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# Phase diagram of polymer blends in confined geometry11footnote 1Workshop on Modern Problems in Soft Matter Theory, Lviv, Aug 27-31, 2000, submitted to the Journal of Molecular Liquids and Condensed Matter Physics

## 1 Introduction

Confining a binary mixture gives rise to a rich interplay between wetting and miscibility behavior. In a porous material or a slit–like pore with identical surfaces the critical point of the mixture is shifted away from its bulk value to lower temperatures and higher compositions of the component prefered by the walls. The phenomenon of capillary condensation which occurs if the two confining boundaries are symmetric is well–known. In some applications (e.g., coatings or dielectrics), however, the surfaces of the film (e.g., a solid substrate and vacuum) interact very differently with the constituents of the mixture. In the opposite limit of antisymmetric walls, i.e., one wall attracts the $`A`$–component with exactly the opposite strength than the other wall the $`B`$–component, an interface localization/delocalization transition occurs close to the wetting transition of the semi–infinite system.

We study the dependence of the phase behavior of a polymer mixture confined into a thin film on the surface interactions and film thickness via self–consistent field calculations and Monte Carlo simulations. Our paper is arranged as follows: In the next section we describe our mean field calculations and discuss the dependence of the phase diagram on the monomer–wall interactions. Then we investigate the effect of fluctuations via simulations of a coarse grained lattice model. The paper closes with a discussion of the anticipated chain length dependence and an outlook on experimental systems.

## 2 Self–consistent field calculations

We calculate the phase behavior of a confined $`AB`$ mixture within the self-consistent field theory of Gaussian polymers. The film comprises a volume $`V_0=\mathrm{\Delta }_0\times L\times L`$. $`\mathrm{\Delta }_0`$ denotes the film thickness, while $`L`$ is the lateral extension of the film. The density at the film surfaces decreases to zero in a boundary region of width $`\mathrm{\Delta }_w`$ according to

$$\mathrm{\Phi }_0(x)=\{\begin{array}{cc}\frac{1\mathrm{cos}\left(\frac{\pi x}{\mathrm{\Delta }_w}\right)}{2}\hfill & \text{}0x\mathrm{\Delta }_w\hfill \\ 1\hfill & \text{}\mathrm{\Delta }_wx\mathrm{\Delta }_0\mathrm{\Delta }_w\hfill \\ \frac{1\mathrm{cos}\left(\frac{\pi (\mathrm{\Delta }_0x)}{\mathrm{\Delta }_w}\right)}{2}\hfill & \text{}\mathrm{\Delta }_0\mathrm{\Delta }_wx\mathrm{\Delta }_0\hfill \end{array}$$
(1)
where $`\mathrm{\Phi }_0`$ denotes the ratio of the monomer density and the value $`\rho `$ in the middle of the film. The thickness $`\mathrm{\Delta }`$ of an equivalent film with constant monomer density $`\rho `$ is $`\mathrm{\Delta }=\mathrm{\Delta }_0\mathrm{\Delta }_w`$. We choose $`\mathrm{\Delta }_w=0.15R_e`$, where $`R_e`$ is the end–to–end distance. Both surfaces interact with the monomer species via a short range potential $`H`$:

$$H(x)=\{\begin{array}{cc}\frac{4\mathrm{\Lambda }_1R_e\left\{1+\mathrm{cos}\left(\frac{\pi x}{\mathrm{\Delta }_w}\right)\right\}}{\mathrm{\Delta }_w}\hfill & \text{}0x\mathrm{\Delta }_w\text{ }\hfill \\ 0\hfill & \text{}\mathrm{\Delta }_wx\mathrm{\Delta }_0\mathrm{\Delta }_w\hfill \\ \frac{4\mathrm{\Lambda }_2R_e\left\{1+\mathrm{cos}\left(\frac{\pi (\mathrm{\Delta }_0x)}{\mathrm{\Delta }_w}\right)\right\}}{\mathrm{\Delta }_w}\hfill & \text{}\mathrm{\Delta }_0\mathrm{\Delta }_wx\mathrm{\Delta }_0\hfill \end{array}$$
(2)
$`H>0`$ is attractive for the $`A`$ monomers and repulsive for the $`B`$ species. The normalization of the surface fields $`\mathrm{\Lambda }_1`$ and $`\mathrm{\Lambda }_2`$, which act on the monomers close to the left and the right surface, is chosen such that the integrated interaction energy between the surface and the monomers is independent of the width of the boundary region $`\mathrm{\Delta }_w`$.

$`A`$ and $`B`$ polymers contain $`N`$ monomers and are structurally symmetric. The polymer conformations $`\{𝐫_\alpha (\tau )\}`$ determine the microscopic $`A`$ monomer density $`\widehat{\mathrm{\Phi }}_A(𝐫)=\frac{N}{\rho }_{\alpha =0}^{n_A}_0^1d\tau \delta \left(𝐫𝐫_\alpha (\tau )\right)`$, where the sum runs over all $`n_A`$ $`A`$ polymers in the system and $`0\tau 1`$ parameterizes the contour of the Gaussian polymer. A similar expression holds for $`\widehat{\mathrm{\Phi }}_B(𝐫)`$. With this definition the semi–grandcanonical partition function takes the form:

$`𝒵`$ $``$ $`{\displaystyle \underset{n_A=1}{\overset{n}{}}}{\displaystyle \frac{e^{+\mathrm{\Delta }\mu n_A/2k_BT}}{n_A!}}{\displaystyle \frac{e^{\mathrm{\Delta }\mu n_B/2k_BT}}{n_B!}}{\displaystyle 𝒫_A[𝐫]𝒫_B[𝐫]\delta \left(\mathrm{\Phi }_0\widehat{\mathrm{\Phi }}_A\widehat{\mathrm{\Phi }}_B\right)}`$ (3)
$`\times \mathrm{exp}\left(\rho {\displaystyle \mathrm{d}^3𝐫\left\{\chi \widehat{\mathrm{\Phi }}_A\widehat{\mathrm{\Phi }}_BH(\widehat{\mathrm{\Phi }}_A\widehat{\mathrm{\Phi }}_B)\right\}}\right)`$
where $`n=n_A+n_B`$ and $`\mathrm{\Delta }\mu `$ represents the exchange potential between $`A`$ and $`B`$ polymers. The functional integral $`𝒫`$ sums over all conformations of the polymers with the statistical weight $`\mathrm{exp}\left(\frac{3}{2R_e^2}_0^1d\tau \left(\frac{\mathrm{d}𝐫}{\mathrm{d}\tau }\right)^2\right)`$ of a non–interacting Gaussian polymer. The second factor enforces the monomer density profile to comply with Eq.(1) (incompressibility). The Boltzmann factor in the partition function incorporates the thermal repulsion between unlike monomers, which is described by the Flory–Huggins parameter $`\chi `$, and the interactions between monomers and surfaces.

In mean field approximation the free energy is obtained as the extremum of the semi–grandcanonical free energy functional:

$`{\displaystyle \frac{𝒢}{nk_BT}}+\mathrm{ln}{\displaystyle \frac{n}{V_0}}\mathrm{ln}𝒬+{\displaystyle \frac{1}{V}}{\displaystyle \mathrm{d}^3𝐫\chi N\mathrm{\Phi }_A\mathrm{\Phi }_B}HN\left\{\mathrm{\Phi }_A\mathrm{\Phi }_B\right\}`$
$`{\displaystyle \frac{1}{V}}{\displaystyle \mathrm{d}^3𝐫\left\{W_A\mathrm{\Phi }_A+W_B\mathrm{\Phi }_B\right\}}+\mathrm{\Xi }\left\{\mathrm{\Phi }_0\mathrm{\Phi }_A\mathrm{\Phi }_B\right\}`$ (4)
with respect to its arguments $`W_A,W_B,\mathrm{\Phi }_A,\mathrm{\Phi }_B,\mathrm{\Xi }`$. $`𝒬_A`$ denotes the single chain partition function:

$$𝒬_A[W_A]=\frac{1}{V_0}𝒟_1[𝐫]𝒫_1[𝐫]e^{_0^1d\tau W_A(𝐫(\tau ))}$$
(5)
and similarly for $`𝒬_B`$; $`𝒬=\mathrm{exp}(\mathrm{\Delta }\mu /2k_BT)𝒬_A+\mathrm{exp}(\mathrm{\Delta }\mu /2k_BT)𝒬_B`$.

The values of $`W_A,W_B,\mathrm{\Phi }_A,\mathrm{\Phi }_B,\mathrm{\Xi }`$ which extremize the free energy functional are denoted by lower–case letters and satisfy the self-consistent set of equations

$$w_A(𝐫)=\chi N\varphi _B(𝐫)H(𝐫)N+\xi (𝐫)\text{and}\varphi _A(𝐫)=\frac{V}{𝒬}\frac{𝒟𝒬_A}{𝒟w_A(𝐫)}$$
(6)
$`\mathrm{\Phi }_0(𝐫)=\varphi _A(𝐫)+\varphi _B(𝐫)`$, and similar expressions for $`w_B`$ and $`\varphi _B`$. Substituting the extremal values of the densities and fields into the free energy functional (4) we calculate the free energy $`G`$ of the different phases. At coexistence the two phases have equal semi–grandcanonical potential.

To calculate the monomer density we employ the end segment distribution which satisfies a diffusion equation. We expand the spatial dependence of the densities and fields in a set of orthonormal functions. This procedure results in a set of non–linear equations which are solved by a Newton–Raphson–like method. We use up to 80 basis functions and achieve a relative accuracy $`10^4`$ in the free energy.

The phase diagram in a thin film ($`\mathrm{\Delta }_0=0.9R_e`$) with antisymmetric surface fields of various strengths is presented in Fig.1. For weak surface fields we find a second–order interface localization/delocalization transition.

Close to the critical point of the bulk enrichment layers form gradually at each surface and stabilize an interface in the center of the film. The films remains laterally homogeneous in this “soft–mode” phase. Only below the second order transition the interface is localized at one wall and $`A`$–rich and $`B`$–rich domains coexist laterally. Upon increasing the monomer–wall interaction strength the transition temperature shifts to lower values.

(a) (b)

Fig.1: (a) Phase diagrams in a film with antisymmetric surface fields. The values of the surface fields $`\mathrm{\Lambda }N`$ are indicated in the key. For $`\mathrm{\Lambda }N0.1425`$ we find a single critical point, while we find two critical points for larger surface fields. (a) displays the phase diagram in the temperature–composition plane, while (b) presents the coexistence curves $`\mathrm{\Delta }\mu _{\mathrm{coex}}(\chi N)`$. (For $`\mathrm{\Lambda }N=0.15`$ the two critical points are indistinguishable on the scale of panel (b)). From .

At large monomer–wall interaction the wetting transition is of first order and we observe also a first order interface localization/delocalization transition. The prewetting coexistence slightly above the first order wetting transition temperature gives rise to two miscibility gaps in a film. At each wall a thin and a thick enrichment layer of the prefered component coexist. These coexistence regions terminate in two critical points which are the analogs of the prewetting critical points at each wall. When we decrease the temperature the miscibility gaps open and form a triple point at which an $`A`$–rich phase, a phase where the interface is delocalized in the middle of the film, and a $`B`$–rich phase coexist. Below the triple temperature an $`A`$–rich and a $`B`$–rich phase coexist.

The two types of phase diagrams are separated by a tricritical interface localization/delocalization transition. For our model we find a tricritical transition at $`\mathrm{\Lambda }N=0.1425`$ and $`\mathrm{\Delta }_0=0.9R_e`$. When we increase the film width the tricritical strength of the surface interactions decreases. At tricriticality, there is only a single critical point, but the binodals are characterized by an exponent $`\beta =1/4`$ in mean field approximation.

Fig.1b presents the coexistence curves as a function of temperature and exchange potential. For a second order or a tricritical transition phase coexistence occurs at $`\mathrm{\Delta }\mu =0`$ due to the symmetry of the system with respect to exchanging $`AB`$. For a first order transition the coexistence curve lays on the symmetry axis $`\mathrm{\Delta }\mu =0`$ for low temperatures. When the temperature rises, it bifurcates at the triple point; each continuation is the thin film analog of the prewetting line at the corresponding surface. Since the coexisting phases do not possess the symmetry of the Hamiltonian, $`\mathrm{\Delta }\mu _{\mathrm{coex}}0`$. For short range monomer–wall interactions the prewetting–like curves deviate linearly from the bulk coexistence value and terminate in critical points.

(a) (b)

Fig.2. (a) Phase diagram for $`\mathrm{\Lambda }N=0.5`$ and various film thicknesses $`\mathrm{\Delta }_0`$. For $`\mathrm{\Delta }_0=2.6R_e`$ and $`0.9R_e`$ the interface localization–delocalization transition is first order, $`\mathrm{\Delta }_0=0.605R_e`$ corresponds to a tricritical transition, while the transition is second order for $`\mathrm{\Delta }_0=0.5R_e`$. (b) Phase diagram as a function of temperature and chemical potential for the same parameters than in (a). From

The interface localization/delocalization transition can also be changed from first to second order by decreasing the film thickness, because the effective interactions between the interface and each wall interfere. The three minimum structure of the effective interface potential close to the triple point changes to a single minimum as the film thickness becomes comparable to the range of the effective interaction between the interface and the wall. The film thickness dependence of the miscibility behavior is presented in Fig.2. For $`\mathrm{\Delta }_0<0.605R_e`$ the interface localization/delocalization transition is second order even though the wetting transition in the semi–infinite system is first order.

Of course, surface interactions in experimental realizations are never strictly antisymmetric or symmetric and it is important which degree of asymmetry is permissible without loosing the qualitative features of the limiting cases. The phase diagram for non–symmetric boundary fields is discussed in Fig.3. The right walls attracts the $`A`$–component of the mixture and the surface fields lead to a first order wetting transition in the semi–infinite system. The monomer–wall interactions at the opposite wall are tuned from attracting $`A`$ (symmetric boundaries, capillary condensation) to attracting $`B`$ (antisymmetric boundaries, interface localization/delocalization).

For symmetric boundaries the critical point is shifted to lower temperatures and higher concentration of the $`A`$ species attracted by both surfaces. The coexistence value of the chemical potential $`\mathrm{\Delta }\mu _{\mathrm{coex}}`$ is shifted to values disfavoring the $`A`$ component and the shift is roughly proportional to the inverse film widths (Kelvin equation). Above the wetting transition temperature an almost pure $`A`$–rich phase coexist with a $`B`$–rich phase. In the latter phase, there are thick enrichment layers of $`A`$ at the walls and the $`B`$ component prevails at the center of the film. When the temperature is lowered towards the wetting transition temperature $`T_{\mathrm{wet}}`$, the thickness of the enrichment layers rapidly decreases. This gives rise to a convex curvature of the $`B`$–rich binodal slightly above $`T_{\mathrm{wet}}`$. Below $`T_{\mathrm{wet}}`$ the coexisting phases are almost pure , i.e., the enrichment layers in the $`B`$–rich phase are negligible and $`\mathrm{\Delta }\mu _{\mathrm{coex}}`$ is independent of temperature.

(a) (b)

Fig.3. (a) Binodals for $`\mathrm{\Delta }_0=2.6R_e`$ and $`\mathrm{\Lambda }_1N=0.5`$. $`\mathrm{\Lambda }_2N`$ varies as indicated in the key. The dashed curve shows the location of the critical points. Filled circles mark critical points, open circles/dashed horizontal lines denote three phase coexistence for $`\mathrm{\Lambda }_2N=0.3675`$ and $`0.5`$. The inset presents part of the phase boundary for antisymmetric boundaries. (b) Coexistence curves in the $`\chi N`$$`\mathrm{\Delta }\mu `$ plane. $`\mathrm{\Lambda }_2N`$ varies according to the key. The “quasi–prewetting” lines for $`\mathrm{\Delta }\mu <0`$ and $`\mathrm{\Lambda }_2N=0.3675`$ and $`0.5`$ are indistinguishable, because they are associated with the prewetting behaviour of the surface with interaction $`\mathrm{\Lambda }_1N=+0.5`$. From

As we reduce the preference of the left wall for the $`A`$ component the system becomes more symmetric and the critical point shifts to more symmetrical composition and higher temperature (i.e., closer to the bulk critical point at $`\chi N=2`$ and $`\varphi =1/2`$). If we make the left wall repulsive for the $`A`$ component (attractive for the $`B`$–component) the character of the transition gradually changes from a bulk–like unmixing transition, where the composition of the two phases varies little spatially across the film but differs between the two phases, to a prewetting–like transition, where an interface runs parallel to the walls and the distance between the wall and the interface is the order parameter. As this change occurs the critical temperature (composition) passes through a maximum (minimum). Upon approaching the strictly antisymmetric limit the coexistence curve (at low temperatures) approaches the bulk value. When it intersects with the prewetting line of the left wall, which attracts the $`B`$–species, a second two phase region opens between a thin and a thick enrichment layer at the left wall.

## 3 Monte Carlo simulations

The self–consistent field calculations presented in the previous section neglect fluctuations. In a cylindrical pore, fluctuations destroy a true phase transition. In a thin film they change the universality class of the critical points from 3D Ising–like in the bulk to 2D Ising–like in a film. Moreover, there is an strong interplay between the wetting behavior of the semi–infinite system and the phase diagram of a film with antisymmetric boundaries and interface fluctuations (i.e., capillary waves) might modify the predictions of the mean field theory.

Being interested in the universal features of the phase diagram we have investigated a coarse grained lattice model of a binary polymer blend via Monte Carlo simulations. In the framework of the bond fluctuation model each monomer occupies the corner of a unit cell of a simple cubic lattice from further occupation. Monomers along the polymer are connected via bonding vectors of length $`2,\sqrt{5},\sqrt{6},3`$ or $`10`$ in units of the lattice spacing. Monomers interact through a square well potential which comprises the 54 nearest sites on the lattice. A contact between like monomers lowers the energy of the system by an amount $`ϵ`$ (measured in units of $`k_BT`$), while a contact between different species increases the energy by the same amount. These interactions set a temperature scale and lead to a liquid–liquid phase separation at $`T=1/ϵ_c=69.3(3)`$ in the bulk. The parameter $`ϵ`$ is related to the Flory–Huggins parameter via $`\chi =2z_cϵ`$, where $`z_c=2.65`$ denotes the number of monomers of other chains in the range of the square well potential.

We work at a chain length $`N=32`$ and monomer number density $`\rho =1/16`$. The molecules end–to–end distance is $`R_e17`$ in units of the lattice spacing. We study thin film of geometry $`L\times L\times \mathrm{\Delta }`$. Periodic boundary conditions are applied in the two lateral directions, while there are hard impenetrable walls a distance $`\mathrm{\Delta }`$ apart. Monomers in the two layers nearest to the walls interact with the boundaries. An $`A`$–monomer close to the right wall decreases the energy by $`ϵ_w=0.16`$, while a $`B`$–monomer increases the energy by the same amount. For symmetrical walls the interactions at the left wall are identical to the right wall; for antisymmetrical walls $`B`$–monomers are attracted by the left wall and $`A`$–monomers repelled. Using the Young equation we have determined the wetting transition temperature to $`T_{\mathrm{wet}}=14.1(7)`$. The wetting transition occurs well inside the strong segregation limit and is of first order.

We use the semi–grandcanonical ensemble, i.e., we fix the temperature and the exchange potential $`\mathrm{\Delta }\mu `$ and monitor the composition $`\varphi `$ and its fluctuations. In addition to Monte Carlo moves which update the conformations of the polymers on the lattice (local hopping attempts and slithering–snake–like motions) we try to change the chain species $`AB`$ at fixed conformation. This semi–grandcanonical simulation scheme is employed in junction with reweighting methods as to encourage the system to sample all compositions with roughly equal probability.

Fig.4. Probability distribution of the composition scaled to unit norm and variance for various film thickness $`\mathrm{\Delta }`$ ($`R_e=17`$ in units of the lattice spacing) and temperatures as indicated in the key. The probability distribution of the 2D tricritical universality class is represented by circles. From

In the simulations we monitor the joint distribution of the composition, energy and monomer–wall interaction; and we use finite size scaling techniques and histogram reweighting methods to locate the critical point. As an example Fig.4, presents the probability distribution of the composition as a function of the film thickness in the vicinity of the tricritical point. The distribution shows a clear three peak structure. The temperature is adjusted such that the ratio of the heights of the central and outer peaks equals 1.2. This value corresponds to the ratio of the distribution of the tricritical universality class. The latter quantity has been measured in simulations of the Blume–Capel model at its tricritical point. To compare the distributions without adjustable parameter we scale them to unit norm and variance. For film thickness $`\mathrm{\Delta }=140.82R_e`$ the shape of the distribution matches closely the universal function and this holds also true for larger systems. For $`\mathrm{\Delta }<0.82R_e`$ we find a second order interface localization/delocalization transition, while there is a first order transition for $`\mathrm{\Delta }>0.82R_e`$.

The probability distribution of the composition yields information about the interaction $`g(l)`$ between the walls and the interface. Since the wetting transition occurs in the strong segregation limit, the coexisting phases in the bulk are almost pure $`\varphi _{\mathrm{coex}}^{\mathrm{bulk}}0`$ or $`1`$ and “bulk”–like composition fluctuations can be neglected. Hence, the distance $`l`$ between the wall and the interface is given by $`l=\mathrm{\Delta }\varphi `$ and the effective interface potential $`g(l)`$ can be measured in the Monte Carlo simulations according to $`g(l)=k_BT/L^2\mathrm{ln}P(\varphi )`$, where $`P(\varphi )`$ denotes the probability distribution of the composition.

Fig.5. Dependence of the effective interface potential $`g(l)/k_BT`$ on the lateral film extension $`L`$ for $`\mathrm{\Delta }=482.8R_e`$ and $`ϵ=0.069`$. The inset presents an enlarged view on the minimum of the localized state. From

The result for the effective interface potential $`g(l)`$ in the vicinity of the triple point is presented in Fig.5. The three minima correspond to the $`A`$–rich phase, the phase with the delocalized interface, and the $`B`$–rich phase. Unlike the situation at the tricritical point the position of the minima does not depend on the lateral system size. However, the effective interface potential does depend on $`L`$; the minima broaden upon increasing the lateral system size $`L`$ and the free energy of the delocalized state decreases with respect to the localized ones. The dependence of $`g(l)`$ on the lateral system size gives rather direct evidence for a renormalization of the effective interface potential by interface fluctuations in the framework of a microscopic model. The interface in the simulations is not ideally flat, but there are long wavelength fluctuations of the local interface position (i.e., capillary waves). Since the interface is not unconstraint, the interface potential imparts a parallel correlation length onto the capillary waves. $`\xi _{}\sqrt{\mathrm{d}g^2/\mathrm{d}^2\varphi }`$. This parallel correlation length is larger in the delocalized state than in the localized one. For the parameters of the simulation the lateral system size and the parallel correlation lengths are of the same order of magnitude. For lateral distances smaller than $`\xi _{}`$ the local position fluctuates like a free interface, for lateral distance that exceed $`\xi _{}`$ interface fluctuations are strongly suppressed. In the simulations the lateral system size $`L`$ also cuts off interface fluctuations when $`L<\xi _{}`$. Interface fluctuations reduce the free energy of the system and the minima corresponding to the delocalized state benefits more from an increase of the lateral system size. This rationalized qualitatively the effect observed in Fig.5 and quantitative description shall be presented elsewhere. The effect is important for accurately locating the triple temperature.

(a) (b)

Fig.6. Phase diagram in terms of composition and temperature (a) and exchange potential and temperature (b) for film thickness $`\mathrm{\Delta }482.8R_e`$. From

The phase diagrams for $`\mathrm{\Delta }2.8R_e`$, as revealed by Monte Carlo simulations in Fig.6, confirm the qualitative predictions of the self–consistent field calculations. For symmetric boundary conditions there is a small shift of the critical point to lower temperatures and higher concentration of the $`A`$ species prefered by the walls. The “bulge” of the $`A`$–poor binodal is a consequence of the vicinity of the prewetting critical point. If the film thickness were larger the coexistence value $`\mathrm{\Delta }\mu _{\mathrm{coex}}`$ would be smaller (Kelvin equation) and the coexistence curve would intersect the prewetting line. In this case there would be a two phase coexistence region also in the case of symmetric boundaries. In the antisymmetric case the phase diagram comprises two critical points – the analogs of the prewetting critical points at each surface. The concomitant miscibility gaps joint to form a triple point ultimately above the temperature of the first order wetting transition temperature of the semi–infinite system. Unlike the mean field predictions, however, the shape of the binodals is much flatter reflecting the 2D Ising behavior close to the critical points.

## 4 Discussion

We have calculated the phase diagram of a symmetric polymer mixture confined into a thin film in mean field approximation and by Monte Carlo simulations. The mean field calculations reveal a rich interplay between the phase behavior in confined geometry and the wetting behavior of the semi–infinite system and the general features of the phase behavior are confirmed by our Monte Carlo results. However, fluctuations result in two modifications of the mean field results: (i) In the vicinity of the critical point we observe 2D Ising critical behavior with much flatter binodals than the parabolic binodals of the mean field universality class. (ii) The effective interface potential is renormalized by capillary waves. This leads, e.g., to a systematic overestimation of the triple temperature by the mean field treatment.

Qualitatively the interplay between the prewetting behavior and the phase diagram in a film with antisymmetric boundaries is not specific to polymer blends but is rather characteristic of all binary mixtures. We expect, however, polymer mixtures, be particluarly suitable model systems for exploring these effects experimentally.

If we measure the incompatibility of the species/temperature by $`\chi N`$ and the length scale in units of the end–to–end distance $`R_e=b\sqrt{N}`$, the typical scale of the free energy in a volume $`R_e^3`$ is given by $`\sqrt{\overline{N}}`$, where where the reduced chain length $`\overline{N}=(\rho R_e^3/N)^2`$ measures the degree of interdigitation.

The importance of fluctuations close to the critical point can be gauged by the Ginzburg criterium. For binary polymer blends one finds that fluctuations are important in the range $`|1\chi _cN/\chi N|Gi`$ with Ginzburg number $`Gi1/\overline{N}`$. The importance of interface fluctuations can be described by the capillary parameter

$$\omega =\frac{k_BT\lambda ^2}{4\pi \sigma _{AB}}=\frac{1}{4\pi \sqrt{\overline{N}}}(\lambda R_e)^2\frac{k_BT\sqrt{\overline{N}}}{\sigma R_e^2}$$
(7)
where $`1/\lambda `$ denotes the characteristic length of the interface potential and $`\sigma `$ is the interface tension. $`\lambda R_e`$ and $`\sigma R_e^2/\sqrt{\overline{N}}k_BT`$ are functions of $`\chi N`$ only. Upon increasing the degree of interdigitation $`\overline{N}`$, the capillary parameter $`\omega 1/\sqrt{\overline{N}}`$ decreases.

In the limit of long chains (or strong interdigitation) these fluctuation effects are suppressed and the self–consistent field theory is believed to describe the confined blend quantitatively appropriately. For the bond fluctuation model $`N=32`$ corresponds to $`\overline{N}91`$ and this chain length of our coarse grained model corresponds roughly to 100-150 repeat units of a real polymer. Since fluctuations do not alter the qualitative mean field scenario for the rather short chains investigated by Monte Carlo simulations, we expect this a fortiori for experimental systems. Furthermore the wetting transition in binary polymer mixtures occurs far below the critical point. Bulk–like composition fluctuations are only of minor importance; the systems are well describable via effective interface Hamiltonians and the effect of interface fluctuations is clearly observable. Additionally, the size of the enrichment layers is set by $`R_e`$ and, hence, is much larger than in atomic liquids. Sophisticated profiling techniques (e.g., nuclear reaction analysis, neutron reflectometry or secondary ion mass spectrometry) are available to accurately determine the thickness of wetting layers in experiments.

Indeed, experiments on polymer mixtures were the first to investigate fluctuation effects in the delocalized state and the wetting transition in polymer blends has been observed experimentally. Our results imply, for instance, that ultrathin enrichment layers with a thickness $`lR_e/5`$ be unstable in the temperature range $`T_{\mathrm{wet}}<T<T_{\mathrm{prewet}}`$. Such instabilities slightly above $`T_{\mathrm{wet}}`$ have been observed for compressible one–component polymer films.

Of course, both the self–consistent field calculations and the Monte Carlo simulations deal with highly idealized models. The effect of architectural asymmetry between the constituents of the mixture or the role of long–range van der Waals interactions between the monomers and the surfaces has not be considered.

### Acknowledgment

It is a great pleasure to thank N.B. Wilding for providing the scaling function of the 2D tricritical universality class (Fig.4). Financial support was provided by the DFG under grant Bi314/17 in the priority program “wetting and structure formation at interfaces” and by the DAAD/PROALAR2000.


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# The origin of runaway stars

## 1 Introduction

Runaway stars (Blaauw, 1961) distinguish themselves from the normal population of early-type stars (spectral type O and B) by their large peculiar velocities (up to 200 km s-1) with respect to the mean Galactic rotation and by their isolated locations. About 30% of the O stars and 5–10% of the B stars are runaways. Since early-type stars are relatively young (a few Myr to $``$50 Myr old), the distances traveled by the runaways are relatively small (a few hundred pc to a few kpc) and it is therefore possible, in some cases, to identify the parent cluster, i.e., the stellar group where the runaway originated (e.g., Blaauw, 1993).

Two mechanisms for the production of runaway stars remain viable, the binary-supernova scenario (Zwicky, 1957; Blaauw, 1961) and the dynamical ejection scenario (Poveda, Ruiz & Allen, 1967; Gies & Bolton, 1986). In the former the runaway receives its velocity after a supernova explosion in a massive close binary; after the explosion the binary (sometimes) dissociates and the secondary starts to move through space with a velocity comparable to its pre-explosion orbital velocity. In the latter scenario the runaway gains its velocity through a dynamical interaction with one or more other stars. The most efficient encounter is that between two hard binaries which, in most cases, results in the ejection of two runaway stars and one eccentric binary (Hoffer, 1983; Mikkola, 1983).

Which of the two mechanisms dominates the creation of runaway stars has been debated vigorously in the past. The modest accuracy and incompleteness of previous data sets did not allow distinguishing convincingly between the two mechanisms: both scenarios were consistent with the statistical properties of the ensemble of runaway stars. The availability of Hipparcos milli-arcsec (mas) astrometry for the nearby stars (ESA 1997), and pulsar astrometry provided by VLBI and timing measurements, stimulated us to revisit this issue, as it allows calculation of the past orbits of these objects with sufficient accuracy to establish their parent group, and the mechanism that formed them. A past encounter between a runaway star and a pulsar would provide compelling evidence for the binary-supernova scenario, while an encounter of two (or more) runaway stars would strongly suggest the dynamical ejection scenario. In the course of this work, we could identify the specific formation scenario for three nearby runaways (the pair AE Aur & $`\mu `$ Col and $`\zeta `$ Oph) with near certainty.

In this Letter we summarize the results for these objects, as together they demonstrate that both mechanisms for the creation of runaways stars operate in nature. Details of the orbit integrations, the Galactic potential used, and the simulations performed to validate the results, as well as a discussion of the other nearby runaway stars and pulsars with accurate astrometry, are reported in Hoogerwerf et al. (2000, HBZ).

## 2 A stellar encounter in Orion

The Orion association (Ori OB1) has three known runaway stars: AE Aur, $`\mu `$ Col, and 53 Ari (Blaauw, 1961). The first two of these form a pair; they have almost similar spectral types (O9.5V and O9.5V/B0), and move in opposite directions at 100 km s-1 each, leaving Ori OB1 about 2.5 Myr ago. These similarities led Blaauw & Morgan (1954) to suggest that the two stars were formed in the same event. Gies & Bolton (1986) proposed that AE Aur, $`\mu `$ Col, and the massive eccentric binary $`\iota `$ Ori (O9III+B1III) are the result of a binary-binary encounter which ejected the two runaways. Both stars have normal rotational velocities (25 and 111 km s-1 for AE Aur and $`\mu `$ Col, respectively) and AE Aur has a normal He abundance. The He abundance of $`\mu `$ Col is unknown. Thus neither runaway shows signs of previous mass transfer in a close binary system, and this most likely excludes the binary-supernova scenario as the origin of the two runaways. Dynamical ejection is by far the favorite scenario for the origin of the high velocities of AE Aur and $`\mu `$ Col.

We supplemented the Hipparcos astrometry with the best available radial velocities in order to retrace the orbits of AE Aur, $`\mu `$ Col and $`\iota `$ Ori. We performed $`2.5\times 10^6`$ orbit integrations to sample the errors in the positions and velocities of the objects (see HBZ). The integrations show that $``$2.5 Myr ago the three stars were very close together: the distribution of minimum separations obtained from the orbit integrations is consistent with the stars being located in exactly the same position in space at the same time, $`2.5\pm 0.2`$ Myr ago. We therefore conclude that the two runaway stars and the binary $`\iota `$ Ori must once have been part of the same cluster, and were all ejected following a dynamical interaction.

A natural question to ask is which cluster hosted the four stars before their encounter? Assuming that the center-of-mass motion of the four stars was similar to that of the parent cluster, and using conservation of linear momentum, provides the position and velocity of the parent cluster $``$2.5 Myr ago. We integrated its orbit forward in time to the present (Figure 1). The resulting properties of the parent cluster, in particular its distance and position on the sky, agree very well with that of the Trapezium cluster (see Table 1 and Figure 1).

Several other properties of the Trapezium cluster strengthen the conclusion that this is the most likely candidate for being the parent of AE Aur, $`\mu `$ Col, and $`\iota `$ Ori. First, the Trapezium is a very young cluster, $``$2 Myr (Palla & Stahler, 1999); its density ($`>`$20,000 stars pc-3 in the center) is still high enough for stellar encounters to occur. At the same time, the Trapezium is old enough to have existed when the runaways left the cluster $``$2.5 Myr ago. Secondly, the Trapezium shows a strong mass segregation (Zinnecker, McCaughrean & Wilking, 1993; Hillenbrand & Hartmann, 1998); this concentration of massive stars increases the probability for dynamical encounters between stars. Thirdly, the binary fraction in the Trapezium is high, 60–100% (Prosser et al., 1994; Weigelt et al., 1999). This also increases the chance of dynamical encounters since binary-binary collisions are the most efficient.

## 3 A supernova in Upper Scorpius

Blaauw (1952) identified the O9.5V star $`\zeta `$ Oph as a runaway originating in the Sco OB2 association. The star could either have left the Upper Scorpius subgroup $``$1 Myr ago or the Upper Centaurus Lupus subgroup $``$3 Myr ago. The intrinsic properties of $`\zeta `$ Oph (observed rotational velocity $`v_{\mathrm{rot}}\mathrm{sin}i=350`$ km s-1 and He abundance $`Y=0.40`$) indicate that the star previously experienced mass transfer in a close binary system. As $`\zeta `$ Oph is single at present (Gies & Bolton, 1986), the binary must have dissociated sometime in the past. This led to the suggestion that $`\zeta `$ Oph is a runaway created in a binary supernova explosion. Finding a compact object formed in the same event would prove that this assumption is correct.

Radio pulsars are the only neutron stars for which reliable and accurate proper motion measurements are available. Of all pulsars in the Taylor, Manchester & Lyne (1993) catalog, only seven are within 1 kpc, and have proper motions with better than 10% accuracy. Six of the seven cannot be related to $`\zeta `$ Oph, based on their (three-dimensional) position and velocity relative to $`\zeta `$ Oph, their position and velocity relative to the Galactic plane, or their characteristic age $`P/(2\dot{P})`$ (see HBZ for details). The pulsar that remains is PSR J1932$`+`$1059 (a.k.a. B1929$`+`$10); it has a characteristic age of $``$3 Myr, and it traversed the Upper Scorpius region about 1 Myr ago if its (unknown) radial velocity $`v_{\mathrm{rad}}=200\pm 50`$ km s-1 (cf. Figure 2).

The pulsar currently moves away from the Galactic plane with a $`z`$-velocity of $``$40 km s-1, and is located at a Galactic latitude of $`b4`$ degrees. Assuming that most neutron stars are created in or near the Galactic disk, PSR J1932$`+`$1059 must have formed either recently or some 50 Myr ago, when its past orbit again crossed the Galactic plane (e.g., Blaauw & Ramachandran, 1998). Taking into account its characteristic age, it is natural to assume that the pulsar was formed recently. The only site of active or recent star formation along the pulsar’s path is Upper Scorpius, and this young stellar group therefore is the only likely birth-site for PSR J1932$`+`$1059.

We integrated the orbits of $`\zeta `$ Oph, the pulsar, and Upper Scorpius back in time in a standard Galactic potential. We performed $`3\times 10^6`$ such integrations to sample the error distibutions in position and velocity. The main uncertainties are the errors in the parallax of $`\zeta `$ Oph ($`7.1\pm 0.7`$ mas) and the pulsar ($`5\pm 1.5`$ mas, Campbell 1995), and the remaining range in $`v_{\mathrm{rad}}`$. The distribution of the minimum distance between $`\zeta `$ Oph and the pulsar is consistent with zero distance, i.e., with both objects being in the same location, $`1.0\pm 0.1`$ Myr ago in Upper Scorpius (Figure 2). This is strong evidence for the binary supernova scenario.

The kinematics of the expanding HI shell which surrounds Upper Scorpius requires a supernova explosion 1–2 Myr ago, and the present-day mass function of the subgroup suggests that originally one more massive star or binary ($``$40 $`M_{}`$) must have been present (de Geus, 1992). The simplest interpretation is that this was a close binary containing $`\zeta `$ Oph and the progenitor of PSR J1932$`+`$1059.

The value of $`P/2(\dot{P})`$ is an uncertain age indicator, and the $`3`$ Myr for PSR J1932+1059 is consistent with the kinematicl age of 1 Myr derived here. The implied period at birth is 0.18 seconds; the current period is 0.22 seconds.

Pulsars are expected to receive a kick velocity $`\stackrel{}{v}_{\mathrm{kick}}`$ at birth (e.g., Lai, 2000). Observations of the ensemble of pulsars suggest that the magnitude of $`\stackrel{}{v}_{\mathrm{kick}}`$ is a few hundred km s-1 (Hartman, 1997; Hansen & Phinney, 1997). Assuming that $`\zeta `$ Oph and PSR J1932+1059 originated in the same binary allows an individual determination of $`\stackrel{}{v}_{\mathrm{kick}}`$. Based on the magnitude of the space velocities, and the angle between the orbits of $`\zeta `$ Oph and the pulsar, we obtain $`|\stackrel{}{v}_{\mathrm{kick}}|=350\pm 50`$ km s-1. New VLBI observations of the proper motion and parallax of PSR J1932+1059 are being obtained by Campbell (priv. comm.), and will make it possible to improve this estimate further.

## 4 Conclusions

The cases described in the previous two sections provide the first specific evidence that both the binary-supernova scenario and the dynamical ejection scenario produce runaway stars. This result is based on a detailed analysis of the orbits of three runaway stars, in contrast to earlier investigations which mainly focused on the statistical properties of a set of runaway stars.

Determination of the fraction of the runaway stars created by either mechanism will put strong constraints on cluster formation theories and on stellar evolution theories. Numerical simulations such as those performed by Portegies Zwart (1999) show that runaway statistics can put limits on, for example, the number of primordial binaries. However, the current samples of runaway stars and pulsars with accurate astrometry are severely incomplete. The Hipparcos Catalog is complete only for $`V<7.39`$ mag (depending on latitude), and less than a third of the O and B stars in it have a measured radial velocity. Because of beamed radio emission, we cannot observe all pulsars, and not all of those that do radiate in our direction have been found in the Solar neighbourhood; of these, only a few have an accurately measured proper motion. Even so, the available data supports the tentative conclusion that both mechanisms contribute about equally to the production of runaway stars (see HBZ).

The approach followed here promises many new results once the next generation of astrometric satellites, e.g., FAME and in particular GAIA, are launched and VLBI techniques are developed fully. These will improve the accuracy of the astrometry for stars and pulsars into the micro-arcsecond regime. With a fainter limiting magnitude, many more runaways will have well-determined positions and velocities. It will then be possible to identify the parent clusters of these objects, and to learn much about the ages and kick velocities of individual pulsars.

It is a pleasure to thank Adriaan Blaauw, Bob Campbell, Nicolas Cretton, Ed van den Heuvel, Rob den Hollander, Michael Perryman and Simon Portegies Zwart for useful comments and suggestions.


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# Inferences from the dark sky: Olbers’ paradox revisited

## 1 Introduction

The observation that the sky at night is dark seems to be in conflict with the idea of an infinite Universe. If the Universe is infinite and contains an unlimited number of stars, our line of sight should meet a star in every direction we observe. Therefore, there should be no apparent gaps between stars on the celestial sphere. Moreover, repeating an argument originally attributed to de Cheseaux (1718-1751) , we note that, in an infinitely populated Universe, the number of stars contained in a spherical shell of radius $`r`$ is $`4\pi nr^2dr`$, where $`n`$ is the number of stars per unit volume. If $`L`$ is the absolute luminosity of a star, the intensity of light at a distance $`r`$ is $`I=L/4\pi r^2`$. Hence the generic shell produces a lighting (in the centre of the shell) equal to $`nLdr`$. Since there is an infinite number of shells, the lighting, in every point of the Universe, should be infinite!

But the sky at night is dark. This apparent contradiction has been named Olbers’ Paradox, following the publication in 1823 of H. W. Olbers’ paper ”On the Transparency of Space” . However, the first assertions about the conflict between the dimensions of the Universe and the nocturnal darkness can be traced back to Digges (1576), Kepler (1610) and Halley (1721) .

Many explanations were given during the centuries in attempts to resolve the paradox. Olbers suggested the presence of interstellar dust obscuring the farthest stars, but simple thermodynamical considerations by J. Herschel (1848)  soon ruled out this explanation. Others invoked hypotheses that required a hierarchic distribution of stars . In 1917 Shapley suggested the idea of an ”island-universe”, that is a limited spatial extension of the stellar system, as a resolution of the paradox. After the discovery of the expansion of the Universe, the redshift was proposed as the fundamental mechanism necessary to ”cut” the radiation coming from the farthest galaxies, hence assuring the darkness of night.

Harrison  suggested that the paradox does not exist even in the context of a classical Universe, in the framework of which it was conceived, because there are too few stars and their lifetimes are too short. In other words the Universe does not contain enough energy to produce a bright sky. Nevertheless, in current literature there are still many misunderstandings about the paradox. It is often explained using the redshift, which, on the contrary, does not have a relevant role . In fact detailed calculations show that in our Universe the luminosity of the sky is determined to order of magnitude by the lifetime of the galaxies, and only affected by a factor of two by the expansion of the Universe (see , which also gives a survey of the recent literature on the subject).

The classical formulation of Olbers’ Paradox tries to explain the fact that the night is dark. In contrast, in the present paper, we use this observed fact to put some constraints on a simple euclidean-newtonian cosmological model. We then draw several necessary conclusions about the origin of the Universe (i.e. the Stellar System) at a finite time in the past.

## 2 The cosmological model

The model of space-time used here is the classical euclidean-newtonian one. The Universe is a euclidean manifold $`\mathrm{}\times \mathrm{}^3`$, with a euclidean metric on $`\mathrm{}^3`$. The time we use is the absolute time of Newton. The generic event is singled out by orthogonal cartesian coordinates $`(t,\stackrel{}{x})\mathrm{}\times \mathrm{}^3`$ . Therefore space has an infinite extension and is isotropic, homogeneous and flat in every region and so it coincides with Newton’s absolute space. The simultaneity we refer to is the newtonian absolute simultaneity. The light signals propagate on euclidean straight lines and the speed of light is finite and equal to $`c`$.

In this model, all matter is in the form of stars. They are distributed in a homogeneous and isotropic way in the regions they fill. Therefore, there are no bunches of stars, such as clusters, galaxies, etc. The number of stars per unit volume does not change with time. This hypothesis is equivalent to assuming that the lifetime of a ”virtual star” is, a priori, unlimited. From an astrophysical point of view, it means that a star does not have chemical, nuclear or gravitational evolution. Of course, based on current knowledge of stellar evolution, this is not true. Yet, from the cosmological point of view, this idea is reasonable if we admit an uninterrupted sequence of stellar generations. For every star that dies, a new one comes up, so the density of ”active” stars does not change over time. As we will see, the comparison of the model with the experimental evidence of the dark at night will allow us to decide between the hypothesis of an ”eternal” stellar system (i.e. an infinite number of generations) or the hypothesis of a stellar system born at a finite time in the past.

Of course, the adopted model does not describe any of the main properties of the contemporary models (such as expansion, curvature, red shift, etc.). Yet, we have chosen this model for two reasons. The first is its metric simplicity, which will let us introduce the concept of ”lookout limit” without mathematical complexity. The second reason is that this model coincides with the model of classical newtonian space-time, historically adopted by Halley, Olbers, Shapley, until the Einstein paper on cosmology (1917) . Finally, we want to note that the closer the global curvature is to zero, the more the euclidean model approximates the curved space-time.

## 3 Lookout limit and background radiation energy density

Let us think of the stars as uniformly distributed in space. We then suppose that each star occupies an average volume $`V`$. Furthermore, each star has a section of area $`\sigma `$. Thus, the probability that our line of sight meets a star surface is

$$p=\frac{\sigma }{V^{2/3}}.$$
(1)
Our line of sight is certain to meet a star, if we observe a number $`N`$ of elementary volumes $`V`$, lined up in sequence, equal to

$$N=\frac{V^{2/3}}{\sigma }.$$
(2)
This is true, of course, if the stars are distributed completely at random in their respective volumes.
The distance reached by the line of sight before meeting a star surface is therefore

$$\delta =V^{1/3}\frac{V^{2/3}}{\sigma }=\frac{V}{\sigma }.$$
(3)
We call this distance lookout limit, after Harrison. It is well known that this quantity coincides with the mean free path $`\lambda `$ of a photon ; in fact $`V=1/n`$, where $`n`$ is the number of stars per unit volume and

$$\lambda :=\frac{1}{\sigma n}=\frac{V}{\sigma }=\delta .$$
(4)
Following Harrison and Kelvin , we will derive an expression for the fraction of sky covered by stellar discs, and then a formula for the radiation energy density (at the point of the observer) due to the whole stellar system.
Let us consider a spherical shell of radius $`r`$ and thickness $`dr`$. Let $`\mathrm{\Omega }(r)`$ be the solid angle free of stellar discs up to the shell $`r`$. Let $`\mathrm{\Delta }\mathrm{\Omega }(r)`$ be the solid angle intercepted by the stars present on the shell $`r`$. The fraction of solid angle intercepted by stars on the shell $`r`$ is

$$\frac{\mathrm{\Delta }\mathrm{\Omega }}{\mathrm{\Omega }}=\frac{totalstellararea}{totalshellarea}=\frac{n\sigma 4\pi r^2dr}{4\pi r^2}=n\sigma dr.$$
(5)
After integration, we obtain an expression for the solid angle still free of stellar discs after a radial path $`r`$

$$\mathrm{\Omega }(r)=\mathrm{\Omega }_0e^{n\sigma r}$$
(6)
where $`\mathrm{\Omega }_04\pi `$.
The solid angle intercepted by the stellar surfaces after a path $`r`$ is therefore

$$\mathrm{\Omega }_0\mathrm{\Omega }(r)=\mathrm{\Omega }_0(1e^{n\sigma r}).$$
(7)
Hence the fraction of intercepted solid angle is

$$\alpha =\frac{\mathrm{\Omega }_0\mathrm{\Omega }(r)}{\mathrm{\Omega }_0}=1e^{n\sigma r}.$$
(8)
$`\alpha `$ is the fraction of sky covered by stellar discs out to the radius $`r`$. We note that if the stellar distribution is spatially unlimited, we can push $`r\mathrm{}`$, and then $`\alpha 1`$, i.e. the whole sky is covered by stars.
Also important is the relation

$$u(r)=4u^{}(1e^{n\sigma r}),$$
(9)
where $`u(r)`$ is the radiation energy density at the centre of a sphere of radius $`r`$, due to all the stars contained in the sphere, and $`u^{}`$ is the radiation energy density at the surface of a star.
This relation can be derived as follows.
In a time $`dt`$ a star emits an energy $`dE=Ldt`$, where $`L`$ is the star’s luminosity. This energy spreads (in the time $`dt`$) on a volume $`4\sigma cdt`$, where $`4\sigma `$ is the surface area of a star with a section of area $`\sigma `$. Therefore we can write $`dE=4u^{}\sigma cdt`$, where $`u^{}=L/(4\sigma c)`$ is the radiation energy density at the surface of the star. The radiated energy $`dE`$ travels until it reaches a distance $`r`$ from the star. Then, in the same time $`dt`$ as before, it spreads on a volume $`4\pi r^2cdt`$. Therefore the radiation energy density at a distance $`r`$ from the source is

$$u=\frac{dE}{4\pi r^2cdt}=\frac{Ldt}{4\pi r^2cdt}=\frac{u^{}\sigma }{\pi r^2}.$$
(10)
Now, the number of stars on a shell of radius $`r`$ is

$$4\pi r^2ndr,$$
(11)
and the fraction of free sky, i.e. not covered by stellar discs at a distance $`r`$ from the observer, is (see eqs. (6), (8))

$$\frac{\mathrm{\Omega }(r)}{\mathrm{\Omega }_0}=e^{n\sigma r}.$$
(12)
Therefore the number of stars not obscured by other stars, i.e. visible at the centre of the shell, is

$$4\pi r^2ndre^{n\sigma r},$$
(13)
and the contribution to the radiation energy density at the centre of the shell due to the stars on the shell is

$$du=4\pi r^2ndre^{n\sigma r}\frac{u^{}\sigma }{\pi r^2}=4u^{}\sigma ne^{n\sigma r}dr.$$
(14)
Integrating this relation between $`0`$ and $`r`$, we obtain formula (9).
Hence $`u`$ represents the energy density of the background sky, or what is today called extragalactic background light. We note that $`u=4u^{}`$ in every star distribution extending to $`r\lambda =1/n\sigma `$. For an infinite spatial extension of the stellar system, the background sky energy density must be of the same order of that on the surface of a star.
The experimental condition of dark sky can be expressed in this context as

$$uu^{}.$$
(15)
We note that the presence of the factor $`e^{n\sigma r}`$ (which accounts for the mutual absorption of light by stars in the Universe) produces a lowering of lighting at any point in space from $`\mathrm{}`$ to $`4u^{}`$.

## 4 Study of the model

We are now able to examine all the cases suggested by the proposed model using the concept of lookout limit, having adopted absolute newtonian space and time, and having supposed that they both have an infinite extension.
For the stellar system, we have the two following possibilities:
I) The distribution of the stellar system is spatially infinite.
II) The distribution of the stellar system is spatially finite. We suppose then that it has a spherical symmetry with a radius $`R`$.
In case I) we can distinguish two subcases:
Ia) The stellar system has existed from an infinite time in the past.
Ib) The stellar system was ”turned on” (all the stars together and simultaneously) at a time $`t_0=T`$ in the past ($`T>0`$)(we take $`t=0`$ as the present time).
In case Ia) it is evident that the sky at night must be luminous. In fact every line of sight should necessarily intercept, sooner or later, a star surface ($`\alpha =1`$). Therefore the celestial sphere must appear luminous, completely filled up by stellar discs, without dark spaces among stellar discs ($`u=4u^{}`$). Case Ia), a spatially infinite Universe, is the model adopted by Halley and Olbers, on the grounds of newtonian considerations. It is in evident conflict with observation, a conflict historically known as Olbers’ Paradox.
In case Ib), only the radiation of stars contained in a sphere of radius $`h=cT`$ (cosmological horizon) can reach us. The radius of this sphere must be compared with the value of the lookout limit $`\lambda `$. We can distinguish the following subcases.
Ib1) If $`\lambda >cT`$ then the night sky could turn out to be ”dark”, that is

$$u(cT)<u(\lambda )=4(1\frac{1}{e})u^{}.$$
(16)
In fact, the lines of sight can extend outward to a distance of $`r=\lambda `$, beyond the ”border” $`r=cT`$ of the stellar system. This situation is consistent with the observed evidence.
Ib2) If $`\lambda <cT`$ then the sky at night must be ”luminous”, that is

$$u(cT)>4(1\frac{1}{e})u^{}.$$
(17)
Of course this possibility is excluded by the experimental evidence.
Let us now study case II). We have two sub-cases here as well:
IIa) The stellar system has existed from an infinite time in the past ($`t_0=\mathrm{}`$);
IIb) The stellar system was ”turned on” at a time $`t_0=T`$ in the past.
In case IIa) we can compare $`\lambda `$ with the radius R of the stellar system:
IIa1) If $`\lambda >R`$ then the night sky could be ”dark”, i.e. $`u(R)<4(11/e)u^{}`$.
IIa2) If $`\lambda <R`$ then the night sky should be ”luminous”, i.e. $`u(R)>4(11/e)u^{}`$.
The first case is in apparent agreement with the empirical evidence. Yet we observe that the assumptions ”R finite” and ”$`t_0=\mathrm{}`$” create problems in the dynamical stability of the system. From the point of view of newtonian mechanics, a homogeneous sphere, with a finite radius and a negligible angular momentum, made of particles interacting only by gravity, has to collapse inwards upon its geometrical centre in a finite time. For such dynamical reasons case IIa1) offers little of physical interest and can be ruled out.
In case IIb), stars were born at a time $`t_0=T`$ in the past. The quantities to be compared are now the lookout limit $`\lambda `$, the radius $`R`$ of the stellar system, and the horizon $`h=cT`$ of the observable spherical region of the stellar system. We have therefore $`6`$ ($`=3!`$) different cases. Their analysis is summarized by the following table.

IIb1) $`cT<\lambda <R`$ (dark sky: $`u(cT)<4(11/e)u^{}`$)

IIb2) $`\lambda <cT<R`$ (luminous sky: $`u(cT)>4(11/e)u^{}`$)

IIb3) $`\lambda <R<cT`$ (luminous sky: $`u(R)>4(11/e)u^{}`$)

IIb4) $`R<\lambda <cT`$ (dark sky: $`u(R)<4(11/e)u^{}`$)

IIb5) $`cT<R<\lambda `$ (dark sky: $`u(cT)<4(11/e)u^{}`$)

IIb6) $`R<cT<\lambda `$ (dark sky: $`u(R)<4(11/e)u^{}`$).
We should point out that in cases IIb) also, with $`R<\mathrm{},t_0=T`$, there could be problems of dynamical instability. We can say that the collapse of the spherical stellar system is unavoidable; nevertheless we can think that the collapse is not observable if we suppose that it is very slow compared with the cosmic time scale (T) (speed of collapse $`c`$).
It is interesting to note that Newton himself investigated the problem of the dynamical stability of a finite spherical system of stars. He knew that such a system should have collapsed after a finite time inwards upon its centre of mass. But, strangely enough, he avoided calculating the time for gravitational collapse. Only in 1902, did Lord Kelvin complete the first cosmological calculus on the collapse time of the whole stellar system . He found that the collapse time does not depend on the initial size of the system. Instead, it depends only on its initial density

$$t_k=\left(\frac{3\pi }{32G\rho _0}\right)^{1/2}.$$
(18)
Assuming an average interstellar distance of 1 pc and a mean mass of 1 solar mass, Kelvin obtained a time for the collapse equal to $`20\times 10^6`$ years. Yet, Kelvin used classical arguments: he ignored the relativistic limit of the speed of light and therefore he obtained such a short collapse time that it was not realistic if compared with the cosmic time scale. If we take into account the limiting speed of light $`c`$, then the collapse time cannot be less than the radius of the universe divided by $`c`$, because the various regions will collapse, at the fastest, with a speed equal to $`c`$.

## 5 Conclusions

The comparison of the cases presented in the above section with the experimental evidence of the dark sky at night, allows us to eliminate cases Ia, Ib2, IIa2, IIb2, IIb3. They produce a luminous sky at night. Only cases Ib1, IIb1, IIb4, IIb5, IIb6 are physically admissible, because they are consistent with the experimental evidence. What property do they share?

The main consideration is that all these cases imply the birth of the Stellar System at a finite time in the past. We note that our model, together with the evidence of the dark sky, is not able to discriminate between a Universe with a finite radius and one with an infinite radius.

Therefore the conclusion that can be drawn from our model is that the experimental evidence of the dark sky implies that the Stellar System was born at a finite time in the past. This important observation was not formulated by Olbers or others (Halley, Kelvin, etc.). Olbers would have been able to infer, from the observed fact of a dark night sky, the birth of the cosmos at a finite time in the past. This could happen because the cosmological model adopted by Olbers (and more or less explicitly by all the scientists until Einstein) is the newtonian one described in section 2. The lookout limit introduced by Harrison is a useful concept which has allowed us to obtain a deeper and more effective understanding of the model.

We want to emphasize that other authors have focused particularly on the luminous lifetime of single stars. But this has prevented them from reaching the relevant conclusions about the lifetime of the whole stellar system, i.e. the Universe. The main hypothesis that allowed us to obtain information about the lifetime of the Universe (the Stellar System) is the one of the ”virtual star”, i.e. a fictitious luminous source that, in principle, has an infinite life. Successive generations of real stars can be modelled as a single virtual star without an a priori fixed lifetime. The check with the observational evidence ($`uu^{}`$) determines, at this point, the lifetime of the virtual star, i.e. of the whole Stellar System. In other words, we could say that classical physics (without hypotheses on nuclear reactions and expansion of the Universe) is able to explain the nocturnal darkness of the sky only by requiring a finite lifetime of the Stellar System.

Finally we want to observe that several authors (e.g. Weinberg) state that in a Big Bang cosmology there is no paradox because the contribution of the various stellar generations is cut at a finite time in the past . This is not always true from our point of view, because we have seen that we can have a ”Big Bang cosmology” (in the newtonian sense, namely that the stellar system was ”turned on” in the past), which nonetheless produces a luminous sky (cases Ib2, IIb2, IIb3). In conclusion, Olbers would not have been able to infer the expansion of the Universe from the observation of the dark sky at night, as several authors  seem to suggest. On the contrary, Olbers and other authors (from the 18th to the early 20th centuries) would have been able to assert that the Universe has had a temporal origin in the past.

Acknowledgements
The authors wish to thank the anonymous referee for useful comments, T.J. Lindsey for style suggestions, and the nice Irish Pub ”Crazy Patrick”, where this paper was conceived.


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# Origin and pressure dependence of ferromagnetism in 𝐴₂𝑀𝑛₂𝑂₇ pyrochlores (𝐴=𝑌, 𝐼𝑛, 𝐿𝑢, and 𝑇𝑙)

## Abstract

Non-conventional mechanisms have been recently invoked in order to explain the ferromagnetic ground state of $`A_2Mn_2O_7`$ pyrochlores ($`A=Y`$, $`In`$, $`Lu`$, and $`Tl`$) and the puzzling decrease of their Curie temperatures with applied pressure. Here we show, using a perturbation expansion in the $`MnO`$ hopping term, that both features can be understood within the superexchange model, provided that the intra-atomic oxygen interactions are properly taken into account. An additional coupling between the $`Mn`$ ions mediated by the $`In(5s)/Tl(6s)`$ bands yields the higher $`T_C`$’s of these two compounds, this mechanism enhancing their ferromagnetism for higher pressures.

preprint: HEP/123-qed

The observation of colossal magnetoresistance (CMR) in $`Tl_{2x}In_xMn_2O_7`$ pyrochlores  challenges our understanding of this phenomenon with important technological applications. In fact, in contrast with their perovskite counterparts, these systems do not present mixed $`Mn^{3+}Mn^{4+}`$ valences, they have a small number of conduction carriers ($`10^3`$ per formula unit) and they do not exhibit Jahn-Teller effect or anomalous spin diffusion, denying both, the usual double exchange and the polaronic mechanisms invoked in that case. Furthermore, in spite of the similar CMR effect observed, the magnetic transition does not occur between a low temperature metal and a high temperature semiconducting state like in the perovskites, but both, the ferro and the paramagnetic phases show metallic behaviour.
These compounds belong to the larger family of $`A_2Mn_2O_7`$ pyrochlores, the metallic behaviour of the $`A=Tl`$ compound being the exception, since all other members are insulators. But they all show long range ferromagnetic ordering, and can be classified in two groups according to their transition temperatures : $`T_C15K`$ for $`A=Y`$ and $`Lu`$, while $`T_C125K`$ for $`A=In`$ and $`Tl`$.
Considering the $`Mn^{4+}O(I)Mn^{4+}`$ bond angle $`\theta `$, a ferromagnetic superexchange picture between nearest neighbour (n.n.) $`Mn`$ ions has been initially suggested . In fact, following the Goodenough-Kanamori-Anderson rules , the $`\theta 132^{}`$ of this pyrochlore structure falls into the range in which a sign reversal of the exchange constants is expected. Using the phenomenological approach for the angular dependence of the exchange interactions for the similar case of $`Cr^{3+}O^2Cr^{3+}`$ ions , Shimakawa et al.  found a slightly ferromagnetic exchange $`J`$ interaction, in agreement with the low Curie temperatures observed for $`Y_2Mn_2O_7`$ and $`Lu_2Mn_2O_7`$. Furthermore, without proposing a particular mechanism, they pointed out the possible role of the hybridisation of the $`In(5s)/Tl(6s)O(2p)Mn(3d)`$ orbitals in enhancing $`T_C`$ in these two compounds .
On the other hand, taking the ferromagnetic ordering as an experimental fact, different theories attempted to explain the CMR effect. Scattering against ferromagnetic fluctuations, relevant in this case with a very low number of carriers ; or simply hybridisation of the localised moments with the itinerant $`Tl(6s)`$ states have been invoked  as possible mechanisms for the CMR.
However, recent measurements showing a decrease of the ferromagnetic $`T_C`$ with increasing applied pressure for all $`A_2Mn_2O_7`$ compounds , have been interpreted as contradicting the original superexchange picture. The data establish that materials with lower $`T_C`$ posses a larger negative pressure shift ( $`dT_C/dP=3.8`$, $`2.5`$, $`1.6`$ and $`0.4K/GPa`$, and $`dlnT_C/dP=24.5`$, $`20.8`$, $`11.2`$ and $`0.3/GPa`$, for $`A=Lu`$, $`In`$, $`Tl`$, and $`In`$, respectively). A more exotic scenario has been suggested, with antiferromagnetic (AF) coupling between n.n. $`Mn`$ ions overcome by longer range ferromagnetic interactions, due to the frustration of the former in the pyrochlore lattice . Also the enhancement of the ferromagnetic coupling in $`Sb`$-substituted $`Tl_2Mn_2O_7`$ compounds has been discussed  as strongly supporting this new proposal. But taking into account the structural parameters of these systems, the justification of the necessary exchange constants seems difficult.
Here we show that the observed weakening of the ferromagnetism with moderate pressures can be understood within the conventional superexchange model, provided that the intra-atomic Hund interaction $`J_H^{Ox}`$ of the oxygen has a significant value while the excitation energy $`\mathrm{\Delta }`$ of the $`O(2p)`$ electrons to the empty $`e_g`$ levels of the localised $`Mn`$ ions is small. Comparison with other oxides should indicate that these can be reasonable assumptions. The resulting exchange interaction $`J`$ is ferromagnetic due to the $`Mn^{4+}O(I)Mn^{4+}`$ bond angle, and when an external pressure is applied $`\mathrm{\Delta }`$ increases while the intra-atomic parameter $`J_H^{Ox}`$ remains unchanged, inducing the observed decrease of $`T_C`$. However, an additional mechanism is still necessary to account for the observed $`T_C`$’s above $`120K`$. We propose a superexchange coupling between the $`Mn(t_{2g})`$ states mediated by the $`In(5s)/Tl(6s)O(2p)`$ bands, which also explains the increase of $`T_C`$ reported later for higher pressures . Although the relevant bands become strongly spin-polarized, the ferromagnetism and the conduction in the $`Tl_2Mn_2O_7`$ compound appear to be less coupled than in the perovskites, in agreement with experimental results .
We now calculate the exchange interaction between two manganese ions of the pyrochlore lattice, forming an angle $`\theta `$ between them through an intermediate full oxygen atom $`O(I)`$. Each $`Mn`$ ion has an inert $`t_{2g}`$ core with $`s=3/2`$ and, for simplification, let us consider just a single empty $`e_g`$ orbital state (in fact, only the orbital directed towards $`O(I)`$ is relevant), onto which an $`O(2p)`$ electron can hope, provided that it has the same spin orientation, e.g. the Hund’s rule energy cost on the $`Mn`$ ion $`J_H^{Mn}`$ is taken as infinite, avoiding hops of antiparallel spins (therefore it is not necessary to include the Coulomb repulsion on the $`Mn`$ ions). The $`O(I)`$ ions mediate the superexchange interaction, the four $`2p`$ electrons moving back and forth between the $`O`$ and the two n.n. $`Mn`$ orbitals within the same plane. We call $`t`$ the $`MnO(I)`$ hopping matrix element, $`\mathrm{\Delta }`$ the energy difference between the $`O(2p)`$ levels $`(p_x,p_y)`$ and the $`e_g`$ state of each $`Mn`$ site $`(d_1,d_2)`$, $`J_H^{Ox}`$ is the Hund’s rule energy on the $`O`$ ions and $`U_p`$ the Coulomb repulsion between two holes on the same $`O`$ atom. These two last parameters are of crucial importance since they will be responsible for the ferromagnetic interaction for the relevant $`MnO(I)Mn`$ angles $`\theta `$ ($`\theta 130.8^{}`$, $`131.4^{}`$, $`132.4^{}`$ and $`133.4^{}`$ for $`A=In`$, $`Lu`$, $`Y`$ and $`Tl`$, respectively).
When the core spins of two n.n. $`Mn`$ ions $`\stackrel{}{s_1}`$ and $`\stackrel{}{s_2}`$ are ferromagnetically aligned, the possible occupations for the parallel hopping spins (e.g. up spins) are: $`d_1p_x>`$, $`d_1p_y>`$, $`d_1d_2>`$, $`p_xp_y>`$, $`p_xd_2>`$ and $`p_yd_2>`$. The corresponding Hamiltonian reads:

$$H_{}=\left(\begin{array}{cccccc}\mathrm{\Delta }& 0& t_2& t_1& 0& 0\\ 0& \mathrm{\Delta }& t_1& t_2& 0& 0\\ t_2& t_1& 2\mathrm{\Delta }+U_pJ_H^{Ox}& 0& t_2& t_1\\ t_1& t_2& 0& 0& t_1& t_2\\ 0& 0& t_2& t_1& \mathrm{\Delta }& 0\\ 0& 0& t_1& t_2& 0& \mathrm{\Delta }\end{array}\right)$$
(1)
where $`t_1t\mathrm{cos}(\theta /2)`$ and $`t_2t\mathrm{sin}(\theta /2)`$, which we solve for $`t/\mathrm{\Delta }<1`$ up to fourth order in the hopping element $`t`$. In previous calculations  the $`J_H^{Ox}`$ and $`U_p`$ terms have been omitted, loosing the contribution that can give rise to the ferromagnetic interaction. We obtain:

$`E_{}={\displaystyle \frac{2t^2}{\mathrm{\Delta }}}+{\displaystyle \frac{2t^4[1+cos^2(\theta )]}{\mathrm{\Delta }^2(\mathrm{\Delta }+\frac{U_p}{2}\frac{J_H^{Ox}}{2})}}+`$ (2)
$`+{\displaystyle \frac{2t^4(U_pJ_H^{Ox})}{\mathrm{\Delta }^3(\mathrm{\Delta }+\frac{U_p}{2}\frac{J_H^{Ox}}{2})}}`$ (3)
Instead, when the two n.n. core $`Mn`$ ions are antiparallel (e.g. $`\stackrel{}{s_1}=up`$ and $`\stackrel{}{s_2}=down`$), there are three spin up and three spin down possible occupations for the four oxygen hopping electrons : $`d_1p_x,d_2p_x>`$, $`d_1p_x,d_2p_y>`$, $`d_1p_x,p_xp_y>`$, $`d_1p_y,d_2p_x>`$, $`d_1p_x,d_2p_y>`$, $`d_1p_y,p_xp_y>`$, $`p_xp_y,d_2p_x>`$, $`p_xp_y,d_2p_y>`$ and $`p_xp_y,p_xp_y>`$, where now the two first index correspond to the spins up and those after the comma to the spins down occupations, respectively. They yield the following Hamiltonian:

$$H_{}=\left(\begin{array}{ccccccccc}2\mathrm{\Delta }+U_p& 0& t_1& 0& 0& 0& t_1& 0& 0\\ 0& 2\mathrm{\Delta }+U_p& t_2& J_H^{Ox}& 0& 0& 0& t_1& 0\\ t_1& t_2& \mathrm{\Delta }& 0& 0& 0& 0& 0& t_1\\ 0& J_H^{Ox}& 0& 2\mathrm{\Delta }+U_p& 0& t_1& t_2& 0& 0\\ 0& 0& 0& 0& 2\mathrm{\Delta }+U_p& t_2& 0& t_2& 0\\ 0& 0& 0& t_1& t_2& \mathrm{\Delta }& 0& 0& t_2\\ t_1& 0& 0& t_2& 0& 0& \mathrm{\Delta }& 0& t_1\\ 0& t_1& 0& 0& t_2& 0& 0& \mathrm{\Delta }& t_2\\ 0& 0& t_1& 0& 0& t_2& t_1& t_2& 0\end{array}\right).$$
(4)
We calculate again the ground state energy up to $`t^4`$ order, obtaining:

$`E_{}={\displaystyle \frac{2t^2}{\mathrm{\Delta }}}+{\displaystyle \frac{2t^4}{\mathrm{\Delta }[(\mathrm{\Delta }+\frac{U_p}{2})^2\frac{(J_H^{Ox})^2}{4}]}}{\displaystyle \frac{t^4J_H^{Ox}sin^2(\theta )}{2\mathrm{\Delta }^2[(\mathrm{\Delta }+\frac{U_p}{2})^2\frac{(J_H^{Ox})^2}{4}]}}+{\displaystyle \frac{3t^4U_p}{\mathrm{\Delta }^2[(\mathrm{\Delta }+\frac{U_p}{2})^2\frac{(J_H^{Ox})^2}{4}]}}`$ (5)
$`{\displaystyle \frac{t^4(J_H^{Ox})^2sin^2(\theta )}{4\mathrm{\Delta }^2(\mathrm{\Delta }+\frac{U_p}{2})[(\mathrm{\Delta }+\frac{U_p}{2})^2\frac{(J_H^{Ox})^2}{4}]}}+{\displaystyle \frac{t^4[2(U_P)^2(J_H^{Ox})^2]}{2\mathrm{\Delta }^3[(\mathrm{\Delta }+\frac{U_p}{2})^2\frac{(J_H^{Ox})^2}{4}]}}{\displaystyle \frac{t^4(J_H^{Ox})^2U_p}{4\mathrm{\Delta }^3(\mathrm{\Delta }+\frac{U_p}{2})[(\mathrm{\Delta }+\frac{U_p}{2})^2\frac{(J_H^{Ox})^2}{4}]}}`$ (6)
The difference of the leading eigenvalues is:

$`J=E_{}E_{}={\displaystyle \frac{2t^4cos^2(\theta )}{\mathrm{\Delta }[(\mathrm{\Delta }+\frac{U_p}{2})^2\frac{(J_H^{Ox})^2}{4}]}}+{\displaystyle \frac{t^4[U_pcos^2(\theta )(\frac{J_H^{Ox}}{2})sin^2(\theta )]}{\mathrm{\Delta }^2[(\mathrm{\Delta }+\frac{U_p}{2})^2\frac{(J_H^{Ox})^2}{4}]}}{\displaystyle \frac{t^4(J_H^{Ox})^2(2sin^2(\theta ))}{4\mathrm{\Delta }^2(\mathrm{\Delta }+\frac{U_p}{2})[(\mathrm{\Delta }+\frac{U_p}{2})^2\frac{(J_H^{Ox})^2}{4}]}}`$ (7)
Thus, to the AF result of Ref.  adds now other terms, which depending on the $`\mathrm{\Delta }`$, $`J_H^{Ox}`$ and $`U_p`$ values, can yield a ferromagnetic coupling for the bond angle of these pyrochlores, without the necessity of invoking more complicated mechanisms. As expected $`J_H^{Ox}`$ must have a significant value, as it is the case for other oxides in which this parameter also induces a ferromagnetic interaction, e.g. $`NaNiO_2`$ with $`\theta 95^{}`$ for n.n. $`Ni`$ ions within the same layer . For $`\theta =135^{}`$ the condition is :

$$J_H^{Ox}>\frac{4}{3}(\mathrm{\Delta }+\frac{U_p}{2})$$
(8)
which means that the $`O(2p)`$ levels must be close to the $`Mn(e_g)`$ state. In Fig. 1 we plot the angular dependence of Eq.(5) for possible parameters for the $`A_2Mn_2O_7`$ pyrochlores.
This first calculation shows that the superexchange alone can explain the ferromagnetic ordering of these compounds at $`15K`$. Furthermore, the observed decrease of $`T_C`$ with pressure, inducing an isomorphic reduction of the lattice parameters , appears as a confirmation of this mechanism : the directional $`e_g`$ levels of the $`Mn`$ ions will go up in energy, instead the intra-atomic $`J_H^{Ox}`$ will not significantly change, the increase of the $`MnO`$ hopping term enhancing the resulting effect. Fig. 2 shows the change of the exchange interaction $`J`$ with $`\mathrm{\Delta }`$, which is an increasing parameter with the applied pressure. In real systems the variation will be stronger due to the simultaneous increase of $`t`$.
However, the systematic study performed by Shimakawa et al.  evidences that there is an additional feature determining $`T_C`$, since the $`A=In`$, $`Tl`$ compounds, with similar $`MnO`$ distances and angles to those of $`A=Y`$, $`Lu`$, have both $`T_C125K`$. The important difference between both groups of pyrochlores is the nature of the $`A`$ atom surrounded by inequivalent oxygen ions (we call $`O(II)`$ the closer ones), which is reflected in the corresponding band structures. For the Y compound the first unoccupied states correspond to the $`Mn(e_g)`$ levels, the $`YO(II)O(I)`$ states having higher energies, i.e. the crystal field splitting is much smaller than the exchange gap. Then the only relevant mechanism is the one calculated before, yielding $`T_C15K`$.
In contrast, the $`In(5s)`$ and $`Tl(6s)O(II)O(I)`$ bands are lower in energy and strongly hybridised with the empty $`e_g`$ orbital . Therefore, the $`t_{2g}`$ electrons can go to these states of energy $`\mathrm{\Delta }^{}`$ (we call $`t^{}`$ the corresponding matrix element) and due to the large $`J_H^{Mn}`$ this hopping will induce a strong ferromagnetic interaction $`J^{}`$ between the $`Mn`$ ions. We can estimate:

$$J^{}\frac{t^2}{\mathrm{\Delta }^{}}110K$$
(9)
which yields $`t^{}0.15eV`$ for $`\mathrm{\Delta }^{}2eV`$. The majority-spin empty band will be strongly polarised parallel to the moment of the $`Mn`$ ions.
On the other hand, we can understand why the conduction band in $`Tl_2Mn_2O_7`$ is strongly polarised in the opposite direction: it will lower its energy by hybridisation with the $`O(I)`$ states that do not participate in the superexchange ferromagnetic coupling.
In those cases, in which the conduction band approaches (as in A=In) or crosses the Fermi level (for A=Tl), we expect a relative smaller decrease of the critical temperature (as observed ) and even a rise of $`T_C`$ for higher pressures, when these bands are modified lowering further their energies. Recent measurements  confirm this change of tendency for $`Tl_2Mn_2O_7`$, i.e. they show an initial decrease followed by an increase of $`T_C`$ with applied pressure, the minimum critical temperature corresponding to $`10Kbar`$. We expect a similar behaviour for A=In, without an enhanced change in the magnetism due to the eventual insulator-metal transition induced by higher pressure. The increase of the ferromagnetic coupling in $`Tl_2(Mn_{2x}Sb_x)O_7`$ (the $`Sb`$-substitution acting as a negative pressure) can be understood within the same picture, more easily than considering  an AF superexchange coupling between n.n. $`Mn`$ ions.
We conclude that when the oxygen intra-atomic interactions are properly included in the calculations, the superexchange between n.n.$`Mn`$ ions suffices to explain the ferromagnetic $`T_C^{}s15K`$ of $`A_2Mn_2O_7`$ pyrochlores, as well as their decrease with applied pressure. Instead, an additional mechanism involving the $`In(5s)/Tl(6s)O(2p)Mn(e_g)`$ bands and the $`t_{2g}`$ electrons is neccessary to account for the higher $`T_C^{}s125K`$ and their non-monotonic behaviour with pressure.