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# 1 Introduction

## 1 Introduction

Quantum-Gravity Phenomenology is an intentionally vague name for a new approach to research on the possible non-classical (quantum) properties of spacetime.

This approach does not adopt a specific formalism for the description of the short-distance structure of spacetime (e.g., “string theory”, “loop quantum gravity” and “noncommutative geometry” are seen as equally deserving mathematical-physics programmes); it is rather the proposal that quantum-gravity research should proceed just in the familiar old-fashioned way: through small incremental steps starting from what we know, combining mathematical-physics studies with experimental studies to reach deeper and deeper layers of understanding of the short-distance structure of spacetime. For various “historical” reasons (mostly connected with the lack of guidance from experiments) research on quantum gravity has wondered off this traditional strategy: the most popular quantum-gravity approaches, such as string theory and loop quantum gravity, could be described as “top-to-bottom approaches”, since they start off with some key assumption about the structure of spacetime at the Planck scale and then they try (with limited, vanishingly small, success) to work their way back to “reality”, the realm of doable experiments. With “quantum-gravity phenomenology” I would like to refer to all studies that are somehow related with the “bottom-to-top approach”, consistently with traditional strategy of physics research.

Since the problem at hand is extremely difficult (arguably the most challenging problem ever faced by the physics community) it appears likely that the two complementary approaches might combine in a useful way: for the “bottom-to-top approach” it is important to get some guidance from the (however tentative) indications emerging from the “top-to-bottom approaches”, while for “top-to-bottom approaches” it might be very useful to be alerted by quantum-gravity phenomenologists with respect to the type of new effects that could be most effectively tested experimentally222It is hard for “top-to-bottom approaches” to obtain a complete description of low-energy physics, but perhaps it would be possible to dig out predictions on some specific spacetime features that appear to deserve special attention in light of the corresponding experimental sensitivities..

Until very recently the idea of a quantum-gravity phenomenology, and in particular of attempts of identification of experiments with promising sensitivity, was very far from the main interests of quantum-gravity research. One isolated idea had been circulating from the mid 1980s: it had been realized that the sensitivity of CPT tests using the neutral-kaon system is such that even small effects of CPT violation originating at the Planck scale333The possibility of Planck-scale-induced violations of the CPT symmetry has been extensively considered in the literature. One simple point in support of this possibility comes from the fact that the CPT theorem, which holds in our present conventional theories, relies on exact locality, whereas in quantum gravity it appears plausible to assume lack of locality at Planckian scales. might in principle be revealed. These pioneering works on CPT tests were for more than a decade the only narrow context in which the implications of quantum gravity were being discussed in relation with experiments, but over the last 4 years several new ideas for tests of Planck-scale physics have appeared at increasingly fast pace, leading me to argue that the times might be right for a larger overall effort in this direction, which indeed could be called “quantum-gravity phenomenology”. At the present time (in addition to the already mentioned CPT tests) there are several examples of experimentally accessible contexts in which conjectured quantum-gravity effects are being considered, including studies of in-vacuo dispersion using gamma-ray astrophysics, studies of laser-interferometric limits on quantum-gravity induced distance fluctuations, studies of the role of the Planck length in the determination of the energy-momentum-conservation threshold conditions for certain particle-physics processes, and studies of the role of the Planck length in the determination of particle-decay amplitudes. These experimental/phenomenological studies might represent the cornerstones of quantum-gravity phenomenology since they are as close as one can get to direct tests of space-time properties, such as space-time symmetries. Other experimental proposals that should be seen as part of the quantum-gravity-phenomenology programme rely on the mediation of some dynamical theory in quantum space-time; comments on these other proposals can be found in Refs..

In these lecture notes I intend to emphasize those aspects of quantum-gravity-phenomenology that are relevant for the astrophysics community. The relevant topic is the one that concerns the faith of the Lorentz symmetry of classical spacetime when the spacetime is quantized. Since the Lorentz symmetry of classical flat (Minkowski) spacetime is verified experimentally to very high accuracy, it appears that any deviation from classical Lorentz symmetry, which might emerge from quantum-gravity theories, would be subject to severe experimental constraints. As a result Lorentz-symmetry tests are a key component of the programme of “quantum-gravity phenomenology”.

My main focus here will be on the faith of Lorentz invariance at the quantum-spacetime level. A large research effort has been devoted to this subject. Most of these studies focus on the possibility that Lorentz symmetry might be “broken” (in a sense clarified later in these notes) at the quantum level; however, I have recently shown that Lorentz invariance might be affected by spacetime quantization in a softer manner: there might be no net loss of symmetries but the structure of the Lorentz transformations might be affected by the quantization procedure. In the following I shall describe rather pedagogically the main differences between the broken-symmetry and my new deformed-symmetry scenario. In addition I will comment on the type of astrophysical observations, involving gamma rays and ultra-high-energy cosmic rays, which could provide evidence of such symmetry-related quantum properties of space-time. An exciting recent development in this area is that certain puzzling gamma-ray and UHE cosmic-ray observations are being actively discussed as possible first manifestations of a quantum property of space-time.

Before going forward with these main points on my agenda for these lecture notes, let me make a parenthetic remark, further claryfing the objectives of quantum-gravity phenomenology: The primary challenge of quantum-gravity phenomenology is the one of establishing the properties of space-time at Planckian distance scales, since most theoretical arguments suggest that this is the characteristic scale of quantum space-time effects. However, there is also recent discussion of the possibility that quantum-spacetime effects might be stronger than usually expected, i.e. with a characteristic energy scale that is much smaller (perhaps in the TeV range!) than the Planck energy. Examples of mechanisms leading to this possibility are found in string-theory models with large extra dimensions and in certain noncommutative-geometry models. Of course, the study of the phenomenology of these models is in the spirit of quantum-gravity phenomenology, but it is, in a sense, to be considered as a sideline development (and it is less challenging than the quantum-gravity-phenomenology efforts that pertain effects originating genuinely at the Planck scale).

## 2 The faith of Lorentz symmetry in quantum spacetime

If Nature hosts some form of “quantization” (even just in the general weak sense of “non-classical” properties) of space-time, this of course would also apply to flat spacetimes (e.g. if spacetime is in general discrete or noncommutative then of course the particular case of flat spacetime will also be described in the same way). One might argue (more or less convincingly) that quantum effects should be stronger in strong-curvature contexts, such as the ones involving black holes, but our capability of detailed experimental studies of such contexts is vanishingly small. Instead, in certain flat-spacetime contexts our experiments reach extremely high precision and therefore even relatively small effects induced by quantum properties of spacetime might be detectable. This is one of the key strategic points of my view on the development of quantum-gravity phenomenology.

In flat quantum spacetimes a key characteristic is the role of the Planck length, $`L_p`$. If the Planck length only has the role we presently attribute to it, which is basically the role of a coupling constant (an appropriately rescaled version of the gravitational coupling $`G`$), no problem arises for FitzGerald-Lorentz contraction, but if we try to promote $`L_p`$ to the status of an intrinsic characteristic of space-time structure (or a characteristic of the kinematic rules that govern particle propagation in space-time) it is nearly automatic to find conflicts with FitzGerald-Lorentz contraction.

For example, it is very hard (perhaps even impossible) to construct discretized versions or non-commutative versions of Minkowski space-time which enjoy ordinary Lorentz symmetry. Pedagogical illustrative examples of this observation have been discussed, e.g., in Ref. for the case of discretization and in Refs. for the case of non-commutativity. The action of ordinary (classical) boosts on discretization length scales (or non-commutativity length scales) will naturally be such that different inertial observers would attribute different values to these lengths scales, just as one would expect from the mechanism of FitzGerald-Lorentz contraction.

There are also dynamical mechanisms (of the spontaneous symmetry-breaking type) that can lead to deviations from ordinary Lorentz invariance; it appears for example that this might be possible in String Field Theory.

Both in String Theory and in Loop Quantum Gravity444As I shall argue more carefully elsewhere, in Loop Quantum Gravity there might even be a fundamental departure from classical Lorentz invariance. This can be deduced from studies arguing that Loop Quantum Gravity predicts a fixed discrete spectrum of area eingevalues, independently of the characetristic scale of curvature of the surface whose area is being measured (and therefore also for flat surfaces in flat spacetimes). One of the primary implications of Lorentz invariance is that the same experiment is seen by different observers in different ways which are however predictably (classically) connected by Lorentz transformations. If, for example, a series of measurements by one observer all give the same result of an area measurement, say the result $`A_0`$, then according to classical Lorentz invariance those same measurements should be seen by another observer as measurements all giving the same but different, say $`A_1`$, result (with $`A_1`$ related to $`A_0`$ by the appropriate boost). When the spectrum of the area of a flat surface in a flat spacetime is discrete this property of classical Lorentz invariance is at risk: the results $`A_0`$ being all the same would reflect the fact that one is dealing with what is an area eigenstate for observer $`O_0`$, and $`A_0`$ should be an eigenvalue of the area operator, but, if the second observer $`O_1`$ is only minutely boosted with respect to $`O_0`$, one should find that $`A_1`$, the boosted value of $`A_0`$, could not possibly be another eigenvalue (if the boost is small enough it will not be sufficient for reaching another eigenvalue in the discrete list of eigenvalues that composes the spectrum of the area operator) and it would be paradoxical for observer $`O_1`$ to find systematically repeated measurement results $`A_1`$. it is also natural to consider certain external-field backgrounds, which, in the appropriate sense (they provide a way to identify a preferred class of inertial observers), break Lorentz invariance.

Departures from ordinary Lorentz invariance are therefore rather plausible at the quantum-gravity level. Here I want to emphasize that there are at least two possibilities: (i) Lorentz invariance is broken and (ii) Lorentz invariance is deformed.

### 2.1 Deformed Lorentz invariance

In order to be specific about the differences between deformed and broken Lorentz invariance let me focus on the dispersion relation $`E(p)`$ which will naturally be modified in either case. Let me also assume, for the moment, that the deformation be Planck-length induced: $`E^2=m^2+p^2+f(p,m;L_p)`$. If the function $`f`$ is nonvanishing and nontrivial and the energy-momentum transformation rules are ordinary (the ordinary Lorentz transformations) then clearly $`f`$ cannot have the exact same structure for all inertial observers. In this case one would speak of an instance in which Lorentz invariance is broken. If instead $`f`$ does have the exact same structure for all inertial observers, then necessarily the transformations between these observers must be deformed. In this case one would speak of an instance in which the Lorentz transformations are deformed, but Lorentz invariance is preserved (in the deformed sense).

While much work has been devoted to the case in which Lorentz invariance is actually broken, the possibility that Lorentz invariance might be deformed was introduced only very recently by this author. An example in which all details of the deformed Lorentz symmetry have been worked out is the one in which one enforces as an observer-independent statement the dispersion relation

$$L_p^2\left(e^{L_pE}+e^{L_pE}2\right)\stackrel{}{p}^2e^{L_pE}=m^2$$
(1)
In leading (low-energy) order this takes the form

$$E^2\stackrel{}{p}^2+L_pE\stackrel{}{p}^2=m^2.$$
(2)
The Lorentz transformations and the energy-momentum conservation rules are accordingly modified.

### 2.2 Broken Lorentz invariance

The case of broken Lorentz invariance requires fewer comments since it is more familiar to the community. In preparation for the following sections it is useful to emphasize that the same dispersion relation (2), which was shown in Refs. to be implementable as an observer-independent dispersion relation in a deformed-symmetry scenario, can also be considered as a characteristic dispersion relation of a broken-symmetry scenario. In this broken symmetry scenario the dispersion relation (2) would still be valid but only for one “preferred” class of inertial observers (e.g. the natural CMBR frame) and it would be valid approximately in all frames not highly boosted with respect to the preferred frame. In highly-boosted frames one might find the same form of the dispersion relation but with different value of the deformation scale (different from $`L_p`$). All this follows from the fact that in the broken-symmetry scenario the laws of transformation between inertial observers are unmodified. Accordingly also energy-momentum conservation rules are unmodified.

Another scenario in which one finds broken Lorentz invariance is the one of canonical noncommutative spacetime, in which the dispersion relation is modified (with different deformation term), but, again, the energy-momentum Lorentz transformation rules are not modified. This example of noncommutative spacetime has been recently shown to be relevant for the description of string theory in certain external-field backgrounds (see, e.g., Ref.).

## 3 Illustrative example: photon-pair pion decay

Before discussing the role that observations of gamma rays and UHE cosmic rays could play in the development of this research area, let me clarify, in this Section, that the differences between the broken-symmetry and the deformed-symmetry case can be very significant for what concerns experimental signatures. This is also important since it proves that the relevant astrophysics observations might not only provide us the first manifestation of a quantum space-time property: they might even distinguish between different quantum pictures of spacetime.

In order to render very explicit the differences between the broken-symmetry and the deformed-symmetry case I consider here the simplest example in which these differences are rather dramatic: photon-pair pion decay. I adopt in one case deformed energy-momentum conservation, as required by the deformed Lorentz transformations of the deformed-symmetry case, while in the other case I adopt ordinary energy-momentum conservation, as required by the fact that the Lorentz transformation rules are unmodified in the broken-symmetry case, but for both cases I impose the same dispersion relation (2).

In the broken-symmetry case, combining (2) with ordinary energy-momentum conservation rules, one can establish a relation between the energy $`E_\pi `$ of the incoming pion, the opening angle $`\theta `$ between the outgoing photons and the energy $`E_\gamma `$ of one of the photons (the energy of the second photon is of course not independent; it is given by the difference between the energy of the pion and the energy of the first photon):

$`\mathrm{cos}(\theta )`$ $`=`$ $`{\displaystyle \frac{2E_\gamma E_\gamma ^{}m_\pi ^2+3L_pE_\pi E_\gamma E_\gamma ^{}}{2E_\gamma E_\gamma ^{}+L_pE_\pi E_\gamma E_\gamma ^{}}},`$ (3)
where indeed $`E_\gamma ^{}E_\pi E_\gamma `$. This relation shows that at high energies (starting at values of $`E_\pi `$ of order $`(m_\pi ^2/L_p)^{1/3}`$) the phase space available to the decay is anomalously reduced: for given value of $`E_\pi `$ certain values of $`E_\gamma `$ that would normally be accessible to the decay are no longer accessible (they would require $`cos\theta >1`$).

In the deformed-symmetry case one enforces the deformed conservation rules

$`E_\pi =E_\gamma +E_\gamma ^{},\stackrel{}{p}_\pi =\stackrel{}{p}_\gamma +\stackrel{}{p}_\gamma ^{}+L_pE_\gamma \stackrel{}{p}_\gamma ^{},`$ (4)
which, when combined again with (2), give rise to the different relation

$`\mathrm{cos}(\theta )`$ $`=`$ $`{\displaystyle \frac{2E_\gamma E_\gamma ^{}m_\pi ^2+3L_pE_\gamma ^2E_\gamma ^{}+L_pE_\gamma E_\gamma ^2}{2E_\gamma E_\gamma ^{}+3L_pE_\gamma ^2E_\gamma ^{}+L_pE_\gamma E_\gamma ^2}}.`$ (5)
Here it is easy to check that one is never led to consider the paradoxical condition $`cos\theta >1`$. There is therefore no severe implication of the deformed-symmetry case for the amount of phase space available for the decays (certainly not at energies around $`(m_\pi ^2/L_p)^{1/3}`$, possibly at Planckian energies).

## 4 An agenda for gamma-ray and UHECR studies

The key points for the phenomenology of quantum-gravity-induced deviations from classical Lorentz invariance are possible deformations of the dispersion relation and possible deformations of the energy-momentum conservation conditions.

Whether or not there is an accompanying deformation of energy-momentum conservation555In the case of deformation of Lorentz symmetry both the dispersion relation and the energy-momentum conservation conditions are modified simultaneously, since they both must reflect the structure of the deformed transformation rules between inertial observers. a deformation of the dispersion relation is expected to give rise to in vacuo dispersion and, possibly (if the space-time has corresponding structure), to birefringence. In vacuo dispersion would provide a striking signature: the speed of massless particles would depend on wavelength666The ordinary dispersion relation is linear for massless particles, and therefore $`dE/dp`$ is wavelength (energy) independent. A nonlinear Planck-length-deformed dispersion relation will instead inevitably lead to wavelength-dependent $`dE/dp`$. and therefore photons that we somehow know to have been emitted simultaneously up to $`\mathrm{\Delta }_0T`$ precision would reach us with relative time delays $`\mathrm{\Delta }_1T`$, where $`\mathrm{\Delta }_1T>\mathrm{\Delta }_0T`$, and one should also find some dependence of $`\mathrm{\Delta }_1T`$ on the amount of time the photon spent travelling in space-time (i.e. time spent under the influence of quantum properties of space-time). As discussed in Refs. this type of effect can be naturally studied in the context of observations of gamma-ray bursts and observations of the high-energy photons emitted by certain blazars, such a Mk421. Certain gamma-ray observatories soon to be operational will have excellent sensitivity toward this type of effect, and in particular GLAST is planning dedicated studies. Interest in such studies is also growing in AMS.

As discussed in the previous Section, also certain aspects of particle-decay physics, at high energies, may carry an important trace of quantum-space-time effects. In that context however the implications of a dispersion-relation deformation do depend strongly on whether there is an associated deformation of energy-momentum conservation (i.e. depend on whether one is dealing with a scenario with deformed symmetries or instead one is dealing with a scenario with broken symmetries). The outlook of these studies based on particle-decay anomalies is described in Ref., also using a related data analysis reported in Ref..

But perhaps the most powerful tool for the experimental investigation of quantum-gravity-induced deviations from ordinary Lorentz invariance is provided by “threshold anomalies”. It is to this topic, which deserves being discussed in detail, that I devote the reminder of the Section. It is intruiging to notice that the prediction of these threshold anomalies appears to be consistent with some puzzling results of astrophysics observations. In two different regimes, UHECRs and multi-TeV photons, the universe appears to be more transparent than expected. UHECRs should interact with the Cosmic Microwave Background Radiation (CMBR) and produce pions. TeV photons should interact with the Infra Red (IR) photons and produce electron-positron pairs. These interactions should make observations of UHECRs with $`E>510^{19}`$eV (the GZK limit) or of gamma-rays with $`E>10`$TeV from distant sources unlikely. Still UHECRs above the GZK limit and Mk501 photons with energies up to 24 TeV are observed.

A CMBR photon and a UHE proton with $`E>510^{19}`$eV should satisfy the kinematic requirements (threshold) for pion production. UHE protons should therefore loose energy, due to photopion production, and should slow down until their energy is below the GZK energy. At higher energies the proton’s mean free path decreases rapidly and it is down to a few Mpc at $`310^{20}`$eV. Yet more than 15 CRs have been observed with nominal energies at or above $`10^{20}\pm 30\%`$ eV. There are no astrophysical sources capable of accelerating particles to such energies within a few tens of Mpc from us. Furthermore, if the CRs are produced homogeneously in space and time, we would expect a break in the CR spectrum around the GZK threshold, which is not seen.

HEGRA has detected high-energy photons with a spectrum ranging up to 24 TeV from Markarian 501 (Mk501), a BL Lac object at a redshift of 0.034 ($`157`$ Mpc). This observation indicates a second paradox of a similar nature. A high energy photon with energy $`E`$ can interact with an IR background photon with wavelength $`\lambda 30\mu m(E/10TeV)`$ and produce an electron-positron pair. The mean free path of TeV photons depends on the spectrum of the corresponding IR background. Recent data from DIRBE and from ISOCOM  suggest that the mean free path for 20TeV photons should be much shorter than the one of 10TeV photons. However, no apparent break is seen in the spectrum of Mk501 in the region $`10`$-$`20`$TeV.

The UHECR paradox is well established. Numerous theoretical models, mostly requiring new physics, have been proposed for its resolution (see Ref. for a recent review). With much less data, and with some uncertainty on the IR background, the Mk501 TeV-photon paradox is less established. However, if indeed this must be considered as a paradox, there are no models for its resolution, apart from the possibility that the IR background estimates are too large. Planned experiments will soon provide us better data on both issues. At present it appears reasonable to assume, just as a working hypothesis, that both paradoxes are real.

The interpretation of these paradoxes as threshold anomalies is appealing for several reasons. In both paradoxes low-energy photons interact with high energy particles. The relevant reactions should take place at a kinematic threshold. In both cases the center-of-mass threshold energies are rather modest and the physical processes involved are well tested and understood. In spite of these similarities, so far, there is no model that explains both paradoxes within a single theoretical scheme (unless the model accommodates an irritatingly large number of parameters). This appears to provide encouragement for the idea that quantum-gravity-induced deviations from ordinary Lorentz invariance might be responsible for both paradoxes777It is of course also possible to consider deviations from Lorentz invariance that do not have quantum-gravity origin, but, as discussed in Refs., the idea of a quantum-gravity origin, besides being conceptually appealing, leads to a natural estimate for the magnitude of the effects, an this estimate appears to fit well the observations (while non-quantum-gravity approaches host a large number of parameters to be freely adjusted to obtain the needed magnitude of the departure from Lorentz-invariance)..

In order to illustrate the mechanism of threshold anomalies, let us consider, for example, the broken-symmetry case already considered in the preceding section. I will now apply it to the kinematics of the process of electron-positron pair production, which is relevant for the Mk501 paradox. Combining (2) with ordinary energy-momentum conservation rules, one can establish that at threshold the energy $`E`$ of the hard Mk501 photon and the energy $`ϵ`$ of the soft background photon must satisfy the relation $`Em_e^2/ϵ+L_pm_e^6/(8ϵ^4)`$. The correction $`L_pm_e^6/(8ϵ^4)`$ is indeed sufficient to push the threshold energy upwards by a few TeV, consistently with the observations. As shown in Refs. (and references therein), an analogous result holds for the photopion threshold, which is relevant for the cosmic-ray paradox.

This type of analysis provides encouragement (of course, very preliminary) for the hypothesis that the two paradoxes might be the first ever manifestation of a quantum (Planck-length related) property of spacetime.

Just like in the case of pion decay, considered in the preceding Section, also for the evaluation of threshold anomalies there are large quantitative differences (which will be discussed in detail in a paper now in preparation) between the case in which Lorentz symmetry is broken and the case in which Lorentz symmetry is deformed. More accurate information on the paradoxes, such as the one that will be provided by Auger, can therefore even start pointing us toward the proper language for the description of the short-distance (quantum) structure of spacetime.

Experimental studies such as the ones planned by Auger will also in general clarify whether the origin of the paradoxes is indeed kinematical. I want to stress that, in this respect, it is important to get high-quality data in the neighbourhood of the expected GZK cutoff, perhaps even more than establishing how far (how high in energy) the cosmic-ray flux extends. In fact, the kinematical mechanism of threshold anomalies leads to the definite general prediction that nothing at all particular should happen at the GZK scale, since the GZK threshold is simply moved forward (or eliminated all together) by the deviations from classical Lorentz invariance. Other attempts of explaining the cosmic-ray paradox instead must coexist with the GZK threshold and therefore (unless huge parametric fine-tuning is allowed) will inevitably predict at least some peculiarity to occur at the GZK scale.


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# 1 Introduction

## 1 Introduction

The internal space-time symmetries of massive and massless particles are dictated by the little groups of the Poincaré group which are isomorphic to the three-dimensional rotation group and the two-dimensional Euclidean group respectively . The little group is the maximal subgroup of the Lorentz group whose transformations leave the four-momentum of the particle invariant. Using the properties of these groups we would like to address the following questions.

On massless particles, there are still questions for which answers are not readily available. Why do spins have to be parallel or anti-parallel to the momentum? While photons have a gauge degree of freedom with two possible spin directions, why do massless neutrinos have only one spin direction without gauge degrees of freedom? The purpose of this note is to address these questions within the framework of Wigner’s little groups of the Poincaré group .

The group of Lorentz transformations is generated by three rotation generators $`J_i`$ and three boost generators $`K_i`$. They satisfy the commutation relations:

$$[J_i,J_j]=iϵ_{ijk}J_k,[J_i,K_j]=iϵ_{ijk}K_k,[K_i,K_j]=iϵ_{ijk}J_k.$$
(1)
In studying space-time symmetries dictated by Wigner’s little group, it is important to choose a particular value of the four-momentum, For a massive point particle, there is a Lorentz frame in which the particle is at rest. In this frame, the little group is the three-dimensional rotation group. This is the fundamental symmetry associated with the concept of spin.

For a massless particle, there is no Lorentz frame in which its momentum is zero. Thus we have to settle with a non-zero value of the momentum along one convenient direction. The three-parameter little group in this case is isomorphic to the $`E(2)`$ group. The rotational degree of freedom corresponds to the helicity of the massless particle, while the translational degrees of freedom are gauge degrees of the massless particle .

In this report, we discuss first the $`O(3)`$-like little group for a massive particle. We then study the $`E(2)`$-like little group for massless particles. The $`O(3)`$-like little group is applicable to a particle at rest. If the system is boosted along the $`z`$ axis, the little group becomes a “Lorentz-boosted” rotation group, whose generators still satisfy the commutation relations for the rotation group. However, in the infinite-momentum/zero-mass limit, the commutation relation should become those for massless particles. This process can be carried out for both spin-1 and spin-1/2 particles. This “group-contraction” process in principle can be extended all higher-spin particles. In this report, we are particularly interested in spin-1/2 particles.

In Sec. 2, we study the contraction of the $`O(3)`$-like little group to the $`E(2)`$-like little group. In Sec. 3, we discuss in detail the $`E(2)`$-like symmetry of massless particles. Secs. 4 and 5 are devoted to the question of neutrino polarizations and gauge transformation.

## 2 Massless Particle as a Limiting Case of Massive Particle

The $`O(3)`$-like little group for a particle at rest is generated by $`J_1,J_2`$, and $`J_3`$. If the particle is boosted along the $`z`$ direction with the boost operator $`B(\eta )=\mathrm{exp}\left(i\eta K_3\right)`$, the little group is generated by $`J_i^{}=B(\eta )J_iB(\eta )`$. Because $`J_3`$ commutes with $`K_3`$, $`J_3`$ remains invariant under this boost. $`J_1^{}`$ and $`J_2^{}`$ take the form

$$J_1^{}=(\mathrm{cosh}\eta )J_1+(\mathrm{sinh}\eta )K_2,J_2^{}=(\mathrm{cosh}\eta )J_2(\mathrm{sinh}\eta )K_1.$$
(2)
The boost parameter becomes becomes infinite if the mass of the particle becomes vanishingly small. For large values of $`\eta `$, we can consider $`N_1`$ and $`N_2`$ defined as $`N_1=(\mathrm{cosh}\eta )^1J_2^{}`$ and $`N_2=(\mathrm{cosh}\eta )^1J_1^{}`$ respectively. Then, in the infinite-$`\eta `$ limit,

$$N_1=K_1J_2,N_2=K_2+J_1.$$
(3)
These operators satisfy the commutation relations

$$[J_3,N_1]=iN_2,[J_3,N_2]=iN_1,[N_1,N_2]=0.$$
(4)
$`J_3,N_1`$, and $`N_2`$ are the generators of the $`E(2)`$-like little group for massless particles.

In order to relate the above little group to transformations more familiar to us, let us consider the two-dimensional $`xy`$ coordinate system. We can make rotations around the origin and translations along the $`x`$ and $`y`$ axes. The rotation generator $`L_z`$ takes the form

$$L_z=i\left\{x\frac{}{y}y\frac{}{x}\right\}$$
(5)
The translation generators are

$$P_x=i\frac{}{x},P_y=i\frac{}{y}.$$
(6)
These generators satisfy the commutation relations:

$$[L_z,P_x]=iP_y,[L_z,P_y]=iP_x[P_x,P_y]=0.$$
(7)
These commutation relations are like those given in Eq.(4). They become identical if $`L_z`$, $`P_x`$ and $`P_y`$ are replaced by $`J_1`$, $`N_2`$ and $`N_3`$ respectively.

This group is not discussed often in physics, but is intimately related to our daily life. When we drive on the streets, we make translations and rotations, and thus make transformations of this $`E(2)`$ group. Football players also make $`E(2)`$ transformations in their fields.

As we shall see in the following section, the translation-like degrees of freedom in the $`E(2)`$-like little group lead to gauge transformations. Then Wigner’s ilttle group is like Einstein’s $`E=mc^2`$ which unifies the energy-momentum relations for both massive and massless particles. The little group unifies the internal space-time symmetries of massive and massless particles, as summarized in Fig. 2. The longitudinal rotation remains as the helicity degrees of freedom during the boost. However, the Lorentz boosted transverse rotations become gauge degrees of freedom, as summarized in Fig. 2.

The content of this table has been thoroughly studied in the literature . Wigner’s original paper was published in 1939 . He worked out there the little groups for massive and massless particles. The task of obtaining the $`E(2)`$-like little group started in the 1953 paper by Inonu and Wigner , and the task was not completed until 1990 . What was known in in 1953 was the Euclidean group applicable to a flat surface, but the solution to the problem required also the cylindrical group hidden in the four-by-four Lorentz-transformation matrices. This has been thoroughly studied in the literature, and Fig 1 gives a complete picture of the contraction procedure.

## 3 Symmetry of Massless Particles

The internal space-time symmetry of massless particles is governed by the cylindrical group which is locally isomorphic to two-dimensional Euclidean group . In this case, we can visualize a circular cylinder whose axis is parallel to the momentum. On the surface of this cylinder, we can rotate a point around the axis or translate along the direction of the axis. The rotational degree of freedom is associated with the helicity, while the translation corresponds to a gauge transformation in the case of photons.

The question then is whether this translational degree of freedom is shared by all massless particles, including neutrinos and gravitons. The purpose of this note is to show that the requirement of invariance under this symmetry leads to the polarization of neutrinos . Since this translational degree of freedom is a gauge degree of freedom for photons, we can extend the concept of gauge transformations to all massless particles including neutrinos.

If we use the four-vector convention $`x^\mu =(x,y,z,t)`$, the generators of rotations around and boosts along the $`z`$ axis take the form

$$J_3=\left(\begin{array}{cccc}0& i& 0& 0\\ i& 0& 0& 0\\ 0& 0& 0& 0\\ 0& 0& 0& 0\end{array}\right),K_3=\left(\begin{array}{cccc}0& 0& 0& 0\\ 0& 0& 0& 0\\ 0& 0& 0& i\\ 0& 0& i& 0\end{array}\right),$$
(8)
respectively. The remaining four generators are readily available in the literature . They are applicable also to the four-potential of the electromagnetic field or to a massive vector meson.

The role of $`J_3`$ is well known . It is the helicity operator and generates rotations around the momentum. The $`N_1`$ and $`N_2`$ matrices take the form

$$N_1=\left(\begin{array}{cccc}0& 0& i& i\\ 0& 0& 0& 0\\ i& 0& 0& 0\\ i& 0& 0& 0\end{array}\right),N_2=\left(\begin{array}{cccc}0& 0& 0& 0\\ 0& 0& i& i\\ 0& i& 0& 0\\ 0& i& 0& 0\end{array}\right).$$
(9)
The transformation matrix is

$`D(u,v)=\mathrm{exp}\left\{i\left(uN_1+vN_2\right)\right\}`$
$`=\left(\begin{array}{cccc}1& 0& u& u\\ 0& 1& v& v\\ u& v& 1(u^2+v^2)/2& (u^2+v^2)/2\\ u& v& (u^2+v^2)/2& 1+(u^2+v^2)/2\end{array}\right).`$ (10)
If this matrix is applied to the electromagnetic wave propagating along the $`z`$ direction

$$A^\mu (z,t)=(A_1,A_2,A_3,A_0)e^{i\omega (zt)},$$
(11)
which satisfies the Lorentz condition $`A_3=A_0`$, the $`D(u,v)`$ matrix can be reduced to

$$D(u,v)=\left(\begin{array}{cccc}1& 0& 0& 0\\ 0& 1& 0& 0\\ u& v& 1& 0\\ u& v& 0& 1\end{array}\right).$$
(12)
While $`A_3=A_0`$, the four-vector $`(A_1,A_2,A_3,A_3)`$ can be written as

$$(A_1,A_2,A_3,A_0)=(A_1,A_2,0,0)+\lambda (0,0,\omega ,\omega ),$$
(13)
with $`A_3=\lambda \omega `$. The four-vector $`(0,0,\omega ,\omega )`$ represents the four-momentum. If the $`D`$ matrix of Eq.(12) is applied to the above four vector, the result is

$$(A_1,A_2,A_3,A_0)=(A_1,A_2,0,0)+\lambda ^{}(0,0,\omega ,\omega ),$$
(14)
with $`\lambda ^{}=\lambda +(1/\omega )\left(uA_1+vA_3\right)`$. Thus the $`D`$ matrix performs a gauge transformation when applied to the electromagnetic wave propagating along the $`z`$ direction .

With the simplified form of the $`D`$ matrix in Eq.(12), it is possible to give a geometrical interpretation of the little group . If we take into account of the rotation around the $`z`$ axis, the most general form of the little group transformations is $`R(\varphi )D(u,v)`$, where $`R(\varphi )`$ is the rotation matrix. The transformation matrix is

$$R(\varphi )D(u,v)=\left(\begin{array}{cccc}\mathrm{cos}\varphi & \mathrm{sin}\varphi & 0& 0\\ \mathrm{sin}\varphi & \mathrm{cos}\varphi & 0& 0\\ u& v& 1& 0\\ u& v& 0& 1\end{array}\right).$$
(15)
Since the third and fourth rows are identical to each other, we can consider the three-dimensional space $`(x,y,z,z)`$. It is clear that $`R(\varphi )`$ performs a rotation around the $`z`$ axis. The $`D`$ matrix performs translations along the $`z`$ axis. Indeed, the internal space-time symmetry of massless particles is that of the circular cylinder .

## 4 Massless Spin-1/2 Particles

The question then is whether we can carry out the same procedure for spin-1/2 massless particles. We can also ask the question of whether it is possible to combine two spin 1/2 particles to construct a gauge-dependent four-potential. With this point in mind, let us go back to the commutation relations of Eq.(1). They are invariant under the sign change of the boost operators. Therefore, if there is a representation of the Lorentz group generated by $`J_i`$ and $`K_i`$, it is possible to construct a representation with $`J_i`$ and $`K_i`$. For spin-1/2 particles, rotations are generated by

$$J_i=\frac{1}{2}\sigma _i,$$
(16)
and the boosts by

$$K_i=(+)\frac{i}{2}\sigma _i,orK_i=()\frac{i}{2}\sigma _i.$$
(17)
The Lorentz group in this representation is often called $`SL(2,c)`$.

If we take the (+) sign, the $`N_1`$ and $`N_2`$ generators are

$$N_1=\left(\begin{array}{cc}0& i\\ 0& 0\end{array}\right),N_2=\left(\begin{array}{cc}0& 1\\ 0& 0\end{array}\right).$$
(18)
On the other hand, for the (-) sign, we use the “dotted representation” for $`N_1`$ and $`N_2`$:

$$\dot{N}_1=\left(\begin{array}{cc}0& 0\\ i& 0\end{array}\right),\dot{N}_2=\left(\begin{array}{cc}0& 0\\ 1& 0\end{array}\right).$$
(19)
There are therefore two different $`D`$ matrices:

$$D(u,v)=\left(\begin{array}{cc}1& uiv\\ 0& 1\end{array}\right),\dot{D}(u,v)=\left(\begin{array}{cc}1& 0\\ uiv& 1\end{array}\right).$$
(20)
These are the gauge transformation matrices for massless spin-1/2 particles .

As for the spinors, let us start with a massive particle at rest, and the usual normalized Pauli spinors $`\chi _+`$ and $`\chi _{}`$ for the spin in the positive and negative $`z`$ directions respectively. If we take into account Lorentz boosts, there are two additional spinors. We shall use the notation $`\chi _\pm `$ to which the boost generators $`K_i=(+)\frac{i}{2}\sigma _i`$ are applicable, and $`\dot{\chi }_\pm `$ to which $`K_i=()\frac{i}{2}\sigma _i`$ are applicable. There are therefore four independent spinors . The $`SL(2,c)`$ spinors are gauge-invariant in the sense that

$$D(u,v)\chi _+=\chi _+,\dot{D}(u,v)\dot{\chi }_{}=\dot{\chi }_{}.$$
(21)
On the other hand, the $`SL(2,c)`$ spinors are gauge-dependent in the sense that

$`D(u,v)\chi _{}=\chi _{}+(uiv)\chi _+,`$
$`\dot{D}(u,v)\dot{\chi }_+=\dot{\chi }_+(u+iv)\dot{\chi }_{}.`$ (22)
The gauge-invariant spinors of Eq.(21) appear as neutrinos in the real world. The Dirac equation for massless neutrinos contains only the gauge-invariant $`SL(2,c)`$ spinors.

## 5 The Origin of Gauge Degrees of Freedom

However, where do the above gauge-dependent spinors stand in the physics of spin-1/2 particles? Are they really responsible for the gauge dependence of electromagnetic four-potentials when we construct a four-vector by taking a bilinear combination of spinors?

The relation between the $`SL(2,c)`$ spinors and the four-vectors has been discussed in the literature for massive particles . However, is it true for the massless case? The central issue is again the gauge transformation. The four-potentials are gauge dependent, while the spinors allowed in the Dirac equation are gauge-invariant. Therefore, it is not possible to construct four-potentials from the Dirac spinors. However, it is possible to construct the four-vector with the four $`SL(2,c)`$ spinors . Indeed,

$`\chi _+\dot{\chi }_+=(1,i,0,0),\chi _{}\dot{\chi }_{}=(1,i,0,0),`$
$`\chi _+\dot{\chi }_{}=(0,0,1,1),\chi _{}\dot{\chi }_+=(0,0,1,1).`$ (23)
These unit vectors in one Lorentz frame are not the unit vectors in other frames. The $`D`$ transformation applicable to the above four-vectors is clearly $`D(u,v)\dot{D}(u,v)`$.

$`D(u,v)\dot{D}(u,v)|\chi _+\dot{\chi }_+>=\dot{\chi }|\chi _+\dot{\chi }_+>(u+iv)|\chi _+\dot{\chi }_{}>,`$
$`D(u,v)\dot{D}(u,v)|\chi _{}\dot{\chi }_{}>=\chi _{}\dot{\chi }_{}>(u+iv)|\chi _+\dot{\chi }_{}>,`$
$`D(u,v)\dot{\chi }(u,v)|\chi _+\dot{\chi }_{}>=|\chi _+\dot{\chi }_{}>.`$ (24)
The component $`\chi _{}\dot{\chi }_+=(0,0,1,1)`$ vanishes from the Lorentz condition. The first two equations of the above expression correspond to the gauge transformations on the photon polarization vectors. The third equation describes the effect of the $`D`$ transformation on the four-momentum, confirming the fact that $`D(u,v)`$ is an element of the little group. The above operation is identical to that of the four-by-four $`D`$ matrix of Eq.(12) on photon polarization vectors.

It is possible to construct a six-component Maxwell tensor by making combinations of two undotted and dotted spinors . For massless particles, the only gauge-invariant components are $`|\chi _+\chi _+>`$ and $`|\dot{\chi }_{}\dot{\chi }_{}>`$ . They correspond to the photons in the Maxwell tensor representation with positive and negative helicities respectively.

It is also possible to construct Maxwell-tensor fields with for a massive particle, and obtain massless Maxwell fields by group contraction . The construction of Maxwell tensors has been thoroughly studied by Weinberg in 1964 .


text:
# Simulations of binary hard-sphere crystal-melt interfaces: interface between a one-component fcc crystal and a binary fluid mixture

## I Introduction

A fundamental understanding of the nucleation, growth kinetics and morphology of crystals grown from the melt requires a detailed microscopic description of the crystal-melt interfaceWoodruff (1973); Tiller (1991); Howe (1997); Adamson and Gast (1997). However, such interfaces are very difficult to probe experimentally and reliable experimental data, especially for structure and transport properties, is rare. It is then not surprising that computer simulations have, in recent years, played a leading role in the determination of the microscopic structure, dynamics and thermodynamics of such systemsLaird (1998).

To date, the vast majority of simulation studies have focused on single component interfacial systems. Such studies range from simple model systems such as hard spheresKyrlidis and Brown (1995); Mori et al. (1995); Laird (1998); Davidchack and Laird (2000) or Lennard-JonesBroughton and Gilmer (1986); Galejs et al. (1989) to more “realistic” systems, such as waterKarim and Haymet (1988); Karim et al. (1990); Hayward and Haymet (2001), siliconAbraham and Broughton (1986); Landman et al. (1986) or simple metalsJesson and Madden (2001); Hoyt et al. (2001). In contrast, there have been but few studies on multicomponent systemsDavidchack and Laird (1996, 1999), in spite of the fact that most materials of technological interest are mixtures (for example, doped semiconductors, alloys and intermetallic compounds). In such systems, the crystal and coexisting fluid have differing composition, in general, and the change in concentration as one traverses the interface from one bulk phase into the other becomes an object of study.

Of particular interest to materials scientists is the degree of interfacial segregation - the preferential adsorption of one component (usually the “solute”) at the interface. In addition, the phase diagrams for multi-component systems are significantly more varied and complex than single component systems due to the additional dimension of concentration. For a binary system several types of solid-liquid equilibria are possible. If the two types of particles are similar, then one typically has coexistence between a binary fluid and a substitutionaly disordered solid of similar structure to that of the pure components. However, if the two types of particles are substantially different in nature, then generally the binary fluid will either be immiscible in the pure coexisting solid, or will coexist with one or more ordered crystal mixtures (e.g. intermetallic compounds). Previous simulation studies on binary crystal-melt interfaces have exclusively focused on the former case, namely the equilibrium between the fluid and a disordered crystal. Davidchack and LairdDavidchack and Laird (1999) recently reported results for a binary hard sphere system in which a substitutionally disordered face-centered-cubic (fcc) crystal coexists with a binary fluid mixture. In a related study, Hoyt et al. examined the crystal-melt interface of a Cu/Ni mixtureHoyt et al. (2001). In both studies the degree of solute segregation was found to be negligible.

In the two studies above, the disordered fcc crystal was stabilized by the fact that the two components were quite similar in size -for example, in the hard-sphere system studied by Davidchack and Laird, the diameters of the two types of spheres making up the system differed only by 10%. In this work, we extend the previous studies to hard-sphere mixtures with significant size asymmetry. For such systems, in which the diameters differ by more than about 85%, the disordered fcc phase is no longer stable and only coexistence of the fluid with ordered crystal structures is possible. In this work we examine the interface between a binary hard-sphere fluid mixture and a coexisting fcc crystal in which the small particle is immiscible.

Our system of choice is a binary hard-sphere mixture in which the ratio of the smaller particle diameter to that of the larger particle is 0.414. Hard spheres are an important reference system for the crystal-melt interfaces of simple systems since the structure, dynamics and phase behavior of dense atomic systems are dominated by packing considerations with only minor influence from the attractive parts of the interactions. For example, it has been recently demonstratedLaird (2001) that the interfacial free energy of close-packed metals can be quantitatively described using a purely hard sphere model. The specific diameter ratio of 0.414 was chosen because, to perform an interface simulation, accurate phase coexistence parameters are required a priori, and the phase diagram for this binary system has been worked out via simulation in some detailTrizac et al. (1997). This phase diagram shows that at low pressures the fluid mixture coexists with a pure fcc crystal of the larger particles, but that at higher pressures the crystal structure in equilibrium with the fluid is a 1:1 (or AB) “intermetallic” compound with an “NaCl” structure (the small and large particles form interpenetrating fcc lattices). (The existence of the “NaCl” structure at this diameter ratio had been predicted earlier, using cell theoryCottin and Monson (1995). The diameter ratio, $`\alpha =0.414`$ is necessary for an “NaCl” structure to attain its maximum packing fraction of 0.793.) Thus, this system allows us to study the interfaces between binary fluids and two types of ordered crystal phases: single component and “NaCl”. In this work we present results for the former, but simulations on the fluid/“NaCl” are under way and will be reported later.

## II Description of the System

We consider a two-component system consisting of hard spheres of differing diameters, given by $`\sigma _A`$ and $`\sigma _B`$. Without loss of generality, it is assumed that $`\sigma _A\sigma _B`$. The interaction between two particles of type $`i`$ and $`j`$, ($`i,j\{A,B\}`$), respectively, is then given by

$$\varphi _{ij}(r)=\{\begin{array}{cc}\hfill \mathrm{},& r\sigma _{ij}\hfill \\ \hfill 0,& r>\sigma _{ij}\hfill \end{array},$$
(1)
where $`r`$ is the distance between the centers of the two interacting spheres, and $`\sigma _{ij}`$ is the distance of closest possible approach. In addition, we define the spheres to be additive, that is, $`\sigma _{ij}=(\sigma _i+\sigma _j)/2`$. The state of the system is then completely described by specifying the total density, $`\rho =\rho _A+\rho _B=N/V`$, the mole fraction, $`x_A`$, of the larger species, and the diameter ratio $`\alpha =\sigma _B/\sigma _A`$. Note that so defined one has $`\alpha (0,1)`$. In a single component system composed of hard spheres of diameter $`\sigma `$ the packing fraction, $`\eta `$ (the fraction of the total volume occupied by the spheres) is given by,

$$\eta =\frac{\pi }{6}\rho \sigma ^3,$$
(2)
where $`\rho `$ is bulk density. For the binary hard sphere system described above the packing fraction is

$`\eta `$ $`=`$ $`\eta _A+\eta _B`$ (3)
$`=`$ $`{\displaystyle \frac{\pi }{6}}\rho \left[x_A\sigma _A^3+x_B\sigma _B^3\right]`$ (4)
$`=`$ $`{\displaystyle \frac{\pi \sigma _A^3}{6}}\rho [x_A+(1x_A)\alpha ^3].`$ (5)
As mentioned in the introduction we are interested in the present study in the interface between an fcc crystal consisting of pure large (type A) spheres and its coexisting binary fluid at a diameter ratio, $`\alpha =0.414`$. The pressure-composition phase diagram for a binary hard sphere system with this diameter ratio has been previously determined by Trizac and coworkersTrizac et al. (1997) and is shown in Fig. 1.

For this study we have chosen the point in the phase diagram where a fluid mixture with a 1:1 composition (that is, $`x_A=0.50`$) coexists with a crystal phase that is an fcc composed of only large particles. We independently calculated the coexistence conditions for this point in the phase diagram and we determine the coexisting pressure to be $`P=20.1\sigma _A^3/kT`$, with packing fractions for the crystal and fluid calculated to be $`\eta _c=0.61`$ and $`\eta _f=0.51`$, respectively.

## III Calculation of Interfacial Profiles

To monitor changes in the structural or dynamical properties across the interface, the system is divided into bins along the $`z`$-axis, defined as that perpendicular to the interfacial plane. Quantities of interest are then calculated for each bin generating a $`z`$-dependent interfacial profile for the specific property (density, concentration, diffusion, etc.) being measured. The techniques of profile generation and analysis are similar to those used earlier in the works of Davidchack and Laird on the singleDavidchack and Laird (1998) and binary hard-sphere systems (with $`\alpha =0.9`$)Davidchack and Laird (1999). In this section these techniques are summarized, with particular attention to the present calculation. The reader is urged to consult the earlier papers if more detail is required.

In our analysis of the simulations, we employ bins of two different resolutions: a coarse scale and a fine scale. Coarse scale bins have a width equal to the layer spacing of the bulk crystal. This spacing is $`0.753\sigma _A`$ for  and $`0.870\sigma _A`$ for . The fine scale is $`1/25`$ of the coarse scale. Fine scale bins reveal in greater detail parameter variations across the interface, but the coarse scale is more useful for observing overall trends in the interfacial profiles. Also for some parameters, such as the diffusion constant, only the coarse scale can be used if one is to achieve meaningful statistical accuracy. For interfacial profiles that exhibit oscillations on the order of the lattice spacing, such as density, the conversion between the fine-scale profiles and coarse-scale profiles to illustrate bulk trends is problematic, since the distance between the peaks of such profiles is not necessarily constant through the interface. The mismatch between the coarse-scale bins and the peak spacing can lead to spurious resultsDavidchack and Laird (1998) if one simply averages over the fine scaled bins to create the coarse scaled profile. For such profiles we employ a Finite Impulse Response filtering procedurePress et al. (1992) to average out the oscillations and reveal coarse-grained trends. Details of the specific filtering procedure we use can be found in Ref. 24.

Below is a description on how the various interfacial properties were determined. In the definitions, the size of the bin is denoted by $`\mathrm{\Delta }z`$ and $`L_x`$, $`L_y`$ and $`L_z`$ are the the dimensions of the simulation box in the $`x`$, $`y`$ and $`z`$ directions, respectively.

* Pressure: The total pressure profile is defined as

$$P(z)=\frac{1}{3}\left\{P_{xx}(z)+P_{yy}(z)+P_{zz}(z)\right\},$$
(6)
where$`P_{kk}`$ is calculated from

$$\frac{P_{kk}}{k_BT}=\rho (z)+\frac{3m}{2L_xL_y\mathrm{\Delta }z\mathrm{\Delta }t<E_k>}\underset{c=1}{\overset{N_c}{}}r_k^{(c)}\mathrm{\Delta }v_k^{(c)},$$
(7)
where $`c`$ indexes the collisions, $`m`$ is the mass of each sphere, $`<E_k>`$ is the average kinetic energy per sphere, $`N_c`$ is the number of collisions that occurred over the time interval $`\mathrm{\Delta }t`$ in the region between $`z\mathrm{\Delta }z`$ and $`z+\mathrm{\Delta }z`$, $`r_k^{(c)}`$ is the $`kth`$ component of the relative distance between the two colliding spheres and $`\mathrm{\Delta }v_k^{(c)}`$ is the $`kth`$ component of the change in velocity for collision $`c`$. The first term in Eq. 7 represents the ideal gas pressure and the second term is the excess part due to sphere interactions.
* Excess Stress Profiles: The local excess stress is calculated from the pressure tensor components.

$$S(z)=P_{zz}(z)\frac{1}{2}\{P_{xx}(z)+P_{yy}(z)\}$$
(8)
In a simulation of an equilibrium interfacial system this quantity should be zero, except in a small region at the interface. Improper preparation or equilibration of the system often manifests itself in the excess of this quantity in the bulk crystal away from the interface. As such this quantity is carefully monitored as a measure of the quality of the simulation. To smooth out the large oscillations in this quantity through the interface, the profile is filtered to easily reveal overall trends. (The local excess stress can be integrated with respect to $`z`$ to give the surface excess stress. For a liquid-vapor interface the surface excess stress is identical to the interfacial free energy, but since the relaxation time for stress in a crystal is generally much longer than a typical simulation time, the surface excess stress and $`\gamma _{sl}`$ can be significantly different for crystal-melt interfacesTiller (1991).)
* Density Profiles and Contour Plots: The fine-scale density profile for a sphere of type $`i`$ is determined from the number density of that type particle in each fine-scale bin.

$$\rho _i(z)=\frac{<N_i(z)>}{L_xL_y\mathrm{\Delta }z}$$
(9)
where $`<N_i(z)>`$ is the average number of spheres of type $`i`$ in the region between $`z\mathrm{\Delta }z/2`$ and $`z+\mathrm{\Delta }z/2`$. To observe overall trends in bulk density (or concentration) changes we also produce filtered density profiles using our FIR filtering procedure discussed above.

In addition to the $`z`$ dependent density profiles, it is also useful to examine the density variations within the x-y planes parallel to the interfacial plane. To do this we divide the system into orthorhombic subcells with a width in the $`z`$ direction equal to the coarse bin spacing and $`x`$ and $`y`$ dimensions of $`0.15\sigma _A`$. By counting the average number of particles of each type in each subcell and dividing by the subcell volume we can produce 2d contour plots of the cross-sectional density variation within each interfacial plane.
* Interface location: We determined the location of the interface from the orientational order parameter profile.

$$q_n(z)=\frac{1}{N_z}\underset{i,j,k}{}cos\left\{n\theta _{xy}(i,j,k)\right\}$$
(10)
where $`n`$ is an integer, $`i,j`$ and $`k`$ are nearest neighbor atoms, $`\theta _{xy}(i,j,k)`$ is the bond angle formed by $`i,j`$ and $`k`$ projected on the $`x,y`$ plane, and $`N_z`$ is the total number of atoms that form bond angles. The average is taken over the number of angles found between $`z\mathrm{\Delta }z/2`$ and $`z+\mathrm{\Delta }z/2`$. The interface in the  orientation is the point along the $`z`$-axis where $`q_4`$($`q_6`$ for the ) is the arithmetic mean of the bulk crystal and liquid values. For comparison, the position of the Gibbs dividing surfaceTiller (1991) is also calculated. We determine the Gibbs dividing surface as the plane along the z-axis such that for the ’solute’ $`i`$, $`\mathrm{\Gamma }^i=0`$ in the equation

$$N^i/A=\rho _S^iz+\rho _L^i(L_zz)+\mathrm{\Gamma }^i$$
(11)
where $`N^i`$ the total number of spheres of type $`i`$, $`A`$ is the area of the interface, $`\rho _S^i`$ and $`\rho _L^i`$ are the bulk densities, $`z`$ is the location of the interface assuming the length of the simulation box runs from $`0`$ to $`L_z`$ and $`\mathrm{\Gamma }^i`$ is the excess particle per unit area of the interface.
* Diffusion coefficient profile: To study the dynamics across the interface, the diffusion coefficient profile is calculated. For a particle of type $`i`$, the diffusion coefficient is defined as follows

$$D_i(z)=\frac{1}{6N_i(z)}\frac{d}{dt}\underset{j=1}{\overset{N_i(z)}{}}𝒓_j(t)𝒓_j(t_0)^2$$
(12)
The term in the summation is the mean squared displacement over a time interval $`tt_0`$ of a total of $`N_i`$ type $`i`$ spheres located between $`z\mathrm{\Delta }z/2`$ and $`z+\mathrm{\Delta }z/2`$ at time $`t_0`$.

## IV Construction and Equilibration of Interface

Initially, blocks of crystal and fluid spheres at the calculated coexistence packing fractions and concentrations were prepared separately. As a reference, the $`z`$-axis is taken to be perpendicular to the interface. The x-y planes for both blocks had the same dimensions so that they would fit perfectly when put together to construct the interface. The plane perpendicular to the interface is made as close to square as possible given the geometric constraints of the specific interfacial orientation under study. This is trivial to achieve with the  orientation but for , the $`x`$ and $`y`$ lengths can only be made approximately equal. The lengths along $`z`$ were made longer than both those in $`x`$ and $`y`$ so that bulk properties will be observed between the two interfaces formed. Periodic boundary conditions are applied in all directions, which results in the two independent crystal-melt interfaces formed along $`z`$. The similarity of the two interfaces is an important monitor on the quality of the simulation. Obviously, if statistically significant differences in structure or dynamics exist between the two interfaces, then the system has not been properly equilibrated.

The crystal block with  orientation was set up with 7776 large spheres. It consisted of 48 crystal layers, each layer having 162 spheres. Using the coexistence packing fraction $`\eta _c=0.61`$, the following dimensions for the  crystal block were used: $`L_x=13.56\sigma _A`$, $`L_y=13.56\sigma _A`$ and $`L_z=36.15\sigma _A`$. Its coexisting fluid had 7776 large spheres and 7776 small spheres (15552 spheres total). The block length is $`L_z=43.78\sigma _A`$. For reasons that will be explained later, this $`L_z`$ gives a packing fraction that is slightly higher than that obtained from the calculated coexistence conditions. For the simulation of the  interface, the crystal block used contained 8190 large spheres, with 45 layers in the $`z`$ direction giving 182 spheres per layer. The crystal block dimensions are $`L_x=13.85\sigma _A`$, $`L_y=12.91\sigma _A`$ and $`L_z=39.13\sigma _A`$. The total number of fluid spheres used was also 15552 as in that for the  simulation with $`L_z=45.09\sigma _A`$, again, giving a packing fraction slightly higher than that predicted for coexistence. Thus the total number of particles in the interface simulations are 23328 and 23742 for the  and  interfacial orientations, respectively.

Both crystal and fluid blocks are equilibrated separately. The two blocks are then put together but a gap equal to $`\sigma _A`$ is left between each of the two crystal-melt interfaces formed to ensure that no initial overlap will occur at the interfaces. The molecular dynamics simulation is then started with only the fluid spheres allowed to move (the crystal spheres remain fixed). The fluid then fills the gaps. To compensate for the decrease in the overall bulk density of the fluid phase during this step, the fluid blocks are prepared at a packing fraction that is slightly higher than the predicted coexistence values (as mentioned earlier). In the next step, the crystal is equilibrated with the fluid spheres held fixed. At this point the interface setup is complete and an equilibration run is started with all spheres moving and with initial velocities assigned according to a Maxwell distribution. In order to efficiently carry out the molecular dynamics simulation of such a large system we use the cell method of Rappaport Rappaport (1995).

The stability of a crystal-melt interface in a simulation is extremely sensitive to the assumed coexistence conditions. In our previous workDavidchack and Laird (1998, 1999), it was found that the predetermined coexistence conditions generally had to be modified slightly in order to create a stationary interface with a zero excess stress in the bulk crystal region. This is necessary because a) the coexistence conditions are often not known a priori to the accuracy required for interface stability and b) the presence of the interface in a finite simulation can shift the coexistence equilibrium slightly. During our preliminary runs for the current system, using the coexistence conditions as calculated by thermodynamic integration of the free energies of separate bulk phases, we found that the resulting interface was stable, but yielded a bulk crystal with negative excess stress. Through experimentation, we found that an equilibrium interface with zero crystal excess stress was possible if the initial fluid packing fraction was increased to $`\eta _f=0.52`$. This had the effect of changing the concentration equilibrium slightly away from a 1:1 mixture in the fluid, as discussed below. Now it is in principle possible to vary both the initial fluid concentration and packing fraction so that the final equilibrium gives precisely a 1:1 fluid mixture, however this procedure is quite tedious and since our choice of the 1:1 fluid at coexistence was arbitrary, the fact that the actual system deviates slightly from this concentration is not important for the purposes of the current study.

To ensure that the system is indeed in equilibrium and that the bulk crystal is free of excess stress, we monitor a variety of properties such as total pressure, bulk crystal stress, fluid bulk densities and interfacial location. The results for the  interface are shown in Fig. 2, which shows that prior to equilibration at about $`t^{}t(kT/m\sigma _A^2)^{1/2}=10000`$ the crystal grows by about 3 crystal lattice planes (see Fig. 2d), accompanied by a pressure drop from 20.6 to its equilibrium value of 20.1 $`\sigma _A^3/k_BT`$ (Fig. 2a). In addition, the average excess stress in the bulk crystal, initially positive, goes to zero (within flucuations) when equilibrium is reached (Fig. 2b). (This average excess stress was calculated by averaging $`S`$ as defined above over the middle 28 layers of the bulk crystal.)

Initially, the bulk densities of both particle types in the fluid are equal, but as the system equilibrates, the bulk density of the small particles increases. This increase is due to the growth of the crystal (see Fig. 2d). Large fluid particles near the crystal freeze, expelling the small particles, which are immiscible in the crystal at this pressure, into the bulk fluid region. Although the bulk fluid initially has a large sphere mole fraction of $`X_A=0.50`$, the value at equilibrium is somewhat lower (0.46 and 0.47 for the and  interfaces, respectively). The equilibrium packing fraction of the bulk fluid slightly reduced from its initial value of $`\eta _f=0.52`$ to 0.51. Once the system is in equilibrium, the interfacial positions are stable and the fluctuation in position is less within one layer spacing.

In the preparation of the  interface some small particles became trapped within some of the interior crystal layers as the crystal grew during equilibration. Since these were in regions where the diffusion constant for the small (and large) particles was found to be zero, it cannot be determined whether these particles would actually be present in a true equilibrium interface. In order to determine the importance of these interstitial small particles in stabilizing the interface, we removed the particles (about 77 total) from the inner 3 crystal layers where they were found. The removal was done at $`t^{}=8000`$ in the equilibration run. Initially the crystal stress became negative, but quickly returned to zero (within fluctuations) as small particles from the bulk diffused in to reoccupy the removed layer closest to the interface (this layer corresponds to layer B in Fig. 5, discussed in the next section). The inner two layers did not fill in. The interfacial position remained stable during this process. The question of true chemical equilibrium is always a tricky one in these types of interface simulationsDavidchack and Laird (1999) due to the extremely slow relaxation of concentration in the deeper crystal layers. However, in this region the concentration of small particles is in any event probably quite small and should not affect our results significantly (except for perhaps the interfacial segregation). As a possible check to this procedure, one could use the Widom insertion method Frenkel (1996) to determine the excess chemical potential, and thus the solubility, of the small particles in the various inner crystal layers, but this was not done here.

The total length of the averaging run after equilibration was $`t^{}=4000`$, which was divided into 40 separate blocks of length $`t^{}=100`$ (corresponds to about 1800 collisions per particle(cpp)),over which the interfacial profiles were averaged. Since the system contains two interfaces, each block average yields two independent profiles (when properly folded about the center of the crystal) Thus, each of the profiles reported here represents an average of 80 block averages.

It is important to compare the two independent interfaces produced in a single interface simulation to ensure that they are statistically identical. Significant differences between the two interfaces are indications of problems with the equilibration procedure. As a diagnostic we determine the excess stress profile (calculated on the fine scale and filtered using the FIR filter described above and in Ref. 24). These filtered stress profiles are shown in Fig. 3 for both the  and  orientations - note that, the crystal is in the middle of the simulation box. The profiles are remarkably symmetric and also show that the excess stress is zero within fluctuations in the bulk crystal region. It should be noted that in contrast to the case for a liquid-vapor interface, the interfacial free energy of a crystal melt interface cannot be determined from the integral of the excess stress profile, as the relaxation time for stress in the crystal is significantly longer than possible simulation timesTiller (1991), and must be determined by other means, such as the recently developed cleaving wall methodDavidchack and Laird (2000). The excess stress profiles shown in Fig. 3 show a significant negative stress region on the crystal side of the interface, indicating that in this region the transverse pressure components are greater than the pressure component normal to the interfacial plane. The precise origin of this unrelaxed crystal stress at the interface is as yet unknown.

As mentioned above, the position of the interface is determined as the value of $`z`$ at which the orientational order parameter for the large spheres is the arithmetic mean of that quantity in the two bulk phases. This quantity is a useful measure of interfacial location as it is monotonic as a function of $`z`$ (so that using the arithmetic mean makes sense) and can be calculated as smooth function without large fluctuations using relatively short simulation runs. Orientational order parameters $`q_4`$ and $`q_6`$, as defined by Eqn. 10, were determined for each particle type. These are shown in Fig. 4. Since the crystal phase is made up of pure large spheres and we want to see how the ordering of particles is changed from bulk crystal to bulk liquid, we determined the interface location from the parameters calculated for large spheres. We also show $`q_4`$ and $`q_6`$ for the small particles and we see that at the interfacial region, the small spheres start developing some order that is similar to the large spheres.

## V Results for the  and  Interfaces

### V.1 Structure

The fine scale density profiles for the  and  interfaces are shown in the upper panels of Figures 5 and 6, respectively. Shown in the lower panels are the corresponding filtered profiles (including the total density profile). The distance along the $`z`$-axis (in units of the large particle diameter, $`\sigma _A`$) is measured relative to the interface center, defined as discussed above by the orientational order profiles. The vertical dotted lines are equally spaced and constructed to correspond with the density minima in between the bulk crystal layers. In both figures, specific interfacial layers are labeled alphabetically for later reference - layers A and G correspond to bulk crystal and liquid, respectively, and layers B-F lie within the interfacial region.

The density profiles for the large particles resemble strongly those for the single component hard sphere interfaceDavidchack and Laird (1998) with the periodic oscillations of the bulk crystal transforming to the uniform density of the fluid over about 7-9 lattice layers as the interface is traversed along the $`z`$-axis. The new feature seen in the present simulation is the decay of the small particle density over a similar distance into the bulk crystal, in which the small particle are immiscible. As the small particle density decreases into the crystal, it develops oscillations with a wavelength closely matching that of the crystal lattice spacing. For the  interface, the oscillations in the small particle density, $`\rho _B(z)`$ line up in phase with those of the large particle density,$`\rho _A(z)`$; whereas, in the  interface the oscillations are out of phase - the peaks of $`\rho _B(z)`$ correspond to minima of $`\rho _A(z)`$. Analysis of the atomic positions indicate that this difference is due to the fact that in the interfacial region the small particles occupy interstitial sites of the large particle fcc lattice - corresponding to the positions that would be occupied in an NaCl structure. These preferred positions lie in the  plane, but lie between the  planes of the bulk fcc lattice. Recall that the NaCl structure is the stable structure for this system at high pressure, so this effect is reminiscent of premelting transitions at solid/vapor interfaces below the bulk melting point, in that the presence of a nearby triple point (in this case the fcc/NaCl/fluid triple point) manifests itself in the presence of the metastable phase (NaCl) at the interface between the two coexisting phases (fcc and fluid).

As in the single component hard-sphere systemDavidchack and Laird (1998), the spacings between the density peaks exhibit some variation across the interface - especially for the  orientation. For each interface, the peak spacing was measured by determining the distance between density peaks in the fine scale profiles. The resulting peak spacings as functions of $`z`$ are shown in Fig. 7. For the large particles the dependence of the spacing on interfacial orientation and $`z`$ is identical to that seen in the single component simulationsDavidchack and Laird (1998). The spacing for the  lattice increases by nearly 20% from the bulk crystal value of 0.76$`\sigma _A`$ to the limiting value of about 0.9$`\sigma _A`$ as the bulk fluid is approached. The spacing for the large particles in the  interface has the same bulk liquid limiting value, but since the bulk crystal spacing is very close to this limiting value, the variation in spacing across the interface is quite small. The changes in peak spacing for the small particles are quite different for the different orientations and loosely follow those of the large particle - in  the small and large particle curves have very similar shape, but are shifted by about $`\sigma _A`$.

It is useful to compare these results directly with the single component caseDavidchack and Laird (1998). In Fig. 8 we plot (upper panel) the fine scale density profiles for the  orientation of both the single component and binary interfaces. The single component data was shifted slightly along $`z`$ to make the liquid peaks commensurate. From this plot one sees that the presence of the small particles has negligble effect on the coexisting liquid density and structure; however, the higher pressure for the binary coexistence does give a crystal phase with a higher density (the peaks are more closely spaced and more localized). The close similarity to the single component system indicates that the structure for the large particles is changed very little due to the presence of the smaller ones - except for the higher density of the crystal. In the lower panel of Fig. 8 is shown the peak spacing for the  single component and binary interfaces - scaled and shifted so that the curves go from zero in the crystal to unity in the fluid. The curves for the large particles are qualitatively similar, but the change in the single component case is less abrupt than that of the binary system.

A convenient measure of the width of the interfacial region is the so-called 10-90 width defined as the distance over which an interfacial profile changes from $`10\%`$ to $`90\%`$ of the higher of the two coexisting bulk values relative to the lower bulk value. Such a definition is only useful for those interfacial profiles which are monotonic across the interface, such as a coarse-grained (filtered) density or diffusion constants. For the filtered large particle densities the 10-90 widths are $`2.6\sigma _A`$ for the  and $`2.4\sigma _A`$ for the  - these are lower by about 0.8$`\sigma _A`$ than those found for the single component systemDavidchack and Laird (1998) which were about 3.3$`\sigma `$ for the two interfaces. From the small particle densities, the widths are larger at $`3.4\sigma _A`$ and $`3.2\sigma _A`$ for the  and  orientations, respectively, The 10-90 region defined by the large particles is within that defined by the small particles. The larger 10-90 width of the small particle filtered density is due to the ability of the small particles to penetrate into the first few crystal lattice layers.

To get a more detailed picture of the transition from crystal-like to fluid-like structure as the interface is traversed it is useful to examine the density distributions within x-y cross-sectional planes parallel to the interface. (The reported distributions are averages taken over 1800 cpp \- details of their calculation can be found in the previous section.) Figures 9 and 10 respectively show the x-y large and small particle density distributions for the  interface orientation as greyscale contour plots. The layer labels A-G correspond to those shown in Fig. 5. Fig. 9 shows that this transition from crystal to fluid occurs over about three layers (C,D and E) for the  interface and that these transition layers are not uniform, but consist of coexisting solid- and liquid-like regions, as was seen in the single-component simulationsDavidchack and Laird (1998). Layer B, although fully crystalline, does possess two vacancy defects at points $`(3.3,3.0)`$ and $`(1.0,5.3)`$. The  contour plots for the small particle density are quite interesting. There is considerable density in layer B where the small particles are present in two types of positions - in the ’NaCl’ interstitial positions and in the positions corresponding to the vacancies of the large particle crystal lattice found in layer B. The interstitial positions are occupied by single small particles, but each vacancy is filled with several small particles. In the single component simulationsDavidchack and Laird (1998) vacancy nucleation at the interface was also seen, in that case the vacancies once formed were highly mobile, migrating into the bulk via a hopping mechanism. In the present simulations, however, once the vacancies are formed in the large particle lattice, they are quickly filled with some number of small particles, which appears to immobilize the defect by suppressing the hopping mechanism - however the evidence for this is anecdotal, as the number of such vacancies is too small to gather meaningful statistics.

To estimate the degree of interfacial segregation, the Gibbs dividing surface for both interfacial orientations was determined according to Eq. 11 and found it to be close to the interface location determined from the orientational order parameters. The surface is at $`z=0.5\sigma _A`$ for  and at $`z=0.9\sigma _A`$ for . At these dividing surfaces, the excess density of solute (here defined as component B) was found to be negligible - indicating minimal interfacial segregation. Of course, for such interfacial simulations, the question of complete chemical equilibrium is generally problematic, as discussed in the previous section; however, we are confident that the concentrations of each particle type from interfacial layer B out to the bulk fluid are in chemical equilibrium (since diffusion is non-negligible there) and that the equilibrium concentrations of small particles in layers deeper into the crystal are probably quite small and will not significantly affect the results presented here.

### V.2 Dynamics

We study the dynamics across the interface by measuring diffusion coefficients in the coarse-scaled bins. The diffusion profiles for the  and  interfaces are shown in Figures 11(a) and 12(a), respectively.

The limiting bulk diffusion coefficient is $`0.012(k_BT\sigma _A^2/m)^{1/2}`$ for the large spheres and $`0.050(k_BT\sigma _A^2/m)^{1/2}`$ for the small particles, independent of the crystal orientation, as expected. When the three Cartesian components of the total diffusion coefficient are separately determined, it is found that diffusion is isotropic throughout the interfacial region.

The larger value of the small particle diffusion constant makes it difficult to compare the diffusion constants of the two components so we also plot for each, the ratio diffusion constant to the average fluid bulk value in Figures 11(b) and 12(b). Here we find the interesting result that the two curves (for both crystal orientations) are similar in shape, but shifted relative to one another by more than 1$`\sigma _A`$. As the interface is traversed from fluid to crystal, the diffusion constant for the large particle goes effectively to zero near $`z=0`$, but the small particles still have significant mobility. In this region, the large particles have become “locked in” to their crystal lattice sites, but the small particles can still move about - primarily by hopping between interstitial sites.

The 10-90 widths from the diffusion coefficient profiles for both orientation and particle types are about $`3\sigma _A`$. But because the diffusion profiles are shifted, the 10-90 widths do not define the same region. If contributions from both particle types are considered, the widths are $`4.5\sigma _A`$ for the  and $`3.9\sigma _A`$ for the  interface. The center of these interfacial regions are shifted by about $`1\sigma _A`$ to the fluid side compared to the interfacial regions defined by the density profiles. To illustrate this more clearly, we show in Fig. 13 all of the order parameter profiles (orientation, diffusion and density) for the  interface, scaled in such a way that they go from unity in the crystal phase to zero in the liquid (for example for the diffusion constants we plot $`1D(z)/D_f`$).

The 10-90 regions for the diffusion constants are offset (toward the liquid side) from those for the filtered density profiles so the interfacial region is wider than any single structural or dynamical quantity would indicate. If one considers the interfacial region as the union of the 10-90 regions for the separate profiles, then the width of the interfacial region is $`4.8\sigma _A`$, greater than that calculated from densities or diffusion coefficients alone.

## VI Summary

We have performed a series of molecular-dynamics simulations to study the crystal-melt interface of a binary hard-sphere system with diameter ratio 0.414. Previous simulation studies on two-component crystal-melt interfaces have focused on equilibrium between a fluid mixture and a substitutionally disordered crystalDavidchack and Laird (1996, 1999), but here we have examined the interface between a fluid mixture (approximately equimolar in concentration) and a coexisting single-component fcc crystal comprised of large particles - in which the small particles are immiscible. Such a coexistence occurs at relatively low pressures in the phase diagram for this diameter ratio - at higher pressures the fluid coexists with a 1:1 ordered crystal with an ‘NaCl’ structure. At a pressure of $`P=20.1\sigma _A^3/kT`$ the two phases coexist at the following packing fractions: $`\eta _c=0.61`$ and $`\eta _f=0.51`$.

Some of the principal results of this study are as follows:

* The interfacial density profiles of the large particles is very similar to that of the single-component hard-sphere system previously studiedDavidchack and Laird (1998), indicating that the presence of the small particle has no significant effect on the interfacial structure of the large particle, except for a compression of the crystal lattice due to the higher pressure. In particular the variation of the spacing between the large particle density peaks is very similar to that found in the single component studies.
* Within the regions of the interface in which the large particles are largely confined to fcc lattice sites, the small particles occupy either vacancy sites in the fcc lattice or ‘NaCl’ interstitial sites. The interstitial sites are single occupied whereas the vacancy sites are found to be occupied by several small particles. The presence of the small particles greatly suppresses the mobility of the fcc vacancies relative to those previously noted in single-component hard-sphere simulationsDavidchack and Laird (1998).
* There does not appear to be significant solute (small particle) segregation at the interface.
* The diffusion profiles of the small and large particles are similar in width (about 3 $`\sigma _A`$), but are shifted relative to one another by about 1 $`\sigma _A`$ along the interface normal ($`z`$ axis). As one traverses the interface from bulk fluid to bulk crystal, the diffusion constant goes to zero for the large particles in a region in which there is still significant small particle mobility. The picture in this region is of large particles localized at fcc lattice sites, with the small particles still diffusing between interstitial site within the lattice of large particles.
* As was found in previous hard-sphere interface studiesDavidchack and Laird (1998, 1999) the total width of the interfacial region is greater than the width determined by any single interfacial profile (such as diffusion or density) as the profiles for the individual quantities can be significantly shifted from one another. Specifically we see that as one moves from the crystal into the fluid the bulk density relaxes first to liquid-like values before significant mobility (diffusion) is observed. Considering both structural and dynamic properties, the interfacial (10-90) width is $`4.8\sigma _A`$.

## VII Acknowledgements

We gratefully acknowledge R.L. Davidchack for helpful conversations, as well as the Kansas Center for Advanced Scientific Computing for the use of their computer facilities. We also would like to thank the National Science Foundation for generous support under grant CHE-9500211.