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# Quantum Principles and Mathematical Computability

## 1 Introduction

Supported by the convergence of many seemingly different models of computation put forward independently by Turing, Post, Markov and others , a thesis on the notion of computatbility has been formed and gained much credibility. The Church- Turing thesis which can be phrased as

> Every function which would naturally be regarded as computable can be computed by a universal Turing machine.

This is neither a theorem nor a conjecture, for it is not and cannot even be hoped to be proven. The thesis simply asserts some correspondence between certain informal concept, that of computability in this case, with certain logically well-defined (i.e. mathematical) object, namely, the universal Turing machine.

The thesis thus imposes an upper limit of what any computing machine can be designed to do. Can this computability notion be enlarged? In principles, there is no reason why not. Proposals to overcome the Turing-machine limit range from the models of mathematical principles such as continous valued neural networks , DNA computing  to those of physical nature based on general arguments , relativity principles, and quantum mechanical principles .

We summarise a quantum computing model in this paper. But first we present the quantum principles in the next section.

## 2 Quantum principles

So, what are the extra-logical features of Quantum Mechanics that would enable an enlargement of computability? Following Feynman, we will employ the gedanken “simple” two-slit experiment, Figure 1, to point out all that can and cannot be known about, but will be manifest in the weird reality of quantum physics. This thought experiment is about a plane wave of electrons – all of the electrons in which have a single, well-defined value for the momentum – passing through two slits one by one before arriving at a detection screen where each electron can be recorded at a definite position on the screen and at a definite moment in (laboratory) time.

### 2.1 Intrinsic randomness

One important property of Quantum Mechanics is the randomness in the outcome of a quantum measurement. Even if we prepare the initial quantum states to be exactly the same in principle, (say, the plane-wave state for the electrons) we can still have different and random outcomes in subsequent measurements (like finding out which slit of the two that an electron so prepared would go through, or where the electron would land on the final screen). Such randomness is a fact of life in the quantum reality of our universe.

To reflect that intrinsic and inevitable randomness, the best that Quantum Mechanics, as a physical theory of nature, can do is to list, given the initial conditions, the possible values for measured quantities and the probability distributions for those values. Both the values and the probability distributions are computable in the sense that they can be evaluated algorithmically to any desirable accuracy 222More precisely mathematically, the wavefunctions generated by unitary (hence, bounded) time-evolution operators are computable, and also are the eigenvalues of hermitean operators corresponding to measured observable values. See  for more details.. This definition of computability of a number when it can be evaluated to any degree of accuracy is sufficient to interpret the number and to establish its relationship with other numbers.

On the other hand, not only the values registered in the measurement of some measurable but also the associated probability distributions are measurable in the sense that they can be obtained to any desirable accuracy by the act of physical measurements . Normally, the values for measurable are quantised so they can be obtained exactly; the probability distributions are real numbers but can be obtained to any given accuracy by repeating the measurements again and again (each time from the same initial quantum state) until the desired statistics can be reached. That is how the computable numbers from Quantum Mechanics can be judged against the measurable numbers obtained from physical experiments. Thus far, there is no evidence of any discrepancy between theory and experiments.

### 2.2 Implied infinity

Randomness is, by mathematical definition, incompressible and irreducible. In Algorithmic Information Theory, Chaitin  defines randomness by program-size complexity: a binary string is considered random when the size of the shortest program that generates that string is not “smaller” than the size of the string itself. We refer the readers to the original literature for more technically precise definitions for the cases of finite and infinite strings.

Another way to see that randomness does entail infinity is given by an interesting argument by Stannett  based on König’s Lemma which states that any finitely-branching tree which contains infinitely many terminal nodes must also contain an infinite path. It is pointed out that a classical algorithm which could generate a truly random binary sequence must contain infinitely many terminal nodes (c.f. the program-size definition for randomness). If this algorithm is recursive then it is possible that it may run forever without halting (that is, along the infinite path enabled by the König’s Lemma) in the generation of some single digit of the sequence. As such, the algorithm does not really exist, for it cannot really generate a sequence if it is stuck indefinitely at the generation of some intermediate bit somewhere in the sequence.

In sharp contrast, we can exploit Nature to generate an infinite binary sequence which is random just by, say, repeatedly detecting which of the two slits (hence the binary valuedness) the plane-wave electron goes through one by one333This possibility might seem to be unremarkable when compared to the tossing of a fabled, unbiased coin until it is pointed out that such a coin cannot exist classically. The same conditions for tossing, i.e. the same initial conditions, will result in the same outcomes as required by the equations of classical physics..

Thus, paradoxically, the quantum reality of Nature somehow allows us to compress the infinitely incompressible randomness into the apparently finite act of preparing the same quantum state over and over again for subsequent measurements!444What is finite here is the time taken to generate each and every digit of the sequence.

Infiniteness implied by randomness is not, however, the only implied infinity that is embraced by quantum reality. Quantum Mechanics suggests that an electron would explore an infinite number of paths in going from one point to another (say, from one slit to a point on the screen, in which case an infinity is somehow “contained” in the finite distance between the slit and the screen!). This infinite multiplicity of the paths taken forms the basis for Feynmann path integral formulation of Quantum Mechanics. An infinity within the finite would normally entail inconsistency – or so one would deduce from mathematical logic. Amazingly, quantum reality manages to maintain the required consistency by changing the outcome of the measurement as soon as we try to detect/confirm the infinity by identifying the paths taken in between the finite separation. This can be illustrated by and is in fact born out in the entirely different pattern (of no interference, see (A) in Fig. 1.) which will be recorded on the screen if we try to detect which of the two slits the electrons have gone through on their way there. The quantum mechanically implied infinity is both needed for and consistent with the finitely measured!

### 2.3 Quantum logic

The above peculiar properties can be captured and manisfest in the peculiarity of Quantum Logic. In contrast to the classical logic of propositional calculus, quantum propositions $`A`$, $`B`$ and $`C`$ (each has a value of being either TRUE or FALSE) do not in general satisfy the distributivity or modularity property ; that is,

$`A(BC)(AB)(AC).`$ (1)
An heuristic example of this inequality can also be found in the gedanken two-slit experiment if we label the propositions as

* $`A`$: the detection of an electron at a position $`x`$ on the final screen;
* $`B`$: the detection of an electron passing through one particular slit (say, the left one in Fig. 1) on its way to the final screen;
* $`C`$: the detection of an electron passing through the other slit on its way to the final screen.

With these choices and with the assumption that the electron intensity is low enough such that on average the electrons arrive at the screen one by one (i.e. no coincidence in the detection), the lhs of (1) represents the detection of an electron at a position $`x`$ on the screen without ever knowing which slit it has gone through to get there. On the other hand, the rhs of (1) represents the detection of an electron at a position $`x`$ on the screen when it is known which slit of the two it definitely has passed through on its way there. The former case experimentally gives rise to an inteference pattern on the screen, built up by the electrons one by one as in (B) of Fig .1. The latter gives rise to a non-interference pattern as in (A) of Fig .1, and thus is distinguishable from the former. In particular, we can find a position $`x`$ on the screen where no electron is ever detected if we have interference (that is, at the node of interference pattern). For this position $`x`$ the truth value of the combined proposition on the lhs of (1) is thus FALSE; while that of the rhs is TRUE. We then have the inequality in (1).

## 3 A quantum algorithm

We will consider the equivalent Hilbert’s tenth problem . This problem, appropriately rephrased, asks for a general algorithm to determine if any given Diophantine equation has a (non-negative) integer solution or not. A Diophantine equation involves polynomial equation of many unknowns and integer coefficients. If we can find a general algorithm asked for by the Hilbert’s tenth problem then we will have a general algorithm for the well-known Turing halting problem; that is, we will be able to tell if any given Turing program will halt or not upon starting with some input.

Classically, there is no such algorithm by the Cantor’s diagonal arguments. For this particular Hilbert’s tenth problem, we can see that its noncomputability originates from the lack of a general method to verify a negative statement concerning solution of a Diophantine equation. By direct subsitution into the Diophantine polynomial, it is straightforward to verify whether a set of integers is indeed a zero of the polynomial as it is claimed or not. But substitution can not be used to verify in general a negative statement that a Diophantine polynomial has no zero as it would require the infinite task of substituting all integers! For a particular equation, such as the Diophantine equation of the Fermat’s last theorem, one may be able to find a specific way to confirm that the equation has no solution. But that specific way is peculiar and only applicable to the equation in consideration, or some related equations, and not to any Diophantine equations in general.

Nevertheless, a quantum algorithm has been proposed recently  for the Hilbert’s tenth problem. We will summarise the main points of the algorithm below and only wish to mention here that we consider quantum algorithms are as good as any algorithms in the sense that they can be implementable in the physical world, occupying finite time duration and finite spatial extent and consuming finite physical resources.

### 3.1 Outlines

Our strategy is that we do not look for the zeroes of the Diophantine polynomial in question, which may not exist, but instead search within the domain of non-negative integers for the absolute minimum of the square of the polynomial, which always exists and is finite. While it is equally hard to find either the zeroes or the absolute minimum in classical computation, we have converted the problem to the realisation of the ground state of a quantum Hamiltonian and there is no known quantum principle against such an act. In fact, there is no known physical principles against it. Let us consider the three laws of thermodynamics concerning energy conservation, entropy of closed systems and the unattainability of absolute zero temperature. The energy involved in our algorithm is finite, being the ground state energy of some Hamiltonian. The entropy increase which ultimately connects to decoherence effects is a technical problem for all quantum computation in general.

It may appear that even the quantum process can only explore a finite domain in a finite time and is thus no better than a classical machine in terms of computability. But there is a crucial difference.

In a classical search, even if the global minimum is encountered, it cannot generally be proved that it is the global minimum (unless it is a zero of the Diophantine equation). Armed only with classical logic, we would still have to compare it with all other numbers from the infinite domain yet to come, but we obviously can never complete this comparison in finite time – thus, the noncomputability.

In the quantum case, the global minimum is encoded in the energy of the ground state of a suitable Hamiltonian. Then, by energetic tagging, the global minimum can be found in finite time and confirmed, if it is the ground state that is obtained at the end of the computation. It is the physical principles that can be utilised to identify and/or verify the ground state. These principles are over and above the mathematics which govern the logic of a classical machine and help differentiate the quantum from the classical. Quantum mechanics could “explore” an infinite domain, but only in the sense that it can select, among an infinite number of states, one single state (or a subspace in case of degeneracy) to be identified as the ground state of some given Hamiltonian (which is bounded from below).

Our proposal is in contrast to the claim in  that quantum Turing machines compute exactly the same class of functions as do Turing machines, albeit perhaps more efficiently. The quantum Turing machine approach considered there is a direct generalisation of that of the classical Turing machines but with qubits and some universal set of one-qubit and two-qubit unitary gates to build up, step by step, dimensionally larger, but still dimensionally finite unitary operations. This universal set is chosen on its ability to evaluate any desirable classical logic function. Our approach, on the other hand, is from the start based on infinite-dimension Hamiltonians and also based on the special properties and unique status of their ground states. The unitary operations are then followed as the Schrödinger time evolutions.

### 3.2 Verification of the ground state

The quantum algorithm is based on the key ingredients of:

* The exactitude, to the level required, of the theory of Quantum Mechanics in describing and predicting physical processes.
* Our ability to physically implement certain Hamiltonians having infinite numbers of energy levels;
* Our ability to physically obtain and verify some state as the desirable ground state;

If any of these is not achievable or approximable with controllable accuracy, the quantum algorithm simply fails and further modifications may or may not work.

Without any known physical principles outlawing these key assumptions, we sketch here an approach to obtain and verify the desirable ground state of the Hamiltonian corresponding to the Diophantine polynomial in consideration.

It is in general easier to implement a hamiltonian $`H_P`$ than to obtain its ground state $`|g`$. We thus should start the computation in yet a different and readily obtainable initial state $`|g_I`$, which is the ground state of some other hamiltonian, $`H_I`$, then deform this hamiltonian $`H_I`$ adiabatically in time into the hamiltonian whose ground state is the desired one, through a time-dependent process represented by an interpolating Hamiltonian $`(s)=(1s)H_I+sH_P`$, for $`s`$ changes from 0 to 1. The theorem of quantum adiabtic processes ensures that we can get arbitrarily close to the ground state $`|g`$ of $`H_P`$. Figures 2 and 3 below give an heuristic illustration of the quantum adiabatic theorem, which can be exploited for optimisation problems.

In order to solve the Hilbert’s tenth problem we need on the one hand such time-dependent physical (adiabatic) processes to arrive at a candidate state. On the other hand, the theory of Quantum Mechanics can be used to verify whether this candidate is the ground state through the usual statistical predictions from the Schrödinger equation with a truncated number of energy states of the time-dependent Hamiltonian $`(s)`$. This way, we can overcome the problem of which states are to be included in the truncated basis for a numerical study of Quantum Mechanics. This also reconciles with the Cantor diagonal arguments which state that the problem could not be solved entirely in the framework of classical computation.

The key factor in the ground state verification is the probability distributions, which are both computable from a numerical study of Quantum Mechanics (that is, with the control in the calculation to reach any desirable accuracy) and measurable in practice (i.e., by repeating the physical processes to obtain the statistics to any desirable accuracy). By matching the calculated with the measured, both of which depend on the evolution time which we can vary, we then can unambiguously identify the ground state of the final Hamiltonian. The information about the existence of solution, or lack of it, for the given Diophantine polynomial can be inferred through some further quantum measurements on this ground state.

It is worth noting that we have here a peculiar situation in which the computational complexity, that is, the evolution time, might not be known exactly before carrying out the quantum computation – although it can be estimated approximately.

## 4 When is a proof a proof?

Proof, be it mathematical or general, is the means to an end: a proof is there to explain, convince or persuade the others (and even oneself) the “truthful” value of certain statement(s).

A classical proof, based on classical logic, starts with a finite number of axioms from which a finite number of subsequent/intermediate statements can be derived with the help of a finite number of inference rules. And it ends with a final statement, the “truth”. All these finiteness requirements are there to ensure the reproducibility of the proof in a finite time and manner. A classical algorithm is a particular case of such a type of proof, with input being (part of) the axioms and output the final “truth”.

Deutsch and some others  see such a classical proof/algorithm as an object, static with intermediate records. On the other hand and in contrast, quantum algorithms are seen as dynamical processes wherein the intermediate “steps” cannot be recorded without destroying the interference and thus the algorithms themselves. The intermediate quantum “steps”, as a matter of facts, cannot be even made out as clearly defined, discrete steps, expressible in terms of classical propositions.

The requirement of finiteness of the number of intermediate steps in a classical proof is no longer relevant (and unobtainable in a quantum proof anyway) if consistency is maintainable and reproducibility is achievable in quantum “proofs”.

For such quantum proofs to be credible, they must be consistent: a statement and its negation cannot be proved at the same time under the same conditions. In basing the notion of proof on the physical reality, the condition of consistency should be automatically and implicitly guaranteed, for after all there is only one reality – or at most one which we can perceive. Signs of inconsistency would not be pointing to something intrinsic of the reality, but would be only because of our perception or understanding of reality. In other words, inconsistency, as we see it, cannot refute the reality; it only hints that it is time we need a new theory of Nature, which in turn may or may not affect the “proof.”

For such quantum proofs to be of some usefulness, they must be repoducible: reproducible in a finite duration of time, reproducible in at different locations and reproducible at different times. The latter two requirements are ensured by the principles of invariance under spatial and temporal translations, which are some of the most cherished physical principles. These principles can be tested, and have been tested extensively to the hisghest accuracy without any failures, via their consequences in the conservation of energy and linear momentum.

But can they, the quantum proofs, be acceptable as proofs? We would prefer an affirmative answer even though the answer to this question might only be a matter of taste.

It should be easier to accept a quantum process a proof if the end result of the quantum process can be verified by classical means – for instance, in a factoring problem, the obtained primes can be easily multiplied together to give back the original number as a check. Similarly, a quantum process should also be acceptable as a valid proof even if such direct verification cannot be carried out as a matter of principle but the result somehow can be verified indirectly through some other (physical or mathematical) handles. This is the case of our algorithm for Hilbert’s tenth problem above where we only need to verify that some state is indeed the ground state, a physical attribute only indirectly linked to the mathematical solutions sought.

The authors whose quotation is quoted at the beginning of this article have also argued that even when, as a matter of principles, there is no direct nor indirect verifications possible, quantum process should still be considered as valid means of proof, simply because of “our acceptance of the physical laws underlying the computing operations.”

## 5 Concluding remarks

In this paper we review the important characters of Quantum Principles and put forward the arguments that these physical principles may help compute some of the classically noncomputable. We also outline a recently proposed quantum algorithm for the Hilbert’s tenth problem, and emphasise the key role of probability distributions in the crucial verification, of a physical nature, for the solution for this classically noncomputable problem.

It remains to be seen if and when the quantum algorithm can be physically realised. If not prohibited by any physical principles, and we know none so far, then we trust that it can be implementable and will be realisable. Whatever the case it may turn out to be, our investigation has already opened up new and interesting directions for Mathematics itself. Our quantum algorithm has inspired a reformulation of the Hilbert’s tenth problem, a problem in the domain of the discrete integers, in terms of a set of infinitely coupled differential equations over continuous variables . This may lead to new insights and/or solution of the problem (recalled that, despite the mathematical noncomputability of Hilbert’s tenth problem, there does exist a general procedure to decide whether any given polynomial with many unknowns and real (continuous) coefficients has real solutions or not .)

Our decidability study here in the framework of Quantum Mechanics only deals with the property of being Diophantine, which does not cover the property of being arithmetic in general (which could involve unbounded universal quantifiers). This entails that our consideration has no direct consequences on Gödel’s Incompleteness theorem.

## Acknowledgement

I am indebted to Alan Head and Peter Hannaford for encouragement and discussions; and would like to acknowledge the discussions with Cristian Calude, Jack Copeland, Toby Ord, Boris Pavlov and Andrew Rawlinson, who also helped me with the Figure 1.


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# Hypersurfaces with flat centroaffine metric and equations of associativity

## 1 Introduction

Centroaffine geometry studies the properties of hypersurfaces $`M^nA^{n+1}`$ which are invariant under the action of the general linear group $`GL(n+1)`$. Since this action preserves the origin (translations are not allowed), one can choose the position vector $`𝐫`$ of a hypersurface as its centroaffine normal. With this normalization, one readily introduces the main centroaffine invariants: the centroaffine metric, the centroaffine cubic form and the Chebyshev covector (see sect. 1; in our presentation we follow the monograph , see also ). These invariants satisfy the compatibility conditions known as the centroaffine Gauss-Codazzi equations. It is well-known that the vanishing of the centroaffine cubic form characterises central hyperquadrics, while the vanishing of the Chebyshev covector is characteristic for proper affine hyperspheres. In this article we consider the third natural class of centroaffine hypersurfaces characterized by the flatness of the centroaffine metric.

The main observation is that, in the flat coordinates of the centroaffine metric, the corresponding Gauss-Codazzi equations reduce to a system of nonlinear PDEs known as the equations of associativity of two-dimensional topological field theory  (to be precise, WDVV equations without the quasihomogeneity condition). This is explained in sect. 3. For surfaces $`M^2A^3`$ these equations reduce to a single PDE of the Monge-Ampere type,

$$f_{xxx}f_{yyy}f_{xxy}f_{xyy}=1,$$

where $`x`$ and $`y`$ are the asymptotic coordinates on $`M^2`$.

The geometry of surfaces $`M^2A^3`$ with a flat centroaffine metric is discussed in sect. 4 and 5 where, in particular, we establish some geometric properties of characteristics of the above PDE.

The review  provides an abundance of exact solutions of the associativity equations. Some of them are listed in sect. 5 and 6. The centroaffine geometry of the corresponding surfaces is currently under investigation.

In sect. 7 a simple loop-group formulation of the linear system governing surfaces with a flat centroaffine metric is proposed which is due to A. Bobenko.

Since the centroaffine metric is proportional to the second fundamental form, hypersurfaces with a flat centroaffine metric (and projective transforms thereof) form a subclass of projective hypersurfaces with conformally flat second fundamental form which was investigated in detail in . Another interesting class of projective surfaces $`M^2P^3`$ (containing projective transforms of surfaces with a flat centroaffine metric as a proper subclass), is characterised by the existence of a one-parameter family of asymptotic deformations which induce constant rescalings of the projective metric and the Darboux cubic form. These generalizations are discussed in sect. 8.

## 2 Hypersurfaces in centroaffine geometry

The position vector $`𝐫=(r^0,r^1,\mathrm{},r^n)`$ of a hypersurface $`M^n`$ in centroaffine geometry satisfies the linear system

$$𝐫_{ij}=\stackrel{~}{\mathrm{\Gamma }}_{ij}^k𝐫_k+g_{ij}𝐫,i,j=1,\mathrm{},n,$$
(1)
which is required to be compatible of the rank $`n+1`$ (here $`𝐫_i=𝐫/u^i,𝐫_{ij}=𝐫/u^iu^j`$ where $`u^1,\mathrm{},u^n`$ are local coordinates on $`M^n`$). Under reparametrizations of $`M^n`$, the objects $`g_{ij}`$ and $`\stackrel{~}{\mathrm{\Gamma }}_{ij}^k`$ transform as the components of a pseudo-Riemannian metric (assumed nondegenerate) and Christoffel’s symbols of an affine connection (called the affine connection of the first kind; we emphasize that it is not the Levi-Civita connection of $`g_{ij}`$). The conformal class of $`g_{ij}`$ is nothing but the second fundamental form of $`M^n`$. The compatibility conditions of system (1) are of the form

$$\begin{array}{c}\stackrel{~}{}_kg_{ij}=\stackrel{~}{}_jg_{ik}\\ \\ \stackrel{~}{R}_{ijk}^s=g_{ik}\delta _j^sg_{ij}\delta _k^s\end{array}$$
(2)
where $`\stackrel{~}{}`$ denotes covariant differentiation in the connection $`\stackrel{~}{\mathrm{\Gamma }}`$, and $`\stackrel{~}{R}_{ijk}^s=_k\stackrel{~}{\mathrm{\Gamma }}_{ij}^s_j\stackrel{~}{\mathrm{\Gamma }}_{ik}^s+\stackrel{~}{\mathrm{\Gamma }}_{ij}^p\stackrel{~}{\mathrm{\Gamma }}_{pk}^s\stackrel{~}{\mathrm{\Gamma }}_{ik}^p\stackrel{~}{\mathrm{\Gamma }}_{pj}^s`$ is the curvature tensor. For our purposes, it will be more convenient to rewrite the compatibility conditions (2) in terms of the Levi-Civita connection $`\mathrm{\Gamma }_{ij}^k`$ of the metric $`g_{ij}`$ and the difference $`(1,2)`$-tensor $`h_{ij}^k`$ defined by

$$\stackrel{~}{\mathrm{\Gamma }}_{ij}^k=\mathrm{\Gamma }_{ij}^k+h_{ij}^k.$$

In this notation, equations (2) can be cast into the form

$$\begin{array}{c}h_{ij}^sg_{sk}=h_{ik}^sg_{sj},_kh_{ij}^s=_jh_{ik}^s,\\ \\ R_{ijk}^s+h_{ij}^ph_{pk}^sh_{ik}^ph_{pj}^s=g_{ik}\delta _j^sg_{ij}\delta _k^s\end{array}$$
(3)
where $``$ denotes covariant differentiation in the Levi-Civita connection $`\mathrm{\Gamma }`$, and $`R_{ijk}^s`$ is the curvature tensor. Equation $`(\text{3})_1`$ implies that the tensor $`h_{ijk}=h_{ij}^sg_{sk}`$ is totally symmetric, defining the centroaffine cubic form of the hypersurface $`M^n`$. The centroaffine metric

$$M=g_{ij}du^idu^j$$

and the centroaffine cubic form

$$C=h_{ijk}du^idu^jdu^k$$

satisfying the compatibility conditions (3) characterize a hypersurface uniquely. Another useful invariant of a hypersurface in centroaffine geometry is the so-called Chebyshev covector,

$$T=T_idu^i=\frac{1}{n}h_{is}^sdu^i,$$

which, as readily follows from $`(\text{3})_2`$, is always a gradient: $`dT=0`$. It is known that the vanishing of the cubic form characterizes central hyperquadrics . The proper affine hyperspheres can be defined as hypersurfaces with the vanishing Chebyshev covector. The main object of our study is the third natural class of centroaffine hypersurfaces, namely, hypersurfaces with a flat centroaffine metric. Notice that the centroaffine metric can be equivalently defined by the formula

$$M=\frac{|d^2𝐫𝐫_1\mathrm{}𝐫_n|}{|𝐫𝐫_1\mathrm{}𝐫_n|}.$$

For hypersurfaces defined explicitly as graphs of functions, $`u^{n+1}=f(u^1,\mathrm{},u^n)`$, the centroaffine metric has the form

$$M=\frac{d^2f}{F}=\frac{d^2F}{F},$$

where $`F=f_iu^if`$ is the Legendre transform of $`f`$, and $`d^2F`$ denotes the second differential. Some global aspects of Riemannian metrics of the form $`d^2F/F`$ were discussed in  and . The condition of flatness of the metric $`d^2F/F`$ results in a system of third order nonlinear PDEs for the function $`F`$ (which looks quite formidable even in the simplest case $`n=2`$). As we demonstrate below, this system is nothing but the equations of associativity (WDVV equations).

Remark.  System (1) appears naturally in the theory of multi-dimensional Schwarzian derivatives. In this setting, one is interested in the mapping from $`M^n`$ into the projective space $`P^n`$ defined as $`(r^0:r^1:\mathrm{}:r^n)`$ in homogeneous coordinates of $`P^n`$. We refer to  for the details. In centroaffine geometry, non-constant rescalings of the position vector $`𝐫`$ are not allowed: they result in non-equivalent hypersurfaces.

## 3 Hypersurfaces with flat centroaffine metric and associativity equations

For hypersurfaces with a flat centroaffine metric one can choose the parametrization such that $`g_{ij}=\eta _{ij}=const`$, so that $`\mathrm{\Gamma }=0,_k=_k`$ and equations (3) take the form

$$\begin{array}{c}h_{ij}^s\eta _{sk}=h_{ik}^s\eta _{sj},_kh_{ij}^s=_jh_{ik}^s,\\ \\ h_{ij}^ph_{pk}^sh_{ik}^ph_{pj}^s=\eta _{ik}\delta _j^s\eta _{ij}\delta _k^s.\end{array}$$
(4)
The first two equations imply the existence of the potential $`f`$ such that

$$h_{ij}^s=\eta ^{sk}_i_j_kf$$

resulting in the following formulae for the centroaffine invariants:

centroaffine metric

$$M=\eta _{ij}du^idu^j;$$

centroaffine cubic form

$$C=d^3f;$$

Chebyshev covector

$$T=\frac{1}{n}d(\mathrm{}f)$$

where $`\mathrm{}`$ denotes the Laplacian in the metric $`\eta _{ij}`$.

In terms of $`f`$, the third set of equations (4) results in a nonlinear system of PDEs known as the equations of associativity in two-dimensional topological field theory . To see this, we introduce one extra coordinate $`u^0`$ and the function

$$F(u^0,u^1,\mathrm{},u^n)=\frac{1}{6}(u^0)^3+\eta _{ij}u^0u^iu^j+f(u^1,\mathrm{},u^n).$$

One can readily verify the following properties, which are in fact the axioms of the associativity equations (in what follows $`\alpha ,\beta ,\gamma =0,1,\mathrm{},n\mathrm{and}i,j,k=1,\mathrm{},n`$).

1. The matrix $`\eta _{\alpha \beta }=\frac{^3F}{_0_\alpha _\beta }`$ is constant and nondegenerate, indeed,

$$\eta _{\alpha \beta }=\left(\begin{array}{cc}1& 0\\ & \\ 0& \eta _{ij}\end{array}\right).$$

2. The objects $`c_{\beta \gamma }^\alpha =\eta ^{\alpha \delta }\frac{^3F}{_\beta _\gamma _\delta }`$ are the structure constants of a commutative associative algebra. Indeed, the only nonzero among them are

$$c_{00}^0=1,c_{ij}^0=\eta _{ij},c_{0j}^i=c_{j0}^i=\delta _j^i,c_{jk}^i=h_{jk}^i,$$

and equations (4) imply the associativity.

The function $`F`$ defines a Frobenius structure  on the manifold with coordinates $`u^0,u^1,\mathrm{},u^n`$, the main ingredients of which are the flat metric

$$(du^0)^2+\eta _{ij}du^idu^j$$

and the symmetric 3-tensor

$$d^3F=(du^0)^3+\eta _{ij}du^0du^idu^j+d^3f.$$

Notice that the centroaffine metric $`M`$ and the cubic form $`C`$ can be obtained by resticting these objects to a hyperplane $`u^0=const`$ in the spirit of . Thus, hypersurfaces with flat centroaffine metric carry an intrinsic induced Frobenius structure. Moreover, one can incorporate the spectral parameter $`\lambda `$ into the equations for the position vector,

$$𝐫_{ij}=\lambda h_{ij}^k𝐫_k+\lambda ^2\eta _{ij}𝐫,$$
(5)
without violating the compatibility conditions (4). In arbitrary parametrization, the linear system (5) takes the form

$$𝐫_{ij}=(\mathrm{\Gamma }_{ij}^k+\lambda h_{ij}^k)𝐫_k+\lambda ^2g_{ij}𝐫,$$
(6)
where $`\mathrm{\Gamma }`$ is the Levi-Civita connection of the flat metric $`g`$. System (6) defines a one-parameter family of hypersurfaces $`M_\lambda ^n`$ with centroaffine metrics

$$M=\lambda ^2g_{ij}du^idu^j$$

and centroaffine cubic forms

$$C=\lambda ^3h_{ijk}du^idu^jdu^k.$$

Therefore, hypersurfaces with a flat centroaffine metric can be equivalently characterized as hypersurfaces possessing nontrivial deformations which induce rescalings of the centroaffine metric and the centroaffine cubic form. For $`\lambda =1`$ we recover the original hypersurface $`M^n`$, the case $`\lambda =0`$ corresponds to a hyperplane, and $`\lambda =1`$ results in the dual hypersurface.

Remark. One can consider the linear system (6) without imposing the restriction that $`\mathrm{\Gamma }`$ is the Levi-Civita connection of $`g`$. In this case the compatibility conditions imply

$$\begin{array}{c}_kg_{ij}=_jg_{ik},_kh_{ij}^p=_jh_{ik}^p,h_{ij}^sg_{sk}=h_{ik}^sg_{sj},\\ \\ h_{ij}^ph_{pk}^sh_{ik}^ph_{pj}^s=g_{ik}\delta _j^sg_{ij}\delta _k^s\end{array}$$
(7)
where $``$ denotes covariant differentiation in the connection $`\mathrm{\Gamma }`$. Moreover, the connection $`\mathrm{\Gamma }`$ must be flat. This class of surfaces will be investigated in some more detail elsewhere.

Examples. In the case $`n=2`$ one can either choose $`\eta =2dxdy`$ (hyperbolic surfaces) or $`\eta =dx^2+dy^2`$ (convex surfaces). Here $`x=u^1`$ and $`y=u^2`$ are asymptoticcoordinates on a surface $`M^2`$. In the hyperbolic case, equations (5) take the form

$$\begin{array}{c}𝐫_{xx}=\lambda f_{xxx}𝐫_y+\lambda f_{xxy}𝐫_x,\\ \\ 𝐫_{xy}=\lambda f_{xxy}𝐫_y+\lambda f_{xyy}𝐫_x+\lambda ^2𝐫,\\ \\ 𝐫_{yy}=\lambda f_{xyy}𝐫_y+\lambda f_{yyy}𝐫_x,\end{array}$$
(8)
with the compatibility condition

$$f_{xxx}f_{yyy}f_{xxy}f_{yyx}=1.$$
(9)
In a similar form (however, without a spectral parameter) the linear problem (8) was presented in . Introducing $`\psi =(\lambda 𝐫,𝐫_x,𝐫_y)^T`$, one can readily rewrite (8) in a matrix form

$$\psi _x=\lambda \left(\begin{array}{ccc}0& 1& 0\\ 0& f_{xxy}& f_{xxx}\\ 1& f_{xyy}& f_{xxy}\end{array}\right)\psi ,\psi _y=\lambda \left(\begin{array}{ccc}0& 0& 1\\ 1& f_{xyy}& f_{xxy}\\ 0& f_{yyy}& f_{xyy}\end{array}\right)\psi $$
(10)
which coincides with the one from . Similarly, in the convex case we have

$$\begin{array}{c}𝐫_{xx}=\lambda f_{xxx}𝐫_x+\lambda f_{xxy}𝐫_y+\lambda ^2𝐫,\\ \\ 𝐫_{xy}=\lambda f_{xxy}𝐫_x+\lambda f_{xyy}𝐫_y,\\ \\ 𝐫_{yy}=\lambda f_{xyy}𝐫_x+\lambda f_{yyy}𝐫_y+\lambda ^2𝐫,\end{array}$$
(11)
with the compatibility condition

$$f_{xxy}^2+f_{xyy}^2f_{xxx}f_{xyy}f_{yyy}f_{xxy}=1.$$
(12)
Particular examples of surfaces with a flat centroaffine metric were discussed in  (surfaces of revolution with the centroaffine metric of constant curvature) and  (centroaffinely flat Chebyshev surfaces).

Introducing the variables $`f_{xxx}=p,f_{xxy}=a,f_{xyy}=b`$ and $`f_{yyy}=q`$, , , one can rewrite (9) in the form

$$p_y=a_x,a_y=b_x,b_y=q_x,pqab=1$$
(13)
which is equivalent to the quasilinear system

$$\left(\begin{array}{c}p\\ a\\ b\end{array}\right)_y=U\left(\begin{array}{c}p\\ a\\ b\end{array}\right)_x,U=\left(\begin{array}{ccc}0& 1& 0\\ 0& 0& 1\\ \frac{1+ab}{p^2}& \frac{b}{p}& \frac{a}{p}\end{array}\right)$$
(14)
investigated in detail in . The characteristics of this system are defined by $`dx+\lambda dy=0`$ where $`\lambda `$ is a root of the characteristic polynomial of the matrix $`U`$,

$$p\lambda ^3a\lambda ^2b\lambda +q=0.$$

Equivalently, characteristics can be defined as the null-curves of the cubic form

$$pdx^3+adx^2dybdxdy^2qdy^3,$$

indeed, $`\lambda =dx/dy`$. The geometry of this cubic form is clarified in section 4.

## 4 Surfaces in centroaffine 3-space

In asymptotic coordinates $`x`$ and $`y`$ (for definiteness, we consider hyperbolic case only), equations (1) take the form

$$\begin{array}{c}𝐫_{xx}=(a+u_x)𝐫_x+p𝐫_y,\\ \\ 𝐫_{xy}=b𝐫_x+a𝐫_y+e^u𝐫,\\ \\ 𝐫_{yy}=q𝐫_x+(b+u_y)𝐫_y,\end{array}$$
(15)
with the compatibility conditions

$$\begin{array}{c}a_y=b_x,a_xp_y=au_x+pu_y,b_yq_x=qu_x+bu_y,\\ \\ pqab=e^u(K+1),\end{array}$$
(16)
where $`K=e^uu_{xy}`$ is the Gaussian curvature of the corresponding centroaffine metric

$$M=2e^udxdy.$$

Notice that in the flat case ($`K=0,u=0`$) equations (16) coincide with (13). Since the only nonzero Christoffel symbols of the centroaffine metric $`M`$ are $`\mathrm{\Gamma }_{11}^1=u_x`$ and $`\mathrm{\Gamma }_{22}^2=u_y`$, we have $`h_{11}^1=a,h_{11}^2=p,h_{12}^1=b,h_{12}^2=a,h_{22}^1=q`$ and $`h_{22}^2=b`$, so that the centroaffine cubic form $`C`$ and the Chebyshev covector $`T`$ take the forms

$$C=e^u(pdx^3+3adx^2dy+3bdxdy^2+qdy^3)$$

and

$$T=adx+bdy,$$

respectively.

Remark. We point out that surfaces with the zero Chebyshev covector are the proper affine spheres, indeed, the substitution of $`a=b=0`$ into $`(\text{16})_2`$ and $`(\text{16})_3`$ implies $`p=q=e^u`$, so that $`(\text{16})_4`$ results in the Tzitzeica equation $`u_{xy}=e^ue^{2u}`$.

Let us consider the form

$$C2TM=e^u(pdx^3adx^2dybdxdy^2+qdy^3)$$

which, at a generic point of our surface, has three distinct zero directions. The three directions conjugate to them are defined by the equation

$$pdx^3+adx^2dybdxdy^2qdy^3=0,$$
(17)
(recall that two directions are called conjugate if they are orthogonal with respect to the metric $`M`$). The null-curves of (17) define a foliation of our surface by three families of curves, which we will call the characteristic 3-web for the reason which is clarified at the end of section 3.

###### Theorem 1

For surfaces with a flat centroaffine metric, the characteristic 3-web is hexagonal.

Proof:

A direct calculation of the curvature form $`\mathrm{\Omega }`$ of the characteristic 3-web results in the formula $`\mathrm{\Omega }=d\omega `$, where the connection form $`\omega `$ is

$$\omega =\frac{3e^u}{r^24st}\left((rK_x2tK_y)dx+(rK_y2sK_x)dy\right),$$

here $`r=ab9pq,s=b^2+3aq,t=a^2+3bp`$. If $`K=0`$, the curvature form $`\mathrm{\Omega }`$ is zero, implying the hexagonality of the characteristic 3-web.

Remark. The class of surfaces with a hexagonal characteristic 3-web includes surfaces with a flat centroaffine metric as a proper subclass. For instance, the form of $`\omega `$ implies that surfaces with the centroaffine metric of constant curvature ($`K`$=const) also have a hexagonal characteristic web. In would be of interest to discuss this class of surfaces in some more detail. The simplest examples of surfaces with centroaffine metric of constant curvature $`K=1`$ are central quadrics (which correspond to $`a=b=p=q=0`$ in the equations (16)). Since in this case (17) is identically zero, the characteristic 3-web is indeterminate.

## 5 Other parametrizations

In asymptotic coordinates $`x`$ and $`y`$, the position vector $`𝐫`$ of a surface with flat centroaffine metric satisfies the equations

$$\begin{array}{c}𝐫_{xx}=\lambda a𝐫_x+\lambda p𝐫_y,\\ \\ 𝐫_{xy}=\lambda b𝐫_x+\lambda a𝐫_y+\lambda ^2𝐫,\\ \\ 𝐫_{yy}=\lambda q𝐫_x+\lambda b𝐫_y,\end{array}$$
(18)
the compatibility conditions of which coincide with (13). After the reparametrization $`(x,y)(t,y)`$ where $`t`$ is defined by

$$dt=pdx+ady,$$
(19)
equations (18) take the form

$$\begin{array}{c}𝐫_{tt}=(\frac{C_t}{C}2\lambda B)𝐫_t+\lambda C𝐫_y\\ \\ 𝐫_{ty}=(\frac{B_t}{C}\lambda A)𝐫_t+\lambda ^2C𝐫,\\ \\ 𝐫_{yy}=(\lambda +\frac{B_y}{C})𝐫_t\lambda A𝐫_y+2\lambda ^2B𝐫,\end{array}$$
(20)
where we have introduced the notation

$$A=a^2/pb,B=a/p,C=1/p.$$
(21)
The compatibility conditions of equations (20) take the form

$$A_t=B_y,B_t=C_y,C_t=(B^2AC)_y.$$

Written in terms of the potential $`F`$ such that $`A=F_{yyy},B=F_{tyy}`$ and $`C=F_{tty}`$, this system reduces to a single PDE

$$F_{ttt}=F_{tyy}^2F_{tty}F_{yyy},$$
(22)
which is yet another form of the associativity equations . Thus, both equations (9) and (22) describe one in the same class of surfaces, however, in different parametrizations. Notice that, in terms of the potentials $`f(x,y)`$ and $`F(x,t)`$, the formulae (19) and (21) take the form

$$t=f_{xx},F_{yyy}=\frac{f_{xxy}^2}{f_{xxx}}f_{xyy},F_{tyy}=\frac{f_{xxy}}{f_{xxx}},F_{tty}=\frac{1}{f_{xxx}},F_{ttt}=\frac{f_{xyy}}{f_{xxx}},$$

and, after being integrated once, simplify to

$$f_{xx}=t,f_{xy}=F_{yy},f_{yy}=F_{tt},x=F_{ty}.$$
(23)
This transformation between (9) and (22) was first proposed in . Taking, for instance, the known polynomial solution of the equation (22),

$$F(t,y)=\frac{t^2y^2}{4}+\frac{t^5}{60},$$

we readily arrive at the formulae

$$f_{xx}=t,f_{xy}=\frac{t^2}{2},f_{yy}=\frac{y^2}{2}+\frac{t^3}{3},x=ty,$$

which, after the substitution of $`t=x/y`$ into the first three equations, give a solution of (9):

$$f(x,y)=\frac{x^3}{6y}+\frac{y^4}{24}.$$

Here we list some further solutions of the equation $`f_{xxx}f_{yyy}f_{xxy}f_{yyx}=1`$ which can be obtained by applying the transformation (23) to the known solutions of (22) as found in :

| $`F_{ttt}=F_{tyy}^2F_{tty}F_{yyy}`$ | $`f_{xxx}f_{yyy}f_{xxy}f_{yyx}=1`$ |
| --- | --- |
| $`F=\frac{t^2y^2}{4}+\frac{t^5}{60}`$ | $`f=\frac{x^3}{6y}+\frac{y^4}{24}`$ |
| $`F=ye^t\frac{y^4}{24}`$ | $`f=\frac{xy^3}{6}+\frac{x^2\mathrm{ln}x}{2}\frac{3x^2}{4}`$ |
| $`F=\frac{y^2e^t}{4}+\frac{e^{2t}}{32}\frac{y^4}{48}`$ | $`f=\frac{xy^3}{12}\frac{x^2\mathrm{ln}y}{2}+\frac{x^2\mathrm{ln}x}{2}\frac{3x^2}{4}`$ |
| $`F=\frac{t^2\mathrm{ln}y}{2}`$ | $`f=\frac{yx^3}{6}+\frac{y^2\mathrm{ln}y}{2}\frac{3y^2}{4}`$ |
| $`F=\frac{y^3t}{6}+\frac{y^2t^3}{6}+\frac{t^7}{210}`$ | $`f=\frac{4y^2}{15}\left(\frac{x}{y}\frac{y}{2}\right)^{5/2}`$ |
| $`F=\frac{y^3t^2}{6}+\frac{y^2t^5}{20}+\frac{t^{11}}{3960}`$ | $`f=\frac{y^4t^3}{6}+\frac{7y^3t^6}{30}+\frac{4y^2t^9}{45}+\frac{y^5}{60}`$, where $`x=y^2t+\frac{yt^4}{2}`$ |

Notice that the second and fourth solutions in the right column differ by the interchange of $`x`$ and $`y`$, which is an obvious symmetry of the corresponding PDE. The last solution is implicit. The geometry of the corresponding surfaces is currently under investigation.

The characteristic parametrization. Introducing the variables $`w^1,w^2,w^3`$ by the formulae

$$w^1+w^2+w^3=2a,w^1w^2+w^1w^3+w^2w^3=a^2pb,w^1w^2w^3=p,$$

one can rewrite equations (13) in a symmetric form ,

$$w_y^1=\left(\frac{w^1w^2w^3}{2w^2w^3}\right)_x,w_y^2=\left(\frac{w^2w^1w^3}{2w^1w^3}\right)_x,w_y^3=\left(\frac{w^3w^1w^2}{2w^1w^2}\right)_x.$$
(24)
This system possesses three characteristic conservation laws

$$\begin{array}{c}(w^2w^3)\left(dx+\frac{w^1+w^2w^3}{2w^1w^2w^3}dy\right),(w^1w^3)\left(dx+\frac{w^1+w^3w^2}{2w^1w^2w^3}dy\right),\\ \\ (w^2w^1)\left(dx+\frac{w^2+w^3w^1}{2w^1w^2w^3}dy\right),\end{array}$$

(we call a conservation law ‘characteristic’ if its null curves are characteristics of the system (24)). After introducing the characteristic coordinates $`\xi `$ and $`\eta `$,

$$\begin{array}{c}d\xi =(w^2w^3)\left(dx+\frac{w^1+w^2w^3}{2w^1w^2w^3}dy\right),d\eta =(w^1w^3)\left(dx+\frac{w^1+w^3w^2}{2w^1w^2w^3}dy\right),\\ \\ d\xi d\eta =(w^2w^1)\left(dx+\frac{w^2+w^3w^1}{2w^1w^2w^3}dy\right),\end{array}$$

equations (18) for the position vector take the form

$$\begin{array}{c}𝐫_{\xi \xi }=(\mathrm{\Gamma }_{11}^1+\lambda h_{11}^1)𝐫_\xi +(\mathrm{\Gamma }_{11}^2+\lambda h_{11}^2)𝐫_\eta +\lambda ^2E𝐫,\\ \\ 𝐫_{\xi \eta }=(\mathrm{\Gamma }_{12}^1+\lambda h_{12}^1)𝐫_\xi +(\mathrm{\Gamma }_{12}^2+\lambda h_{12}^2)𝐫_\eta +\lambda ^2F𝐫,\\ \\ 𝐫_{\eta \eta }=(\mathrm{\Gamma }_{22}^1+\lambda h_{22}^1)𝐫_\xi +(\mathrm{\Gamma }_{22}^2+\lambda h_{22}^2)𝐫_\eta +\lambda ^2G𝐫,\end{array}$$
(25)
where the coefficients of the centroaffine metric $`M=Ed\xi ^2+2Fd\xi d\eta +Gd\eta ^2`$ are given by

$$\begin{array}{c}E=\frac{w^1w^2w^3(w^2w^1w^3)}{(w^2w^1)^2(w^2w^3)^2},F=\frac{w^1w^2(w^3)^2}{(w^1w^2)^2(w^1w^3)(w^2w^3)},\\ \\ G=\frac{w^1w^2w^3(w^1w^2w^3)}{(w^1w^2)^2(w^1w^3)^2},\end{array}$$

and $`\mathrm{\Gamma }_{jk}^i`$ are the components of the corresponding Levi-Civita connection. The coefficients $`h_{jk}^i`$ are of the form

$$\begin{array}{c}h_{11}^1=\frac{(w^2)^2w^1w^2w^1w^3w^2w^3}{(w^2w^1)(w^2w^3)},h_{22}^2=\frac{(w^1)^2w^1w^2w^1w^3w^2w^3}{(w^1w^2)(w^1w^3)},\\ \\ h_{12}^1=\frac{w^2w^3}{(w^1w^2)(w^1w^3)},h_{11}^2=h_{22}^1=0,h_{12}^2=\frac{w^1w^3}{(w^2w^1)(w^2w^3)}.\end{array}$$

We point out that the components $`E,F`$ and $`G`$ of the flat metric $`M`$ satisfy the identity

$$(EGF^2)^2+F(E+F)(G+F)=0.$$

In coordinates $`\xi `$ and $`\eta `$, the characteristic 3-web is defined by the equation $`d\xi d\eta (d\xi d\eta )=0`$, and is manifestly hexagonal. The compatibility conditions of equations (25) take the form

$$\begin{array}{c}\frac{w^3w^2}{w^1}w_\xi ^1=\frac{w^3w^1}{w^2}w_\eta ^2,\\ \\ \frac{w^2w^3}{w^1}(w_\xi ^1+w_\eta ^1)=\frac{w^1w^2}{w^3}w_\eta ^3,\\ \\ \frac{w^1w^3}{w^2}(w_\xi ^2+w_\eta ^2)=\frac{w^2w^1}{w^3}w_\xi ^3,\end{array}$$

and, upon the introduction of variables $`u^i=1/w^i`$, simplify to

$$\begin{array}{c}(u^3u^2)u_\xi ^1=(u^3u^1)u_\eta ^2,\\ \\ (u^2u^3)(u_\xi ^1+u_\eta ^1)=(u^1u^2)u_\eta ^3,\\ \\ (u^1u^3)(u_\xi ^2+u_\eta ^2)=(u^2u^1)u_\xi ^3.\end{array}$$
(26)
System (26) can be represented in the equivalent exterior form

$$\omega ^1d\xi =0,\omega ^2d\eta =0,\omega ^3(d\xi d\eta )=0,$$

with the 1-forms

$$\begin{array}{c}\omega ^1=\frac{(u^2u^3)du^1+(u^1u^3)du^2+(u^2u^1)du^3}{2(u^2u^3)\sqrt{(u^2u^1)(u^3u^1)}},\\ \\ \omega ^2=\frac{(u^2u^3)du^1+(u^1u^3)du^2+(u^1u^2)du^3}{2(u^3u^1)\sqrt{(u^2u^1)(u^2u^3)}},\\ \\ \omega ^3=\frac{(u^2u^3)du^1+(u^3u^1)du^2+(u^2u^1)du^3}{2(u^2u^1)\sqrt{(u^3u^1)(u^2u^3)}}\end{array}$$

satisfying the structure equations of the $`SO(2,1)`$ group,

$$d\omega ^1=\omega ^2\omega ^3,d\omega ^2=\omega ^3\omega ^1,d\omega ^3=\omega ^2\omega ^1.$$
(27)
Therefore, one can set

$$\omega ^1=p^1d\xi ,\omega ^2=p^2d\eta ,\omega ^3=p^3(d\xi d\eta ),$$

and the substitution into (27) implies the 3-wave system

$$p_\eta ^1=p^2p^3,p_\xi ^2=p^1p^3,p_\xi ^3+p_\eta ^3=p^1p^2.$$
(28)
It should be pointed out that the equivalence of the associativity equations and the N-wave system was first observed by Dubrovin . The explicit sequence of transformations shown above (which maps (9) into (28)) was presented in , see also .

## 6 Examples

Particular exact solutions of the system (13) correspond to special surfaces with a flat centroaffine metric.

Example 1. Solutions of system (14) with a degenerate hodograph (rarefaction waves) are of the form

$$p=\phi (x+cy),a=c\phi (x+cy)+\mu ,b=c^2\phi (x+cy)\frac{1}{\mu },q=c^3\phi (x+cy)+c^2\mu \frac{c}{\mu },$$

where $`c`$ and $`\mu `$ are arbitrary constants and $`\phi `$ is an arbitrary function of $`x+cy`$. The corresponding potential $`f`$ is

$$f(x,y)=\psi (x+cy)+\frac{\mu }{2}x^2y\frac{1}{2\mu }xy^2+\frac{1}{6}(c^2\mu c/\mu )y^3,$$

here $`\psi ^{\prime \prime \prime }=\phi `$. The corresponding equations (18) (where we have set $`\lambda =1`$) take the form

$$\begin{array}{c}𝐫_{xx}=(c\phi +\mu )𝐫_x+\phi 𝐫_y,\\ \\ 𝐫_{xy}=(c^2\phi \frac{1}{\mu })𝐫_x+(c\phi +\mu )𝐫_y+𝐫,\\ \\ 𝐫_{yy}=(c^3\phi +c^2\mu \frac{c}{\mu })𝐫_x+(c^2\phi \frac{1}{\mu })𝐫_y.\end{array}$$

In the new parametrization $`t=(x+cy)/2,s=(xcy)/2`$, these equations can be rewritten as

$$\begin{array}{c}𝐫_{ss}=(2\mu +\frac{1}{c\mu })𝐫_s\frac{2}{c}𝐫,\\ \\ 𝐫_{st}=\frac{1}{c\mu }𝐫_t\\ \\ 𝐫_{tt}=(4c\phi +2\mu \frac{2}{c\mu })𝐫_t\frac{1}{c\mu }𝐫_s+\frac{2}{c}𝐫,\end{array}$$
(29)
implying

$$(𝐫c\mu 𝐫_s)_s=2\mu (𝐫c\mu 𝐫_s),(𝐫c\mu 𝐫_s)_t=0.$$

Therefore,

$$𝐫=e^{2\mu s}𝐑_\mathrm{𝟎}+e^{\frac{s}{c\mu }}𝐑(t)$$

where $`𝐑_\mathrm{𝟎}`$ is a constant vector and $`𝐑(t)`$ satisfies the ODE

$$𝐑^{\prime \prime }=\left(4c\phi +2\mu \frac{2}{c\mu }\right)𝐑^{}+\left(\frac{2}{c}\frac{1}{c^2\mu ^2}\right)𝐑.$$

Hence, $`𝐑(t)`$ is a planar curve (which can be arbitrary since $`\phi `$ is an arbitrary function of $`t`$), and the intersection of our surface with the plane spanned by $`𝐑_\mathrm{𝟎}`$ and $`𝐑`$ has parametric equation $`(e^{2\mu s},e^{\frac{s}{c\mu }})`$.

Example 2. One can show that, in appropriate asymptotic parametrization, surfaces of revolution with a flat centroaffine metric correspond to the solution

$$a=y\alpha (\xi ),b=x\beta (\xi ),p=y^3\rho (\xi ),q=x^3\gamma (\xi )$$

where $`\xi =xy`$ and the functions $`\alpha ,\beta ,\rho ,\gamma `$ satisfy the ODEs

$$\alpha ^{}=3\rho +\xi \rho ^{},\alpha +\xi \alpha ^{}=\beta +\xi \beta ^{},\beta ^{}=3\gamma +\xi \gamma ^{},\xi ^3\rho \gamma \xi \alpha \beta =1.$$

The general solution of this system can be parametrized in the form

$$\alpha =2G+\xi G^{},\beta =2H+\xi H^{},\rho =G^{},\gamma =H^{}$$

where the functions $`G(\xi )`$ and $`H(\xi )`$ solve the quadratic system

$$\xi ^2(HG)=ϵ\xi +\nu ,2\xi ^2HG=\mu \xi ,$$

$`ϵ,\nu ,\mu `$ being arbitrary constants. In a different parametrization, these surfaces were also discussed in . Equivalently, the above solutions can be characterized in terms of the corresponding potential

$$f(x,y)=F(\xi )+(s_1\xi +s_2)\mathrm{ln}x+(r_1\xi +r_2)\mathrm{ln}y,$$

where $`\xi =xy`$ and $`s_1,s_2,r_1,r_2`$ are arbitrary constants. Calculation of the third order derivatives of $`f`$ gives

$$\begin{array}{c}a=f_{xxy}=y(\xi F^{\prime \prime \prime }+2F^{\prime \prime }+\frac{s_1}{\xi }),b=f_{xyy}=x(\xi F^{\prime \prime \prime }+2F^{\prime \prime }+\frac{r_1}{\xi }),\\ \\ p=f_{xxx}=y^3(F^{\prime \prime \prime }\frac{s_1}{\xi ^2}+2\frac{s_2}{\xi ^3}),q=f_{yyy}=x^3(F^{\prime \prime \prime }\frac{r_1}{\xi ^2}+2\frac{r_2}{\xi ^3})\end{array}$$

(so that $`H=F^{\prime \prime }+r_1/\xi r_2/\xi ^2,G=F^{\prime \prime }+s_1/\xi s_2/\xi ^2`$), and the substitution into (9) implies the quadratic equation for $`F^{\prime \prime }`$,

$$\xi ^2(F^{\prime \prime })^2+(r_1+s_1)\xi F^{\prime \prime }(r_2+s_2)F^{\prime \prime }\frac{r_1s_2+r_2s_1}{\xi }+\frac{r_2s_2}{\xi ^2}+\frac{1}{2}\xi +s=0,$$

where $`s`$ is a constant of integration.

Some further explicit solutions of equation (9) can be sought in the form

$$f=y^{3/2}F(x),$$
(30)
where $`F`$ satisfies the ODE $`(F^2)^{\prime \prime \prime }=16/3`$, implying $`F(x)=\sqrt{\frac{8}{9}x^3+\alpha x^2+\beta x+\gamma }`$, $`\alpha ,\beta ,\gamma `$ being arbitrary constants. Another possible choice is

$$f=y^3F(\xi ),\xi =x/y,$$
(31)
implying the following third order ODE for $`F`$,

$$6FF^{\prime \prime \prime }4\xi F^{}F^{\prime \prime \prime }+2\xi (F^{\prime \prime })^22F^{}F^{\prime \prime }=1.$$

A more general self-similar substitution is

$$f=(xy)^{3/2}F(xy^\mu )$$

where $`\mu =\mathrm{const}`$. For $`\mu =0`$ and $`\mu =1`$ this reduces to (30) and (31), respectively.

## 7 The loop group formulation of surfaces with a flat centroaffine metric

The results of this section are due to A. Bobenko. Substituting $`\psi =e^{\frac{2}{3}\lambda f_{xy}}\phi `$ into (10), we obtain the equivalent traceless representation

$$\phi _x=\lambda \left(\begin{array}{ccc}\frac{2}{3}a& 1& 0\\ 0& \frac{1}{3}a& p\\ 1& b& \frac{1}{3}a\end{array}\right)\phi ,\phi _y=\lambda \left(\begin{array}{ccc}\frac{2}{3}b& 0& 1\\ 1& \frac{1}{3}b& a\\ 0& q& \frac{1}{3}b\end{array}\right)\phi ,$$
(32)
where we have set $`f_{xxx}=p,f_{xxy}=a,f_{xyy}=b,f_{yyy}=q`$. Let us introduce the loop group of $`3\times 3`$ matrices

$$G=\left\{\phi (\lambda )\right|T(\phi ^t(\lambda ))^1T=\phi (\lambda ),\mathrm{det}\phi (\lambda )=1\},T=\left(\begin{array}{ccc}1& 0& 0\\ 0& 0& 1\\ 0& 1& 0\end{array}\right),$$

with the corresponding loop algebra

$$g=\left\{A(\lambda )\right|TA^t(\lambda )T=A(\lambda ),\mathrm{tr}A(\lambda )=0\}.$$

Lemma. Let $`\phi (t,\lambda )G`$ be such that $`\phi _t\phi ^1`$ is linear in $`\lambda `$, and $`\phi _t\phi ^1|_{\lambda =0}=0`$. Then

$$\phi _t\phi ^1(t,\lambda )=\lambda \left(\begin{array}{ccc}2A& C& D\\ D& A& P\\ C& B& A\end{array}\right).$$

This readily implies the following

Proposition. Let $`\phi (u,v,\lambda )G`$ be an immersion of an open domain of $`R^2`$ such that $`d\phi \phi ^1`$ is linear in $`\lambda `$, and $`d\phi \phi ^1|_{\lambda =0}=0`$. Then there exists a change of variables $`(u,v)(x,y)`$ bringing the frame equations into the form (32).

## 8 Projective generalizations of hypersurfaces with a flat centroaffine metric

There exist two particularly interesting projectively invariant classes of hypersurfaces containing projective transforms of hypersurfaces with flat centroaffine metric.

Hypersurfaces with conformally flat second fundamental form were investigated in ,  and  (notice that this property makes sense only for hypersurface of dimension greater than two). Among previosly known examples one should mention the second order envelopes of one-parameter families of nondegenerate hyperquadrics (in particular, projective transforms of surfaces of revolution) as well as special projections of the Segre variety $`P^2\times P^2P^8`$ into $`P^5`$. We point out that projective transforms of hypersurfaces with flat centroaffine metric provide further examples of this type. Indeed, the conformal class of the second fundamental form of a hypersurface with flat centroaffine metric is $`\eta _{ij}du^idu^j`$, which is manifestly conformally flat.

Surfaces in $`P^3`$ possessing asymptotic deformations which induce rescalings of the projective metric and the Darboux cubic form. Let us recall that the position vector $`𝐑`$ of a surface $`M^2`$ in the projective space $`P^3`$ satisfies the linear system

$$\begin{array}{c}𝐑_{xx}=\beta 𝐑_y+\frac{1}{2}(V\beta _y)𝐑\\ \\ 𝐑_{yy}=\gamma 𝐑_x+\frac{1}{2}(W\gamma _x)𝐑\end{array}$$
(33)
where $`\beta ,\gamma ,V,W`$ are functions of the asymptotic coordinates $`x`$ and $`y`$ satisfying the compatibility conditions \[16, p. 120\]

$$\begin{array}{c}\beta _{yyy}2\beta _yW\beta W_y=\gamma _{xxx}2\gamma _xV\gamma V_x\\ \\ W_x=2\gamma \beta _y+\beta \gamma _y\\ \\ V_y=2\beta \gamma _x+\gamma \beta _x.\end{array}$$
(34)
The most important projective invariants are the projective metric

$$2\beta \gamma dxdy$$

and the conformal class of the Darboux cubic form

$$\beta dx^3+\gamma dy^3.$$

Paticularly interesting classes of projective surfaces are characterized by additional relations among $`\beta ,\gamma ,V`$ and $`W`$, for instance

– isothermally-asymptotic surfaces ($`\beta =\gamma `$);

– projectively applicable surfaces ($`\beta _y=\gamma _x`$);

– surfaces of Jonas ($`\beta _x=\gamma _y`$);

etc (see , , ).

Here we consider another class of projective surfaces characterised by the additional relation

$$\beta _{yyy}=\gamma _{xxx},$$
(35)
which allows one to introduce the spectral parameter $`\lambda `$ into (33):

$$\begin{array}{c}𝐑_{xx}=\lambda \beta 𝐑_y+\frac{1}{2}(\lambda ^2V\lambda \beta _y)𝐑\\ \\ 𝐑_{yy}=\lambda \gamma 𝐑_x+\frac{1}{2}(\lambda ^2W\lambda \gamma _x)𝐑.\end{array}$$
(36)
Since the projective metric and the conformal class of the cubic form of the one-parameter family of surfaces $`M_\lambda ^2`$ defined by (36) are

$$2\lambda ^2\beta \gamma dxdy$$

and

$$\beta dx^3+\gamma dy^3,$$

respectively, one can say that the surfaces satisfying (35) possess one-parameter families of asymptotic deformations which rescale the projective metric and preserve the conformal class of the Darboux cubic form. As $`\lambda `$ varies, we continuosly change from the initial surface ($`\lambda =1`$) to a quadric ($`\lambda =0`$), and then to the dual surface ($`\lambda =1`$). Surfaces satisfying the condition (35) were discussed in  and . Changing in the equations (8) from $`𝐫`$ to $`𝐑=e^{\frac{1}{2}\lambda f_{xy}}𝐫`$, we readily rewrite $`(\text{8})_1`$ and $`(\text{8})_3`$ in the form (36), where

$$\beta =f_{xxx},\gamma =f_{yyy},V=\frac{1}{2}f_{xxy}^2+f_{xxx}f_{xyy},W=\frac{1}{2}f_{xyy}^2+f_{yyy}f_{xxy}$$

and $`f`$ satisfies the associativity equation (9). Therefore, projective transforms of surfaces (8) form a proper subclass of the integrable class of surfaces characterized by the condition (35).

## 9 Acknowledgements

It is a great pleasure to thank A. I. Bobenko for numerous discussions and for proving the material presented in sect. 7. This research was partially supported by SFB 288 and the EPSRC grant GR/N30941.


text:
# Structure and dynamics of the interface between a binary hard-sphere crystal of NaCl type and its coexisting binary fluid

## I Introduction

The kinetics of crystal growth and nucleation from the melt is highly dependent upon the structure, dynamics and thermodynamics of the crystal-melt interfaceTiller91 . Given the difficulties in obtaining unambiguous information from experiments, most of what is currently known about the microscopic phenomenology of such interfaces is obtained via computer simulationLaird98 . Although most simulation studies have focused on single component systemsBroughton86b ; Broughton86c ; Karim88 ; Laird89c ; Davidchack98 ; Hayward01 ; Hoyt01 , there has been recent interest in multicomponent interfacesDavidchack96 ; Davidchack99 ; Sibug-Aga02 ; Hoyt02 . All of these studies have involved crystal phases that are either disordered or pure face-centered cubic (FCC) lattices. In this work we present results for the structure and dynamics of the interface between an ordered two-component hard-sphere crystal with a sodium chloride (NaCl) structure and a binary hard-sphere fluid. Such a system can be viewed either as as a prototype to understand the interface between inter-metallic compounds and their coexisting fluid phases or as a model two-component colloidal dispersion.

The hard-sphere interaction was chosen for this study since it is an important reference model for the study of simple liquids Hansen86  and liquid mixtures Young93 . This is especially true with regard to phenomena associated with the freezing transition. For example, it has been recently shown that the interfacial free energy of close-packed metals can be described with quantitative accuracy using a hard-sphere model Laird01 . In addition, recent phase boundary calculations have shown that binary hard spheres form a wide range of crystal structures depending on the ratio, $`\alpha =\sigma _B/\sigma _A`$, of the diameter of the small spheres (labeled B), $`\sigma _B`$ to that of the larger spheres (labeled A), $`\sigma _A`$. A substitutionally disordered FCC crystal is the stable phase for $`1.0>\alpha >0.85`$ Kranendonk91a  while for $`\alpha <0.85`$, only ordered crystal structures are seen to be stable, including AB, AB2 and AB13 structures Trizac97 ; Cottin95 ; Eldridge93a ; Eldridge93b ; Eldridge95 . A detailed study of the disordered FCC crystal/melt interface for $`\alpha =0.9`$ has been recently reported Davidchack99 .

In this work, we examine two-component hard-sphere mixtures with a considerably larger size asymmetry of $`\alpha =0.414`$. This size ratio is significant in the theory of binary alloys in that it is the largest asymmetry in which the small spheres can be accommodated in the interstitials of a densest close-packed crystal of larger spheres. The phase diagram for this value of $`\alpha `$ has been determined as a function of pressure and mole fraction using MC and MD simulations by Trizac and coworkersTrizac97  and is reproduced in Fig. 1. At low pressures, the binary fluid coexists with a pure FCC crystal of large spheres, whereas at higher pressures (above $`50kT/\sigma _A^3`$) the coexisting solid phase is an ordered 1:1 crystal of the sodium chloride (NaCl) type. Earlier cell theory calculations also predicted the stability of the NaCl at this diameter ratio Cottin95 . Other AB structures such as the CsCl and the zinc blende have been shown to be unstable at this diameter ratios Cottin95 ; Eldridge95 . Throughout the text we will be using AB to also refer to the NaCl structure.

A detailed study of the low pressure pure FCC/binary fluid system has been recently reported Sibug-Aga02 . In that work, the coexistence between the crystal and an approximately 1:1 binary mixture was examined, corresponding to a pressure of $`20.1kT/\sigma _A^3`$, which is approximately twice the coexistence pressure ($`11.55kT/\sigma `$) of the pure single component system. As the pressure is increased the mole fraction of large spheres in the fluid phase, $`X_A^f`$, decreases, and at a pressure of about $`50kT/\sigma _A^3`$ the fluid coexists with an AB crystal of NaCl type (see Fig. 1). In this work, we examine in detail the microscopic structure and dynamics of the interface between the high pressure AB crystal and its melt. To do this, we have chosen a point in the phase diagram with $`X_A^f=0.097`$ . At this mole fraction, the fluid coexists with the NaCl crystal at a pressure of $`53kT/\sigma _A^3`$. Details of the simulation methodology and interface equilibration procedure are outlined in the next section followed by presentation of the results of the study in Section III and concluding remarks in section IV.

## II Simulation Details

Molecular-dynamics simulations are performed on a two-component system of hard spheres of differing diameters, $`\sigma _A`$ and $`\sigma _B`$, with $`\sigma _A<\sigma _B`$ (Type $`A`$ particles are assumed to be the larger spheres). The interaction potential between two spheres is defined by the following pairwise interaction potential

$$\varphi _{ij}(r)=\{\begin{array}{cc}\hfill \mathrm{},& r\sigma _{ij}\hfill \\ \hfill 0,& r>\sigma _{ij}\hfill \end{array},$$
(1)
where $`i,j\{A,B\}`$, $`r`$ is the distance between the centers of the two interacting spheres, and $`\sigma _{ij}=(\sigma _i+\sigma _j)/2`$ is the distance of closest possible approach between two spheres with diameter $`\sigma _i`$ and $`\sigma _j`$, respectively. The system is completely defined by specifying the diameter ratio $`\alpha \sigma _B/\sigma _A`$, the mole fraction of large particles, $`x_A`$ and the total number density, $`\rho `$. The total volume occupied by the hard spheres relative to the volume available to the system is given by the packing fraction,

$$\eta =\frac{\pi \sigma _A^3}{6}\rho [x_A+(1x_A)\alpha ^3],$$
(2)
where $`\rho =\rho _A+\rho _B=N/V`$ is the total density, $`x_A`$ is the mole fraction of the larger species, and $`\alpha =\sigma _B/\sigma _A`$ is the diameter ratio.

The procedures for interface construction and equilibration of binary interfaces employed in this study are similar to those used in our earlier workSibug-Aga02  on the low-pressure coexistence in this system (single component FCC ($`x_A=1`$)/binary fluid mixture). Since the general interface preparation process is described at length in that work, only those details specific to the current system are described here. The interested reader is encouraged to consult reference Sibug-Aga02  for a more complete description.

To construct an interface, fluid and crystal blocks are prepared separately using the calculated coexistence conditions. At a pressure of 53 $`kT/\sigma _A^3`$, we independently determined the packing fractions of the coexisting crystal and fluid to be $`\eta ^c=0.683`$ and $`\eta ^f=0.490`$, respectively In the preparation of a fluid block, it is a usual practice to initially position particles in a lattice at a density lower than coexistence. As the system is allowed to equilibrate the lattice melts, giving a fluid configuration, which is then compressed to the coexistence density. For the system under study here this procedure is not feasible since the size asymmetry ($`\alpha =0.414`$) and the mole fraction of small particles ($`X_B^f=0.903`$) in the fluid system are both large. (It should be noted that for this value of $`\alpha `$ the large sphere volume is over 14 times that of the small particle.) To construct the fluid phase we began with an FCC lattice of small particles at a number density equal to the desired total number density of the fluid mixture. A number of particles, corresponding to the target mole fraction of large spheres, are then chosen at random from this lattice. A molecular dynamics run is started from this initial configuration and the diameter of randomly chosen particles is periodically increased until the correct large sphere diameter is attained. The amount of increase in the diameter at each stage depends on the maximum increase that is possible without creating particle overlap. The preparation of the crystal is straightforward as the small particles easily inserted into the interstitial sites of the large sphere FCC lattice.

After equilibration of separate crystal and fluid systems, they are placed in contact within the simulation box. Due to the periodic boundary conditions, two interfaces are formed. Note that packing fraction used in the preparation of the initial fluid block is slightly different from the predicted $`\eta ^f`$ because a gap of $`1\sigma _A`$ is placed between the crystal and fluid blocks to avoid any initial overlap that may occur when the two blocks are combined. The fluid particles are then allowed to move while the large particles are fixed so the initial gaps are then filled with the fluid particles. The initial fluid packing fraction is adjusted until an unstressed bulk crystal is obtained when the two blocks are combined and equilibrated

In this study, we examine both the  and  orientations of this NaCl crystal/binary fluid interface. For reference, we define the $`z`$-axis to be perpendicular to the interfacial plane. Periodic boundary conditions are applied in $`x`$, $`y`$, and $`z`$ directions. The length in the $`z`$-direction, $`L_z`$, is a sum of lengths of the two separate blocks in the $`z`$-direction and the $`2\sigma _A`$-gap initially left between the two blocks. The total number of particles used are 22,032 and 22,752 for the  and  orientations, respectively. The details of the system sizes used are summarized in Table 1. As the systems studied are large, we have implemented the cell method technique Rappaport95  to efficiently carry out the molecular-dynamics simulations Rappaport95 . Equilibration was done for about $`4\times 10^5`$ collisions per particle(cpp). During sampling, the run was divided into blocks of $`2600`$ cpp each. The sampling run was over a length of $`30`$ blocks, but since each block gives two independent measures of interfacial properties when the system is properly folded at the center of the crystal, the results reported are averages taken over 60 samples.

In the course of such simulations the position of the interfacial plane can shift due to Brownian motion or due to melting or freezing of the crystal. To prevent such motion from artificially broadening the interfacial profiles it is necessary to monitor the position of the interfacial plane during the sampling runs. The standard measure of interfacial position for a planar interface is the Gibbs dividing surfaceTiller91  defined for a multicomponent system as the value of $`z`$ where the surfaces excess number of “solvent” particles is zero. However, accurate calculation of the Gibbs dividing surface requires relatively long simulation runs and is then unsuitable for a method of monitoring the time dependence of interfacial position. In our previous studiesDavidchack98 ; Sibug-Aga02 , we find that a more suitable measure can be obtained from measurement of orientational order parameter profile as a function of $`z`$. The orientational order parameter is defined as follows

$$q_n(z)=\frac{1}{N_z}\underset{i,j,k}{}cos\left[n\theta _{xy}(i,j,k)\right],$$
(3)
where $`n=4`$ for the  orientation and $`n=6`$ for the , $`i,j`$ and $`k`$ are nearest neighbor large particles, $`\theta _{xy}(i,j,k)`$ is the bond angle formed by $`i,j`$ and $`k`$ projected on the $`x,y`$ plane, and $`N_z`$ is the total number of particles that form bond angles. The average is taken over the number of angles found between $`z\mathrm{\Delta }z/2`$ and $`z+\mathrm{\Delta }z/2`$, where $`\mathrm{\Delta }z`$ is equal to the layer spacing of the bulk crystal.

We show in Fig. 2 the order parameters, $`q_4`$ and $`q_6`$, of the two particle types for the  (upper panel) and  (lower panel) orientations. As expected $`q_4`$ ($`q_6`$) is small in the  () interface where 6-fold (4-fold) symmetry dominates. We define the interfacial position relative to the midpoint of the orientational order profile for the large particles. That is, $`z=0`$ in all of the $`z`$dependent profiles presented in this study is defined as the point at which the orientational order parameter has decayed halfway from its crystal to fluid value. This order parameter is suitable as a measure of interfacial position since it is smoothly monotonically decreasing and can be calculated accurately for very short runs. The parameter profiles of the small particles are not smoothly varying because at the interfacial region, some number of small particles cluster together to occupy large particle vacancies at the interfacial region (as will be seen in the density plots presented in the next section) disrupting the smooth transition from crystal-like to fluid-like value of the orientational order parameter.

Analysis of the interfacial position as a function of time shows that during the equilibration run the crystal exhibits some initial growth, but quickly stabilizes before the averaging runs are begun. Brownian motion of the solid phase, as monitored by motion of the inner layers of the crystal, was found to be negligible due to the large system size and no correction was necessary.

## III Simulation Results for the  and  Interfaces

### III.1 Structure: Density profiles and contour plots

The structural variation of the system across the interface is determined by calculating the density profile for each particle type.

$$\rho _i(z)=\frac{<N_i(z)>}{L_xL_y\mathrm{\Delta }z}$$
(4)
where $`i`$ denotes a particle type, $`\mathrm{\Delta }z`$ is $`1/25`$ of the crystal layer spacing, $`<N_i(z)>`$ is the average number of particles of type $`i`$ in the region between $`z\mathrm{\Delta }z/2`$ and $`z+\mathrm{\Delta }z/2`$.

The density profiles of the two particle types are shown in Fig. 3(a) and (b) for the  and  orientations, respectively. As expected for an NaCl-type lattice, the small and large particle peaks are in phase in  and exactly out of phase in . This is similar to the registry of particle density peaks found at the interfacial region of the lower pressure pure FCC/binary fluid system Sibug-Aga02  . Due to the higher pressures in this study, the crystal peaks are much sharper than those seen in the lower pressure binary systemSibug-Aga02  or in the single component interfaceDavidchack98 . The small side peaks in the NaCl density are due to the filling of large particle vacancies in the lattice structure with several smaller particles - as discussed below. In order to reveal any change in the lattice spacing through the interface and to index the interfacial planes for later use, vertical dotted lines separated by the bulk crystal lattice spacing were added to Fig. 3. Labels $`a`$ to $`i`$ in the  profile marks some layers whose cross-sectional density distributions have been determined and will be discussed later. For both orientations, there is no discernible change in the lattice spacing as the interface is traversed from crystal to fluid, in contrast to what was seen in our previous studies where the crystal was either a pure or disordered FCC latticeDavidchack98 ; Davidchack99 ; Sibug-Aga02 . In those studies there was a significant increase in the lattice spacing in the  orientation as the fluid side of the interface was approached.

The oscillations in the fine scale density profiles shown in Fig. 3 make it difficult to see the overall trend in bulk density, so we have processed these profiles using a Finite Impulse Response filter NumRec ; Davidchack98  to reveal the non-oscillatory component of the density variation. The resulting filtered density profiles are shown in Fig. 4. The 10-90 width of these bulk density profiles provides a measure of the interfacial width. (The 10-90 width of a monotonically varying interfacial profile is the distance over which the profile changes from 10% to 90% of the higher of two coexisting bulk values, relative to the lower bulk value.) The 10-90 width derived from the large particle density profile of the  orientation \[see Fig. 4(a)\] is $`2.6\sigma _A`$, corresponding to the region between $`z=2.2\sigma _A`$ to $`z=0.4\sigma _A`$. For the small particles the 10-90 width is smaller at 2.3$`\sigma _A`$ and the 10-90 region ($`z=1.7\sigma _A`$ to $`z=0.6\sigma _A`$) is shifted slightly toward the fluid, relative to the 10-90 region of the large spheres. Combining these two regions, the interfacial region of the  orientation defined by the densities has a width of $`2.8\sigma _A`$. The total interfacial width defined for the densities for the  orientation ($`2.9\sigma _A`$) is not significantly different than that for . The interfacial widths of the large particle density profiles are identical to those found in our earlier lower pressure FCC/binary fluid interface study Sibug-Aga02  for the same diameter ratio, but narrower than the 3.3$`\sigma `$ widths found in the single component systemDavidchack98 . In contrast, the small particle interfacial widths found here are much smaller than those found in the lower pressure study, where they were found to be about 3.3$`\sigma _A`$. As a consequence, the overall interface for the NaCl/fluid is slightly narrower than the lower pressure pure FCC/fluid interface.

To get a detailed understanding of the structural transition across the interface between the two coexisting phases, we have determined the cross-sectional density distributions within layers parallel to the interfacial plane. For each layer, the 2-D density distribution is defined as

$$\rho _i^z(x,y)=\frac{<N_i^z(x,y)>}{\mathrm{\Delta }x\mathrm{\Delta }y\mathrm{\Delta }z}$$
(5)
where $`i`$ denotes a particle type, $`\mathrm{\Delta }x=\mathrm{\Delta }y=0.12\sigma _A`$, $`\mathrm{\Delta }z`$ is the crystal layer spacing, which is $`0.74\sigma _A`$ for . The average number of particles of type $`i`$ in the volume given by $`\mathrm{\Delta }x\mathrm{\Delta }y\mathrm{\Delta }z`$ is $`<N_i^z(x,y)>`$. In Figs. 5 and 6 are density contour plots of the  interface for the large and small particles, respectively. Layers $`a`$ to $`i`$ are as labeled in Fig. 3(a), where $`a`$ is deep into the bulk crystal, $`i`$ is in the bulk fluid and $`b`$ to $`h`$ are interfacial regions. The decrease in density peak height of the large (Type A) spheres in Fig. 3 starting at layer $`b`$ is initially due to the presence of lattice vacancies as shown in Fig. 5. Small particle vacancies also start to appear in layer $`b`$ of Fig. 6. We also find by comparing Figs. 3 and 5 for layers $`c`$ and $`d`$ that the side peaks appearing at these layers are due to the accumulation of small particles in the large sphere vacancies. The structure of this vacancy filling is interesting in that the large particle is typically replaced by 6 small particles (although a small number of vacancies filled with 5 or 7 small spheres do occur) with little disturbance to the surrounding lattice. This can be seen in Fig. 7 where a snapshot of one of these filled vacancies in layer $`c`$ is shown. A uniform 2-D density distribution begins to develop in layer $`G`$ for both particle types indicating that, although the $`z`$dependent density profiles still has some oscillations in this region, the structure is that of an inhomogeneous fluid at a wall.

Of particular interest to materials scientists is the degree of interfacial segregation - the preferential adsorption (or desorption) of one component (usually the “solute”) at the interface. This quantity is defined relative to the Gibbs dividing surface. The Gibbs dividing surface of a planar interface is definedTiller91  as the plane along the $`z`$axis giving a vanishing surface excess solvent particle number, $`\mathrm{\Gamma }_{\text{solvent}}`$, defined in the equation

$$N^{\text{solvent}}/A=\rho _c^{\text{solvent}}z+\rho _f^{\text{solvent}}(L_zz)+\mathrm{\Gamma }_{\text{solvent}}$$
(6)
where $`N^{\text{solvent}}`$ the total number of solvent particles spheres, $`A`$ is the area of the interface, $`\rho _c^{\text{solvent}}`$ and $`\rho _L^{\text{solvent}}`$ are the bulk densities, $`z`$ is the location of the interface assuming the length of the simulation box runs from $`0`$ to $`L_z`$. Defining the small particles as the ’solvent’, we find that the Gibbs dividing surfaces are at $`z=0.49\sigma _A`$ and $`z=0.93\sigma _A`$ relative to the position calculated from the large particle order parameter for the  and  orientations, respectively. Surface excess of the ’solute’ particles, $`\mathrm{\Gamma }^A`$ was found to be negligible, indicating the absence of interfacial segregation, a result that is consistent for other crystal/melt systems that have been investigated Davidchack98 ; Hoyt01 ; Sibug-Aga02 .

### III.2 Transport: Diffusion coefficient profiles

Inhomogeneities in the transport properties within the interfacial region can be examined by calculating $`z`$dependent diffusion coefficient profiles, defined for a particle of type $`i`$ by

$$D_i(z)=\underset{t\mathrm{}}{lim}\frac{1}{6N_i(z)}\frac{d}{dt}\underset{j=1}{\overset{N_i(z)}{}}[𝒓_j(t)𝒓_j(t_0)]^2.$$
(7)
The term in the summation is the mean-squared displacement over a time interval $`tt_0`$ of a total of $`N_i`$ type $`i`$ particles located between $`z\mathrm{\Delta }z/2`$ and $`z+\mathrm{\Delta }z/2`$ at time $`t_0`$, where $`\mathrm{\Delta }z`$ is the layer spacing in  and is twice the layer spacing in .

Figure 8(a) shows the diffusion coefficient profiles for the current study (dotted lines), including for comparison the results previously reported for the lower pressure FCC/binary fluid interface Sibug-Aga02  (solid lines). Only the  results are shown as the diffusion profiles for the  interfaces are not statistically different. The error bars are small and so are not shown for clarity of the plots. The bulk fluid value for the large particles in the lower pressure FCC/binary fluid system is $`0.012(kT\sigma _A^2/m)^{1/2}`$ and that for the small particles is $`0.050(kT\sigma _A^2/m)^{1/2}`$. Since the AB/fluid system has a higher pressure and larger fluid packing fraction, the bulk fluid diffusion coefficient values are lower: $`0.008(kT\sigma _A^2/m)^{1/2}`$ for the large particles and $`0.029(kT\sigma _A^2/m)^{1/2}`$ for the small particles. The difference in magnitude between the small and large particle diffusion constants makes it difficult to compare the two diffusion profiles. For a clearer comparison in Fig. 8(b) we plot the data in Fig.8(a) normalized relative to the bulk fluid values. Traversing the system from fluid to crystal, we find a region of width greater than $`1\sigma _A`$ where the small particles have nonzero diffusion coefficient while the large particles have have effectively zero diffusion. Both high- and low-pressure systems exhibit this shift in the change from crystal-like to fluid-like motion of the two particle types.

As was done for structural transition, we can also define the extent of dynamical transition by determining the 10-90 region from diffusion coefficient profiles. From the diffusion coefficient profile of the large particles this region starts from $`z=0.7\sigma _A`$ up to $`z=1.3\sigma _A`$, resulting to a width equal to $`2.0\sigma _A`$ and centered at $`z=0.3\sigma _A`$. The small particles define an interfacial region that starts from $`z=2.2\sigma _A`$ and ends at $`z=0.6\sigma _A`$. These boundaries give a width of $`2.8\sigma _A`$, which is 40% greater than the width from diffusion of the large particles. Also, the midpoint is shifted by $`1.1\sigma _A`$ to the fluid side relative to the midpoint of the region defined by the large particles.

As in our previous studies on hard-sphere interfacesDavidchack98 ; Sibug-Aga02  the regions defined each of the individual density and diffusion coefficient profiles do not all coincide, so we take a union of these 10-90 regions to define the full interfacial region. Taking into account all profiles, the NaCl/binary fluid hard-sphere interface studied here has an overall 10-90 width of $`3.5\sigma _A`$, corresponding to layers $`c`$ to $`g`$ in Fig. 3. As perhaps expected for the higher pressure system, this interfacial region is narrower than the one found for lower pressure FCC/binary fluid interfaceSibug-Aga02 , which was found to be $`4.8\sigma _A`$. To summarize all of the profile data for quick inspection we show in Fig. 9 all order parameters profiles, normalized such that we have all values equal to unity in the bulk crystal and zero in the bulk fluid for the  interface. Except for differences in the overall interfacial width, this plot is qualitatively quite similar to the corresponding plot for our earlier low-pressure FCC/binary fluid simulations in that the transition of densities for both particle types and the diffusion of the small particles is observed over approximately the same region, while the transition for the large particle diffusion is shifted by about $`1\sigma _A`$ (1.3$`\sigma _A`$ in the earlier study). Another notable feature in this plot is that the transition for the orientational order parameter, which we use to locate the interfacial plane, occurs at about the center of these two transition regions.

## IV Summary

Using molecular-dynamics simulation, we have investigated the structure and dynamics of the  and  crystal-melt interfaces of the AB(NaCl)/binary fluid system for a two-component hard-sphere system in which the ratio of small to large particle diameter is $`\alpha =0.414`$. This system was at a pressure of $`53kT/\sigma _A^3`$ that is at the lower range of the NaCl crystal/fluid coexistence region. These simulations complement our earlier workSibug-Aga02  on the pure FCC/binary fluid interface found in this same system at lower pressure ($`20.1kT/\sigma _A^3`$). We find that the higher pressure AB/binary-fluid interface has a narrower interfacial region of $`3.5\sigma _A`$ compared to the lower pressure FCC/binary fluid system at the same diameter ratio, which had an interfacial region of width $`4.8\sigma _A`$. In addition, the crystal side of the higher pressure binary interface exhibited much higher vacancy defect concentrations than either the low pressure binary system or the single-component interfaceDavidchack98 . In the interfacial region, all vacancies in the large particle lattice were found, with little distortion in the surrounding lattice, to be filled with an average of 6 small particles. Similar to what was seen in the lower pressure FCC/binary fluid interface, the transition regions for both density profiles and the small particle diffusion constant are approximately coincident whereas the diffusion profile for the large particles is shifted relative to the others by about $`1\sigma _A`$ toward the liquid side of the interface.

ACKNOWLEDGMENTS

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-9900211.