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# Ordering mechanisms in confined diblock copolymers

## 1 Introduction

Block copolymers (BCP) are polymeric systems where each polymer chain is composed of several chemically distinct homopolymer blocks, connected together by a covalent bond. At high temperatures, BCP have a disordered phase, while at low temperatures, the macroscopic phase separation is hindered because the two (or more) immiscible sub-chains cannot be detached from each other as they try to phase separate. Hence, BCP phase separate into a variety of micro-ordered structures, with characteristic size which depends on the BCP chain length and other system parameters . The morphology and structure of the prevailing phase depends on the lengths of constituent sub-chains (also called blocks), the chemical interactions between the blocks, the temperature and the chain architecture. The BCP micro-domain size ranges from about $`10`$ to several hundreds nanometers. This fundamental periodicity should be distinguished from the macro-domain size of several micrometers where one ordered phase (e.g., a lamellar phase) breaks into many domains (or grains) each having of a different orientation and separated by grain boundaries.

Block copolymers can be viewed as composite materials from the mechanical point of view . By connecting together a stiff (rod-like) block with a flexible (coil) block, one can obtain a material which is rigid, but not brittle . Moreover, the interplay between flexibility and toughness can be controlled by temperature. Different chain architecture (ring or star-like) may lead to novel mechanical and flow properties . In addition, BCPs have many industrial uses because the length scales involved are smaller or comparable to the wavelength of light. These applications include waveguides, photonic band gap materials and other optoelectronic devices  and dielectric mirrors .

Recent studies have highlighted the role of an applied electric field in creating well aligned BCP structures. An electric field has been applied to a polymer film confined by one smooth and one topographically-patterned electrodes. The field creates an instability in the polymer film which replicates the pattern on the electrode . In BCPs, electric field is effective in aligning micro-domains in a desired direction, as has been shown theoretically  and experimentally . In a thin film, for example, further removal of one polymer component can facilitate the creation of anti-reflection coatings for optical surfaces  or a surface with highly ordered features. Lastly, cylindrical domains of polystyrene (PS)/polymethylmethacrylate (PMMA) diblock copolymer have been used by Russell, Steiner, Thurn-Albrecht and co-workers as a basis to an array of long and aligned conducting domains (nano-wires) with typical size in the range of 100 nm .

The present paper deals with several mechanisms that can be used to achieve a desired ordering in a BCP melt. We consider in Sec. 2 thin films of A/B BCPs between two flat, parallel surfaces. In the disordered phase we give a description of the polymer density as a function of a pre-designed and fixed chemical pattern on the surface. The decay of surface $`q`$-modes into the bulk is analyzed on the level of a linear-response theory. The influence of confining surfaces on lamellar BCPs is studied in Sec. 3. We find that for a one dimensional striped surface pattern (composed of regions of alternating A and B preference) the lamellae are tilted with respect to the parallel surfaces. In this tilted state the lamellae adjust their periodicity to the surface one, leading to a better surface coverage. If the surface and lamellar periodicities are equal, the lamellae are formed perpendicular to the surfaces. Alignment of confined lamellae by external electric fields is studied in Sec. 4. It is shown that because different polymers have different values of the dielectric constant, the electrostatic energy favors an orientation of lamellae in a direction perpendicular to the confining electrodes. This electrostatic tendency can be used to overcome interfacial interactions with the bounding electrodes and align structures in a desired direction.

## 2 Confined di-BCP in the disordered phase

Let us consider first an A/B di-BCP melt in the high temperature and disordered state, above the Order-Disorder Temperature (ODT) defined below. The BCP is confined by one or two flat, chemically patterned surfaces. Although the bulk BCP is disordered above the ODT, there is an oscillatory decay of the A/B block correlations and resulting ordering induced by the surface is rather complex. In the vicinity of the ODT this ordering can become long range leading to a strong effect. With the definition of the order parameter $`\varphi (𝐫)\varphi _A(𝐫)f`$ as the local deviation of the A monomer concentration from its average, the bulk free energy can be written as:

$$\frac{Nb^3F_b}{k_BT}=\left\{\frac{1}{2}\tau \varphi ^2+\frac{1}{2}h\left(^2\varphi +q_0^2\varphi \right)^2+\frac{1}{6}\mathrm{\Lambda }\varphi ^3+\frac{u}{24}\varphi ^4\right\}\mathrm{d}^3r$$
(1)
$`d_0=2\pi /q_0`$ is the fundamental periodicity in the system, and is expressed by the polymer radius of gyration $`R_g`$ through $`q_01.95/R_g`$. The parameter $`\tau =2\rho N\left(\chi _c\chi \right)`$ measures the distance from the critical point ($`\tau =0`$) in terms of the Flory parameter $`\chi 1/T`$. At the critical point (or equivalently the ODT) $`\chi _c10.49/N`$. In addition, $`b`$ is the Kuhn statistical segment length, $`h=1.5\rho c^2R_g^2/q_0^2`$ and $`\rho =1/Nb^3`$ is the chain density per unit volume. $`\mathrm{\Lambda }`$ and $`u`$ are the three- and four-point vertex functions calculated by Leibler . Below we restrict ourselves to lamellar phases of symmetric BCPs ($`f=\frac{1}{2}`$, $`\mathrm{\Lambda }=0`$), and set for convenience $`c=u/\rho =1`$ throughout the paper.

BCPs  and other systems with spatially modulated phases  have been successfully described by Eq. (1) or similar forms of free energy functionals. The free energy, Eq. (1), describes a system in the disordered phase having a uniform $`\varphi =0`$ for $`\chi <\chi _c`$ (positive $`\tau `$), while for $`\chi >\chi _c`$ (negative $`\tau `$), the system is in the lamellar phase for $`f=\frac{1}{2}`$, $`\mathrm{\Lambda }=0`$, and can be described approximately by a single $`q`$-mode $`\varphi =\varphi _L\mathrm{exp}(i𝐪_\mathrm{𝟎}𝐫)`$. The amplitude of the sinusoidal modulations is given by $`\varphi _L^2=8\tau /u`$. The validity of Eq. (1) is limited to a region of the phase diagram close enough to the critical point where the expansion in powers of $`\varphi `$ and its derivatives is valid, but not too close to it, because then critical fluctuations become important . This limit employed hereafter is called the weak segregation limit.

The presence of chemically heterogeneous surfaces is modeled by adding short-range surface interactions to the free energy of the form,

$$F_s=\left[\sigma (𝐫_𝐬)\varphi (𝐫_𝐬)+\tau _s\varphi ^2(𝐫_𝐬)\right]\mathrm{d}^2𝐫_𝐬$$
(2)
The integration is carried out over the position of the confining surfaces parameterized by the vector $`𝐫_𝐬`$. The surface field $`\sigma (𝐫_𝐬)`$ has an arbitrary but fixed spatial variation and is coupled linearly to the BCP surface concentration $`\varphi (𝐫_𝐬)`$. Preferential adsorption of the A block ($`\varphi >0`$) onto the entire surface is modeled by a constant $`\sigma <0`$ surface field, resulting in parallel-oriented layers (a perpendicular orientation of the chains). One way of producing such a surface field in experiments is to coat the substrate with random copolymers . If the pattern is spatially modulated, $`\sigma (𝐫_𝐬)0`$, then the A and B blocks are attracted to different regions of the surface. The coefficient of the $`\varphi ^2`$ term in Eq. (2) is taken to be a constant surface correction to the Flory parameter $`\chi `$ . A positive $`\tau _s`$ coefficient corresponds to a suppression of surface segregation of the A and B monomers.

For simplicity we consider first BCP confined by one surface located at $`y=0`$ as is depicted in Fig. 1 (a). A generalization to two parallel surfaces is straightforward and will be given later. The surface chemical pattern $`\sigma (𝐫_s)=\sigma (x,z)`$ can be decomposed in terms of its $`q`$-modes

$$\sigma (x,z)=\underset{𝐪}{}\sigma _𝐪\mathrm{e}^{i(q_xx+q_zz)}$$
(3)
where $`𝐪=(q_x,q_z)`$, and $`\sigma _𝐪`$ is the mode amplitude. Similarly, $`\varphi `$ can be written as a sum

$$\varphi (𝐫)=\underset{𝐪}{}\varphi _𝐪(y)\mathrm{e}^{i(q_xx+q_zz)}$$
(4)
Close to the ODT the free energy is stable to second order in $`\varphi `$, and higher order terms (i.e. the $`\varphi ^4`$ term) can be neglected. Then $`\varphi (𝐫)`$ is inserted into Eq. (1) and an integration over the $`x`$ and $`z`$ coordinates is carried out. Minimization with respect to $`\varphi _𝐪(y)`$ yields the Euler-Lagrange equation

$$\left[\tau /h+\left(q^2q_0^2\right)^2\right]\varphi _𝐪+2(q_0^2q^2)\varphi _𝐪^{\prime \prime }+\varphi _𝐪^{\prime \prime \prime \prime }=0$$
(5)
Note that the equation is linear and that the Fourier harmonics $`\varphi _𝐪`$ are not coupled. The boundary conditions are rather complicated because they couple the value of the amplitude and its derivatives at the surface. They result from minimization of the full free energy expression, Eqs. (1) and (2)

$`\varphi _𝐪^{\prime \prime }(0)+(q_0^2q^2)\varphi _𝐪(0)`$ $`=`$ $`0`$ (6)
$`\sigma _𝐪/h+2\tau _s\varphi _𝐪(0)/h+(q_0^2q^2)\varphi _𝐪^{}(0)+\varphi _𝐪^{\prime \prime \prime }(0)`$ $`=`$ $`0`$ (7)
Since Eq. (5) is linear, its solution is a sum of exponentials,

$`\varphi _𝐪(y)=A_𝐪\mathrm{exp}(k_𝐪y)+B_𝐪\mathrm{exp}(k_𝐪^{}y)`$ (8)
where the modulation constant $`k_𝐪`$ and the amplitude $`A_𝐪`$ are given by

$`k_𝐪^2`$ $`=`$ $`q^2q_0^2+i\sqrt{\tau /h}`$ (9)
$`A_𝐪`$ $`=`$ $`\sigma _q\left(4\tau _s+2\mathrm{I}\mathrm{m}(k_𝐪)\sqrt{\tau h}\right)^1`$
In the above $`\mathrm{Re}(k_𝐪)>0`$ ensuring that $`\varphi _𝐪0`$ as $`y\mathrm{}`$. This restricts the solution $`\varphi _𝐪`$ to be a sum of only two (out of four) exponential terms.

The two lengths, $`\xi _q=1/\mathrm{Re}(k_𝐪)`$ and $`\lambda _q=1/\mathrm{Im}(k_𝐪)`$, correspond to the exponential decay and oscillation lengths of the $`q`$-modes, respectively. For fixed $`\chi `$, $`\xi _q`$ decreases and $`\lambda _q`$ increases with increasing $`q`$. Close to the ODT and for $`q>q_0`$ we find finite $`\xi _q`$ and $`\lambda _q(\chi _c\chi )^{1/2}`$. However, all $`q`$-modes in the band $`0<q<q_0`$ are equally “active”, i.e., these modes decay to zero very slowly in the vicinity of the ODT as $`y\mathrm{}`$: $`\xi _q(\chi _c\chi )^{1/2}`$ and $`\lambda _q`$ is finite. Therefore, the propagation of the surface imprint (pattern) of $`q`$-modes with $`q<q_0`$ into the bulk can persist to long distances, in contrast to surface patterns with $`q>q_0`$ which persist only close to the surface. The $`q=q_0`$ mode has both lengths $`\xi _q,\lambda _q`$ diverging as $`(\chi _c\chi )^{1/4}`$ for $`\chi \chi _c`$.

In Fig. 2 we give examples of the polymer morphologies in the case of three simple surface patterns. A uniform surface \[in (a), $`\sigma =\sigma _0`$ is constant\] causes exponentially decaying density modulations to propagate in the $`y`$-direction. A striped surface \[in (b), $`\sigma =\sigma _q\mathrm{cos}(qx)`$\] creates a disturbance that is periodic in the $`x`$-direction, while decays exponentially in the $`y`$-direction. The combined surface pattern \[in (c), $`\sigma =\sigma _0+\sigma _q\mathrm{cos}(qx)`$\] induces density modulations which are the sum of the ones in (a) and (b).

A more complex chemical pattern, shown in Fig. 3 (a), consists of V shaped stripes on the $`y=0`$ surface. The polymer density in parallel planes with increasing distance from the surface is shown in (b) and (c). Note how the frustration induced by the tips of surface chemical pattern \[in (a)\] is relieved as the distance from the surface increases. Surprisingly, similar morphology is observed when two grains of lamellar phase meets with a tilt angle, creating a tilt grain boundary in bulk systems.

Our treatment of confined BCP can be easily generalized to the case of two flat parallel surfaces . The governing equation is still Eq. (5), but now there are four boundary conditions instead of the two in Eqs. (6) and (7). Figure 4 shows how two simple surface patterns can be used to achieve a complex three-dimensional polymer morphology, even though the melt is in its bulk disordered phase. The stripes on the two surfaces are rotated by 90 with respect to each other. A symmetric “checkerboard” morphology appears in the mid-plane.

Up to this point, the BCP melt was assumed to be in its bulk disordered phase (above the bulk ODT point). When a melt in the lamellar phase (below ODT) is confined in a thin film, the morphology is dictated by a complex interplay between the natural periodicity and the imposed film thickness.

## 3 Confined lamellar BCP

In this section we describe the ordering of lamellar BCPs confined by one or two surfaces. The phase behavior of thin BCP films in the lamellar phase subject to uniform surface fields has been investigated numerically using self-consistent field (SCF) theory  and Monte-Carlo simulations , and was found to consist of parallel, perpendicular and mixed lamellar phase denoted $`L_{}`$, L and $`L_M`$, respectively. The latter $`L_M`$ phase has parallel lamellae extending from one surface, which are jointed in a T-junction defect with perpendicular lamellae extending from the opposite surface . At a given inter-surface spacing, increasing the (uniform) surface interactions promotes a parallel orientation with either A-type or B-type monomers adsorbed onto the surface. However, if the spacing $`L`$ between the surfaces is incommensurate with the lamellar periodicity, or the incompatibility $`\chi `$ is increased, a perpendicular orientation is favored .

In the treatment given below, a new effect can be observed when the surfaces are taken to be non-uniform, “striped”, with regions of alternating preferences to the A and B blocks \[see Fig. 1 (c)\]. The stripe periodicity $`d_x`$ is assumed to be larger than the natural (bulk) periodicity, $`d_x>d_0`$, and the stripes are modeled by

$$\sigma (x,z)=\sigma _q\mathrm{cos}(q_xx)$$
(10)
and are translational invariant in the $`z`$-direction. The surface $`q`$-mode is $`q_x=2\pi /d_x<q_0`$.

Contrary to the system above the ODT, a linear response theory assuming small order parameter as a response to the surface field is inadequate here, since the bulk phase has an inherent spatially varying structure. The surface effects are contained in the correction to the order parameter

$$\delta \varphi (𝐫)\varphi (𝐫)\varphi _b(𝐫)$$
(11)
where $`\varphi _b`$ is a “tilted” bulk lamellar phase given by

$`\varphi _b`$ $`=`$ $`\varphi _L\mathrm{cos}\left(q_xx+q_yy\right)`$ (12)
$`q_x`$ $`=`$ $`q_0\mathrm{cos}\theta ,q_y=q_0\mathrm{sin}\theta ,`$ (13)
The bulk ordering is depicted schematically as tilted lamellae in Fig. 1 (c). For the correction order parameter $`\delta \varphi `$ we choose

$$\delta \varphi (x,y)=g(y)\mathrm{cos}(q_xx).$$
(14)
This correction describes a lamellar ordering perpendicular to the surface, and commensurate with its periodicity $`d_x=2\pi /q_x`$. The overall morphology of the lamellae is a superposition of the correction field $`\delta \varphi `$ with the tilted bulk phase, having a periodicity $`d_0`$. The region where the commensurate correction field $`\delta \varphi `$ is important is dictated by the amplitude function $`g(y)`$. The total free energy $`F=F_b+F_s`$ is now expanded about its bulk value $`F[\varphi _b]`$ to second order in $`\delta \varphi `$. The variational principle with respect to $`g(y)`$ yields a master equation:

$$\left[A+C\mathrm{cos}(2q_yy)\right]g(y)+Bg^{\prime \prime }(y)+g^{\prime \prime \prime \prime }(y)=0,$$
(15)
with parameters $`A`$, $`B`$ and $`C`$ given by:

$`A=\tau /h+q_y^4,B=2q_y^2,C=\tau /h.`$ (16)
This linear equation for $`g(y)`$ is similar in form to Eq. (5) describing the density modulation of a BCP melt in the disordered phase. The lamellar phase is non-uniform and this results in a $`y`$-dependency of the term in square brackets. The above equation is readily solved using the proper boundary conditions (for more details see refs. ).

In Fig. 5 we present results for a BCP melt confined by one sinusoidally patterned surface, $`\sigma (x)=\sigma _q\mathrm{cos}(q_xx)`$, with no average preference to one of the blocks, $`\sigma =0`$, for several values of surface periodicity $`d_x`$ and for fixed value of the Flory parameter $`\chi >\chi _c`$. The main effect of increasing the surface periodicity $`d_x`$ with respect to $`d_0`$ is to stabilize tilted lamellae, with increasing tilt angle. Note that even for $`d_x=d_0`$ \[Fig. 5a\] yielding no tilt, the perpendicular lamellae have a different structure close to the surface as is induced by the surface pattern. Although the surface interactions are assumed to be strictly local, the connectivity of the chains causes surface-bound distortions to propagate into the bulk of the BCP melt. In particular, this is a strong effect in the weak-segregation regime we are considering.

So far in this section we have considered the semi-infinite problem of a BCP melt confined by one patterned surface. It is of experimental and theoretical interest to study thin films of BCP when they are confined between a heterogeneous (patterned) surface and a second chemically homogeneous surface. This situation is encountered when a thin BCP is spread on a patterned surface. The second interface is the film/air interface and is homogeneous. Usually the free surface has a lower surface tension with one of the two blocks. This bias can be modeled by adding a constant $`\sigma _0`$ term to the $`\sigma (x)`$ surface field. For simplicity, we assume that the surface at $`y=\frac{1}{2}L`$ has purely sinusoidal stripes while at $`y=\frac{1}{2}L`$ the surface is attractive to one of the A/B blocks with a constant preference:

$`\sigma (x)`$ $`=`$ $`\sigma _q\mathrm{cos}(q_xx),\text{at }y=\frac{1}{2}L,`$
$`\sigma (x)`$ $`=`$ $`\sigma _0,\text{at }y=\frac{1}{2}L\text{.}`$ (17)
A neutral surface at $`y=\frac{1}{2}L`$ is obtained as a special case with $`\sigma _0=0`$. The expression (12) for the bulk tilted phase is modified ($`yy+\frac{1}{2}L`$) in order to match the stripe surface pattern at $`y=\frac{1}{2}L`$,

$$\varphi _b=\varphi _L\mathrm{cos}\left[q_xx+q_y(y+\frac{1}{2}L)\right]$$
(18)
The homogeneous surface field at $`y=\frac{1}{2}L`$ induces a lamellar layering parallel to the surface, since the two A/B blocks are covalently linked together. The simplest way to account for this layering effect is to include an $`x`$-independent term $`w(y)`$ in our ansatz, Eq. (14), for the order parameter:

$$\delta \varphi (x,y)=g(y)\mathrm{cos}(q_xx)+w(y).$$
(19)
The tilted lamellar phase confined by one homogeneous and one patterned surface is a generalization of the mixed (perpendicular and parallel) lamellar phase, usually referred to as $`L_M`$. The latter morphology occurs when the surface imposed periodicity $`d_x`$ is equal to the bulk periodicity $`d_0`$. This “T-junction” morphology, shown in Fig. 6, has perpendicular lamellae extending from the patterned surface. The homogeneous field at the opposite surface favors a parallel orientation of the lamellae. The crossover region between the two orientations is found in the middle of the film, and its morphology depends on temperature (the $`\chi `$ parameter). The effect of the homogeneous field is evident, as parallel ordering extends from the top surface. We see here that strong enough modulated surface fields stabilize the tilted lamellar phases and, in particular, the $`L_M`$ phase.

In the discussion above we have considered ordering mechanisms where the interaction of the polymers with the confining surfaces is mediated to regions far from the surfaces because of chain connectivity. We now turn to discuss orientation of BCP films in presence of external electric fields. This is a bulk ordering mechanism that does not originate from surface interactions.

## 4 Alignment by electric fields

A well known mechanism to cause orientation or structural changes in polarized media is the “dielectric mechanism”. This effect is based on the fact that when a material with inhomogeneous dielectric constant is placed in an electric field $`E`$, there is an electrostatic free energy penalty for having dielectric interfaces perpendicular to the field . Thus, a state where $`\epsilon `$ is perpendicular to the field $`𝐄`$ is favored. For layered materials such as lamellar BCP phases, the strength of this effect is proportional to $`(\epsilon _A\epsilon _B)^2E^2`$, where $`\epsilon _A`$ and $`\epsilon _B`$ are the dielectric constants of the two micro-domains, and is enhanced when the difference in polarizabilities is large.

Let us first consider lamellae confined in a thin film with no electric field. We will then include an electric field and see its influence. For simplicity and brevity of presentation we assume that the Flory parameter $`\chi `$ does not change on the surface, $`\tau _s=0`$. We also concentrate on uniform surface fields with equal magnitudes, $`\sigma (y=\frac{1}{2}L)=\pm \sigma `$, $`\sigma (y=\frac{1}{2}L)=\pm \sigma `$. If the surface affinity $`\sigma `$ is sufficiently large, the lamellae will order in a parallel arrangement as was discussed in the previous sections. These lamellae stretch or compress, increasing the bulk free energy, in order to decrease their surface energy. We mention below an adaptation  to the strong stretching approximation of Turner  and Walton et al. . The lamellar period is $`d_0=2\pi /q_0`$ and $`m`$ is the closest integer to $`L/d_0`$. Depending on the value of $`\sigma `$, an integer ($`n=m`$) or half integer ($`n=m+\frac{1}{2}`$) number of lamellae fill the gap between the two surfaces. In the former case the ordering is symmetric (the same type of monomers adsorbed onto both surfaces), while in the latter it is asymmetric (A monomers adsorbed on one surface, whereas B monomers adsorbed on the other surface). The parallel lamellae are described by an order parameter $`\varphi _{}`$ given by

$$\varphi _{}(x,y)=\pm \varphi _L\mathrm{cos}[q_{_{}}(y+\frac{1}{2}L)]$$
(20)
The wavenumber is $`q_{_{}}=2\pi n/L`$, and the choice of $`\pm `$ signs in Eq. (20) is such that the surface interactions, Eq. (2), are minimized. The perpendicular lamellae have the unperturbed bulk periodicity $`d_0=2\pi /q_0`$ and their order parameter is simply given by

$$\varphi _{}(x,y)=\varphi _L\mathrm{cos}(q_0x)$$
(21)
We consider now the case where an electric field is turned on, in a direction that is perpendicular to the surfaces. Under conditions of constant voltage difference across the electrodes situated at the two bounding surfaces, the minimum of the free energy is obtained by maximizing the capacitance. Since the A- and B-monomers have different dielectric constants, the effect of the electric field is to align the BCP layers parallel to the field, i.e. perpendicular to the surfaces. At a certain field strength this tendency starts to dominate over the preference induced by the surfaces to have parallel lamellae. Further increase of $`E`$ above the threshold value gives rise to a perpendicular lamellar ordering.

In the weak segregation regime, the small value of density modulations $`\varphi `$ has been used  in order to write the electrostatic free energy as

$`{\displaystyle \frac{Nb^3F_{\mathrm{el}}}{k_BT}}=\beta {\displaystyle (\widehat{𝐪}𝐄)^2\varphi _𝐪\varphi _𝐪\mathrm{d}^3q}`$ (22)
$`\beta ={\displaystyle \frac{(\epsilon _A\epsilon _B)^2Nb^3}{4(2\pi )^4k_BT\epsilon }}`$ (23)
Here $`\varphi _𝐪`$ is the Fourier transform of $`\varphi (𝐫)`$: $`\varphi (𝐫)=\varphi _𝐪\mathrm{exp}(i𝐪𝐫)d𝐪`$, and $`\widehat{𝐪}=𝐪/q`$ is a unit vector in the $`𝐪`$-direction. Copolymer modulations with a non-vanishing component of the wavenumber $`𝐪`$ along the electric field, have a positive contribution to the free energy. In other words, there is a free energy penalty for having dielectric interfaces in a direction perpendicular to the electric field. In Eq. (23), $`\epsilon _A`$ and $`\epsilon _B`$ are the dielectric constants of the pure A and B-blocks, respectively , and $`\epsilon =\frac{1}{2}(\epsilon _A+\epsilon _B)`$ is the average dielectric constant in the symmetric BCP film ($`f=\frac{1}{2}`$). In the weak segregation regime, the spatial variations in $`\varphi `$ are small and $`\epsilon `$ varies linearly with $`\varphi `$,

$`\epsilon (\varphi )`$ $``$ $`({\displaystyle \frac{1}{2}}+\varphi )\epsilon _A+({\displaystyle \frac{1}{2}}\varphi )\epsilon _B`$ (24)
$`=`$ $`\epsilon +(\epsilon _A\epsilon _B)\varphi `$
The total free energies of the parallel and perpendicular lamellae per unit area of the film are then given by

$`F_{}`$ $`=`$ $`{\displaystyle \frac{1}{4}}\left[\tau +h\left(q_0^2q_{_{}}^2\right)^2+2\beta E^2+{\displaystyle \frac{u}{16}}\varphi _L^2\right]\varphi _L^2L+\mathrm{\Sigma }`$ (25)
$`F_{}`$ $`=`$ $`{\displaystyle \frac{1}{4}}\left[\tau +{\displaystyle \frac{u}{16}}\varphi _L^2\right]\varphi _L^2L`$ (26)
$`\mathrm{\Sigma }=(\pm \varphi _L\pm \varphi _L)\sigma `$ is the total surface interaction per unit area \[Eq. (2)\] at the two walls, and is negative. The $`\pm `$ sign is determined from the $`\pm `$ sign of the order parameter in Eq. (20). When the two surfaces are chemically identical, two similar signs in $`\mathrm{\Sigma }`$ mean symmetric ordering with an integer number of lamellae between the electrodes ($`\mathrm{\Sigma }=\pm 2\varphi _L\sigma `$). In an antisymmetric ordering with a half-integer number of confined lamellae, $`\mathrm{\Sigma }=0`$ as the two wall preferences cancel each other.

In Fig. 7 we compare the relative stability of parallel and perpendicular lamellae as a function of surface interaction strength $`\sigma `$ (on the vertical axis) and surface separation $`L`$ (on the horizontal axis). In (a) the electric field is zero. Parallel lamellae are favored when surface separation $`L`$ is close to an integer value (recall that we take in this example two surfaces with the same polymer affinity $`\sigma `$). Perpendicular ordering is favored when lamellae frustration is largest, i.e. when $`L/d_0`$ is approximately a half-integer number. A degeneracy between the two states occurs for these values of $`L`$ when the surface interactions vanish, $`\sigma =0`$. For more details and a generalization to surfaces with different affinity for the A and B blocks see ref. . In (b) an electric field is applied in a direction perpendicular to the electrodes. As a consequence, perpendicular lamellae are favored and the boundary line between the light and dark regions in Fig. 7 is shifted upward to higher $`\sigma `$ values.

In the strong segregation regime ($`\chi \chi _c`$), thin BCP films subjected to external electric field can be analyzed as well. Since in this regime the correlation length is not larger than the system size (in contrast to the weak segregation limit mentioned above), another finite length scale enters into the problem. The result is that the system has three possible states: parallel state in which parallel lamellae span the whole film, a perpendicular state, and a mixed state with parallel lamellae near the surfaces and perpendicular lamellae in the middle of the film. These three states are separated by three critical fields $`E_1`$, $`E_2`$ and $`E_3`$.

In Fig. 8 (a) we show the phase diagram in the $`\delta `$$`E`$ plane, where $`\delta `$ is the dimensionless difference between then A and B-block surface energies and $`E`$ is the strength of applied electric field. Transition from parallel to mixed lamellae at $`E=E_1`$ occurs if $`\delta `$ is above some threshold value, $`\delta ^{}`$. It is then followed by a transition between the mixed and perpendicular states at $`E=E_2`$. If $`\delta `$ is small, $`\delta <\delta ^{}`$, there is a direct transition from parallel to perpendicular lamellae at $`E=E_3`$.

A different cut through the phase diagram in the $`L`$$`E`$ (while keeping $`\delta `$ constant) is shown in Fig. 8 (b). A transition between parallel and mixed states occurs at $`E=E_1`$, followed by a second transition at $`E=E_2`$ from the mixed to the perpendicular state, provided that surface separation is large enough, $`L>L^{}`$. When $`L<L^{}`$ a direct transition between parallel and perpendicular lamellae occurs at $`E=E_3`$.

## 5 Summary

Several ordering mechanisms in confined BCPs are considered in this paper. Above the order-disorder temperature the polymer density near a chemically patterned surface is given as a function of the surface pattern. It is shown that each surface $`q`$-mode of the chemical pattern arises its own density mode, and that these modes can be regarded as uncoupled (linear response theory). The decay of these density modes into the bulk (away from the surfaces) is analyzed. In the weak segregation regime employed here, surface correlations become long range and hence simple chemical patterns (as in Fig. 4) can yield complex copolymer morphology, even though the bulk is in its disordered phase.

We describe lamellar BCP when they are confined by striped surface whose periodicity is larger than the lamellar periodicity. We find that in this case lamellae will tend to tilt with respect to the surface in order to optimize their surface interactions. The deviations from the perfect lamellar shape, induced by the surfaces, are obtained. These undulations of the lamellar interface are more prominent as the ODT is approached. Mixed lamellar phases appear when one surface has chemically patterns in the form of stripes while the other is uniform.

We examine the effect of an external electric field on the phase behavior of parallel and perpendicular lamellae. In the absence of any external electric field, we recover the previously obtained phase diagram . The influence of electric field \[Fig. 7 (b)\] is to favor the perpendicular lamellae: the region where parallel lamellae are stable is pushed up-wards in the phase diagram. We present as well the phase diagrams in the strong segregation regime. In this regime there are three possible system states (parallel, perpendicular and mixed) with three critical fields which separate them, as can be seen in Figure 8 (a) and (b).

The analytical calculations presented here together with other experimental and numerical studies are useful tools towards obtaining well controlled structures in the nanoscale. Indeed, the technical details employed should not obscure some simple results which are rather universal: the use of two simple one-dimensional striped surface patterns in order to achieve a complex three-dimensional morphology \[Fig. 4\], and surface field periodicity that facilitates control of tilt angle \[Fig. 5\]. Finally, tuning the strength of electric field and surface separation (or interaction) as an external perturbation to create parallel, mixed or perpendicular lamellae \[Fig. 8\]. These mechanisms call for further application-oriented studies as well as theoretical ones.

Acknowledgments Partial support from the U.S.-Israel Binational Foundation (B.S.F.) under grant No. 98-00429 and the Israel Science Foundation founded by the Israel Academy of Sciences and Humanities — centers of Excellence Program is gratefully acknowledged. One of us (Y.T.) acknowledges support from the Chateaubriand Fellowship Program.

Figure Captions

* Figure 1. Schematic illustration of the coordinate system for BCP confined by one \[part (a)\] or two \[part (b)\] planar and parallel surfaces. (c) Lamellae are formed tilted with respect to the surface if the surface periodicity $`d_x`$ is larger than the natural one $`d_0`$.
* Figure 2. A BCP melt confined by one surface at $`y=0`$. B-monomer density is high in dark regions, while A monomers are in light regions. In (a) the surface is uniform, $`\sigma =0.3`$ and in (b) it has stripes given by $`\sigma =0.3\mathrm{cos}(\frac{2}{3}q_0)`$. The “combined” effect is shown in part (c) where $`\sigma =0.3+0.3\mathrm{cos}(\frac{2}{3}q_0x)`$ has a uniform and modulated part. The Flory parameter is $`N\chi =10.2`$, $`\tau _s=0`$ and lengths in the $`x`$ and $`z`$ directions are scaled by the lamellar period $`d_0`$.
* Figure 3. Propagation of surface pattern into the bulk. The surface pattern in the $`y=0`$ plane is shown in (a), where white (black) show regions preferring A (B) monomers. Parts (b) and (c) are contour plots of the polymer density at $`y=3d_0`$ and $`y=8d_0`$, respectively. $`N\chi =9.5`$ and $`\tau _s=0`$.
* Figure 4. BCP melt confined by two flat parallel striped surfaces, depicted in parts (a) and (c), and located at $`y=d_0`$ and $`y=d_0`$, respectively. The melt morphology in the mid-plane ($`y=0`$) is shown in part (c). The Flory parameter is $`N\chi =9`$ and $`\tau _s=0`$.
* Figure 5. Tilted lamellar phase between two parallel patterned surfaces close to a patterned bounding surface. (See also Fig. 1c). The surface patterning is modelled by the term $`\sigma _q\mathrm{cos}(2\pi x/d_x)`$. The lamellae tilt angle $`\theta =\mathrm{arccos}(d_0/d_x)`$ increases as the periodicity of the surface $`d_x`$ increases: $`\theta =0`$ for $`d_x=d_0`$ in (a), $`\theta 48.1^o`$ for $`d_x=\frac{3}{2}d_0`$ in (b) and $`\theta 70.5^o`$ for $`d_x=3d_0`$ in (c). In the plots $`\sigma _q/hq_0^3\varphi _L=1`$. The Flory parameter $`N\chi =11.5`$ and $`\tau _s/hq_0^3=0.1`$.
* Figure 6. A BCP confined film showing a crossover from perpendicular lamellae at the $`y=\frac{1}{2}L=2d_0`$ surface to parallel lamellae at the other surface, $`y=\frac{1}{2}L`$. The pattern on the bottom surface, $`\sigma (x)=\sigma _q\mathrm{cos}(q_0x)`$, has the bulk periodicity $`d_0`$, and amplitude $`\sigma _q=2hq_0^3`$, while the top surface ($`y=\frac{1}{2}L`$) is homogeneously attractive to the B polymer (in black), $`\sigma _0=4hq_0^3`$. The Flory parameter is given by $`N\chi =10.7`$ and $`\tau _s/hq_0^3=0.4`$.
* Figure 7. The stability of $`L_{}`$ (in light) vs. $`L_{}`$ lamellae (dark), as a function of wall separation $`L`$ and interfacial interaction parameter $`\sigma `$. The latter is taken as $`\sigma >0`$ on both surfaces. In (a) the electric field strength is zero, while in (b) $`E\sqrt{\beta }=0.02`$. The $`L_{}`$ phase is pushed upward in the stability diagram in (b), removing the degeneracy between $`L_{}`$ and $`L_{}`$ that occurs for neutral walls ($`\sigma =0`$) for $`L/d_0`$ being an integer number. The Flory parameter is $`\chi N=11`$.
* Figure 8. (a) Phase diagram in the $`E`$-$`\delta `$ plane. $`\delta `$ is the difference between the A and B-block surface energies. When $`\delta <\delta ^{}`$, there is a direct transition between parallel and perpendicular lamellae at $`E=E_3`$. For $`\delta >\delta ^{}`$, a transition between parallel and mixed states occurs at $`E=E_1`$, followed by a second transition between mixed and perpendicular states when $`E=E_2>E_1`$. (b) Similar diagram, but in the $`E`$-$`L`$ plane, where $`L`$ is surface separation $`d_0`$ is the lamellar period and $`\delta =5`$.


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# MEASUREMENT OF THE CONDUCTANCE OF A HYDROGEN MOLECULE

Present address:\]Universit Denis Diderot (Paris 7), Groupe de Physique des Solides UMR 75 88, 2 place Jussieu, 75251 Paris Cedex 05, France.

Recent years have shown steady progress in research towards molecular electronics Aviram and Ratner (1998); Langlais et al. (1999) where molecules have been investigated as switches Gao et al. (2000); Collier et al. (1999); Reed et al. (2001), diodes Metzger and Cava (1998), and electronic mixers Chen et al. (1999). In much of the previous work a Scanning Tunnelling Microscope was employed to address an individual molecule. As this arrangement does not provide long-term stability, more recently metal-molecule-metal links have been made using break junction devices Reed et al. (1997); Kergueris et al. (1999); Reichert et al. (2002). However, it has been difficult to establish unambiguously that a single molecule forms the contact Emberly and Kirczenow (2001). Here, we show that a single H2 molecule can form a stable bridge between Pt electrodes. In contrast to results for other organic molecules, the bridge has a nearly perfect conductance of one quantum unit, carried by a single channel. The H2-bridge provides a simple test system and a fundamental step towards understanding transport properties of single-molecule devices.

In this work we employ a mechanically controllable break junction Muller et al. (1992); van Ruitenbeek (1997) at low temperatures (4.2 K) to produce pure metallic contacts of atomic size. The inset in Fig. 1 shows a typical conductance curve for a clean Pt contact111We concentrate on results obtained for Pt wires, but conductance histograms suggest similar behaviour for Pd. that is recorded while gradually decreasing the contact size by ramping up the piezovoltage (black curve). The conductance is expressed in terms of the quantum unit, $`G_0=2e^2/h`$ , with $`e`$ the electron charge and $`h`$ Planck’s constant. The jumps in the conductance are the result of sudden atomic rearrangements in response to the applied strain Rubio et al. (1996). After the conductance has dropped to a value corresponding to a single atom, which for Pt is in the range 1.2–2.3 $`G_0`$, the contact suddenly breaks. In order to extract the common features in these conductance curves the data of a large series of conductance curves are collected into a conductance histogram. The main panel in Fig. 1 shows such a histogram for Pt contacts (black). It is dominated by a large peak at 1.4–1.8 $`G_0`$, which represents the range of conductance values for contacts having a single atom in cross section (for a recent review see Ref. Agraït et al. (2002a)). The histogram drops sharply to zero for lower conductance values, as is typically found for Pt contacts in absence of adsorbates and impurities. Remarkably, the character of the conductance curves and the shape of the resulting histogram change dramatically when a small quantity of hydrogen gas is admitted to the vacuum pot (grey curves). The critical amount is difficult to establish since most hydrogen is expected to condense on the walls of the container,222The equilibrium H2 gas pressure at a temperature of 4.2 K is about $`10^6`$ mbar. but the results are not very sensitive to the precise quantity. The peak at the position characteristic for Pt disappears and a large weight is added in the entire range below that value. On top of this background a distinct peak close to 1 $`G_0`$ is found, which grows for larger currents through the contact, while the background is suppressed. For still larger bias voltages, above 200 mV, we recover the histogram for clean Pt. The low-conductance tail and the peak at 1 $`G_0`$ reappear upon lowering the bias again. The bias dependence of the histograms is attributed to local heating by the current. For moderate bias the weakly bound physisorbed H2 is evaporated, and only above 200 mV the chemically bonded hydrogen molecules are removed from the Pt surface.

We concentrate now on the remarkable fact that in the presence of hydrogen there appears to be a frequently occurring stable configuration that has a conductance of nearly unity, an example of which is shown in the inset of Fig. 1, and which is responsible for the sharp peak just below 1 $`G_0`$ in the histogram. We can select this configuration by recording conductance traces of the type shown in the inset, and stop the motion of the electrodes as soon as we find a plateau at 1 $`G_0`$. In order to investigate the structure of the contact on this plateau we use point contact spectroscopy (PCS). PCS was originally developed by Yanson Yanson (1974); Jansen et al. (1980) for contacts that are large compared to the atomic scale. One measures the differential conductance, $`G_\mathrm{d}=dI/dV`$ , as a function of the dc bias voltage. The electrons in the contact are accelerated to an excess energy $`eV`$. When this energy reaches that of the main phonon modes of the metal inelastic scattering results in an enhanced probability for the electrons to scatter back through the contact, which is seen as a drop in $`G_\mathrm{d}`$. Recently, this principle has been applied to single-atom metallic contacts and chains of atoms Untiedt et al. (2000); Agraït et al. (2002b), and a theoretical description for localised vibration modes in quantum point contacts has been developed Bonča and Trugman (1995); Emberly and Kircznow (1999). Vibration modes for individual molecules have been observed before, using inelastic electron tunnelling spectroscopy (IETS) in a low-temperature STM Stipe et al. (1998). Although the principle is similar, the conductance increases at the vibration energy in IETS, while it decreases in PCS. Experimentally, a great advantage is the short data acquisition time for a spectrum in our experiment, 10 s compared to 1–10 h for IETS Stipe et al. (1998). This is attributed mainly to a lower shot noise level as result of the lower resistance of the junction, and due to the quantum suppression of shot noise for a single-channel contact van den Brom and van Ruitenbeek (1999); the lower junction impedance also allows us to work at a higher modulation frequency.

Fig. 2 shows the differential conductance and its derivative taken at a 1 $`G_0`$-plateau for the Pt/H2 system. We find a pronounced single resonance at about 63.5 mV, symmetrically for both voltage polarities. The energy is much higher than the typical phonon modes for metals, which are found between 5 and 25 mV Khotkevich and Yanson (1995). The width of the resonance is about 14 mV and is much larger than expected from the thermal and instrumental broadening. A similar large ’intrinsic width’ has been observed in IETS Stipe et al. (1998) and it probably results from the short lifetime of the molecular vibration excitations due to the strong coupling to the metal. We observe a modest variation in the position of the main signal between different experiments, which is likely due to variations in the bonding configuration of the hydrogen to the Pt electrodes. The frequencies obtained from 23 spectra for Pt/H2 are shown by the open circles in Fig. 3, having a mean value of 64 mV and a standard deviation of 4 mV.

In order to test the interpretation of the observed resonance we repeated the experiment using the isotopes D2, and HD. From 23 spectra for Pt/D2 we obtain a distribution of energies shown by open squares in Fig. 3, being centred at 47 mV, while 20 spectra obtained for Pt/HD (bullets) are found to be centred at 51 mV . The inset to Fig. 3 shows the same distributions with energies scaled by the expected ratios for the vibration energies $`\omega _{H_2}/\omega _{D_2}\sqrt{m_{D_2}/m_{H_2}}=\sqrt{2}1.414`$, and $`\omega _{H_2}/\omega _{HD}\sqrt{m_{HD}/m_{H_2}}=\sqrt{3/2}1.225`$, confirming our interpretation of the conduction through a hydrogen molecule. Note in particular that this excludes the possibility of conductance through a hydrogen atom, since this would have resulted in a two-peak distribution of frequencies for HD.

Experimental information on the number of conductance modes can be obtained from the fluctuations in $`G_\mathrm{d}(V)`$ as a function of voltage by measuring their root-mean square amplitude $`\sigma _{\mathrm{GV}}`$ following the method described in Ref. Ludoph and van Ruitenbeek, 2000. For a contact with a single conductance channel with transmission probability $`T<1`$ the dominant contribution to the fluctuations results from interference of partial waves reflected at the contact itself and those reflected on defects nearby. The wavelength of the electrons changes as a function of the bias voltage, producing random variations in the interference and thus in the conductance. For $`T=1`$ the reflection at the contact vanishes resulting in a suppression of the fluctuations. Fig. 4 shows that the peak in the conductance histogram at 0.95 $`G_0`$ coincides with a pronounced minimum in $`\sigma _{\mathrm{GV}}`$. From the finite value of at the minimum Ludoph and van Ruitenbeek (2000) we extract a value for the transmission $`T=0.97\pm 0.01`$, confirming that the conductance through the molecule is almost entirely carried by one channel. This finding also excludes other configurations for which the conductance would be carried through several parallel channels and confirms that we have only a single molecule.

Hydrogen is known to bind strongly to a Pt surface, and Pt surfaces catalyse hydrogen dissociation. Little is known about the catalytic activity of this system at 4.2 K, but it is likely that a small energy barrier is present that prevents H2 dissociation under these conditions. In the experiment we cannot rule out the formation of contacts with atomic hydrogen, but the ones that we have been able to fully analyse have a molecular bridge. We have verified the stability of the H2-bridge configuration using density functional calculations employing the Gaussian 98 program Frisch et al.  with the SDD relativistic effective core basis set Andrae et al. (1990) and the B3LYP functional Becke (1993). Calculations were performed starting with a linear chain of four Pt atoms, and the results were verified to be insensitive to adding more atoms to the length of the Pt chain. Performing first-principles molecular dynamics we find that a H2 molecule bonded to the side of a Pt chain spontaneously moves as a whole into the chain when the bonds between the Pt atoms are being stretched. The energy gain is 2.0 eV, as compared to free H2 and two Pt2 chain fragments at infinity. The binding energy of the Pt atoms in the chain is 2.75 eV per bond. H2 will therefore never move spontaneously into the chain but first requires an external force to stretch a Pt-Pt bond, which is a way to supply chemical energy to a single bond. In order to obtain the longitudinal vibrational modes of H2 in a Pt chain, we have explicitly calculated the potential energy curves. For the center of mass motion of H2 we obtain an excitation energy of 61.5 meV, using equilibrium bond distances in a linear arrangement of 0.08 nm and 0.21 nm for H-H and Pt-H, respectively. This vibration mode fits very closely the observed excitation energy. The internal vibration mode of H2 is too high in energy ($`430`$ meV) to be observed in the experiment since the contact becomes unstable at bias voltages above about 200 mV.

The conductance of the hydrogen bridge was calculated using a model of a chain of Pt-H-H-Pt, sandwiched between two jellium bulk electrodes. We refer to Ref. Lang, 1995 for more details on the computation method. For the equilibrium bond distances we find a conductance of 0.9 $`G_0`$, in close agreement with experiment. We have not attempted to obtain the eigenchannel decomposition of the conductance.

The conduction through the molecule involves mainly the H2 antibonding states, but the hybridisation with the Pt metal states is strong enough to largely fill the HOMO-LUMO gap. It is surprising that the closed-shell configuration of H2 permits such strong bonding with Pt, while the molecular character is largely conserved. The latter is evidenced by the calculated H-H bond distance, which is close to that of the free molecule, and the fact that in the simulations upon further stretching the bridge finally breaks at the Pt-H bond. A Pt one-atom contact is expected to have five conductance channels due to the partially occupied $`d`$-orbitals. It appears that the insertion of a hydrogen molecule has the effect of filtering out a single one from these five channels, with nearly perfect transmission.

It will be interesting to attempt to extend our technique to more complex molecules with built-in functional groups. Although most organic molecules are expected to have a conductance many orders of magnitude below the quantum unit, our experiments confirm Lang and Avouris (2001) that full transmission of a single channel is possible when the coupling to the leads is sufficiently strong. Very recently two groups have demonstrated conductance through single metalorganic molecules Park et al. (2002); Liang et al. (2002), for which the charge-state of the metal ions could even be controlled by a gate electrode. In stead of using mechanical adjustment of the contact size as in our experiments the size of the metal contacts to the molecule was reduced exploiting electromigration. This further illustrates that we are rapidly developing the tools to study and control electron transport at single-molecule level.

We gratefully acknowledge discussions with Alfredo Levy Yeyati and Søren Kynde Nielsen and we thank David Bakker and Marcel Pohlkamp for valuable assistance in the experiments. CU and YN have been supported by European Community Marie Curie Fellowships.


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# The Structure of the Pion and Nucleon, and Leading Neutron Production at HERA

## 1 Introduction

The ZEUS Collaboration has published data on leading neutron production in neutral current $`e^+p`$ collisions at HERA. The data have been anticipated because of the light they cast on the structure of the pion and nucleon.

In  the ZEUS Collaboration uses an effective flux method to determine the photon-pion total cross section at high W, and the deep inelastic structure function of the pion, $`F_2^\pi (x,Q^2)`$111 The notation used follows . W is a center of momentum frame energy. $`x`$ is a Bjorken scaling variable. $`Q^2`$ is the virtuality of the exchanged photon.. In this note, the method is described; its assumptions and inherent difficulties are discussed; and the problem of error is confronted. Implications of the ZEUS data are examined critically for the role of meson exchange in the production of leading neutrons and for the structure of the pion.

## 2 Meson Exchange Picture of Leading Baryon Production

Leading baryons are those produced with small transverse momentum, $`p_T`$, and carrying a large fraction $`x_L`$, of the incoming proton’s energy. They are thought to represent the conserved baryon current because the squared 4-momentum transfer, $`t`$, between the incoming proton and outgoing baryon is small(, Fig. 1).

The production data for leading baryons can be understood in terms of meson exchanges. Consider the specific case $`\gamma pXn`$. The cross section for the production of a leading neutron is given by a sum over all possible meson exchanges between the photon and proton which lead to an outgoing neutron at the proton vertex(, Fig. 1):

$$\sigma _{\gamma pXn}(x_L,t,W^2)a_{\gamma ,p}(t)\underset{i}{}f_{i/p}(x_L,t)\sigma _{\gamma i}((1x_L)W^2,t)$$
(1)
where $`i=\pi ,\rho `$, or $`a_2`$ meson; $`\sigma _{\gamma i}`$ is the total $`\gamma i`$ cross section; $`f_{i/p}`$ is the splitting function for $`pn`$ via $`i`$ exchange; and $`a_{\gamma ,p}`$ is a form factor which accounts for rescattering of the neutron (absorption) due to the finite size of the projectile. Projectiles other than the photon, and produced baryons other than the neutron are treated similarly. For example, in the reaction $`ppXp`$ the $`\omega `$ and $`f_2`$ mesons, and the pomeron $`IP`$ also contribute. There are complications. The direct production of baryons which decay, such as $`\mathrm{\Delta }n\pi `$, leads to the indirect production of nucleons; there can be two-meson exchange, and different exchanges can interfere; the form factor, $`a_{\gamma ,p}`$, can depend on $`x_L`$ and perhaps on the exchanged meson $`i`$. The simple factorization assumed in Eqn. 1 is only an approximation.

## 3 Leading Neutron Production and Pion Exchange

In hadro-production experiments (projectile=$`p,\pi `$) leading neutron production is believed to be dominated by pion exchange. The spectrum of leading neutrons in $`pp`$ collisions at Fermilab and the ISR is fairly well represented by a single term (one-meson-exchange) of the form

$$\sigma _{ppXn}=\frac{1}{4\pi }\frac{g^2}{4\pi }\frac{2t}{(tm_\pi ^2)^2}(1x_L)^{12t}\sigma _{\pi p}\left((1x_L)W^2,t=0\right)$$
(2)
where $`m_\pi `$ is the mass of the pion, $`g^2/4\pi =14.5`$, and $`\sigma _{\pi p}`$ is the measured, on-mass-shell, $`\pi p`$ total cross section. The splitting function

$$f_{eff}(x_L,t)=\frac{1}{4\pi }\frac{g^2}{4\pi }\frac{2t}{(tm_\pi ^2)^2}(1x_L)^{12t}$$
(3)
is very close to that expected from pure one-pion exchange. The result is simple, but surprising. Note in Eqn. 3 the absence of

* an absorptive factor $`a(t)`$;
* an off-mass-shell correction, that is, a $`t`$ dependence to $`\sigma (\pi p)`$;
* contributions from $`\rho `$ and $`a_2`$ exchange, and $`\mathrm{\Delta }`$ production.

The self-consistency of the meson exchange picture requires the presence of such ‘backgrounds’. In addition, the value, 14.5, of the $`p\pi ^0p`$ coupling constant is larger than recent estimates which suggest that $`g^2/4\pi `$ lies in the range (13.5–14.1).

The ZEUS Collaboration has reviewed (see , §10.1) the expected backgrounds to one-pion exchange which are known both from experimental measurements (eg. $`\mathrm{\Delta }`$ production) and from theoretical calculations (eg. absorption). The effects are large, roughly 20-30%, apparently confounding the experimental observation embodied in Eqns. 2 and 3; however,

* $`\rho `$, $`a_2`$ exchange and $`\mathrm{\Delta }`$ production increase neutron production, while absorptive effects decrease neutron production
* absorption preferentially removes $`\rho `$ and $`a_2`$ compared to $`\pi `$ exchange because $`a(t)`$ decreases with increasing $`t`$ and the contribution of the higher mass mesons increases relative to the pion at high $`t`$.

The conclusion to draw is that simple one-pion exchange agrees well with the hadro-production data because of a fortuitous near cancellation of absorptive effects and background contributions. The large value of the effective coupling constant (14.5) implies that the cancellation is not perfect, and that there is a residual $`5`$% contribution to the normalization. $`f_{eff}`$ is not the true pion flux, but rather an effective pion flux in the presence of competing and ‘compensating’ processes.

## 4 The Effective Flux

The effective flux of pions in the proton (effective splitting function) can be defined by experiment as the deconvolution of the measured semi-inclusive differential cross section for $`ppXn`$ and the measured $`\pi p`$ total cross section,

$$f_{eff}(x_L,t)\frac{d\sigma _{ppXn}}{dx_Ldt}/\sigma _{\pi p}$$
(4)
where deconvolution is written as division. By construction and definition $`f_{eff}`$ corrects one-pion exchange in $`pp`$ collisions for $`\rho `$ and $`a_2`$ exchange, $`\mathrm{\Delta }`$ production, rescattering and off-mass-shell effects, etc. From Eqn. 1 it is seen that a ‘model’ for $`f_{eff}`$ is

$$f_{eff}a_{p,p}(t)\underset{i}{}f_{i/p}(x_L,t)\sigma _{ip}((1x_L)W^2,t)/\sigma _{\pi p}\left((1x_L)W^2,t=0\right)$$

It is important to emphasize: experiments find that a convenient parameterization of $`f_{eff}`$ is given by Eqn. 3. Because of the universal behavior of hadronic cross sections $`f_{eff}`$ is also expected to work for $`\pi p`$ and $`\gamma p`$ collisions.

## 5 The Structure of the Pion and the Effective Flux

It has been proposed to measure the structure function of the pion $`F_2^\pi `$ at HERA using virtual $`\gamma ^{}\pi `$ collisions assuming pion exchange dominates the interaction $`\gamma ^{}pXn`$, just as it does in hadro-production.

A vital consistency check for any extraction of $`F_2^\pi `$ using the electro-production of leading neutrons is the demonstration that the photo-production of leading neutrons is in accord with the hadro-production measurements. The importance of the photo-production data arises because:

* $`W`$ is the single relevant leptonic variable ($`Q^2=0`$).
* the $`W`$ dependence of measured hadronic cross sections closely follows a simple universal behavior; at high $`W`$ the hadronic total cross sections behave as a power law $`W^{2(\alpha _{IP}1)}`$, where $`\alpha _{IP}`$ is a constant independent of the projectile and target.
* the photo-production ($`Q^2<0.02`$ GeV2) and transition region ($`0.1<Q^2<0.74`$ GeV2) data from HERA are in good agreement with vector dominance in which the photon behaves like an exchanged vector meson and the collision is hadronic.

In contrast to photo-production, the situation in electro-production is less well understood. The additional degree of freedom quantified by $`Q^2`$ adds complication. Rescattering, background composition and levels, and factorization properties can vary with $`Q^2`$. Moreover, in deep inelastic scattering ($`Q^24`$ GeV2) the chief interest lies in measuring the $`W`$ (that is $`x`$, $`xQ^2/W^2`$ at low $`x`$) dependence of the cross section. In summary, a prerequisite for a believable determination of $`F_2^\pi `$ using high $`Q^2`$ electro-production data is a consistent determination of $`\sigma _{\gamma \pi }`$ using photo-production data.

A standard technique for determining $`\sigma (\gamma \pi )`$ involves fitting the observed differential cross section for $`\gamma pXn`$ while simultaneously correcting for background exchanges, Delta production, absorption, and off-mass-shell effects. This procedure has the important advantage of providing an estimate of the size of the contributing sub-processes and giving a transparent estimate of the error. It has the disadvantage that there is a large number of effects to be accounted for, with a corresponding large degree of freedom. The parameters must be guessed, fit, or fixed by experiment.

The effective flux is used instead to directly determine $`\sigma (\gamma \pi )`$ without determining the individual sub-processes. This has the advantages of simplicity and directness, but the disadvantage that no information is obtained about the relative importance of the various processes which contribute. The error is difficult to estimate (see §6) because the amount of pion exchange present is not unambiguously determined. If pion exchange does not contribute, the result, although well defined, is meaningless.

The arguments which follow (in §5.1 and §5.2) give the essence of what obtains from the ZEUS measurement.

### 5.1 $`\sigma (\gamma \pi )`$ at high $`W`$

The $`\gamma \pi `$ total cross section is obtained from the photo-production data using

$$\sigma (\gamma \pi )=\frac{d\sigma (\gamma pXn)/dx_L}{f_{eff}}$$

where the variable $`t`$ has been integrated out in the numerator. Substitution for $`f_{eff}`$ from its definition in Eqn. 4 shows that $`\sigma (\gamma \pi )`$ can be determined from (double) ratios

$$\frac{\sigma (\gamma \pi )}{\sigma (\gamma p)}=\frac{{\displaystyle \frac{d\sigma (\gamma pXn)/dx_L}{\sigma (\gamma p)}}}{{\displaystyle \frac{d\sigma (ppXn)/dx_L}{\sigma (pp)}}}\frac{\sigma (\pi p)}{\sigma (pp)}$$
(5)
of measured quantities.

The ZEUS Collaboration has observed that the relative rate of neutron production in photo-production at HERA is half that of $`pp`$ collisions. It follows from Eqn. 5 that $`\sigma (\gamma \pi )/\sigma (\gamma p)`$ is half $`\sigma (\pi p)/\sigma (pp)`$. Therefore, as ZEUS deduces directly,

$$\sigma (\gamma \pi )\sigma (\gamma p)/3$$

rather than two-thirds as expected from Regge factorization or the counting of valence quarks (the Additive Quark Model).

An important consistency check, which the ZEUS Collaboration has performed (, Fig. 6 & 8), is that the neutron energy and angular distributions are described by $`f_{eff}`$.

### 5.2 $`F_2^\pi `$ at low $`x`$

The double ratio (Eqn. 5) is robust for hadro- and photo-production; however, for electro-production, absorptive rescattering decreases as $`Q^2`$ increases, as discussed in  and  (see also , Fig. 9). At low $`Q^2`$ ($`Q^21`$ GeV2), $`F_2^\pi `$ and $`\sigma (\gamma ^{}\pi )`$ are related by

$$F_2^\pi \frac{Q^2}{4\pi ^2\alpha }\sigma (\gamma ^{}\pi )$$
(6)
which, in analogy with $`\rho `$ dominance in $`\gamma p`$ interactions, can be written as

$$F_2^\pi \frac{Q^2}{4\pi ^2\alpha }\frac{m_\rho ^2}{m_\rho ^2+Q^2}\sigma (\gamma \pi )$$
(7)
where $`m_\rho `$ is the mass of the $`\rho `$ meson.

Equations 6 and 7 connect the photo-production $`\gamma \pi `$ cross section to the transition region $`\gamma ^{}\pi `$ cross section; together with the corresponding equations for $`\gamma ^{()}p`$ interactions,

$$\frac{\sigma (\gamma ^{}\pi )}{\sigma (\gamma \pi )}\frac{\sigma (\gamma ^{}p)}{\sigma (\gamma p)}$$
(8)
obtains. In the kinematic region $`0<Q^2<4`$ GeV2 the ratio of neutron production (i.e. tagged divided by all) increases. To maintain Eqn. 8 an absorptive correction needs to be applied. Rescattering decreases, and the effective flux must increase correspondingly in order to maintain consistency between photo-production, the transition region, and deep inelastic scattering. The ZEUS data require for deep inelastic scattering (DIS) $`f_{eff}f_{eff}^{\mathrm{DIS}}=1.3f_{eff}`$.

The measurements show that 2.5% of deep inelastic scattering events, independent of $`x`$ and $`Q^2`$, have a leading neutron with $`0.64<x_L<0.82`$ and $`p_T<0.66x_L`$ GeV (, Fig. 10). The constancy of the ratio of neutron production in DIS as a function of $`x`$ and $`Q^2`$ implies that $`F_2^\pi (x,Q^2)=kF_2^p((1x_L)x,Q^2)=kF_2^p(0.27x,Q^2)`$ with a constant of proportionality $`k`$ given by

$$k=\frac{0.025}{f_{eff}^{\mathrm{DIS}}(x_L,t)𝑑x_L𝑑t}=0.25$$

where the integration is over the $`x_L`$ and $`t(p_T)`$ range covered by the ZEUS measurement. Because $`F_2^p(x)(1/x)^\lambda `$ with $`\lambda 0.2`$

$$F_2^\pi (x,Q^2)F_2^p(x,Q^2)/3$$

## 6 Discussion

For the determination of $`F_2^\pi `$ the effective flux method requires little theoretical input. Only the general concepts of meson exchange theory are needed. The data, hadro-production, photo-production and electro-production, determine everything. Note especially that

* one-pion-exchange is not assumed. It is only assumed that pion exchange dominates neutron production.
* the contribution of backgrounds is not neglected. The method accounts for $`\rho `$ and $`a_2`$ exchange and for indirect neutron production through $`\mathrm{\Delta }`$ production and decay.
* the exact composition and relative contribution of the backgrounds is unimportant.
* absorptive effects are measured.
* the consistency of the photo-production ($`Q^2<0.02`$ GeV2), transition region ($`0.1<Q^2<0.74`$ GeV2), and DIS ($`Q^2>4`$ GeV2) analyses requires and defines an absorptive correction.

If absorption approximately compensates for background exchanges in hadro- and photo-production, as the data suggest, then the 30% rise in neutron ratio between photo-production and DIS is a measure of the relative contribution of the backgrounds.

The effective flux gives a normalization of $`\sigma (\gamma \pi )`$ which differs by a factor of two from that expected by Regge factorization or valence quark counting. The disagreement follows directly from the experimental observation that the relative rate of neutrons in photo-production is half that observed in hadro-production. Can $`f_{eff}`$, which is determined by $`pp`$ collisions, be wrong by a factor of two when used for photo-production?

Background exchanges and absorptive effects are of the same magnitude, but contribute with opposite signs. The ZEUS leading neutron data show that the relative size of absorptive effects is approximately 20-30%. Background processes must contribute at approximately this level, in agreement with estimates from phenomenological studies (reviewed in, §10.1). With this in mind, a conservative estimate for the error on using $`f_{eff}`$ for photo-production is obtained by assuming that pion exchange contributes $`50`$% and that the backgrounds change by $`50`$% on moving from $`pp`$ to $`\gamma p`$ collisions. The change in $`f_{eff}`$ is then $`25`$%. Suppose that the low neutron rate is not due to a small photon-pion cross section, but rather due to changes in absorption or backgrounds. Then absorption must increase or backgrounds decrease strongly in the photon-proton system compared to the proton-proton system.

If the meson exchange picture underestimates the normalization of $`\sigma (\gamma \pi )`$ by a factor of two, the theory is wrong, misapplied, or there is a significant missing ingredient. Then one cannot extract with any confidence the $`x`$ and $`Q^2`$ behavior of $`F_2^\pi `$.

If the photo-production result is disbelieved, the ZEUS data can be taken as evidence that meson exchange plays little role in the production of leading nucleons at HERA. One then argues that the ZEUS measurement is merely a reflection of $`F_2^p`$, arising because of factorization (limiting fragmentation) at the proton vertex and baryon conservation.

On the other hand, the experimental evidence for the meson exchange picture is good (see references in ). One can accept the picture and the normalization of $`\sigma (\gamma \pi )`$ and $`F_2^\pi `$ implied by the ZEUS data. In this case some conjectures can be make:

* the $`x`$ dependence of $`F_2`$ for all hadrons is similar at low $`x`$ and is determined mainly by the QCD evolution equations, only weakly by the valence structure of the hadron.
* the number of partons at low $`x`$ in the pion is 1/3 that of the proton; since the charged radius of the pion is 2/3 the proton’s, the volume density of partons in the pion is approximately the same as in the proton.
* there is a large probability for the proton to be found in a meson-nucleon or meson-Delta Fock state (the nucleon within the nucleon); the proton is a loosely bound meson-nucleon system composed of infinitely bound partons.
* the quark-antiquark sea of a hadron is generated mainly by valence-valence interactions (three for the proton and one for the pion), and not by self interactions.

Moreover, there is a significant violation of the quark counting rules and Regge factorization.

## 7 Conclusions

In the context of the meson exchange picture of leading baryon production, the leading neutron data from ZEUS, taken together with the hadro-production data from Fermilab and the ISR, make a statement about the normalization of $`\sigma (\gamma \pi )`$. With the assumption that the $`x`$ and $`Q^2`$ dependence of the difference between pion exchange and the backgrounds is weak, $`F_2^\pi `$ can be extracted from the data. The normalization is the firmer of the determinations. If the normalization fixed by the photo-production data is incorrect, then an extraction of $`F_2^\pi `$ is doubtful since the self-consistency of the picture is questionable. In particular, the $`x`$ and $`Q^2`$ dependence extracted from the data is questionable because the high $`Q^2`$ region is less well understood than photo-production, both experimentally and phenomenologically.

If the determination of $`F_2^\pi `$ using the effective flux method is correct, then the ZEUS data have important implications for the structure of the nucleon and the pion.

## Acknowledgments

I thank the ZEUS Collaboration for many useful discussions and for its efforts in publishing the inclusive leading neutron data. I thank John Martin and Malcolm Derrick for helpful comments.


text:
# Quasi-molecular lines in Lyman wings of cool DA white dwarfs

## 1 Introduction

Structures in the Lyman $`\alpha `$ and Lyman $`\beta `$ line wings have been identified with free-free transitions which take place during binary close collisions of the radiating H atom and a perturbing atom or ion (Allard et al. 1998a, 1998b, 1999). The characteristics of these features (position, amplitude, and shape), due to the formation of quasi-molecules during collisions between the radiating atom and perturbers, depend directly on the potential energy curves correlated to the atomic levels of the transition (Allard & Kielkopf 1982).

Two satellite absorption features at 1058 Å and 1076 Å due to collisions of atomic hydrogen with protons were first identified in the spectrum of the DA white dwarf Wolf 1346, as observed with the Hopkins Ultraviolet Telescope (Koester et al. 1996). These satellites in the red wing of Lyman $`\beta `$ are in the Far Ultraviolet Spectroscopic Explorer (FUSE) spectral range (Moos et al. 2000); furthermore, Lyman $`\beta `$ profiles are also the subject of an ongoing study of the far ultraviolet spectrum of dense hydrogen plasmas.

In Allard et al. (1998a) we presented theoretical profiles of Lyman $`\beta `$ perturbed solely by protons. The calculations were based on the accurate theoretical H$`{}_{}{}^{+}{}_{2}{}^{}`$ molecular potentials of Madsen & Peek (1971) to describe the interaction between radiator and perturber, and dipole transition moments of Ramaker & Peek (1972). The line profiles were included as a source of opacity in model atmospheres for hot white dwarfs, and the predicted spectra compared well with the observed ORFEUS and FUSE spectra (Koester et al. 1998; Wolff et al. 2001).

Ab initio calculations of Drira (1999) of electronic transition moments for excited states of the H2 molecule and molecular potentials of Detmer et al. (1998) allowed us to compute Lyman $`\beta `$ profiles perturbed by neutral atomic hydrogen (Allard et al. 2000). The appearance of a broad satellite situated at 1150 Å makes necessary to take into account the total contribution of both the Lyman $`\alpha `$ and Lyman $`\beta `$ wings of H perturbed simultaneously by neutrals and protons.

We show that the shape of the wings in the region between Lyman $`\beta `$ and Lyman $`\alpha `$ is particularly sensitive to the relative abundance of the neutral and ion perturbers responsible for the broadening of the lines.

These new profiles have been used to predict synthetic spectra for cool DA white dwarfs which present structures at 1600 Å and 1400 Å in the Lyman $`\alpha `$ wing due respectively to quasi-molecular absorption of the H2 and H$`{}_{}{}^{+}{}_{2}{}^{}`$ molecules. These last two structures have been demonstrated to be a very sensitive temperature indicators in DA white dwarfs. The relative strength of these two satellite features depends very strongly on the degree of ionization in the stellar atmosphere, and thus on the stellar parameters $`T_{\mathrm{eff}}`$ and $`\mathrm{log}g`$ (Koester & Allard 1993; Koester et al. 1994; Bergeron et al. 1995).

## 2 Theoretical line profiles

### 2.1 Theory

We use a general unified theory in which the electric dipole moment varies during a collision; a detailed description of the theory as applied to the shape of the Lyman lines has been given by Allard et al. (1999). The obtained line profiles fit the spectra of laser-produced hydrogen plasmas (Kielkopf & Allard 1998).

Our approach requires prior knowledge of accurate theoretical molecular potentials to describe the interaction between radiator and perturber, and knowledge of the variation of the radiative dipole moment with atom-atom and atom-ion separation for each molecular state. This effect is important when the dipole moment varies in the region of inter-nuclear distance where the satellite is formed, and thus cannot be neglected. In the case of Lyman $`\beta `$ satellites, due to H-H+ collisions, we have shown that large changes (up to 60 %) in the intensity of the satellites may occur when the variation of the dipole moment is taken into account (Allard et al. 1998a). This result is also valid for other lines; it increases by a factor of about 2 the main satellites of Lyman $`\alpha `$ (Allard et al. 1999). Previous line profile calculations using constant dipole moment have been used to interpret IUE (International Ultraviolet Explorer) and Hubble Space Telescope spectra by Koester & Allard (1993), Koester et al. (1994), and Bergeron et al. (1995). The synthetic spectra presented here used improved Lyman $`\alpha `$ line profiles of Allard et al. (1998b) which have been already included in stellar atmosphere programs for the computation of stellar atmosphere model and synthetic spectra of $`\lambda `$ Bootis stars. A comparison of these calculations with observations made with the IUE demonstrated that these last improvements are of fundamental importance for obtaining a better quantitative interpretation of the spectra and for determining stellar atmospheric parameters (Allard et al. 1998b).

### 2.2  Lyman $`\beta `$ in H-H collisions

The Lyman profiles and satellites are calculated at the low densities met in the atmospheres of stars. The typical particle densities (1015 to 1017 cm-3) allows us to use an expansion of the autocorrelation function in powers of density as described in Allard et al. (1994) and Royer (1971). Line profiles are normalized so that over $`1/\lambda =\omega `$ (cm-1) they integrate to 1.

The only line feature of the Lyman $`\beta `$ profile is a broad absorption line satellite situated at 1150 Å due to the $`\mathrm{B}^{\prime \prime }\overline{\mathrm{B}}^1\mathrm{\Sigma }_u^+\mathrm{X}^1\mathrm{\Sigma }_g^+`$ molecular transition of H2 (Fig. 1). The recent ab initio calculations of A. Spielfiedel (2001, private communication) have shown that for the isolated radiating atom ( $`R\mathrm{}`$ ) this transition is not asymptotically forbidden as it was explicitly stated in Allard et al. (2000).

The line satellite shown in Fig. 1 presents a shoulder at 1120 Å, a similar shape has been obtained for the 1600 Å satellite. In Fig. 6 of Allard et al. (1999) both theory and experiment show an oscillatory structure between the satellite and the line, with a minimum at about 1525 Å. These oscillations are an interference effect (Royer 1971; Sando & Wormhoudt 1973), and are expected to depend on the relative velocity of the collision and therefore on temperature.

This satellite of Lyman $`\beta `$ is quite far from the unperturbed Lyman $`\beta `$ line center, actually closer to the Lyman $`\alpha `$ line. It is therefore necessary to take into account the total contribution of both the Lyman $`\alpha `$ and Lyman $`\beta `$ wings of H perturbed simultaneously by neutrals and protons and to study the variation of this part of the Lyman series with the relative density of ionized and neutral atoms.

### 2.3  Lyman $`\beta `$ in H-H and H-H+ collisions

In Allard et al. (1998a) we presented Lyman $`\beta `$ profiles perturbed by protons. The line profile calculations were done without using the expansion in density and then were valid from the center to the far wing and allowed a comparison of the amplitudes of the satellites to the line core. The profiles at different densities of H+ were displayed in Fig. 8.

In Fig. 2 we show the sum of the profiles of Lyman $`\alpha `$ and Lyman $`\beta `$ perturbed by collisions with neutral hydrogen and protons for different densities $`n_H`$ .

We can see that a ratio of 5 between the neutral and proton density is enough to make the quasi-molecular H2 satellite appear in the far wing. Note that the 1120 Å shoulder of the satellite is still visible in the total profile.

## 3 Synthetic spectra for DA white dwarfs

We now take into account these absorption features of the H$`{}_{}{}^{+}{}_{2}{}^{}`$ and H2 quasi-molecules to calculate synthetic spectra for DA white dwarfs. Atmosphere models and synthetic spectra have been calculated using the computer programs TLUSTY and SYNSPEC (Hubeny 1988; Hubeny & Lanz 1992, 1995). The LTE model atmospheres assume a pure hydrogen composition including the quasi-molecular opacities.

Below $`T_{\mathrm{eff}}`$=15 000 K, the atmosphere of DA white dwarfs become convective, and model atmospheres for these stars are usually calculated using several variants of the standard mixing-length theory. According Bergeron et al. (1992), we used the so-called ML2 prescription with $`\alpha =0.6`$, which was shown to provide excellent internal consistency between ultraviolet and optical temperatures.

The temperature range where both H2 and H$`{}_{}{}^{+}{}_{2}{}^{}`$ Lyman $`\beta `$ satellites are visible is relatively small; roughly between 14500 to 11000 K (Fig. 3-upper panel). This dependence of the theoretical profiles on temperature is extremely strong because of the relative importance of perturbations by neutral versus ionized hydrogen. The satellite appearance is then very sensitive to the degree of ionization and may be used as a temperature diagnostic.

In order to see all the Lyman line satellites, synthetic spectra are plotted from 1020 to 1800 Å (Fig. 3-lower panel). Below $`T_{\mathrm{eff}}`$= 13000 K the H$`{}_{}{}^{+}{}_{2}{}^{}`$ starts to disappear but the broad H2 satellite at 1150 Å is still present and the one at 1600 Å slowly increases.

## 4 FUSE observations of G 231–40

### 4.1 Observations and data reduction

G 231–40 (WD$ 2117+539$) is a cool DA white dwarf located at Galactic coordinates $`l=95.0^o`$ and $`b=3.3^o`$; it is a relatively bright white dwarf: $`V=12.3`$. This target was observed with FUSE as part of the French Guaranteed Time Observing Programs (program Q210). Two exposures were obtained on 2001 July 3 in time-tagged photon address mode (TTAG) with the object in the large aperture (LWRS). The total duration was $`1.6`$ h (see Table 1). Details of the FUSE instrument may be found in Moos et al. (2000) and Sahnow et al. (2000).

The one-dimensional spectra were extracted from the two-dimensional detector images and calibrated using version 2.0.5 of the CalFUSE pipeline. The eight FUSE detector segments of the two exposures (i.e. 16 spectra) were co-added and projected on a $`0.16`$ Å-pixel base, i.e. pixels about 25 times larger than the original FUSE detectors pixels. This degradation of the FUSE spectral resolution (typically $`\lambda /\mathrm{\Delta }\lambda 15000`$ for this kind of target in the large slit; see Hébrard et al. 2002; Wood et al. 2002) is of no effect on the shapes of the large stellar features which we study and allows us to increase the signal-to-noise ratio. At this resolution, no spectral shifts were detected between the 16 different co-added spectra.

Poor quality edge of each segment were not included in the sum. We used the following spectral ranges for each segment: $`10101085`$Å (SiC1A), $`910992.5`$ Å (SiC1B), $`9221005`$ Å (SiC2A), $`10161101`$ Å (SiC2B), $`10041081.5`$ Å (LiF1A), $`10961187`$ Å (LiF1B), $`10871181`$ Å (LiF2A), and $`10121073`$ Å (LiF2B). As the LiF1B segment presents a known large-scale distortion (“the worm”, D. Sahnow 2000, private communication) in the flux calibration around $`11201170`$ Å (see, e.g., Hébrard et al. 2002), we normalized the large-scale shape of the LiF1B segment to the shape of the LiF2A segment, using a polynomial fit. We also did not include the part of the LiF2A spectra in the ranges $`1134.61135.6`$ Å and $`1151.51153`$ Å because they were deteriorated by the so-called “walk” problem, which is a distortion in the FUSE spectra at airglow wavelengths ($`\lambda \mathrm{\hspace{0.33em}1134}`$ Å N i and $`\lambda \mathrm{\hspace{0.33em}1152}`$ Å O i lines in the present case) caused by variation of position with pulse height (D. Sahnow 2001, private communication). The final FUSE spectrum is plotted in Fig. 4. Note that the interstellar N i $`\lambda \mathrm{\hspace{0.33em}1134}`$ Å triplet is detected on this line of sight.

Since 2001, repeated observations of standard white dwarfs indicate a slow degradation in the effective area of the FUSE spectrograph. The decline affects the flux up to 20%, and that mainly for the LiF2A channel. A dime-dependent flux correction is in development for a future version of the pipeline, but is not included in the CalFUSE version 2.0.5.

In order to complement the $`9101187`$ Å FUSE spectrum, we retrieved two IUE low dispersion spectra of G 231–40 from the STScI MAST archive. These spectra were obtained in March 1983 and they were reduced using the NEWSIPS processing (see Table 1). They yield the spectral coverage $`11501980`$ Å at a resolution of about $`7`$ Å (Wegner 1984). The flux calibration of the FUSE and the IUE spectra are in good agreement (see Fig. 4, lower panel).

### 4.2 Comparison with theoretical spectra

As a change in temperature can be compensated by a change in surface gravity we have used $`\mathrm{log}g`$ determined from optical analysis. Holberg et al. (1998) give (14 490; 7.85) for ($`T_{\mathrm{eff}}`$; $`\mathrm{log}g`$), the atmospheric parameters being determined from spectroscopic observations by Bergeron et al. (1992). Model atmospheres and synthetic spectra were calculated in the range 15 500 to 14 500 K by steps of 100K, using $`\mathrm{log}g`$=7.85.

H- opacity (Wishart 1979) has been added in the atmosphere model calculation and gives a feature at 1130 Å also present in the FUSE observation (see Fig. 4).

Fig. 4-upper panel shows the comparison of the FUSE observation with our best fit obtained for $`T_{\mathrm{eff}}`$=14 800 K. The decreasing of sensitivity on the segment LiF2A (Sect. 4.1) is the main explanation of the difference between the data and the model between 1120 and 1180 Å. The H2 satellite (1150 Å) is no more visible, as expected, in this range of temperature.

Fig. 4 shows a good agreement between the FUSE and IUE observations of Lyman lines and predicted spectra over the whole range from 1020 to 1800 Å using atmospheric parameters determined from the optical range.

The feature near $`\lambda \mathrm{\hspace{0.17em}995}`$Å due to a Lyman $`\gamma `$ satellite, which is visible in the spectra of hotter objects, is no more present in the temperature range of G 231–40 (the flux of G 231–40 is below $`1\times 10^{14}`$erg cm-2 s-1 Å-1 at $`995`$Å). It was visible in FUSE observations of CD $-$38$^∘$ 10980 (Wolff et al. 2001), HUT spectrum of Wolf$ 1346$ (Koester et al. 1996), and in some ORFEUS spectra (Koester et al. 1998). It was also recently seen in FUSE spectra of Sirius~B (Holberg et al. 2002). This feature, due to a Lyman $`\gamma `$ satellite, is now included in our calculations. We have shown that a larger temperature is required to get it detectable (Allard et al. 2002).

## 5 Conclusion

From theoretical profiles including the new Lyman $`\beta `$ opacities it can be predicted that Lyman $`\beta `$ satellites should be detectable roughly between 25000 K to 11000 K. Within this range in a very small domain of temperatures, the whole profile should present H2 and H$`{}_{}{}^{+}{}_{2}{}^{}`$ satellites of the Lyman $`\alpha `$ and Lyman $`\beta `$ lines. FUSE observations of cooler white dwarfs in the ZZ Ceti range stars would offer the best opportunity to determine accurate stellar parameters as $`T_{\mathrm{eff}}`$ and $`\mathrm{log}g`$ for these stars.

###### Acknowledgements.

This work is based on data obtained for the French Guaranteed Time by the NASA-CNES-CSA FUSE mission operated by the Johns Hopkins University. I. H. would like to thank the PNPS (Programme National de Physique Stellaire) for travel support to IAP where part of this work was done. We would like to thank Jean Dupuis for useful comments on this work.


text:
# Parallaxes of Brown Dwarfs at USNO

## 1. Introduction

Parallaxes of late-M, L, and T dwarfs have been measured from images taken over the past several years with the 1.55 m Strand astrometric telescope at the U.S. Naval Observatory. The present results have been published recently by Dahn et al. (2002). The parallaxes are necessary for many purposes, including comparison with evolutionary models, analyzing the kinematics, determining ages, determining temperatures, and identifying outlying objects (perhaps binaries or young objects). When faint companions to bright stars with Hipparcos parallaxes are included, there are now nearly 30 field L dwarfs with measured and published distances, but only five T dwarfs published to date. In this paper, we discuss two applications of the parallax data to our understanding of L dwarfs.

## 2. Predicting Absolute Magnitudes

In Figure 1, the absolute magnitude $`M_J`$ is plotted. ($`M_J`$ is used because it scales more closely with luminosity than $`M_I`$ or $`M_K`$ do.) The five known binary pairs of L dwarfs are labelled in the middle panel – they are plotted after correcting their magnitudes from the combined light to the individual components. The figure shows that both spectral type and $`IJ`$ color can be used to predict $`M_J`$ for M7 through L8 spectral types.

The scatter in the $`JK`$ color of L dwarfs makes that color less accurate for use in predicting $`M_J`$. We need more data before drawing conclusions about T dwarfs.

## 3. The Near-IR Colors of L Dwarfs

The $`JHK`$ colors of L dwarfs are known to have a poor correlation with spectral type (e.g. Leggett et al. 2002) and with absolute magnitude and temperature (Kirkpatrick et al. 2000; Dahn et al. 2002). The right-hand panel of Figure 1 reinforces that conclusion. The $`JHK`$ colors are believed to be controlled by the amount of dust in the atmospheres of these cool objects: the distribution of dust particle sizes, the vertical distribution of dust clouds, and perhaps the existance of holes or bands between dust clouds are likely to be relevant factors (e.g. Ackerman & Marley 2001; Burrows et al. 2002; Tsuji 2002).

In an effort to understand what factor(s) cause dust to vary between otherwise-similar objects, in Figure 2 we repeat the right-hand panel of Figure 1 to show four potential correlations. Figure 2 uses data from the literature (Basri et al. 2000; Basri 2001; Kirkpatrick et al. 1999; 2000; 2001; Martín et al. 1999; Reid et al. 2002; Tinney & Reid 1998) for lithium detection, H$`\alpha `$ emission, tangential velocity, and rotation velocity. Some trends are already known: lithium is detected more frequently at fainter absolute magnitudes, while H$`\alpha `$ equivalent widths drop and rotation velocities increase. However, based on the available data, there is no obvious tendency for the $`JK`$ color to correlate with any of these parameters at a given absolute magnitude. Perhaps several factors influence the dust content of the atmospheres of L dwarfs and mask any one-parameter correlation.

## 4. Future work

We need data (parallax and other) for more L dwarfs. We really need data for more T dwarfs. Parallaxes for more T dwarfs will be coming from Tinney (this volume) and from parallaxes with the USNO IR camera (Vrba et al. in preparation).

### Acknowledgments.

Many objects discussed here were first identified from the 2MASS and SDSS surveys, and we are grateful to our colleagues for notifying us of objects in advance of publication.

## References

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Basri, G. 2001, in ASP Conf. Ser. 223, 11th Cool Stars Workshop, eds. Garcia-Lopez, R. Rebolo, & M.R. Zapatero-Osorio, (San Francisco: ASP), 261

Basri, G., Mohanty, S., Allard, F., Hauschildt, P.H., Delfosse, X., Martín, E.L., Forveille, T., & Goldman, B. 2000, ApJ, 538, 363

Burrows, A., Burgasser, A.J., Kirkpatrick, J.D., Liebert, J., Milsom, J.A., Sudarsky, M.D., & Hubeny, I. 2002, ApJ, 573, 394

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text:
# Comment on “Black holes constrain varying constants”

## Abstract

A recent paper  claims that the increase of the proton electric charge $`e`$ leads to a (forbidden) decrease of black hole entropy, therefore, possible evidence for variation of $`\alpha =e^2/\mathrm{}c`$  must be interpreted as a decrease of the speed of light. We argue that purely theoretical consideration of black holes possibly cannot give any model-independent limitations on variation of fundamental constants.

The entropy $`S`$ is, in fact, a dimensionless function. Indeed, we can measure temperature in more natural energy units and take the Boltzmann constant $`k=1`$ or just consider $`S/k`$. It is convenient to present the dimensionless entropy of a charged black hole in terms of dimensionless parameters:

$$S=\pi [\mu +\sqrt{\mu ^2Z^2\alpha }]^2$$
(1)
Here $`\mu =M/M_P`$, $`M`$ is the black hole mass,$`M_P=(\mathrm{}c/G)^{1/2}`$ is the Plank mass, $`Z`$ is the black hole charge in units of the proton charge. This expression does not contain explicitly any parameters which have dimension  (speed of light, proton electric charge, etc.). Therefore, in this case we may only discuss variation of two dimensionless parameters: mass of the black hole in units of the Plank mass ($`\mu `$) and $`\alpha `$ . Similar arguments were presented in a recent comment .

However, the question remains: can we extract any limitations on variation of $`\mu (t)`$ and $`\alpha (t)`$? We should recall that the event horizon area $`A`$ of the black hole is quantized . Because of the relation between the entropy $`S`$ and the horizon area $`A`$ one also can obtain the entropy quantization:

$$S=\frac{c^3}{4G\mathrm{}}A=\pi \gamma n$$
(2)
where $`\gamma `$ is a numerical constant, $`n`$=1,2,… is an integer (in fact, in Ref.  a neutral black hole has been discussed; for the validity of eq. (2) we possibly need an extra condition $`n>>1`$). This quantization condition gives us $`\mu `$ as a function of $`\alpha `$ and the number of quanta $`n`$:

$$\mu =\frac{M}{M_P}=\frac{\gamma n+Z^2\alpha }{2\sqrt{\gamma n}}$$
(3)
One may compare this result with that for the hydrogen atom where we have energy levels in atomic units $`me^4/\mathrm{}^2`$ as a function of the principal quantum number $`n`$. These levels also depend on $`\alpha `$ if we include relativistic corrections. Actually, such a dependence of transition frequencies on $`\alpha `$ in many-electron atoms (this dependence was calculated in ) was used in  to measure the $`\alpha `$ variation. Therefore, the time dependence of $`\alpha `$, possibly, does not lead to any specific problems for the black holes, it just gives us the dependence $`\mu (t)`$. The entropy in this case does not change.

We may even ignore this quantization condition and consider a heavy “classical” black hole. One can suggest that the dependence $`\alpha (t)`$ will lead to a zero or negative expression under the square root sign in eq. (1) which also appears in the formula for the horizon area (see a similar suggestion for variation of the charge $`e`$ in Ref. ). Here again an atomic analogy may be useful. The energy of the 1s level in the Dirac equation in the Coulomb field is given by the following expression:

$$E=mc^2\sqrt{1Z^2\alpha ^2}$$
(4)
Here the energy includes the rest mass $`mc^2`$. If we take $`Z=1371/\alpha `$ and begin to increase $`\alpha `$ the expression under the square root becomes negative and the stationary state 1s disappears (for the nucleus of any finite size it does not happen at energy $`E=0`$ but the problem appears again for $`E=mc^2`$). This only means that the system becomes non-stationary. The strong Coulomb field creates an electron-positron pair, the positron goes to infinity and the nuclear charge reduces to an allowed value ($`Z`$ to $`Z1`$). The same may happen to the black hole: after some radiation it becomes “normal”. Therefore, the possibility of a negative expression under the square root sign in eq. (1) or (4) does not mean that certain variations of $`\alpha `$ are forbidden.

This consideration provokes another question. Can Nature use variation of fundamental constants to eventually eliminate black holes? For an external observer the free fall of a body to the horizon requires an inifinite time. If by that time the horizon disappears we may arrive at some interesting problems. However, the job of elimination of black holes, possibly, can be done more efficiently by Hawking radiation.

Of course, this consideration is too simplistic and does not involve any particular model of the fundamental constant variation. However, it is clear that one can not obtain any model independent limits for the separate variation of $`e`$ and $`c`$ from the consideration of the black hole entropy since eq. (1) for this entropy does not contain $`e`$ and $`c`$. Moreover, it does not seem to be easier to derive reliable limits on variation of the fundamental constants by considering such complicated objects as black holes instead of usual atoms, nuclei and stars.

I am grateful to Michael Kuchiev for stimulating discussions.