2}}{\displaystyle \frac{dSdS^{}}{s_b^2}\delta \varphi (r)V(|rr^{}|)\delta \varphi (r^{})}`$ (18)
The Fourier transform $`\delta \varphi (r)=S\frac{d^2q}{(2\pi )^2}\delta \varphi _qe^{i\mathrm{𝐪𝐫}}`$ allows us to investigate the formation of structures. It leads to

$$\delta F=\frac{1}{2}\frac{S^2}{s_b}\frac{d^2q}{(2\pi )^2}𝒱_q|\delta \varphi _q|^2\mathrm{with}𝒱_q=\frac{T}{\varphi _0(1\varphi _0)}+\frac{1}{s_b}V_q$$
(19)
If $`V_q`$, the Fourier transform of $`V(𝐫)`$, is sufficiently negative (attractive) for a given mode $`q`$ then $`𝒱_q<0`$ and the mode is unstable. Substituting the expression for $`V(𝐫)`$, we obtain

$$𝒱_q=2k_BT\left[\frac{1}{2\varphi _0(1\varphi _0)}+\left(E_a\frac{1}{(1+(bq)^2)^{3/2}}+E_r\frac{1}{k^2+q^2}\right)\right]$$
(20)
In the absence of long range repulsion, the most unstable mode is always $`q=0`$ (macrophase separation), and the liquid/gas transition is observed provided $`2E_a\varphi _0(1\varphi _0)>k__BT`$. Because of the membrane-mediated long range repulsion, the function $`𝒱_q`$ presents a minimum if $`E_r>\frac{3}{2}E_a(kb)^410^3E_a`$ (for the typical numbers $`b5`$nm and $`k^130`$nm). One sees that although the strength of membrane-mediated interaction (Eq (16)) is expected to be quite small: $`E_r10^2k__BT`$ (see sec. V.A, or ref.usPNAS  for a more detailed analysis), it is of much longer range, and should be competent to produce a well ordered phase.

The phase separation occurs preferentially for a mode given by $`𝒱_q/q=0`$, and periodic arrays of dense and dilute regions are observed. In the limit $`kb1`$ the structure have a typical size $`2\pi /q^{}`$ which is independent of the range of the repulsion: $`q^{}b=(2E_r/3E_a)^{1/4}\frac{1}{4}`$. It thus defines dense stripes of width about $`5`$ particle diameters, which agrees quite well with the experimental observations. The existence of a stripe phase at the surface of the biological structures known as caveolae is thus quantitatively consistent with the existence of a membrane-mediated repulsion between proteins described by Eq (16).

This analysis does not help us to discriminate between circular domains and stripes. Computer simulation have clearly shown that this transition indeed exists for high enough surface coveragesearPRE ; searJCP .

Note that the formation of striped mesostructures in membrane have been predicted on the basis of curvature effects onlyleibler ; leiblerandelman . However, it can be shown that their existence at the surface of invagination of such large curvature as the caveolae ($`R50`$nm) is inconsistent with the existence of invaginations with a well defined size.

## IV Far field interactions of non circularly symmetric inclusions

If the force distribution of the inclusions is not circularly symmetric then no general analytic solution to Eq (12) exists. However we can still proceed by examining the far-field interactions of slightly asymmetric inclusions. In order to do this we will parameterize the asymmetry of the $`s^{\mathrm{th}}`$ inclusion by

$$D_{ij}^{(s)}=d^2𝐫^{}r_i^{}r_j^{}\psi ^{(s)}(𝐫^{})=\left(\begin{array}{cc}c+ϵ^{(s)}& 0\\ 0& cϵ^{(s)}\end{array}\right)$$
(21)
where $`i`$ and $`j`$ are cartesian indices, $`c`$ controls the average (isotropic) magnitude and $`ϵ`$ controls the anisotropy of a slightly “elliptical” force distribution, extended in the $`x`$-direction and contracted in the $`y`$-direction (for $`ϵ>0`$). This force distribution can be rotated by the usual rotation matrix $`R(\theta )`$ to obtain the effective moment $`R_{im}(\theta ^{(s)})R_{jn}(\theta ^{(s)})D_{mn}^{(s)}`$ of an “elliptical” force distribution rotated by an angle $`\theta ^{(s)}`$ relative to the $`x`$-axis. This expression involves two rotations, one for each factor of $`𝐫^{}`$ in Eq (21).

It is important to first note is that the interaction can be separated into two terms, one that is an integral involving $`K_0(k|𝐫𝐫^{}+𝐫^{\prime \prime }|)`$ and the other that is an integral involving $`\mathrm{log}k|𝐫𝐫^{}+𝐫^{\prime \prime }|`$. The first of these terms gives a contribution to the interaction potential that is dominated by a term like Eq (16), with corrections due to the asymmetry that are smaller (and also asymptotically exponentially short ranged). This conclusion is independent of the precise choice of asymmetry, provided only that it is small. The contribution from the second term is more interesting and can be shown to give rise to a small but long ranged correction $`\delta \mathrm{\Phi }`$ to the interaction potential. This can be best understood by way of multipole-like expansion of $`\mathrm{log}k|𝐫\stackrel{~}{𝐫}|`$ where $`|\stackrel{~}{𝐫}||𝐫|`$ and we choose the direction of $`𝐫=r\widehat{x}`$ to define the $`x`$-axis (the 1 direction), without loss of generality. Thus $`\stackrel{~}{r}_1`$ and $`\stackrel{~}{r}_2`$ are the $`x`$ and $`y`$ components of $`\stackrel{~}{r}`$ and

$$\mathrm{log}k|𝐫\stackrel{~}{𝐫}|=\mathrm{log}kr\frac{\stackrel{~}{r}_1}{r}+\frac{\stackrel{~}{r}_2^2\stackrel{~}{r}_1^2}{2r^2}\frac{\stackrel{~}{r}_1^33\stackrel{~}{r}_1\stackrel{~}{r}_2^2}{3r^3}+\frac{6\stackrel{~}{r}_1^2\stackrel{~}{r}_2^2\stackrel{~}{r}_1^4\stackrel{~}{r}_2^4}{4r^4}+O\left(\frac{1}{r^5}\right)$$
(22)
The conditions of no overall force $`d^2𝐫^{}\psi (𝐫^{})=0`$ and no overall moment $`d^2𝐫^{}𝐫^{}\psi (𝐫^{})=0`$ for each inclusion mean that the first non-vanishing contribution to $`\delta \mathrm{\Phi }1/r^4`$, the classical result for electrostatic quadrupole-quadrupole interactions in two dimensions. Using $`\stackrel{~}{𝐫}=𝐫^{}𝐫^{\prime \prime }`$ in Eq (22) to leading order in $`1/r`$ we have222From $`\delta \mathrm{\Phi }=\frac{1}{4\pi \gamma r^4}d^2𝐫^{}d^2𝐫^{\prime \prime }\psi ^{(1)}(𝐫^{})\psi ^{(2)}(𝐫^{\prime \prime })\frac{3}{2}\left(4x^{}x^{\prime \prime }y^{}y^{\prime \prime }(x^2y^2)(x^{\prime \prime 2}y^{\prime \prime 2})\right)`$ hence $`\delta \mathrm{\Phi }=\frac{1}{4\pi \gamma r^4}R_{im}(\theta ^{(1)})R_{jn}(\theta ^{(1)})D_{mn}(ϵ^{(1)})R_{kp}(\theta ^{(2)})R_{lq}(\theta ^{(2)})D_{pq}(ϵ^{(2)})𝒢_{ijkl}`$ with the interactions defined by the kernal $`𝒢_{ijkl}=\frac{3}{2}(4\delta _{i1}\delta _{j2}\delta _{k1}\delta _{l2}(\delta _{i1}\delta _{j1}\delta _{i2}\delta _{j2})(\delta _{k1}\delta _{l1}\delta _{k2}\delta _{l2}))`$ and the result follows by contracting over all indices.

$`\delta \mathrm{\Phi }`$ $`=`$ $`{\displaystyle \frac{1}{4\pi \gamma }}{\displaystyle d^2𝐫^{}d^2𝐫^{\prime \prime }\psi ^{(1)}(𝐫^{})\psi ^{(2)}(𝐫^{\prime \prime })\mathrm{log}k|𝐫𝐫^{}+𝐫^{\prime \prime }|}`$ (23)
$`=`$ $`{\displaystyle \frac{3ϵ^{(1)}ϵ^{(2)}}{2\pi \gamma r^4}}\mathrm{cos}2(\theta ^{(1)}+\theta ^{(2)})`$
This result demonstrates that elliptical inclusions attract if arranged so that $`\theta ^{(1)}+\theta ^{(2)}=n\pi `$ with $`n`$ an integer, as reported in an earlier study of rod-like inclusionsgolestanian . This condition represents a degenerate family of orientations in which the orientation of the quadrupoles has reflectional symmetry about the mid plane. This perturbative interaction is long-ranged, scaling like $`1/r^4`$. Interestingly this dominates the exponentially short ranged repulsion from Eq (16) for large enough separations.

There is a straightforward way to understand the appearance of an algebraic potential for anisotropic inclusions. The physics of Eq (5) and is that of the Poisson equation in which the force distribution is analogous to the electrostatic charge. The potential due to a point charge in 2D is therefore Eq (6). Gauss law tells us that there is no field outside a circularly symmetric charge distribution that has no overall charge (imbalance). This condition is analogous to our requirement here that there be no overall force $`d^2𝐫^{}f(𝐫^{})=0`$ by Newton’s law. If there is no field the potential is constant (zero without loss of generality) and no forces act on the inclusions. However, if we relax the condition that the force (charge) distribution is circularly symmetric there is no longer a simple symmetry argument that the radial and azimuthal components of the field must be zero. Indeed they are not. As is usual in multipole expansions in electrostatics an algebraic potential results. It is here analogous to the quadrupole-quadrupole interaction in electrostatics, since there are no dipole moments $`d^2𝐫^{}𝐫^{}f(𝐫^{})=0`$. This is due to the fact that there can be no external first force moment (torque) on the membrane if it is not anchored to any external structure against which the moment can act.

The physical consequences of these interactions are potentially significant. In spite of the fact that the dominant interaction is repulsive the surface concentration of membrane inclusions may often be maintained at fairly high surface fractions by the regulatory mechanisms of the living cell. The composition of the surface coats of caveolae may be further enriched in several important membrane components, including cholesterol and proteins in the caveolin family, as well as othersreview1 ; lisantiJCB94 . This means that there is an effective surface pressure, driven by a chemical potential difference that forces the inclusions to partially overcome their repulsion. In this situation the attractive $`O(ϵ^{(1)}ϵ^{(2)})`$ interactions might become significant, leading to an in plane anisotropic phase separation such as is observed in model systemsgelbart ; searPRE ; searJCP ; seul  and on the coats of caveolaerothberg . For caveolae the typical interactions seem too weak usPNAS  to be solely responsible for the stripe morphology, which may rather be dominated by specific attractions, see section III cterm1b . Finally the existence of an attractive interaction that can arise from fluctuations in the inclusion force distribution (shape), as parameterized by $`ϵ`$, suggests the possibility of an attractive, fluctuation driven force reminiscent of Van der Waals forces. This mechanism should extend to systems such as wetting droplets at gas-liquid interfaces. These can potentially exert much stronger forces on the interface, resulting in a more exaggerated effect (see section V.2).

## V Origin of the force distribution

Up to this point we have merely postulated the existence of a force distribution $`\psi (𝐫^{})`$ due to a membrane bound inclusion. This force can arise from direct mechanical effects, such as due to the geometry and shape of the inclusion, e.g. the protein clathrin, or entropic effects due to the asymmetric anchoring of, e.g. flexible hydrophilic polymers, to a membrane. The budding of caveolae is now thought to be driven by the protein caveolin which is known to form small oligomers resembling a number of polypeptide chains extending only from the cytoplasmic side of the membranelisantiPNAS95 ; monier95 .

We have in mind that we have demonstrated that interactions should exist in general, but haven’t yet adressed the question of how big they might typically be. We are particularly interested in any models that can be chosen to be broadly comparable with membrane proteins. In this section we will present two examples of models for the origin of a force distribution arising from anchored polymer chains. This approach represents the application of a simple, and hence rather “idealised”, theory drawn from polymer physics. Its exact quantitative applicability to polypeptide chains is almost certainly limited to a small subset of peptide sequences which either resemble a diffuse random coil or a dynamic, dense hydrophobic globule. Nontheless in the absence of any detailed microscopic information on a specefic inclusion’s configuration and stability the approaches that we outline below probably represent the best chance for us to obtain a rough idea of the likely scale of the effects that we have described in this article. It is quite possible that the forces exerted by membrane proteins with significant well defined tertiary structure may be somewhat higher than the estimates that we will present below. This encourages us to consider our estimates as approximate lower bounds on the scale that these effects might reach.

In polymer physics terminology the two models that we consider for the force applied by a membrane-bound polymer will correspond to the two limiting of “good” and “poor” solvent conditions respectivelydegennes . We will discuss below how these models might apply to caveolin homo-oligomers. Other recent studies of the physics of flexible polymers grafted onto tensionless fluid membraneslipowsky2 ; carlos ; lipowsky1a ; lipowsky1b  undoubtedly share similar motivation. One feature that these earlier studies all have in common is that there is only an attraction for polymer force distributions that overlap one-another on the surface of the membrane and, when this is the case, the interaction is attractive. This is opposite in sign to the interactions that we predict on membranes that bear tension, see Eq (16). Furthermore our interactions are extended, with ranges $`k^1`$.

### V.1 Anchored polymers and polymer aggregates: Good solvent conditions

Motivated by possible biophysical relevance we investigate the effect of flexible polymer chains anchored to a small patch of membrane, of radius $`a`$. We assume that the chains are in a good solvent, i.e. that they are found in extended, hydrated random coil configurations. The chains form a hemisphere of outer radius $`b>a`$, see figure 1. This model may be used to treat polymer homo-oligomers made up of a general number $`Q`$ of chains. As such it shares many features with those that are known for caveolin homo-oligomerslisantiPNAS95 .

Within the “corona” of the polymer hemisphere, at radial distances $`b<r<a`$ from the center of the polymer aggregate, there exists a characteristic correlation length $`\xi (r)`$ for the polymer chains which crudely, represents the spatial distance between collisions between the segments of a chain with other chains or the membranedegennes . The conservation of number of chains impliesdaoudcotton  $`\frac{1}{2}4\pi r^2Q\xi (r)^2`$ for $`a<r<b`$. This is since the surface area of a hemisphere of radius $`r`$ is filled by close packed blobs, up to a constant of order unity. From this one may immediately deduce the scaling of the correlation length $`\xi (r)=\left(\frac{2\pi }{Q}\right)^{\frac{1}{2}}r`$. The work done in generating each blob is $`k_BT`$, independent of the blob size. Thus we may write the pressure in this region as the energy per blob divided by the volume of a blobdaoudcotton

$$f(𝐫)=\frac{k_BT}{\xi (r)^3}=\left(\frac{Q}{2\pi }\right)^{\frac{3}{2}}\frac{k_BT}{r^3}$$
(24)
for $`a<r<b`$. For $`r>b`$ the pressure is here assumed to be zero333In nature there will often be a smooth crossover around $`r=b`$. Nonetheless we consider our approximation to be as good as any alternative and insist that, at large distances, the pressure must ultimately vanish due to the finite lengths of the polymer chains. The pressure in the core binding region is assumed to be constant and must involve a total force equal and opposite to that applied by the corona so that no average force acts, as required by Newton’s second law.

$$f(r)=\{\begin{array}{cc}E_oa^3& \mathrm{if}0<r<a\hfill \\ \frac{E_o}{2(1a/b)}r^3& \mathrm{if}a<rb\hfill \end{array}$$
(25)
where $`E_o=f(0)a^3=2k_BT(1a/b)(Q/2\pi )^{3/2}`$ is a characteristic energy related to the force applied at the center of the aggregate. This model represents one approximate framework for the understanding of forces applied by membrane biopolymers, see Fig 1. It possesses several important features: It involves no average force being applied to the membrane. It involves no average first force moment by symmetry. The first non-vanishing moment is the second, corresponding to a bending moment with magnitude controlled by $`r^2f(r)d^2rE_oa`$ with the characteristic energy scale $`E_o>k__BT`$ that is entropic in origin.

Models similar to this have been proposed elsewherelipowsky2 ; carlos ; lipowsky1a ; lipowsky1b  although, as emphasized previously, the physical behavior of these inclusions on fluid membranes that are under tension is rather different.

We now proceed to give an estimate of the membrane deformation and interaction potentials due to membrane-bound biopolymers within the good solvent polymer brush model described above.

For biological membranes primarily comprised of a bilayer of phospholipids the tension and rigidites are typicallyevans ; sheetz

$$\kappa =10k_BT40k_BT\kappa _{bio}=20k_BT\gamma =10^510^3J/m^2\gamma _{bio}=10^4J/m^2$$
(26)
where $`x_{bio}`$ refers to what we would take as a single “typical” value for biological membranes. From this we obtain the lengthscale

$$k^1=6nm100nmk_{bio}^1=30nm$$
(27)
which may crudely be identified with the range of the interactions.

#### V.1.1 Membrane deformation due to the inclusion

The deformation at $`r=0`$ is

$$u_{brush}(r=0)=\frac{E_0}{\kappa }\alpha $$
(28)
in a frame where $`u=0`$ at infinity. This therefore represents the total magnitude of the normal deviation of the membrane expressed in terms of a dimensionless ratio $`\frac{E_0}{\kappa }`$ and a characteristic length $`\alpha `$.

For parameters that might be typical of caveolin homo-oligomers, $`a=2\mathrm{n}\mathrm{m}`$ and $`b=5\mathrm{n}\mathrm{m}`$, we find

$$\alpha (k^1=6\mathrm{n}\mathrm{m})=0.7\mathrm{nm}\alpha (k^1=30\mathrm{n}\mathrm{m})=1.5\mathrm{nm}\alpha (k^1=100\mathrm{n}\mathrm{m})=2\mathrm{n}\mathrm{m}$$
(29)
much the same as for slightly larger inclusions with $`a=1nm`$ and $`b=10nm`$

$$\alpha (k^1=6\mathrm{n}\mathrm{m})=1.3\mathrm{nm}\alpha (k^1=30\mathrm{n}\mathrm{m})=2.7\mathrm{nm}\alpha (k^1=100\mathrm{n}\mathrm{m})=4\mathrm{n}\mathrm{m}$$
(30)
#### V.1.2 Membrane mediated interaction energy between inclusions

The interaction energy is expressed as

$$\mathrm{\Phi }_{brush}=\frac{E_0^2}{\kappa }\beta $$
(31)
which is the product of an energy $`E_0^2/\kappa `$, typically of the order of $`k__BT`$, and a dimensionless number $`\beta `$. For $`a=2\mathrm{n}\mathrm{m}`$ and $`b=5\mathrm{n}\mathrm{m}`$

$$\beta (k^1=6\mathrm{n}\mathrm{m})=\mathrm{3\; 10}^2\beta (k^1=30\mathrm{n}\mathrm{m})=10^3\beta (k^1=100\mathrm{n}\mathrm{m})=10^4$$
(32)
while for $`a=1\mathrm{n}\mathrm{m}`$ and $`b=10\mathrm{n}\mathrm{m}`$ we find instead

$$\beta (k^1=6\mathrm{n}\mathrm{m})=0.13\beta (k^1=30\mathrm{n}\mathrm{m})=\mathrm{5\; 10}^3\beta (k^1=100\mathrm{n}\mathrm{m})=\mathrm{5\; 10}^4$$
(33)
### V.2 Poor solvent conditions

If the polymer chains are more hydrophobic, and the solvent conditions are poor, the polymer chains may collapse into a tight, roughly hemispherical, region from which water is largely exuded. This represents the natural opposite limit to the good solvent polymer model considered above. In the poor solvent case we propose to model the inclusion as if it were a fluid droplet that partially ‘wets’ the membrane surfaceleger . At any point on the circumference of the drop the forces per unit length (due to the surface energy) are in equilibrium. Resolving these force perpendicular to the membrane we find a total force acting upward

$$F=2\pi \sigma \mathrm{sin}\theta $$
(34)
where $`b`$ is the radius of the drop, $`\sigma `$ is the energy cost per unit area of producing the interface between the inclusion and the external poor solvent, typically water, and $`\theta `$ is the contact angle given by Young’s lawleger . Since we are in equilibrium this force must be balanced by the force acting on the interface between the drop (inclusion) and the membrane for $`r<b`$. To find the corresponding pressure we need only consider the partial wetting droplet as if it formed part of a larger sphere. The pressure is constant everywhere inside the sphere and is given by the Laplace law

$$P=\frac{E}{V}=\frac{2\sigma }{R},$$
(35)
where $`R=b/\mathrm{sin}\theta `$ is the radius of the sphere. The radius $`R`$ can therefore be related to the volume of the drop (and $`b`$) by simple geometry. Hence we may write the pressure distribution as

$$f(𝐫)=\frac{\sigma }{R}\left(b\delta (rb)2\mathrm{\Theta }(br)\right)$$
(36)
where $`\mathrm{\Theta }(x)`$ is the Heaviside unit step function.

This model represents a different possible physical origin for the pressure distribution that might be valid, e.g. for surface-anchored hydrophobic polymers in the poor solvent regime, when little water penetrates the protein chains, see Fig 2. It also preserves the same features as the good solvent polymer model: It involves no average applied force or first force moment and has a bending moment $`r^2f(r)d^2rE_ob`$ that is enhanced by the localization of part of the force distribution around the exterior circumference $`r=b`$ of the inclusion’s footprint on the membrane. The characteristic energy scale is now chemical in origin, as it is controlled by chemical parameters such as $`\sigma `$. It is difficult to give a quantitative scale for this although typical oil water interfacial tensions of $`\sigma _{ow}>3\times 10^2\mathrm{Jm}^2`$ suggest $`E_o>\sigma _{ow}b^2180k__BT`$ with $`b5`$nm. This large energy suggests thermodynamically “strong” interactions.

#### V.2.1 Membrane deformation due to the inclusion

For $`b=10\mathrm{n}\mathrm{m}`$, $`\sigma =40dyn/cm`$444The wetting drop is characterized by a surface tension, which for highly hydrophobic chains approaches the oil-water tension $`\sigma =10dyn/cm40dyn/cm=2.510k_BT/\mathrm{nm}^2`$, and a curvature radius for the surface of the drop $`R=1100\mathrm{n}\mathrm{m}`$. These combines to give a pressure $`f_b=\sigma /R=\mathrm{2.5\; 10}^210k_BT/\mathrm{nm}^3`$. We arbitrarily choose $`b=R/2`$ to give an idea of the scales and define the energy unit $`E_b=f_bb^3=\sigma R^3/8`$, so $`E_b=0.3k_BT10^4k_BT`$. With $`\sigma _{bio}=40dyn/cm=10k_BT/\mathrm{nm}^2`$ and $`R_{bio}=10\mathrm{n}\mathrm{m}`$ we obtain $`f_{b,bio}=1k_BT/\mathrm{nm}^3`$ and $`E_{b,bio}=125k_BT`$. We give only the results for $`\sigma =40dyn/cm`$ and for $`\kappa =20k_BT`$ for compactness. With thses values $`k^1=990\mathrm{n}\mathrm{m}`$.  the membrane’s normal deformation at $`r=0`$ is

$$u_0(k^1=9\mathrm{n}\mathrm{m})=37\mathrm{n}\mathrm{m}u_0(k^1=30\mathrm{n}\mathrm{m})=65\mathrm{n}\mathrm{m}u_0(k^1=90\mathrm{n}\mathrm{m})=92\mathrm{n}\mathrm{m}$$
(37)
for $`b=100\mathrm{n}\mathrm{m}`$ $`\sigma =40dyn/cm`$

$$u_0(k^1=9\mathrm{n}\mathrm{m})=2700\mathrm{n}\mathrm{m}u_0(k^1=30\mathrm{n}\mathrm{m})=15\mu \mathrm{m}u_0(k^1=90\mathrm{n}\mathrm{m})=37\mu \mathrm{m}$$
(38)
#### V.2.2 Membrane mediated interaction energy between inclusions

The interaction potential energy has a simple analytical form:

$$\mathrm{\Phi }=\frac{1}{2\pi \gamma }\zeta ^2K_0(kr)=\frac{E_b^2}{2\pi \kappa }(kb)^2K_0(kr)\beta ^2$$
(39)
with

$$\beta =\frac{2\pi }{(kb)^2}(I_0(kb)\frac{2}{kb}I_1(kb))$$
(40)
For $`b=10\mathrm{n}\mathrm{m}`$ and $`\sigma =40dyn/cm`$ the energy scale $`E_0`$ (simply the potential $`\mathrm{\Phi }`$ divided by $`K_0(kr)k_BT`$) is

$$E_0(k^1=9\mathrm{n}\mathrm{m})=25E_0(k^1=30\mathrm{n}\mathrm{m})=2E_0(k^1=90\mathrm{n}\mathrm{m})=0.2$$
(41)
for $`b=100\mathrm{n}\mathrm{m}`$ $`\sigma =40dyn/cm`$

$$E_0(k^1=9\mathrm{n}\mathrm{m})=10^9E_0(k^1=30\mathrm{n}\mathrm{m})=\mathrm{3\; 10}^6E_0(k^1=90\mathrm{n}\mathrm{m})=\mathrm{2\; 10}^5$$
(42)
## VI Conclusions

We show that a model for the interactions between inclusions bound to fluid membranes can be solved exactly for circularly symmetric inclusions bound to membranes that are under tension. We argue that proteins bound to cell membranes can apply no average force, or first moment of force, to the membrane unless they are also anchored to an external structure, such as the cytoskeleton. By this we mean that the total of any and all forces that the membrabe protein acts to apply downwards against the membrane must exactly equal the magnitude of similar forces applied upwards. This is a consequence of Newton’s laws of motion.

We proposed idealized models for the origin of these forces due to either entropic or direct chemical interactions. The interactions between two circularly symmetric inclusions are repulsive and are asymptotically exponentially short ranged with a typical extent on biological membranes that is of the order of $`k^130`$nm. This result contrasts with the attraction predicted to appear between similar inclusions on tensionless membranes. For non circularly symmetric inclusions we predict an additional algebraically long-ranged attractive contribution.

We discuss how competing attractive and repulsive interactions are known to sometimes produce a stripe-like morphology. These phases are reminiscent of the stripes observed on the surface of caveloae, which we refer to as “gnarly buds”, and we discuss how a similar lateral phase separation could occur in these systems with typical length scales comparable to the ranges of the interactions.

We believe that the results discussed here may have wider applications in understanding biological phenomena, including lateral phase separation in phospholipid membranes and endocytotic budding. Indeed, a detailed theoretical analysis of the formation of caveolae invaginations on model phospholipid membranes utilizes many of the results derived here usPNAS .

###### Acknowledgements.

We acknowledge helpful discussions with Robin Ball and George Rowlands (Warwick), Albert Johner (Strasbourg) and Michael Lisanti (Albert Einstein College of Medicine). MST acknowledges the support of the Royal Society (UK) in the form of a University Research Fellowship.

## Appendix: Uniqueness of the solution for the equilibrium membrane displacement due to an arbitrary force distribution

Equations 9 and 10 permit the calculation of the equilibrium membrane displacement due to an arbitrary force distribution. This solution is unique, as may be demonstrated as follows.

We may add to our solution any solution of the homogeneous version of equation (3) without changing the result. Let $`u_1(𝐫)`$ satisfy

$$^2\left(^2k^2\right)u_1(𝐫)=0$$
(43)
and the boundary conditions imposed. Multiplying by $`u_1(𝐫)`$ and integrating we have

$$u_1(𝐫)^2\left(^2k^2\right)u_1(𝐫)d^2𝐫=0.$$
(44)
Integrating by parts and noting that the integrated terms are zero by virtue of the boundary conditions we obtain

$$\left[\left(^2u_1(𝐫)\right)^2+k^2\left(u_1(𝐫)\right)^2\right]d^2𝐫=0.$$
(45)
The integrand is everywhere positive so we must have $`^2u_1(𝐫)=0`$ and $`u_1(𝐫)=0`$ everywhere. Thus the only admissible solution of the homogeneous equation is $`u(𝐫)`$ = constant this correspond only to a redefinition of the zero of the displacement and so without loss of generality we take this constant to be zero. This freedom of choice is a consequence of the translational symmetry of the problem in the direction perpendicular to the planar membrane.


text:
# PULSAR WIND NEBULAE: THEORETICAL ASPECTS AND OBSERVATIONAL CONSTRAINTS

## INTRODUCTION

Pulsars are expected to be born inside the supernova explosions of massive stars, which provide the surroundings for the initial evolution of their wind nebulae (Reynolds and Chevalier, 1984). The PWNe (pulsar wind nebulae) initially expand in the freely expanding ejecta of the supernova. Eventually, the reverse shock wave from the supernova interaction with the surrounding medium makes its way back to the center where it can crush the PWN. This later phase of evolution has recently been the subject of detailed studies (van der Swaluw et al.,, 2001; Blondin et al., 2001). In particular, Blondin et al. (2001) noted that the reverse shock is likely to be asymmetric so that the PWN can be displaced from its position over the pulsar. This scenario provides an explanation for the displacement of the radio emitting PWN in the Vela remnant (Bock et al., 1998) and other remnants.

Here, I emphasize PWNe that are likely to be in the earlier phase of evolution, before the reverse shock effects. Recent discoveries at X-ray and radio wavelengths have substantially increased the number of such objects. In § 2, the possible members of this class are listed. For objects with an approximately constant pulsar power, the expansion in a supernova is treated in § 3. Constraints implied by the energy in the nebulae are discussed in § 4. The conclusions are in § 5.

## YOUNG PULSAR WIND NEBULAE

A list of probable young PWNe in which central pulsars have been identified is given in Table 1; these objects are plausibly interacting with ejecta.

The second column gives the observed pulsar period, $`P`$, and the third column gives the characteristic pulsar age, $`t_{ch}=P/2\dot{P}`$. If the pulsar is born rotating much more rapidly than the current rate and the braking index is $`n=3`$, then $`t_{ch}`$ is the actual age. If the pulsar is born with a period close to its current period, it can be younger than $`t_{ch}`$. Alternatively, if the pulsar is born spinning rapidly and has a braking index $`n<3`$, it can be older than $`t_{ch}`$. The fourth column is an estimate of the actual age. For 0540–69 (Kirshner et al., 1989) and G292.0+1.8 (Murdin and Clark, 1979), the age estimate is from the size of the nebula and velocities found from optical spectroscopy. For the other objects with ages, the estimate is from a tentative supernova identification, given in the next column. The identification of the Crab with SN 1054 is generally considered very secure, but the other identifications are less secure. There is still some uncertainty over whether all of the events are in fact supernovae, e.g., SN 386 (Stephenson and Green, 2002). The next column indicates whether an extended supernova remnant is observed around the PWN, and the penultimate column indicates whether there is evidence for ejecta swept up by the PWN.

There are indications that these nebulae are in the early phase of interaction with freely expanding ejecta. One expectation in this picture is that the PWN should shock and sweep up a shell of supernova ejecta (Reynolds and Chevalier, 1984; Chevalier and Fransson, 1992). The shock wave is initially expected to be radiative, but it becomes nonradiative due to the decline in the supernova density. A good example of an ejecta shell is the complex of filaments in the Crab Nebula. In this case, there is evidence for the shock wave in the ejecta (Sankrit and Hester, 1997); it may be in the process of making a transition from radiative to nonradiative. For 3C 58, there is evidence for X-ray emission from swept-up ejecta (Bocchino et al., 2001), implying the presence of a nonradiative shock. The optical emission from 0540–69 may be from a radiative shock (Kirshner et al., 1989; Chevalier and Fransson, 1992). The optical emission from G292.0+1.8 appears to be from the vicinity of the PWN (Murdin and Clark, 1979; Hughes et al., 2001), but the relation between them has not yet been determined.

Another expectation of the model with expansion in ejecta is that the pulsar should be centrally located within the PWN. This appears to be true for the objects listed in Table 1, although in most cases the PWN has an asymmetric boundary. The PWN in G292.0+1.8 is substantially off the center of the surrounding supernova remnant, which has led to the suggestion that the pulsar has a velocity $`770\mathrm{km}\mathrm{s}^1`$ (Hughes et al., 2001). If this is the case, the pulsar is expected to move to a place in the ejecta where it is comoving with the surrounding gas and it is surrounded by uniformly expanding ejecta. Some degree of asymmetry may develop if there is a gradient in the surrounding density distribution.

## MODELS FOR 3C 58 AND G11.2–0.3

If we assume that 3C 58 and G11.2–0.3 are associated with SN 1181 and SN 386, respectively, models for the PWNe can make use of the fact that the characteristic age is much larger than the true age, so that the pulsars have not significantly spun down. This allows the assumption that the pulsar power, $`\dot{E}`$, is constant during the evolution.

We begin by considering the expansion of the PWN into the inner parts of the supernova ejecta. The density distribution into which the PWN initially expands can be estimated from explosion models. Chevalier and Fransson (1992) used simple power law models for the density distribution. More detailed models have been considered by Matzner and McKee (1999), who give asymptotic forms for the the final density distribution at low and high velocities. For the cases to be studied here, the asymptotic low velocity density profile is applicable over the time of interest. For an explosion in a star with a radiative envelope, the inner density profile, using eq. (46) of Matzner and McKee (1999), can be expressed as

$$\rho t^3=4.3\times 10^8\left(\frac{v}{1000\mathrm{km}\mathrm{s}^1}\right)^{1.06}\left(\frac{M_{ej}}{10M_{}}\right)^{1.97}E_{51}^{0.97}\mathrm{g}\mathrm{cm}^3\mathrm{s}^3,$$
(1)
where $`v=r/t`$ is the free expansion velocity, $`M_{ej}`$ is the total ejected mass, and $`E_{51}`$ is the explosion energy in units of $`10^{51}`$ ergs. For a star with a convective envelope, the density distribution may be flatter, but the density at $`1000\mathrm{km}\mathrm{s}^1`$ is close to the above value.

The expansion of a PWN in a density distribution can be approximately treated as a thin shell driven by a uniform pressure wind bubble with adiabatic index $`\gamma =4/3`$ (Ostriker and Gunn, 1971; Chevalier, 1977; Reynolds and Chevalier, 1984). The radius can be found analytically if the pulsar power, $`\dot{E}`$, is constant and the surrounding medium has a power law density distribution. As discussed above, this may be the case for 3C58 and G11.2–0.3. Then, from eq. (2.6) of Chevalier and Fransson (1992), we have

$$R_p=0.59\dot{E}_{38}^{0.254}E_{51}^{0.246}\left(\frac{M_{ej}}{10M_{}}\right)^{0.50}\left(\frac{t}{10^3\mathrm{yr}}\right)^{1.254}\mathrm{pc},$$
(2)
where $`\dot{E}_{38}`$ is $`\dot{E}`$ in units of $`10^{38}\mathrm{erg}\mathrm{s}^1`$. In cases where $`R_p`$, $`\dot{E}`$, and $`t`$ are known, we can solve for $`M_{ej}/E_{51}^{0.49}`$; because $`E_{51}1`$ is expected, we have an estimate of the total ejecta mass. These quantities are known for 3C 58 and G11.2–0.3 if the historical supernova identifications are assumed, and the results are given in Table 2. These estimates involve a spherical approximation for PWNe that are apparently not spherical, but an average radius can be taken (Woltjer et al., 1997; Roberts et al., 2002). The assumed distances are 3.2 kpc for 3C 58 (Roberts et al., 1993) and 5 kpc for G11.2–0.3 (Green et al., 1988). The expected values of $`M_{ej}`$ for a core collapse supernova are typically several $`M_{}`$ or more. In the case of a very fast Type Ic supernova, SN 1994I, $`M_{ej}`$ was only $`1M_{}`$ (Iwamoto et al., 1994), which is an extreme case. The point is that the model leads to a value of $`M_{ej}`$ that is smaller than expected for 3C 58. The radius is larger than would be expected if it were expanding into a normal supernova. There is no problem with G11.2–0.3.

Another constraint comes from the amount of mass swept up by the wind bubble, $`M_{sw}`$. An integration over the central density shows that $`M_{sw}1.0\dot{E}R_p^2t^3`$, fairly independent of supernova density distribution. Values of $`M_{sw}`$ deduced in this way for 3C 58 and G11.2–0.3 are given in Table 2. The value of $`0.002M_{}`$ deduced for 3C 58 can be compared to the $`0.1M_{}`$ found from X-ray observations (Bocchino et al., 2001). Again, there is a problem with the model mass being too low. The mass could be brought into agreement with the observed value if the age were increased by a factor $`3`$.

These models assume that the supernova ejecta are swept into a thin shell that remains spherically symmetric. However, the shell is being accelerated and is subjected to Rayleigh-Taylor instabilities, which can decrease the coupling between the pulsar wind bubble and the swept up gas. In the limit that there is no further acceleration after the ejecta are shocked, the PWN radius (eq. ) is increased by a factor of 1.4. The masses $`M_{ej}`$ and $`M_{sw}`$ are increased by a factor of 2, which does not change the conclusion about the difficulties with 3C 58.

The model with constant $`\dot{E}`$ can be used to predict the internal energy in the PWN. This energy is reduced from the total deposited energy, $`\dot{E}t`$, because of work done on the surrounding supernova gas. For a range of flat central density distributions, the internal energy is $`0.45\dot{E}t`$ (Table 1 of Chevalier and Fransson 1992). The internal energy in a PWN has relativistic particle and magnetic field components; a minimum value for the total energy in particles and fields can be found from the synchrotron luminosity and the emitting volume (e.g., Pacholczyk 1970). Tam et al. (2002) discuss the radio emission from the PWN in G11.2–0.3. The value of the minimum energy deduced from the radio emission for the two PWNe is given in Table 3. The actual energy must be larger when a larger frequency range is considered. It can be seen that there is not a problem with the energy for G11.2–0.3, but that the energy in 3C 58 appears to be larger than that expected for the observed pulsar and the designated age. A larger age for 3C 58 would allow a larger energy to be deposited in the nebula.

There are thus several arguments for 3C 58 being older than SN 1181, even though Stephenson and Green (2002) consider the identification to be secure. The problems are that the PWN is too large to be expanding into a normal supernova, the expected mass swept up by PWN smaller than observed, and the internal energy is larger than can be supplied by the pulsar. A larger age for the remnant is consistent with the slow expansion of 3C 58 observed at both radio (Bietenholz et al., 2001) and optical (Fesen et al., 1988) wavelengths.

## ENERGY EQUIPARTITION IN PWNe

One of the important properties of a PWN is the relative amount of energy in particles and in magnetic fields. In the Crab Nebula, there is approximate equipartition overall in these energies. In the detailed MHD model of Kennel and Coroniti (1984) for the Crab Nebula, this property is produced by the choice of the $`\sigma `$ parameter, the ratio of Poynting flux to particle kinetic energy flux in the pulsar wind. The value $`\sigma 0.003`$ is deduced; the magnetic field is relatively weak in the wind and is increased by the shock compression and further compression in the decelerating postshock flow. This value of $`\sigma `$ is close to the upper limit that is allowed in this kind of model, or the flow would not be able to decelerate to meet the outer boundary condition, but there is no particular reason for this value to be produced.

One way to estimate the overall magnetic field in a PWN is from the synchrotron break frequency, $`\nu _{br}`$, and the age of the PWN. The determination of $`\nu _{br}`$ depends on the spectrum of the nebula. There is increasing evidence that the particle spectrum injected into PWNe typically has at least one intrinsic spectral break. Models for the radio to X-ray emission with a single power law injection spectrum generally fail (Reynolds and Chevalier, 1984), and the well-observed Crab Nebula spectrum requires an injection spectrum with a break (e.g., Amato et al., 2000). With synchrotron losses, the spectrum develops a further break.

Two PWNe for which there is age information and information on $`\nu _{br}`$ are 3C 58 and MSH 15–52. As discussed above, 3C 58 may be older than 821 years, which I consider as a lower limit; a lower limit on the age yields an upper limit on the magnetic field. MSH 15–52 has been suggested to be the remnant of SN 185, although G315.4–2.3 is another candidate for the remnant of this supernova (Stephenson and Green, 2002). However, the large size of the nebula associated with MSH 15–52 (Gaensler et al., 2001) indicates that it is not significantly younger than 1700 years.

The determination of $`\nu _{br}`$ depends on the interpretation of the overall spectrum of the PWN. For 3C 58 and MSH 15–52, as for most PWNe, there are detections at only radio and X-ray wavelengths. However, the fact that the extent of the X-ray emission is comparable to that of the radio emission in both cases indicates that $`\nu _{br}`$ is not much lower than X-ray energies, assuming that particles originate close to the pulsar and move out in the nebula. In the case of 3C 58, the X-ray spectrum steepens at large radii, showing that synchrotron losses are significant in the X-ray regime (Torii et al., 2000). An estimate of $`h\nu _{br}`$ is thus $`0.5`$ keV, which is consistent with the fact that the X-ray spectrum is somewhat steeper than the spectrum from radio to X-ray wavelengths. The implications for the magnetic field and magnetic energy are given in Table 4. The magnetic field strength in MSH 15–52 can be estimated from similar arguments (Gaensler et al., 2001) and is given in Table 4. In this scenario, the low frequency breaks are intrinsic to the injected particle spectrum; this is a controversial point and there have been discussions of the low frequency breaks in terms of synchrotron losses (e.g., Woltjer et al., 1997 on 3C 58 and Roberts et al., 2002 on G11.2–0.3).

It is also possible to estimate minimum magnetic plus particle energy, $`E_{min}`$, from the radio synchrotron emission ($`10^710^{11}`$ Hz). The results, given in Table 4, show that the magnetic energy is considerably less than the total internal energy in both cases, so that the nebulae are particle dominated. In the context of the Kennel and Coroniti (1984) model, this would require a remarkably low Poynting energy flux in the pulsar wind. However, the result is consistent with the finding in the Kennel and Coroniti (1984) model that a particle dominated wind is needed to produce a shock front and deceleration of the flow to match the outer boundary. This suggests that pulsar winds may have a range of magnetizations, giving rise to a range of nebular properties. If cases with a highly magnetized wind occur, they would give rise to something other than a standard pulsar wind nebula. In this limit, the wind termination shock moves in to the pulsar (Rees and Gunn, 1974; Emmering and Chevalier, 1987) so that the immediate surroundings of the pulsar are in communication with the ambient medium.

## 1 DISCUSSION AND CONCLUSIONS

The increasing number of PWNe are providing many examples which can be compared to models initially developed for the Crab Nebula. In a model with interaction with freely expanding supernova ejecta, the PWN properties can provide a check on the age estimate for the nebula. Such models have previously been developed for the Crab Nebula, MSH 15-52, and 0540–69 (Chevalier and Fransson, 1992). Recent observational results on 3C 58 and G11.2–0.3 allow similar models to be considered for these objects, which are of special interest because of their possible identifications with historical supernovae. The models indicate that 3C 58 is older than SN 1181, but that G11.2–0.3 is consistent with being the remnant of SN 386. These tentative conclusions need to be followed up by more detailed studies of the remnants. In both cases, the model predicts that the PWN is driving a shock front into freely expanding ejecta. Gas shocked in this way may have been observed in 3C 58 (Bocchino et al., 2001), but further observations are needed. Such gas has not yet been observed in G11.2–0.3. The external supernova remnant interaction also provides constraints on the system. This interaction is clearly seen in G11.2–0.3 (Roberts et al., 2002), but not in 3C 58, implying interaction with low density surroundings for that case.

Another finding here is that the 3C 58 and MSH 15-52 PWNe are particle dominated, which requires that the pulsar winds have a very low magnetization parameter. This property may be one of the reasons why these PWNe have low efficiencies of X-ray luminosity production compared to the pulsar power (Chevalier, 2000). 3C 58, G292.0+1.8, G11.2–0.3, MSH 15-52, and G54.1+0.3 all have significantly lower levels of X-ray luminosity production efficiency than the Crab Nebula.

## ACKNOWLEDGEMENTS

I am grateful to the referee and editor for helpful comments. This work was supported in part by NASA grants NAG5-8130 and NAG5-13272.

email address for R. A. Chevalier: rac5x@virginia.edu