text:
# Conjecture 1 (Cameron–Erdős)

The Cameron–Erdős Conjecture
Ben Green111Supported by a Fellowship of Trinity College, Cambridge and a grant from the EPSRC, United Kingdom. Mathematics Subject Classification: 11B75.

## Abstract

A subset $`A`$ of the integers is said to be sum-free if there do not exist elements $`x,y,zA`$ with $`x+y=z`$. It is shown that the number of sum-free subsets of $`\{1,\mathrm{},N\}`$ is $`O(2^{N/2})`$, confirming a well-known conjecture of Cameron and Erdős.

1. Introduction. If $`A`$ is any subset of an abelian group then we say that $`A`$ is sum-free if $`(A+A)A=\mathrm{}`$, that is if there do not exist $`x,y,zA`$ for which $`x+y=z`$. The study of such sets goes back at least 30 years, and over 10 years ago Cameron and Erdős  raised the question of enumerating the sum-free subsets of $`[N]=\{1,\mathrm{},N\}`$. They noted that any set of odd integers is sum-free, as is any subset of $`\{N/2,\mathrm{},N\}`$, but that it is hard to think of many sum-free sets which are not essentially of this form. Thus they advanced the following conjecture.

###### Conjecture 1 (Cameron–Erdős)

The number of sum-free subsets of $`[N]`$ is $`O(2^{N/2})`$.

There has been some progress on this conjecture. Writing $`\text{SF}(N)`$ for the collection of sum-free subsets of $`[N]`$, Alon , Calkin  and Erdős and Granville (unpublished) showed independently that

$$|\text{SF}(N)|=\mathrm{\hspace{0.33em}2}^{N/2+o(N)}.$$
(1)
Results in a rather different direction were obtained by Freiman  and by Deshouillers, Freiman, Sós and Temkin . In , for example, it was shown that the number of sum-free subsets of $`[N]`$ with cardinality at least $`5N/12+2`$ is at most $`O(2^{N/2})`$. Let us also mention that Calkin and Taylor  showed that the number of subsets of $`[N]`$ containing no solutions to $`x+y+z=w`$ is $`O(2^{2N/3})`$, an estimate which is basically sharp.
It is natural to ask for estimates for $`\text{SF}(\mathrm{\Gamma })`$, the number of sum-free subsets of some finite abelian group $`\mathrm{\Gamma }`$. When $`\mathrm{\Gamma }=/p`$ ($`p`$ prime) this question is perhaps even more natural than the question of Cameron and Erdős. It was first considered explicitly by Lev and Schoen , who showed that

$$|\text{SF}(/p)|\mathrm{\hspace{0.33em}2}^{0.498p}.$$

Their result was improved by Ruzsa and the author , who obtained the estimate

$$|\text{SF}(/p)|\mathrm{\hspace{0.33em}2}^{p/3+o(p)}.$$

This is tight except for the $`o(p)`$ term. For more general abelian groups $`\mathrm{\Gamma }`$, work started by Lev, Łuczak and Schoen  in the case $`|\mathrm{\Gamma }|`$ even was continued by Ruzsa and the author , who obtained reasonably precise estimates for all abelian groups.
The objective of the present paper is to prove the conjecture of Cameron and Erdős.

###### Theorem 2

The number of sum-free subsets of $`[N]`$ is asymptotically $`c(N)2^{N/2}`$, where $`c(N)`$ takes two different constant values according as $`N`$ is odd or even.

It is extremely likely that our methods extend to give, for example, much tighter bounds on $`|\text{SF}(/p)|`$ but we do not pursue such matters here.
2. A strategy for counting sum-free sets. The purpose of this section is to outline the broad strategy that we will use to count sum-free subsets of $`[N]`$. Our method falls conveniently into two parts, which are dealt with in detail in the two sections immediately following this one. We have tried to make these sections as independent as possible. Our strategy, then, is as follows.
Part I. We find some family $``$ of subsets of $`[N]`$ with the following properties. Firstly, each $`A`$ is almost sum-free, meaning that the number of additive triples (triples with $`x+y=z`$) in $`A`$ is $`o(N^2)`$. Secondly, $``$ does not contain too many sets; in fact, $`||=2^{o(N)}`$. Finally, every sum-free subset of $`[N]`$ is contained in some member of $``$.
Part II. Given $`A\text{SF}(N)`$, we consider some set $`A^{}`$ with $`AA^{}`$. As $``$ is so small, the number of $`A`$ for which $`|A^{}|\left(\frac{1}{2}\frac{1}{120}\right)N`$ is $`o(2^{N/2})`$. If, however, $`|A^{}|\left(\frac{1}{2}\frac{1}{120}\right)N`$ then it is possible to say something about the structure of $`A^{}`$, and hence about the structure of almost all $`A\text{SF}(N)`$.
What we will actually show is that almost all $`A\text{SF}(N)`$ consist either entirely of odd numbers, or else are contained in the interval $`\{(N+1)/3,\mathrm{},N\}`$. The author was delighted to discover that, in their original paper , Cameron and Erdős gave an elegant argument leading to an estimate for the number of sum-free subsets of $`\{(N+1)/3,\mathrm{},N\}`$. This argument, together with our work in the present paper, constitutes an affirmative solution to Conjecture 1.
3. Construction of $``$. Granularizations. In this section we complete Part I of the program outlined in §2 by constructing the family $``$. This was basically achieved in the paper of Ruzsa and the author . Since it is not quite a trivial matter to isolate results from that paper in the form that we need them, we repeat some of the material from  here.
We begin with a small amount of notation concerning Fourier transforms. We will be working on the group $`G=/p`$, where $`p`$ is a prime. If $`f:G`$ is a function and if $`rG`$ then we define the Fourier transform $`\widehat{f}`$ by

$$\widehat{f}(r)=\underset{xG}{}f(x)e(rx/p)$$

where, as usual, $`e(\theta )=e^{2\pi i\theta }`$. If $`f,g`$ are two functions then we define their convolution $`fg`$ by

$$(fg)(x)=\underset{yG}{}f(y)g(xy).$$

Observe that $`(fg)\widehat{}(r)=\widehat{f}(r)\widehat{g}(r)`$. Finally, we remark that if $`AG`$ then we will identify $`A`$ with its characteristic function: that is, we write $`A(x)=1`$ if $`xA`$ and $`A(x)=0`$ otherwise. Observe that if $`A,BG`$ are two sets then $`(AB)(x)`$ is the number of representations of $`x`$ as $`a+b`$ with $`aA`$, $`bB`$.
Let $`p[2N,4N]`$ be a prime, let $`M`$ be a positive integer, and let $`d(/p)^{}`$. Let $`A[N]`$ be a set, and regard $`A`$ as a subset of $`/p`$ in the obvious manner. Suppose that $`|A|=\alpha p`$. Consider a partition of $`/p`$ into arithmetic progressions $`I_i`$, $`i/M`$, of common difference $`d`$ defined by

$$I_i=\{\lambda d:\frac{\overline{i}p}{M}\lambda <\frac{\overline{(i+1)}p}{M}\},$$
(2)
where $`\overline{i}`$ denotes the least positive residue of $`i`$. Each of these progressions has length either $`L`$ or $`L1`$, where $`L=p/M`$. Let $`ϵ_1>0`$ be a real number, and let

$$T=\{i/M||AI_i|ϵ_1|I_i|\}.$$

Finally, define the granularization $`A^{}`$ of $`A`$ (with respect to the length $`d`$ and the parameter $`ϵ_1`$) by

$$A^{}=\underset{iT}{}I_i.$$

It is easy to see that we have

$$|A^{}A|ϵ_1p.$$
(3)
One of the key results of  is that, provided $`d`$ has a certain property (for which we will use the term “good length”) the set $`A^{}`$ retains some of the additive features of $`A`$. In fact, we will be able to show that $`A^{}`$ is almost sum-free.
Let us now say what we mean by the statement “$`d`$ is a good length”. Let $`ϵ_2,ϵ_3>0`$ be two further real numbers and set $`\delta =\frac{1}{16}ϵ_1^2ϵ_2ϵ_3^{1/2}\alpha ^{1/2}`$. Let $`R`$, $`|R|=k`$, be the set of all $`r0`$ for which $`|\widehat{A}(r)|\delta p`$. We say that $`d`$ is a good length for $`A`$ (with respect to the parameters $`ϵ_1,ϵ_2,ϵ_3`$) if

$$dr/p\frac{1}{4L}\left(\frac{\delta p}{|\widehat{A}(r)|}\right)^{1/2}$$
(4)
for all $`rR`$. The following proposition was (essentially) the main result of . It clarifies the rôle of $`ϵ_2`$ and $`ϵ_3`$, which have not so far featured.

###### Proposition 3

Suppose that $`d`$ is a good length for $`A`$. Then the granularization $`A^{}`$ has the property that $`A+A`$ contains all $`x`$ for which $`A^{}A^{}(x)ϵ_2p`$, with at most $`ϵ_3p`$ exceptions.

Proof. We claim that if $`d`$ is a good length then the function

$$g(x)=\frac{1}{2L1}\underset{j=(L1)}{\overset{L1}{}}e(jdx/p)$$
(5)
satisfies

$$|\widehat{A}(x)||1g(x)^2|\delta p$$
(6)
for all $`x`$. This automatically holds for $`x=0`$, as $`g(x)=1`$, and also whenever $`|\widehat{A}(x)|\delta p`$, since $`g(x)[1,1]`$. For any $`x/p`$ we may estimate $`1g(x)`$ as follows. Writing $`t`$ for the distance of $`t`$ from the nearest integer we have the inequality $`1\mathrm{cos}2\pi t2\pi ^2t^2`$. It follows that

$`1g(x)`$ $`=`$ $`{\displaystyle \frac{2}{2L1}}{\displaystyle \underset{j=1}{\overset{L1}{}}}\left(1\mathrm{cos}{\displaystyle \frac{2\pi jdx}{p}}\right)`$ (7)
$``$ $`{\displaystyle \frac{4\pi ^2}{2L1}}{\displaystyle \underset{j=1}{\overset{L1}{}}}{\displaystyle \frac{jdx}{p}}^2`$
$``$ $`{\displaystyle \frac{4\pi ^2}{2L1}}{\displaystyle \frac{dx}{p}}^2{\displaystyle \underset{j=1}{\overset{L1}{}}}j^2`$
$``$ $`{\displaystyle \frac{2\pi ^2L^2}{3}}{\displaystyle \frac{dx}{p}}^2.`$
Hence

$`|\widehat{A}(x)||1g(x)^2|`$ $``$ $`2|\widehat{A}(x)||1g(x)|`$
$``$ $`14L^2dx/p^2|\widehat{A}(x)|`$
It is now easy to see that $`d`$ being a good length is exactly the property required to make (6) hold.
Now to establish the proposition we define a function $`a_1`$ by

$$a_1(n)=\frac{1}{|P|}(AP)(n)=\frac{1}{|P|}|A(P+n)|,$$

where $`P=\{(L1)d,\mathrm{},0,d,2d,\mathrm{},(L1)d\}`$. Observe that $`\widehat{a}_1(x)=\widehat{A}(x)g(x)`$. Thus we have, by two applications of Parseval’s identity, that

$`{\displaystyle \underset{n}{}}\left|(AA)(n)(a_1a_1)(n)\right|^2`$ $`=`$ $`p^1{\displaystyle \underset{x}{}}\left|\widehat{A}(x)^2\widehat{a}_1(x)^2\right|^2`$ (8)
$`=`$ $`p^1{\displaystyle \underset{x}{}}|\widehat{A}(x)|^4\left(1g(x)^2\right)^2`$
$``$ $`p^1\left(\underset{x}{sup}|\widehat{A}(x)||1g(x)^2|\right)^2{\displaystyle \underset{x}{}}|\widehat{A}(x)|^2`$
$`=`$ $`\alpha p\left(\underset{x}{sup}|\widehat{A}(x)||1g(x)^2|\right)^2.`$
(6) therefore implies that

$$\underset{n}{}\left|(AA)(n)(a_1a_1)(n)\right|^2\alpha \delta ^2p^3.$$
(9)
Now if $`nA^{}`$ then there is a progression of common difference $`d`$ and length $`L`$ containing $`n`$ which contains at least $`ϵ_1L/2`$ points of $`A`$. This progression is contained in $`[n(L1)d,\mathrm{},n+(L1)d]`$. Hence $`a_1(n)`$ is certainly at least $`ϵ_1/4`$, and so $`a_1(n)ϵ_1A(n)/4`$ for all values of $`n`$. It follows immediately that $`(a_1a_1)(n)ϵ_1^2(A^{}A^{})(n)/16`$ for all $`n`$, and hence that if $`A^{}A^{}(n)ϵ_2p`$ then $`a_1a_1(n)ϵ_1^2ϵ_2p/16`$. We are to show that there are not many points $`n`$ for which this is true whilst $`AA(n)=0`$. Letting $`B`$ denote the set of these “bad” points, observe that $`nB`$ implies that

$$\left|(AA)(n)(a_1a_1)(n)\right|^2\frac{ϵ_1^4ϵ_2^2p^2}{256}.$$

Substituting into (9) gives the bound

$$|B|\frac{256\alpha \delta ^2}{ϵ_1^4ϵ_2^2}pϵ_3p$$

(this explains our choice of $`\delta `$).
We defer for a while the issue of whether there are any good lengths. Our next result says that the conclusion of Proposition 3 is enough to guarantee that if $`A`$ is sum-free then $`A^{}`$ is almost sum-free.

###### Proposition 4

Suppose that $`A`$ is sum-free. Let $`ϵ>0`$, set $`ϵ_1=ϵ`$, $`ϵ_2=ϵ^2/144`$, $`ϵ_3=ϵ^2/80`$ and let $`A^{}`$ be the granularization of $`A`$ with respect to some good length $`d`$. Then $`A^{}`$ contains at most $`ϵp^2`$ triples $`(x,y,z)`$ with $`x+y=z`$.

Proof. The choice of $`p`$ (that is, $`p2N`$) guarantees that $`A`$ is sum-free when considered as a subset of $`/p`$. Suppose without loss of generality that $`d=1`$, and suppose for a contradiction that the proposition is false. Recall the notation we set up at the start of the section, particularly the definitions of the intervals $`I_i`$ and the set $`T/m`$. We begin by claiming that there are at least $`ϵM^2/4`$ triples $`(i,j,k)T^3`$ for which $`i+j=k`$ or $`k+1`$. Indeed note that if $`x+y=z`$ and if $`xI_i`$, $`yI_j`$ and $`zI_k`$ then $`i+j=k`$ or $`k+1`$. However for a fixed triple $`(i,j,k)`$ with this property there are at most $`4p^2/M^2`$ triples $`(x,y,z)`$, so our claim follows from a simple double count. For definiteness suppose that there are at least $`ϵM^2/8`$ triples $`(i,j,k)T^3`$ with $`i+j=k`$ (the argument when there are many triples with $`i+j=k+1`$ is very similar). Let $`K`$ be the set of all $`kT`$ for which $`TT(k)ϵM/16`$ so that, by an easy averaging argument, we have $`|K|ϵM/16`$.

Suppose that $`i+j=k`$ with $`i,j,kT`$, and suppose that $`z`$ lies in the middle $`(1ϵ/2)`$ of $`I_k`$. Then the number of representations of $`z`$ as $`x+y`$ with $`xI_i,yI_j`$ is at least $`ϵp/8M`$. Therefore if $`kK`$ we have $`A^{}A^{}(z)ϵ^2p/144`$. Note, however, that since $`kT`$ the middle $`(1ϵ/2)`$ of $`I_k`$ contains at least $`ϵp/4M`$ points of $`A`$.

We have now shown that there are at least $`ϵ^2p/64`$ elements $`xA`$ for which $`A^{}A^{}(x)ϵ^2p/144`$. By the property of $`A^{}`$ described in Proposition 3 we see that $`A+A`$ contains an element of $`A`$, contrary to our assumption that $`A`$ is sum-free.
We now look at the issue of finding a good length.

###### Proposition 5

Let $`A/p`$ have cardinality $`\alpha p`$. A good length for $`A`$ with parameters $`ϵ_1,ϵ_2,ϵ_3`$ exists if

$$p>(4L)^{256\alpha ^2ϵ_1^4ϵ_2^2ϵ_3^1}.$$
(10)
Proof. It follows by a standard application of the pigeonhole principle that a $`d`$ satisfying (4) exists if

$$p>(4L)^k\left(\underset{rR}{}\frac{|\widehat{A}(r)|}{\delta p}\right)^{1/2}.$$
(11)
We claim that this inequality is a consequence of the hypothesis on $`p,L,ϵ_1,ϵ_2`$ and $`ϵ_3`$ in the statement of the proposition. Indeed, observe that Parseval’s identity implies that

$$\underset{rR}{}|\widehat{A}(r)|^2\alpha p^2,$$
(12)
from which the arithmetic-geometric mean inequality gives

$$\underset{rR}{}|\widehat{A}(r)|\left(\frac{\alpha p^2}{k}\right)^{k/2}.$$

It follows that the right side of (11) is at most

$$(4L\alpha ^{1/4}\delta ^{1/2}k^{1/4})^k,$$
(13)
which is an increasing function of $`k`$ in the range $`k<\left(\frac{256L^4}{e}\right)\frac{\alpha }{\delta ^2}`$. However another consequence of (12) is the inequality $`k<\alpha /\delta ^2`$, and hence (13) is itself bounded above by $`(4L)^{\alpha /\delta ^2}`$. Recalling our choice of $`\delta `$ confirms the claim, and hence there is a $`d`$ for which (4) holds.
To get the conclusion of Proposition 4 we required $`ϵ_1=ϵ`$, $`ϵ_2=ϵ^2/144`$ and $`ϵ_3=ϵ^2/80`$. It is an easy but slightly tedious task to check that if we put $`ϵ=(\mathrm{log}N)^{1/11}`$ and $`M=N\mathrm{exp}((\mathrm{log}N)^{1/12})`$ then, at least for $`N`$ sufficiently large, $`A`$ has at least one good length. For the remainder of the section we assume that the parameters $`ϵ`$ and $`M`$ take these values.
We are now in a position to define our family of sets $``$. Take $``$ to consist of all sets which can be formed in the following manner. For all $`d(/p)^{}`$ consider the decomposition (2) of $`/p`$ into progressions $`I_i`$ ($`i/m`$) with common difference $`d`$. Let $`𝒢`$ be the collection of sets which are unions of progressions $`I_i`$, for some $`d`$. Now throw away from $`𝒢`$ all those sets which have more than $`ϵp^2`$ additive triples, giving a new collection $``$. Finally, let $``$ consist of all subsets of $`[N]`$ which can be obtained by adding at most $`ϵp`$ elements to some $`H[N]`$, $`H`$.
This may seem complicated. It turns out, however, that we can rather easily establish the following rather clean proposition concerning $``$ which contains all the information we need for subsequent sections.

###### Proposition 6

The family $``$ has the following properties:
*(i)* Every member of $``$ has at most $`o(N^2)`$ additive triples;
*(ii)* If $`A`$ is sum-free then $`A`$ is contained in some member of $``$;
*(iii)* $`||2^{o(N)}`$.

Proof. (i) By definition every set in $``$ has at most $`ϵp^2`$ additive triples, and thus the same is true of sets of the form $`H[N]`$, $`H`$. By adding $`ϵp`$ elements to such an $`H`$, we cannot create more than $`3ϵp^2`$ new additive triples. The result follows from the fact that $`p4N`$.
(ii) Set $`ϵ_1=ϵ`$, $`ϵ_2=ϵ^2/144`$ and $`ϵ_3=ϵ^2/80`$. Choose a good length $`d`$ for $`A`$ with respect to $`ϵ_1,ϵ_2,ϵ_3`$, and consider the granularization $`A^{}`$ with respect to $`d`$ and $`ϵ_1`$. By Proposition 4 this lies in $``$, and the result follows from (3).
(iii) There are $`p1`$ choices for $`d`$, and then $`2^M`$ ways to pick elements of $`𝒢`$. Thus $`||p2^M`$, and so $`||`$ is at most $`p2^M`$ times the number of subsets of $`[N]`$ of size at most $`ϵN`$. This is clearly $`2^{o(N)}`$.
4. The structure of almost sum-free sets. In this section we study large almost sum-free sets. The results may be regarded as “almost” versions of the results of Freiman . Freiman’s methods do not seem to generalise easily to almost sum-free sets, so we have been forced to devise our own arguments. We will need one further piece of notation. If $`K`$ is a positive real number and if $`AG`$ is a subset of an abelian group, we will write $`D(A,K)`$ for the set of all $`xG`$ which have at least $`K`$ representations as $`aa^{}`$ with $`a,a^{}A`$. We call this the set of $`K`$-popular differences of $`A`$.
In this section the objects $`I_i`$, $`M`$ and $`ϵ`$ are not the same as in the previous section.

###### Proposition 7

Let $`ϵ=o(N)`$ and suppose that $`A[N]`$ has at most $`ϵN^2`$ additive triples, and that $`|A|=(\frac{1}{2}\eta )N`$ where $`\eta 1/50`$ *(*$`\eta `$ is allowed to be negative*)*. Then one of the following alternatives occurs:
*(i)* With the possible exception of at most $`32ϵ^{1/8}N`$ elements, $`A`$ is contained in some interval of length $`(\frac{1}{2}+3\eta +60ϵ^{1/8})N`$;
*(ii)* At most $`54ϵ^{1/8}N`$ elements of $`A`$ are even.

Throughout what follows we shall assume that $`|A|=(\frac{1}{2}\eta )N`$, $`\eta 1/50`$ and that $`A`$ has at most $`ϵN^2`$ additive triples.

###### Lemma 8

We have

$$\frac{1}{2}|D(A,ϵ^{1/2}N)|+|A|N(1+2ϵ^{1/2}).$$
(14)
Proof. We have $`\left|\left(D(A,ϵ^{1/2}N)_{>0}\right)A\right|ϵ^{1/2}N`$, or else $`A`$ would contain more than $`ϵN^2`$ additive triples. The result follows quickly from this and the observation that $`d`$ is $`K`$-popular if and only if $`d`$ is.

###### Lemma 9

For all but at most $`8ϵ^{1/4}N`$ values of $`a`$, at least $`|A|16ϵ^{1/4}N`$ of the differences $`aa^{}`$ with $`a^{}A`$ lie in $`D(A,32ϵ^{1/2}N)`$.

Proof. Consider the graph on vertex set $`A`$ in which $`a`$ is joined to $`a^{}`$ if $`aa^{}`$ is not in $`D(A,32ϵ^{1/2}N)`$. It has at most $`64ϵ^{1/2}N^2`$ edges. The number of vertices with degree more than $`16ϵ^{1/4}N`$ is thus at most $`8ϵ^{1/4}N`$.
The next lemma, which is an application of basic graph theory, is , §4, Proposition 1. We specialise the result to the case we need.

###### Lemma 10 (Lev,Łuczak, Schoen)

Let $`S`$ be a subset of an abelian group $`\mathrm{\Gamma }`$, $`|\mathrm{\Gamma }|N`$. Suppose that $`|D(S,8ϵ^{1/2}N)|2|S|16ϵ^{1/4}N`$. Then there is a set $`XS`$, $`|SX|4ϵ^{1/4}N`$, with $`XXD(S,8ϵ^{1/2}N)`$.

Now partition $`[N]`$ into intervals $`I_i`$ such that the smallest element of $`I_i`$ is $`2iϵ^{1/8}N`$. Let $`j`$ be minimal so that $`I_j`$ contains at least $`9ϵ^{1/4}N`$ points of $`A`$. Then, by Lemma 9, there is some $`mI_i`$ such that at least $`|A|16ϵ^{1/4}N`$ of the differences $`am`$, $`aA`$, lie in $`D(A,32ϵ^{1/2}N)`$. Let $`k`$ be maximal so that $`I_k`$ contains at least $`9ϵ^{1/4}N`$ points of $`A`$. Again, there is $`MI_k`$ so that at least $`|A|16ϵ^{1/4}N`$ of the differences $`am`$, $`aA`$, lie in $`D(A,32ϵ^{1/2}N)`$. Clearly for at least $`|A|32ϵ^{1/4}N`$ values of $`a`$ both $`am`$ and $`aM`$ are popular. Furthermore

$$|A[1,m]|\frac{9ϵ^{1/4}N}{ϵ^{1/8}}\mathrm{\hspace{0.33em}9}ϵ^{1/8}N,$$

and a similar inequality holds for $`|A[M,N]|`$. Thus there is a set $`BA`$, with the following properties:

1. $`B`$ is contained in $`\{m+1,\mathrm{},M\}`$;
2. $`|B||A|50ϵ^{1/8}N`$;
3. For all $`bB`$ the differences $`bm`$ and $`bM`$ are both in $`D(A,32ϵ^{1/2}N)`$.

Observe that the first and second of these points imply that $`Mm>N/4`$. Now let $`t=Mm`$. Following Lev and Smeliansky , consider the projection map $`\pi :/t`$. We note some simple facts about this map in a lemma.

###### Lemma 11

*(i)* $`|\pi (A)||A|50ϵ^{1/8}N`$;
*(ii)* Let $`\delta >0`$. If $`dD(A,4\delta N)`$ then $`\pi (d)D(\pi (A),\delta N)`$;
*(iii)* If $`dD(\pi (A),8\delta N)`$ then some element of $`\pi ^1(d)`$ lies in $`D(A,\delta N)`$.

Proof. (i) Clearly $`|\pi (A)||\pi (B)|=|B|`$.
(ii) If $`d=aa^{}`$ then $`\pi (d)=\pi (a)\pi (a^{})`$. For different representations of $`d`$ as $`aa^{}`$, certain of these representations of $`\pi (d)`$ may be the same. However, since $`t>N/4`$, no element of $`/t`$ has more than 4 preimages under $`\pi `$ which lie in $`A`$. The result follows.
(iii) If $`\pi (d)=\pi (a_i)\pi (a_i^{})`$ then $`a_ia_i^{}=d+\lambda _it`$ for some $`\lambda _i`$. As $`t>N/4`$ and $`N<a_ia_i^{}<N`$ there are at most 8 possible values for $`\lambda _i`$. Thus for at least one value of $`i`$ there are $`\delta N`$ solutions to $`a_ia_i^{}=d+\lambda _it`$.
It is immediate from part (iii) of this lemma that $`|D(A,\delta N)||D(\pi (A),8\delta N)|`$. However we can do better than this, since for several $`d`$ at least two of the elements $`\pi ^1(d)`$ are popular differences. Indeed, for any $`bB`$ we have $`bm,bMD(A,32ϵ^{1/2}N)`$, but $`bmbM(modt)`$. Certainly $`\pi (bm)D(\pi (A),8ϵ^{1/2}N)`$ by Lemma 11(ii). Thus, by Lemma 11(iii), we have

$`|D(A,ϵ^{1/2}N)|`$ $``$ $`|D(\pi (A),8ϵ^{1/2}N)|+|B|`$ (15)
$``$ $`|D(\pi (A),8ϵ^{1/2}N)|+|A|50ϵ^{1/8}N.`$
Combining this with (14) gives

$$|D(\pi (A),8ϵ^{1/2}N)|\mathrm{\hspace{0.33em}2}N(1+30ϵ^{1/8})3|A|.$$
(16)
Now we must have $`|D(\pi (A),8ϵ^{1/2}N)|2|\pi (A)|16ϵ^{1/4}N`$, since otherwise (16) and Lemma 11(i) would give $`|A|(\frac{2}{5}+100ϵ^{1/8})N`$, which is contrary to our assumption about $`|A|`$. Thus Lemma 10 applies, and we may pass to a subset $`X\pi (A)`$ with

$$|X||A|54ϵ^{1/8}N$$
(17)
and

$$XXD(\pi (A),8ϵ^{1/2}N).$$
(18)
We distinguish three further cases.
Case 1. $`|X|t/2`$. Then $`XX`$ is all of $`/t`$, and so (16) and (18) yield

$$t\left(\frac{1}{2}+3\eta +60ϵ^{1/8}\right)N.$$
(19)
But we know that, with at most $`18ϵ^{1/8}N`$ exceptions, the elements of $`A`$ lie in the interval $`\{m+1,\mathrm{},M\}`$ which has length $`t`$. This is alternative (i) of Proposition 7.
Case 2. $`|XX|2|X|t/3`$. Then (16),(17) and (18) give $`|A|(\frac{7}{15}+40ϵ^{1/8})N`$, contrary to assumption.
Case 3. $`|XX|<2|X|t/3`$. Then, by Kneser’s theorem on the addition of sets in abelian groups (see , Theorem 4.2), $`XX`$ is a union of cosets of some subgroup $`H/t`$ of index 2. Thus $`t`$ is even and $`\pi ^1(X)`$ consists of integers of just one parity. That is, either at least $`|A|54ϵ^{1/8}N`$ elements of $`A`$ are odd, or else at least that many are even. The latter possibility is, however, easily excluded; any subset of $`\{2,4,6,\mathrm{},2N/2\}`$ of cardinality at least $`12N/25`$ contains at least $`N^2/100`$ additive triples. This concludes the proof of Proposition 7.
An immediate corollary of Propositions 6 and 7 is the following result of Alon , Calkin  and Erdős and Granville (unpublished).

###### Proposition 12 (Alon,Calkin,Erdős–Granville)

$`|\text{SF}(N)|=2^{N/2+o(N)}`$.

Proof. It follows from Proposition 7 that if $`F[N]`$ has $`o(N^2)`$ triples then $`|F|(\frac{1}{2}+o(1))N`$. The result now follows from Proposition 6.
A much more important corollary for us will be the following description of almost all sum-free subsets of $`[N]`$.

###### Corollary 13

With $`o(2^{N/2})`$ exceptions, all sum-free subsets of $`[N]`$ consist entirely of odd numbers, or else are contained in $`\{(N+1)/3,\mathrm{},N\}`$.

Proof. Let $`A\text{SF}(N)`$, and let $`F`$ contain $`A`$. The number of $`A`$ for which $`|F|\left(\frac{1}{2}\frac{1}{120}\right)N`$ is certainly $`o(2^{N/2})`$, so suppose that $`|F|\left(\frac{1}{2}\frac{1}{120}\right)N`$. Proposition 7 then applies. Suppose first of all that alternative (ii) of that proposition holds, so that $`A`$ contains $`o(N)`$ even numbers. Suppose that $`A`$ contains at least one even number, $`t`$ say. If $`t<N/2`$ then we may select $`N/8`$ disjoint pairs $`(x,x+t)`$ of odd numbers, and $`A`$ cannot contain both of the elements of any of them since it is sum-free. The number of choices for $`A`$ is thus no more than $`2^{N/4+o(N)}3^{N/8}=o(2^{N/2})`$. If $`tN/2`$ then a very similar argument applies with pairs $`(x,tx)`$. Thus all but $`o(2^{N/2})`$ of the sum-free sets with $`o(N)`$ even numbers consist entirely of odd numbers.

Now suppose that alternative (i) of Proposition 7 holds. If

$$\left|A[\left(1\frac{1}{120}\right)N,N]\right|\mathrm{\hspace{0.33em}32}ϵ^{1/8}N$$
(20)
then, using the fact that $`A[1,\left(1\frac{1}{120}\right)N]`$ is sum-free together with Theorem 12, we see that there are just $`o(2^{N/2})`$ possibilities for $`A`$. Suppose, then, that (20) fails to hold. Since Proposition 7, (i), holds we infer that $`A`$ is contained in the interval $`[\left(\frac{1}{2}\frac{1}{30}256ϵ^{1/8}\right)N,N]`$ with the exception of at most $`32ϵ^{1/8}N`$ elements. Suppose that $`A`$ contains some element $`t\{1,\mathrm{},(N+1)/3\}`$. Then we may select $`N/124`$ totally disjoint pairs $`(x,x+t)`$ with $`xN/2`$, and $`A`$ can contain at most one element from each of them. This means that the number of choices for $`A`$ is no more than $`3^{N/12}2^{\left(\frac{1}{3}+\frac{1}{30}+o(1)\right)N}`$ which, it can be checked, is $`o(2^{N/2})`$.
As we remarked in the introduction, Cameron and Erdős  addressed the issue of counting sum-free subsets of $`\{(N+1)/3,\mathrm{},N\}`$. They discovered that the number of such sets is asymptotically $`c(N)2^{N/2}`$, where $`c(N)`$ takes two different constant values depending on whether $`N`$ is odd or even. Combining their result with the work of this paper, then, leads to Theorem 2.
Concluding remarks. The paper  of Cameron and Erdős can be hard to locate and so we have written up their argument and posted it on the web . The author would like to thank Imre Ruzsa for the many conversations which led to the papers  and which, naturally, have had a significant bearing on the present work.

Ben Green
Trinity College, Cambridge, England.
email: bjg23@hermes.cam.ac.uk


format: text

text:
# Crossover between Mean-Field and Ising Critical Behavior in a Lattice-Gas Reaction-Diffusion Model

## I Introduction

Nonequilibrium phase transitions and pattern formation occur in a broad variety of physical, chemical, biological, and sociological systems.Haken (1975); Mikhailov (1990) Such complex behavior sometimes resembles more familiar phenomena in equilibrium systems. However, there are also some fundamental differences due in part to the lack of free energy minimization or detailed-balance constraints for nonequilibrium systems. The latter feature also provides a challenge for development of a rigorous theoretical framework. Nonetheless, the spatial-temporal behavior of nonequilibrium transitions can be effectively studied using one of two paradigms. The first is through a set of partial differential equations (e.g., reaction-diffusion equation for chemical reactions), where phase transitions are related to bifurcations of the underlying nonlinear dynamics.Haken (1975); Mikhailov (1990) By default, criticality is governed by mean-field (MF) behavior, although Ginzburg criteria can be developed to characterize noise-dominated regimes.Nitzan and Ortoleva (1980) The second approach utilizes microscopic interacting particle systems of which nonequilibrium lattice-gas models form an important subclass. For these models, one can successfully apply techniques such as finite-size-scaling, and concepts including that of universality classes familiar from critical phenomena in equilibrium phase transitions.Marro and Dickman (1999)

Many types of nonequilibrium phase transitions have been studied: continuous transitions to absorbing states Marro and Dickman (1999) (which are often in the universality class of directed percolation), discontinuous transitions between reactive and inactive states,Ziff et al. (1986); Evans et al. (2002) and order-disorder transitions,Liu and Evans (2000) all of which occur in adsorption-desorption or reaction models; driven lattice-gases Marro and Dickman (1999); Schmittmann and Zia (1998) (where the driving breaks detailed balance); dynamic Ising models with both spin flip and spin exchange dynamics, but at two different temperatures leading to interesting crossover phenomena.Gonzalez-Miranda et al. (1987) For some of these systems, it is possible to derive rigorous reaction-diffusion equations in the hydrodynamic limit of rapid exchange or diffusion.de Masi et al. (1985); Evans et al. (2002)

In this paper, we consider specifically surface reaction models, which incorporate adsorption-desorption and reaction steps, as well as surface mobility. Our motivation is that these models not only contain the essential ingredients to elucidate complex phenomena observed in real surface catalysis, but also exhibit many fascinating features of the above idealized models. On the one hand, they exhibit complex dynamics and phase transitions associated with the reaction mechanism (and perhaps with adspecies interactions), but also surface diffusion rates provide a key parameter which can tune behavior. In fact, while many theoretical studies have considered the regime of limited or zero mobility, it is the hydrodynamic regime of rapid mobility that is most often realized in experiments.Evans et al. (2002)

Our focus here is on first-order phase transitions and associated critical phenomena in models for CO oxidation on metal surfaces, behavior analogous to that of the ferromagnetic Ising model. The central question is “how does critical behavior depend on surface mobility”, anticipating that MF behavior could well apply in the hydrodynamic regime, but that a crossover may occur to non-MF behavior for lower mobility. Through precise finite-size-scaling (FSS) studies of simulation data, we confirm this prediction and quantify crossover behavior. We also comment on experimental realization of crossover for CO oxidation in high-pressure nanoscale systems.

## II Reaction model: specification and behavior

We now describe our lattice-gas reaction-diffusion model, where gas (ads) denote gas-phase (adsorbed-phase) species. The following steps are implemented using a square lattice of adsorption sites with periodic boundary conditions. (i) CO(gas) adsorbs on single empty sites at rate $`p=p_{\mathrm{CO}}`$ (chosen between 0 and 1) and desorbs with rate $`d`$. (ii) O2(gas) adsorbs dissociatively onto a pair of diagonally adjacent empty sites at rate $`p_{\mathrm{O}_2}=1p_{\mathrm{CO}}`$, provided all six neighbors are free of O(ads). This “eight-site” rule reflects strong nearest-neighbor (NN) O(ads)-O(ads) repulsions. Since O(ads) is treated as immobile, this adsorption rule ensures that O(ads) never occupy adjacent sites. (iii) adjacent CO(ads) and O(ads) react at rate $`k`$ (set to unity here). (iv) CO(ads) hops to adjacent empty sites at rate $`h`$. This model has also been discussed elsewhere, e.g., Refs. Evans et al., 2002; Liu and Evans, 2000.

Conventional kinetic Monte Carlo (KMC) simulations are used to assess model behavior for finite $`h`$. Noting that mobility of CO(ads) is often very high under ultra-high vacuum conditions, we also perform a direct analysis of limiting behavior for $`h=\mathrm{}`$ using a “hybrid” treatment: here the distribution of O(ads) is described within a lattice-gas framework, but one only tracks the number of CO(ads) and assumes that they are randomly distributed on sites not occupied by O(ads).Evans et al. (2002) For very large $`h`$ and low O-coverages, this is valid.

We now briefly review the steady state behavior of this model for an infinite system. *First*, consider the case of finite $`h<\mathrm{}`$.Ziff et al. (1986); Evans et al. (2002) For low $`d`$, one typically finds a first-order transition at some $`p=p_{\mathrm{CO}}=p^{}`$ between a reactive state with low CO-coverage $`\theta _{\mathrm{CO}}`$ (for $`p<p^{}`$) and an inactive state with high $`\theta _{\mathrm{CO}}`$ (for $`p>p^{}`$). The transition disappears as $`d`$ increases above some critical value $`d_c(h)`$. *Second*, consider the hybrid model with $`h=\mathrm{}`$.Evans et al. (2002); Liu and Evans (2000) Here one finds a region of bistability with both reactive and inactive states (the discontinuous transition at $`p=p^{}`$ for finite $`h`$ corresponding to the equistability point). Bistability disappears at a cusp bifurcation upon increasing $`d`$ above some $`d_c(\mathrm{})`$. A coherent picture for both cases of infinite and finite $`h`$ comes from the observation that decreasing $`h`$ decreases the degree of metastability or hysteresis in the system.

Next, we describe how behavior changes for finite $`L`$. For the reaction model with finite $`h`$, the discontinuous transition in the $`\theta _{\mathrm{CO}}`$ versus $`p_{\mathrm{CO}}`$ mentioned above is rounded for finite $`L`$, but becomes sharper as $`L`$ increases. The trend is analogous to behavior for the equilibrium Ising model in finite systems. In the hybrid model with $`h=\mathrm{}`$, there is also a smooth transition in the $`\theta _{\mathrm{CO}}`$ versus $`p_{\mathrm{CO}}`$ for finite $`L`$. This reflects the feature that for $`L<\mathrm{}`$, the system can make noise-induced jumps between the low $`\theta _{\mathrm{CO}}`$ reactive and high $`\theta _{\mathrm{CO}}`$ inactive states, and that the relative weight of these states changes smoothly with $`p_{\mathrm{CO}}`$. This transition also becomes sharper with increasing $`L`$, occurring at the equistability point for $`L\mathrm{}`$. See Ref. Liu and Evans, 2002 for details.

Finally, to place our study in a broader context, we note that our CO oxidation model corresponds to a modified version of the Ziff-Gulari-Barshad (ZGB) model,Ziff et al. (1986) and its extension with desorption of CO(ads). The key modifications in our model are inclusion of: a) hopping of CO(ads); b) NN exclusion of O(ads); and c) finite rather than infinite reaction rate. All these features are important for realistic modeling of CO oxidation. However, it is primarily the *first* feature \[hopping of CO(ads)\] which impacts the critical behavior of the reactive-inactive transition studied in this paper. Furthermore, it is clear that our conclusions about critical behavior would apply to the ZGB model, modified to include desorption and hopping of CO(ads). The *second* feature \[NN exclusion of O(ads)\] results in an oxygen poisoning transition in the ZBG modelZiff et al. (1986) being replaced by an order-disorder transition.Liu and Evans (2000) This does not affect critical behavior of the reactive-inactive transition, with one caveat. For small $`h`$, NN exclusion does also lead to a loss of the reactive-inactive transition (see Sec. IV). The *third* modification to the original ZGB model is that instead of $`k=\mathrm{}`$, we choose $`k=1`$, i.e., the reaction rate equals the total adsorption rate. The choice is of course somewhat arbitrary, but the basic behavior of these models does not change varying the reaction rate from $`O(1)`$ to $`\mathrm{}`$. For further discussion of effects of varying $`k`$ on the steady state bifurcation diagram, see Ref. Evans and Tammaro, 1999.

## III Critical point determination and FSS analysis

Unlike the Ising model, transitions in reaction model do not involve simple symmetry-breaking. As in the liquid-vapor phase separation problem, one needs to locate the critical point in a two parameter space, i.e., $`(p,d)`$ for the reaction model. However here one also has the disadvantage that computationally efficient techniques for equilibrium systems (e.g., histogram-reweighting and cluster algorithms) do not apply. Thus, when using numerical techniques such as FSS, careful analysis of simulation data is necessary. Below, we briefly describe our procedure.

There are several reasonable ways to define the effective transition point $`p=p_L^{}`$ for finite $`L`$. One natural choice is the point where the change in the relevant order parameter (i.e., the CO coverage $`\theta _{\mathrm{CO}}`$) is greatest. All choices should converge to the same value as $`L`$ diverges (for fixed $`d<d_c`$), and should yield the same critical exponents in the FSS analysis described below. For a given $`d<d_c`$, we measure CO-coverage $`\theta _{\mathrm{CO}}`$ versus $`p`$ for two different system sizes, say $`L`$ and $`2L`$. We find that a convenient definition of $`p_L^{}`$ is the point where the curves cross, i.e., where $`\theta _{\mathrm{CO}}(p_L^{})_L=\theta _{\mathrm{CO}}(p_L^{})_{2L}`$. The technique is similar in its underlying motivation to a method for equilibrium first-order transitions by Borgs and Janke.Borgs and Janke (1992)

After determining the transition pressure $`p^{}`$ for each $`d`$ value, one can study the critical behavior using the usual FSS techniques. For example, the quantity $`\chi _LL^2(\theta _{\mathrm{CO}}^2\theta _{\mathrm{CO}}^2)`$, which is related to susceptibility in equilibrium systems, is assumed to have the following behavior

$$\chi _L=L^{\gamma /\nu }\stackrel{~}{\chi }_{\mathrm{Ising}}\left[(dd_c)L^{1/\nu }\right],$$
(1)
if the transition belongs to the Ising universality class. Here $`\nu =1`$ and $`\gamma =7/4`$ are the critical exponents for the correlation length and susceptibility respectively (in 2D). In contrast, for the MF universality class, one has Mon and Binder (1993); Luijten et al. (1996)

$$\chi _L=L^{D/2}\stackrel{~}{\chi }_{\mathrm{MF}}\left[(dd_c)L^{D/2}\right],$$
(2)
where $`D=2`$ is the spatial dimension of the system so that $`L^D`$ is the volume (or area in our case) of the system. Defining $`R_L\chi _{2L}/\chi _L`$, in either case, one has

$$R_L(d_c)2^{\stackrel{~}{\gamma }},\text{ as }L\mathrm{}$$
(3)
where the size scaling exponent $`\stackrel{~}{\gamma }`$ is $`D/2=1`$ for the MF universality class, and $`\gamma /\nu =7/4`$ for the Ising universality class.

Since one does not know the value of $`d_c`$ a priori, a convenient way to determine both the critical point and exponent is by finding the crossing point of $`R_L(d)`$ and $`R_{2L}(d)`$, so that

$$R_L\left(d_c^L\right)=R_{2L}\left(d_c^L\right)=2^{\stackrel{~}{\gamma }_L}.$$
(4)
$`\stackrel{~}{\gamma }_L`$ can be considered as the effective critical exponent for finite systems (see Sec. IV). Note that in determining $`d_c^L`$ and $`\stackrel{~}{\gamma }_L`$, we need simulations of system of linear sizes $`L`$, $`2L`$, and $`4L`$.

Figure 1 shows $`R_L`$ versus $`d`$ for the hybrid model. The FSS argument above predicts that $`R_L`$ for different $`L`$’s will cross at $`(d_c,R_c)`$ where $`R_c=2`$ for MF criticality, and $`R_c=2^{7/4}3.364`$ for Ising (in 2D) criticality. Figure 1 clearly shows MF behavior for system up to $`L=128`$. Note that in the limit of $`L\mathrm{}`$, $`R_L`$ is a step function with $`R_L=4`$ when $`d<d_c`$, and $`R_L=1`$ when $`d>d_c`$.Privman and Fisher (1983)

Table 1 lists the effective critical exponent obtained using the above procedure for the hybrid model. All estimates for $`\stackrel{~}{\gamma }_L`$ are close to unity, consistent with the prediction of MF universality class where $`\stackrel{~}{\gamma }=1`$.Mon and Binder (1993) Extrapolation to $`L=\mathrm{}`$ assuming a $`1/L^2`$ finite size correction (consistent with MF criticality) gives $`d_c=0.05258(5)`$ and $`p_c=0.41327(5)`$. Assuming a $`1/L`$ finite size correction for $`\stackrel{~}{\gamma }_L`$ gives $`\stackrel{~}{\gamma }=0.995(6)`$. It is possible that corrections to scaling are described by other exponents. However, our analysis shows that the range of system sizes is large enough so that the value of $`d_c`$ and the consistency with MF behavior is not dependent on the form of the corrections. Note that MF behavior occurs despite the presence of spatial correlations in the distribution of O(ads) due to limited mobility of O(ads) and interactions between O(ads).Liu and Evans (2000)

Figure 2 shows $`R_L`$ versus $`d`$ for the reaction model with finite $`h=1`$. The crossing point appears to approach $`2^{7/4}`$ as $`L`$ increases, consistent with the prediction of Ising universality. Limitations in analysis of larger system sizes precludes definitive convergence of FSS results for either the hybrid model (Fig. 1 or finite $`h`$ (Fig. 2. However, comparing these cases reveals very different behavior, and we argue that the above assignment of universality classes is quite reasonable and natural.

From the slope of $`R_L`$ at the crossing point and the scaling form $`\stackrel{~}{\chi }[(dd_c)L^\theta ]`$ in Eqs. (1) and (2) one can also estimate the exponent related to the rounding of the critical region due to finite sizes. Using results in Fig. 1 we find that $`\theta =1.0(1)`$ for the largest system sizes, consistent with the MF value $`\theta =D/2=1`$. Uncertainties in the data of Fig. 2 are too large to obtain accurate estimate of $`\theta `$, but they are consistent with the Ising value $`1/\nu =1`$. In two dimensions, $`\theta `$ can not be used to distinguish between the MF and Ising universality class.

We note one previous study by Tomé and Dickman Tomé and Dickman (1993) of the ZGB lattice-gas model Ziff et al. (1986) for CO oxidation (O2 adsorption on adjacent sites, infinitely fast reaction, no CO diffusion) modified to include CO-desorption. They measure the shift of the critical point with system size and found that $`d_c(L)d_c(\mathrm{})L^\lambda `$ where $`\lambda =1`$ consistent with results of the two-dimensional Ising model. Indeed, using a similar method, we found that $`\lambda 1`$ for $`h=1`$ and $`\lambda 2`$ for the hybrid model.Pavlenko et al.  This result is consistent with our conclusion regarding universality classes. However, care must be taken with the interpretation of the shift exponent, $`\lambda `$, because it is sensitive to the boundary conditions (which were chosen to be periodic in both the above studies) in the case of MF universality where hyperscaling is violated.Privman and Fisher (1983) For example, choosing free boundary conditions (which modifies adsorption and reaction processes near the boundaries) could lead to modified $`\lambda `$ for the hybrid model.

## IV Crossover behavior

Table 2 shows the variation with $`h`$ of the critical point $`d_c`$ for the CO poisoning transition obtained using FSS. The $`h=\mathrm{}`$ value is taken from the hybrid model. By analogy with equilibrium studies, discussed below and in Ref. Mon and Binder, 1993, we assume that the shift of $`d_c(h)`$ away from the limit of $`h\mathrm{}`$ scales as $`1/h`$ (although there could be logarithmic corrections).

As an interesting aside, we note that extrapolation behavior to the regime of small $`h`$ suggests that $`d_c(h)`$ vanishes at $`h=h_t0.2`$. Thus, for small $`0<h<h_t`$, the CO poisoning transition is continuous for $`d=0`$, and does not exist for $`d>0`$. This is in contrast to the ZGB model where a first-order CO poisoning transition exists even for immobile CO. For the case of $`d=0`$ and $`h<h_t`$, our epidemic analysis (cf. Ref. Marro and Dickman, 1999) indicates that the transition to the absorbing (CO poisoned) state, belongs to the directed percolation universality class.

Thus, to summarize our results for the critical point in our reaction model with $`k=1`$, we find that the critical desorption rate $`d_c`$ increases from $`d_c=0`$ for (small) $`h=h_t`$ to $`d_c=0.0527`$ for $`h=\mathrm{}`$. In contrast, for the ZGB model (no NN exclusion of O) with $`k=\mathrm{}`$, modified to include CO desorption and CO mobility, one finds that $`d_c=0.04`$Brosilow and Ziff (1992); Tomé and Dickman (1993) for $`h=0`$ increasing to $`d_c=2/3`$ for $`h=\mathrm{}`$.Evans and Tammaro (1999) Further refining this ZGB-type model to incorporate $`k=1`$ (rather than $`k=\mathrm{}`$), one finds that $`d_c=0.03`$Evans and Bartelt (1994) for $`h=0`$ increasing to $`d_c=0.142`$ for $`h=\mathrm{}`$.Tammaro et al. (1995).

Of more central interest to this paper is the variation with $`h`$ of the (effective) critical exponents. Upon increasing the CO diffusion rate, $`h`$, how does one crossover from Ising criticality (applying for finite $`h>h_t`$) to the MF criticality of the hybrid model (which corresponds to first taking the limit of $`h\mathrm{}`$). A related question is: for finite (possibly large) $`h`$, how does critical behavior depend on finite system size?

In the literature on crossover studies, effective exponents are usually defined as the slope of the log-log plot of the measured critical quantities versus deviation from the critical point, e.g., $`\gamma _{\mathrm{eff}}d\mathrm{ln}\chi /d\mathrm{ln}|dd_c|`$. A different definition, which is more amenable to numerical simulations is to fix the parameters at the critical point, while changing the system size $`L`$. The effective (reduced) exponent can then be defined as $`\stackrel{~}{\gamma }_{\mathrm{eff}}d\mathrm{ln}\chi /d\mathrm{ln}L`$. In principle, this derivative (or its finite difference approximation) should be evaluated at the critical point for the infinite system, $`d_c`$. In practice, $`d_c`$ is unknown a priori, and estimation by extrapolation produces additional errors (particularly using simulation data for limited system size). Thus instead, one just uses $`d_c^L`$ obtained from the FSS analysis in Eq. (4), and therefore $`\stackrel{~}{\gamma }_L`$ also from Eq. (4) as the effective exponent.

Figure 3(a) shows $`\stackrel{~}{\gamma }_L`$ versus variable $`1/h`$ for $`h=0.5`$, 1, 2, 4, and 10. The system size is indicated in the figure. As Fig. 3(a) shows, $`\stackrel{~}{\gamma }`$ approaches 1 as $`h\mathrm{}`$, and approaches 7/4 when $`h`$ is small. This behavior can be understood in terms of the theoretical framework presented below.

Phenomenological analysis of nonequilibrium dynamics (and more specifically of critical phenomena) in Hamiltonian systems with nonconserved order parameters has traditionally been formulated in terms of time-dependent Ginzburg-Landau equations (TDGLE).Hohenberg and Halperin (1977) For multi-component order parameter, $`\varphi _\alpha `$, the TDGLE has the general form

$$\frac{\varphi _\alpha (𝐱,t)}{t}=\mathrm{\Gamma }\frac{\delta F}{\delta \varphi _\alpha (𝐱,t)}+\zeta _\alpha (𝐱,t),$$
(5)
where $`\zeta _\alpha `$ is Gaussian white noise terms. Here $`F`$ is the coarse-grained free energy functional, which for an Ising-type model (with single-component order parameter) with interactions of range $`R`$ can be written as Mon and Binder (1993); Luijten et al. (1996)

$$F=𝑑𝐱\left[V(\varphi )+\frac{1}{2}\left|R\varphi \right|^2\right].$$
(6)
The quartic potential $`V(\varphi )`$ converts from double- to single-well form with increasing temperature through the critical point. This type of formulation extends to nonequilibrium reaction systems characterized by a vector $`𝐜`$ of adspecies concentrations where the TDGLE are replaced by reaction-diffusion equations (RDE) of the form

$$𝐜(𝐱,t)/tV_{\mathrm{eff}}(𝐜)/𝐜+𝖣𝐜+\zeta .$$
(7)
Analogous to $`V`$, the effective potential $`V_{\mathrm{eff}}`$ converts from double- to single-well passing through the critical point via the bistable region. In our problem, the diffusion tensor satisfies $`𝖣h`$ (the microscopic hop rate) except for small $`h`$.cri (a) Thus, comparing the RDE with TDGLE after performing the functional differentiation, it is clear that $`h^{1/2}`$ plays the role of $`R`$. This result is reasonable if one recognizes these types of reaction-diffusion models (with finite reaction rate and typically large diffusion rates) exhibit a characteristic diffusion length, $`L_{\mathrm{diff}}`$, which scales like $`L_{\mathrm{diff}}(h/K)^{1/2}`$. Here, $`h`$ is the microscopic hop rate, and $`K`$ is some effective rate for the overall adsorption-reaction process. See Refs. Evans et al., 2002; Imbihl and Ertl, 1995. Thus, refining the above statement, we can say that $`L_{\mathrm{diff}}`$ plays the role of $`R`$. Finally, we also note that from analysis of either the TDGLE or the RDE for infinite systems, it is long known that fluctuations dominate close enough to the critical point for spatial dimension $`D<4`$.

Recently, extensive studies have been performed on finite size effects in equilibrium Ising-type systems with long-range interactions. From scaling and renormalization procedures,Mon and Binder (1993); Luijten et al. (1996) as well as numerical simulations,Luijten et al. (1997) it has been shown that the crossover from MF to Ising behavior in finite $`L\times L`$ systems is governed by the ratio $`L/R^2`$. Thus, by analogy, one expects that the crossover for reaction-diffusion systems is governed by $`L/h`$ (in 2D). However, equilibrium and reactions-diffusion systems are quite different in detail: the Hamiltonian formulation, which is central to analysis of the former, does not exist for the latter; the microscopic nature of diffusion is distinct from that of long-range interactions. Thus, it is appropriate to test numerically the above scaling hypothesis. In Fig. 3(b), we replot the data in Fig. 3(a) using scaling variable $`L/h`$. Data collapse, while imperfect for $`L=8`$, is quite good for $`L>16`$, supporting our proposal that that $`L/h`$ is the correct size scaling variable.

Of course, it would be preferable to set the phenomenological analysis on a more rigorous footing. In general, the strategy of extending mean-field-type formulations to include noise via stochastic partial differential equations can be unreliable. An alternative rigorous approach is to attempt to map the exact master equations for the model onto a stochastic field theory.Täuber (2002) This strategy has been applied for a variety of toy reaction-diffusion models, e.g., demonstrating that the introduction of diffusion can modify the number of adsorbing states and the universality class in pair-contact models with diffusion.Hinrichsen (2000) However, these models are quite different from our reaction-limited monomer-dimer type models, where the utility of the rigorous approach has yet to be demonstrated.

## V Conclusions

Catalytic CO oxidation on noble metal surfaces provides a convenient (and important) chemical system for which lattice-gas modeling can be used to rigorously assess criticality in a reaction-diffusion system. We have systematically studied the role that CO diffusion plays on the criticality of the CO poisoning transition. We find a crossover from MF criticality for fast diffusion \[which occurs despite spatial correlations in the distribution of O(ads)\], to Ising criticality for limited diffusion. The natural variable describing this crossover is proposed based on phenomenological arguments. The proposition is supported by numerical simulations.

Recent experiments on CO oxidation in nanoscale systems can probe fluctuations and critical behavior.Suchorski et al. (1999, 2001) Thus, the considerations of this paper, including the study of crossover as a function of system size, become particularly relevant. Furthermore, the crossover behavior described in this study may be realized physically as one makes the transition from low-pressure to high-pressure catalysis. The latter could produce a decrease by many orders of magnitude of the diffusion rates (relative to other rates) that results from the higher surface coverages. cri (b)

###### Acknowledgements.

DJL and JWE were supported by the USDOE-BES through Ames Laboratory which is operated for the USDOE by Iowa State University under Contract No. W-7405-Eng-82. N.P. gratefully acknowledges the support from the Alexander von Humboldt Foundation. We also thank Prof. Ronald Imbihl for useful suggestions.


text:
# Dynamical effects in multifragmentation at intermediate energies.Experiment performed at GANIL

## Introduction.

The physical characteristics (shapes, excitation energies, angular momentum, radial flow, …) of the hot nuclei formed in nucleus-nucleus collisions are obtained by comparisons between models and data. Statistical decay models are widely used and dedicated to describe the decay of hot fully equilibrated systems, defined as systems having reached energy, shape and isospin equilibrium Weis37 ; Bohr39 ; SIMON ; SMM ; MMMC ; Moretto95 ; Moretto97 ; Tso95 ; Charity88 . However other experimental works show strong effects of the entrance channel on the decay modes of the formed hot systems Stu92 ; Lec95 ; Plagnol2000 ; Bocage2000 ; Davin2002 ; Gingras2002 ; Lefort2000 ; Dore2000b ; Cas93 ; Ste95 ; Tok95 ; Mon94 ; Glassel83 ; Lar97 . These effects which are not taken into account in the statistical decay models can provide complementary information on the nuclei such as the characteristics of the nucleon-nucleon interaction Cussol2002 ; West98 ; Reis98 ; Gut90  and/or the viscosity of the nuclear matter.

Up to now, these entrance channel effects have been studied by tracking deviations from the standard fission process in the quasi-projectile break-up Bocage2000 ; Davin2002 ; Ste95 ; Cas93 ; Glassel83 . Such deviations have been seen on the angular distributions, which show the focusing of the break-up axis along the quasi-projectile velocity direction. Associated with this focusing, highly asymmetrical break-ups have also been observed, whereas symmetrical break-ups were expected. The corresponding relative velocities were higher than the value predicted by the Viola systematics Viola . These aligned break-ups represent up to 75% of the binary break-up for the Xe+Sn system Bocage2000 . In this paper, we will extend these studies performed for binary break-up to higher fragment multiplicities to test to what extent these effects are present for other exit channels. We will present systematic studies on experimental data only, over a wide range of system sizes, incident energies and projectile/target asymmetries. There will be no attempt to compare these data to theoretical calculations.

We have studied the decay of different quasi-projectiles formed in several projectile-target collisions from 25 to 90 $`\mathrm{A}\mathrm{MeV}`$. In the first section, we present the experimental set-up, the studied sytems and the selections which have been applied on the data. In the second section the charge distributions, the associated velocity and angular distributions obtained for the different systems are shown. The third section is devoted to the evolutions of some experimental observables as a function of the break-up asymmetry of the quasi-projectile. In the last section our conclusions are given.

## I The experimental set-up

The experiments were performed at the GANIL facility with the INDRA detector. The different systems which will be presented in this article are Ni+Ni at 52 and 90 $`\mathrm{A}\mathrm{MeV}`$, Xe+Sn from 39 to 50 $`\mathrm{A}\mathrm{MeV}`$, Ta+Au at 33 and 39 $`\mathrm{A}\mathrm{MeV}`$, Ta+U at 33 and 39 $`\mathrm{A}\mathrm{MeV}`$ and U+U at 24 $`\mathrm{A}\mathrm{MeV}`$. Target thicknesses were respectively 193 $`\mu \mathrm{g}/\mathrm{cm}^2\mathrm{of}\mathrm{Au}`$ for the experiment with the Au target, 179 $`\mu \mathrm{g}/\mathrm{cm}^2\mathrm{of}\mathrm{Ni}`$ for the Ni + Ni experiment and 330 $`\mu \mathrm{g}/\mathrm{cm}^2\mathrm{of}\mathrm{Sn}`$ for the Xe + Sn experiment. The 100 $`\mu \mathrm{g}/\mathrm{cm}^2`$ uranium target was deposited between two 20 $`\mu \mathrm{g}/\mathrm{cm}^2`$ carbon foils . We will show afterwards the method used to separate the events corresponding to the uranium target from those corresponding to the carbon backing. Typical beam intensities were 3-4 $`\times 10^7`$ pps. Events were registered when at least four charged particle detectors fired (eight for the collisions with the Ta projectile).

The INDRA detector INDRA1 ; INDRA2  can be schematically described as a set of 17 detection rings centered on the beam axis. In each ring the detection of charged products was provided with two or three detection layers. The most forward ring, $`2^{}\theta _{lab}3^{}`$, is made of phoswich detectors (plastic scintillators NE102 + NE115). Between $`3^{}`$ and $`45^{}`$ eight rings are constituted by three detector layers: ionization chambers, silicon and ICs(Tl). Beyond $`45^{}`$, the eight remaining rings are made of double layers: ionization chambers and ICs(Tl). The total number of detection cells is 336 and the overall geometrical efficiency of INDRA detector corresponds to 90% of 4$`\pi `$. Isotopic separation is achieved up to Z=3-4 in the last layer (ICs(Tl)) over the whole angular range ($`3^{}\theta _{lab}176^{}`$). The charge resolution in the forward region ($`3^{}\theta _{lab}45^{}`$) is one unit up to Z$``$50. In the backward region ($`\theta _{lab}45^{}`$) a charge resolution of one unit is obtained up to Z$``$20 . The energy resolution is about 5% for ICs(Tl) and ionization chambers and better than 2% for Silicon detectors.

The binary character of the collisions is clearly seen on figure 1 which plots the correlation between the charge $`Z`$ and the velocity component parallel to the beam $`V_z`$ of each detected fragment. The fragments are roughly distributed around two areas: one around the quasi-projectile velocity and charge ($`V_z4cm/ns`$ and $`Z75`$) and one around the quasi-target velocity ($`V_z4cm/ns`$). Due to the experimental thresholds, the fragments emitted by the quasi-target are not detected efficiently. Then, for this analysis, only the fragments produced by the quasi-projectile are taken into account. Due to the quasi symmetry of most of the studied systems, a fragment (Z$``$3) is assumed to be emitted by the quasi-projectile if its velocity component parallel to the beam axis is higher than the velocity of the center of mass $`V_{c.m.}`$.

In order to have enough information to perform our studies, only events for which more than 80% of the incident linear momentum was detected are selected ($`Z_iV_i^z>0.8Z_{proj}V_{proj}^z`$ where $`Z_i`$ and $`Z_{proj}`$ are the charge of the fragment $`i`$ and the charge of the projectile respectively and $`V_i^z`$ and $`V_{proj}^z`$ their velocity components parallel to the beam axis in the laboratory frame).

The events are sorted according to the multiplicity $`M_{imf}`$ of fragments (Z$``$3) emitted by the quasi-projectile.

The use of a $`4\pi `$ multi-detector gives a very good coverage of the quasi-projectile emissions. The angular, charge and velocity or energy distributions are precisely obtained. This allows the study of the internal correlations in one event like the correlation between the fragments relative velocities and the break-up direction. It will be shown later that this is a powerful tool to distinguish different reaction mechanisms.

As said previously, the uranium was deposited between two carbon layers. Thus, for the systems with this target, there will be a mixing of reactions on the backing (C) and on the target (U). The separation between these two reactions is done by using the angular distribution of the quasi-projectile. For a fixed incident energy, the grazing angle for the heavy target is larger that the grazing angle for the light one. The values of this angle are summarized in table 1.

Two contributions are then expected for the quasi-projectile diffusion angle $`\theta _{QP}`$. The quasi-projectile (QP) is reconstructed with the fragments whose velocities are greater than $`V_{c.m.}`$. Such distributions are shown in figures 2 to 4. In the first two figures, the dashed line corresponds to the system with the Ta projectile and the Au target and the full line corresponds to the system with the Ta projectile and the U target and C backing. Reactions on the C backing clearly show up at small angles, while the distributions at large angles, from their similarities with those arising from Ta+Au, can be attributed to reaction on U only. A clear selection of Ta+U reactions is ensured by selecting events with $`\theta _{QP}>10^{}`$. For the U+C,U system (figure 4), the two contributions (U target and C backing) are better separated due to the larger difference between the values of the grazing angles. The same cut ($`\theta _{QP}=10^{}`$) was applied to separate the contributions from the uranium target and the carbon backing. For this system, the contribution of the uranium target at small angles is weaker compared to the Ta+C,U systems.

## II Size and velocity hierarchy

We will first look at simple and direct observables like the fragment charge distributions, the corresponding distributions of the velocity component parallel to the beam ($`V_z`$) and the angular distributions for the different systems. The angle $`\theta _{F/QP}`$ is the angle between the velocity of the fragment in the quasi-projectile (QP) frame and the velocity of the quasi-projectile in the center of mass frame (see figure 5). The events are sorted according to the multiplicity, $`M_{imf}`$, of the forward fragments ($`V_z>V_{c.m.}`$). In each event, the fragments are sorted according to their charge.

Charge, $`V_z`$ and $`\mathrm{cos}(\theta _{F/QP})`$ distributions are shown on figure 6. The uppermost row corresponds to the charge distribution, the middle row to the $`V_z`$ distribution and the lowermost row to $`\mathrm{cos}(\theta _{F/QP})`$distribution. The different columns correspond to the different fragment mutiplicities (from $`M_{imf}`$=2 to $`M_{imf}`$=4 from left to right). On each panel, the shading of the distribution darkens according to the rank of the fragment in the event.

One spectacular observation is that the velocity distributions are strongly correlated to the charge sorting: the heaviest fragment is in average the fastest one, the second heaviest fragment is the second fastest one and so on. For the $`\mathrm{cos}(\theta _{F/QP})`$ distributions, the distribution of the heaviest fragment is peaked at forward angles ( $`\mathrm{cos}(\theta _{F/QP})`$$`1`$): the emission direction of this fragment is close to the quasi-projectile velocity direction. Such pictures were not expected in case of a fragmentation of a fully equilibrated quasi-projectile, for which the fragments are emitted in all directions without a particular hierarchy for the velocities. This hierarchy effect (the ranking in charge induces on average the ranking in $`V_z`$ and the $`\mathrm{cos}(\theta _{F/QP})`$ distribution of the heaviest fragment is forward-peaked) suggests an entrance channel effect.

Similar results are observed for the corresponding distributions for most of other systems. The heaviest fragment is the fastest one and its direction of emission is close to the quasi-projectile velocity direction whatever the system size and whatever the incident energy. The hierarchy between the size of the fragment and its velocity is observed for the Ta + Au (figures 6 and 7 ), Xe+Sn (figures 8, 9 and 10 ) and Ni+Ni systems (figures 11 and 12). This effect is strong on the Ta+Au system and is slightly weaker for the Xe+Sn and the Ni+Ni systems. For the Xe+Sn system, the anisotropy of the heaviest fragment angular distribution increases slightly with the incident energy.

For the Ta+U system (events with $`\theta _{QP}>10^{}`$, figures 13 and 14 ), the same hierarchy effect is observed as for the Ta+Au system. For the Ta + C,U system (figures 15 and 16 ), this hierarchy effect is still observed for high multiplicities ($`M_{imf}`$$`3`$), but is not present for $`M_{imf}`$=2. This is due to the mixing between the carbon backing and the uranium target mentioned in the previous section. For $`M_{imf}`$=2, the two fragments have almost the same charges, the velocities are similar and the whole range of $`\mathrm{cos}(\theta _{F/QP})`$is covered. The contribution of the Ta+C collisions is stronger and stronger when $`M_{imf}`$ decreases. This contribution is especially seen for $`M_{imf}`$=2 (compare leftmost columns of figures 13 and 15 for 33 $`\mathrm{A}\mathrm{MeV}`$ and figures 14 and 16 for 39 $`\mathrm{A}\mathrm{MeV}`$) where the distributions are completely different. The Ta+C collisions lead to the formation of an incomplete fusion nucleus, which decays through fission. In this case, no hierarchy in velocities or no privileged angles of the heaviest fragment are expected.

For the U+U system (figure 17, events with $`\theta _{QP}>10^{}`$) the hierarchy effect is observed for $`M_{imf}`$$`3`$ but is not observed for $`M_{imf}`$=2. Due to the high fissility of uranium, the $`M_{imf}`$=2 events correspond mainly to the fission process. However, events for which the charge of the heaviest fragment is close to 80 are still present. They correspond to asymmetric binary break-ups which are not expected for the fission of such a heavy nucleus. These asymmetric break-ups are not present for the U+C system (figure 18, leftmost column, $`\theta _{QP}<10^{}`$) and no hierarchy effect is seen: these observations are consistent with the fission of a fully equilibrated nucleus. For $`M_{imf}`$$`3`$, the velocities of the two heaviest fragments are similar and their $`\mathrm{cos}(\theta _{F/QP})`$ distributions are flat. For the other fragments, the hierarchy effect is present. This could be due to a two-step process in which the hierarchy effect is present at the early stage of the collision, followed by the fission of the heaviest fragment due to the high value of its charge.

To summarize this section, a hierarchy effect (the ranking in charge induces the ranking in $`V_z`$ and the $`\mathrm{cos}(\theta _{F/QP})`$ distribution of the heaviest fragment is forward-peaked) is seen for many system sizes and incident energies. These observations are not consistent with the decay of a fully equilibrated nucleus for which no hierarchy effect is expected. This “hierarchy effect” is consistent with a strong deformation of QP or QT during the collision which is followed by the break-up of these elongated nuclei in two or more fragments (neck formation and break-up, see figure 19). The fragments emitted by this neck reflect its internal structure: its size at the center of mass is on average thinner than close to the quasi-projectile or quasi-target, and the velocity modulus in the center of mass frame of the nucleons in the neck close to the center of mass are smaller than those of nucleons close to the quasi-target or to the quasi-projectile.

This leads to the “hierarchy effect” observed experimentally. The velocity gradient can be tracked by studying the relative velocities between the heaviest fragment and the others. In the proposed scenario, this relative velocity is expected to be larger than the one obtained from the decay of a fully equilibrated nucleus. For the heaviest systems, the standard fission process superimposes on the neck formation and break-up. The two contributions are clearly seen for Ta and U projectiles. In these cases, deviations from the standard fission can be easily tracked.

## III Internal correlations

In the previous section, we have evidenced a “hierarchy effect”, indicating a strong entrance channel influence on the fragmentation of the quasi-projectile. We will study in this section correlations between some observables to verify whether the fragmentation scenario proposed above resists a more detailed analysis. If an elongated quasi-projectile is formed and breaks quickly, the relative velocities between the fragments should be higher along the QP velocity direction than in any other direction, because the incident energy is not fully damped in internal degrees of freedom in such a process. Within this assumption, the heaviest fragment focused along the QP velocity has a high velocity because it is a remnant of the projectile. In the case of the fragmentation of a fully equilibrated QP, the relative velocity should be independent of the break-up direction.

For $`M_{imf}`$=2, the relative velocity between the two fragments can be easily determined, while it is not the case for higher multiplicities. We have seen in the previous section that the heaviest fragment has the same properties whatever the value of $`M_{imf}`$: it is the fastest one and it is focused in the direction of the quasi-projectile in the center of mass frame. We can use this property to define the break-up direction $`\theta _{prox}`$ as the direction of the heaviest fragment with respect to the quasi-projectile velocity, and the relative velocity $`\stackrel{}{V_{rel}}`$ as the difference of the velocity of the heaviest fragment $`\stackrel{}{V_1}`$ and the velocity of the center of mass of all other fragments detected with a velocity greater than $`V_{c.m.}`$. They are determined as follows:

$$\stackrel{}{V_{rel}}=\stackrel{}{V_1}\frac{_{i=2}^{M_{imf}}Z_i\stackrel{}{V_i}}{_{i=2}^{M_{imf}}Z_i}$$
(1)
where $`Z_i`$ is the charge of the $`i^{th}`$ fragment ($`Z_i>Z_{i+1}`$) and $`\stackrel{}{V_i}`$ its velocity

$$\mathrm{cos}(\theta _{prox})=\frac{(\stackrel{}{V_1}\stackrel{}{V_{QP}}).\stackrel{}{V_{QP}}}{|\stackrel{}{V_1}\stackrel{}{V_{QP}}||\stackrel{}{V_{QP}}|}$$
(2)
where $`\stackrel{}{V_{QP}}`$ is the velocity of the quasi-projectile. All the velocities in formulae 1-3 are expressed in the center of mass frame. With this definition, $`\theta _{prox}`$ is identical to $`\theta _{F/QP}`$ of the heaviest fragment (see figure 5).

$$\stackrel{}{V_{QP}}=\frac{_{i=1}^{M_{imf}}Z_i\stackrel{}{V_i}}{_{i=1}^{M_{imf}}Z_i}$$
(3)
Let us study the behaviour of the $`\mathrm{cos}(\theta _{prox})`$ distributions. The experimental distributions are shown on figures 20 and 21 for the Ta + Au system at 33 and 39.6 $`\mathrm{A}\mathrm{MeV}`$ respectively. On each figure, the columns correspond to different values of $`M_{imf}`$ and the rows to different ranges in charge of the heaviest detected fragment $`Z_1`$. This cut in $`Z_1`$ was done due to the particular behavior of the heaviest fragment. It is also correlated to the asymmetry of the break-up as in fission: the highest values of $`Z_1`$ correspond to the more asymmetric break-ups (one big fragment and small other ones) and the lowest values of $`Z_1`$ correspond to the most symmetric break-ups (equal size fragments). It can be seen on these figures that the $`\mathrm{cos}(\theta _{prox})`$ distributions are in most cases peaked at 1 (emission along the direction of the QP velocity). The most forward peaked $`\mathrm{cos}(\theta _{prox})`$ distributions are obtained for the most asymmetric break-ups (high values of $`Z_1`$) and this for all values of $`M_{imf}`$. This is not expected in the case of a fragmentation of a fully equilibrated nucleus. An angular momentum effect would lead to a forward-backward symmetry in angular distributions.

For the most symmetric break-ups (low values of $`Z_1`$) and the greater IMF multiplicities, the distribution becomes less forward peaked. In this case, the fragments having almost the same charge, the ranking in charge is meaningless. Consequently the memory of the direction of the QP in the fragmentation process is blurred. Another possible scenario could be the occurrence of the fragmentation of a fully equilibrated QP. It will be seen later that the cut at $`V_{c.m.}`$can also influence these distributions.

Is there a connexion between the strength of the anisotropy of the $`\mathrm{cos}(\theta _{prox})`$ distributions and the violence of the collisions? The latter has been estimated by using the sum of the transverse energies $`E_{t12}`$ of light charge particles ($`Z2`$). This global variable has been widely used as an impact parameter selector in previous studies Plagnol2000 ; Bocage2000 . The low values of transverse energies correspond to peripheral collisions and the high values to the most violent collisions. The reduced transverse energy distributions ($`E_{t12}/E_{c.m.}`$ where $`E_{c.m.}`$ is the energy available in the center of mass) are presented in figure 22 for Ta+Au collisions at 39.6 $`\mathrm{A}\mathrm{MeV}`$. The shapes of these distributions depend weakly on the value of $`M_{imf}`$ and strongly on that of $`Z_1`$. This is in agreement with $`Z_1`$ being the remnant of the QP. The average $`E_{t12}`$ value decreases when going from symmetrical (first row) to asymmetrical break-ups (last row) as already shown for the lighter Ar+Ni system Dore2000a . The last row corresponds to the most asymmetrical and aligned break-ups (see figure 21). The transverse energies of the associated particles are low and correspond to peripheral collisions. The first row corresponds to the most symmetrical break-ups and to more wider $`\mathrm{cos}(\theta _{prox})`$ distributions. The transverse energies of the associated particles are high and correspond to more central collisions.

It is interesting to observe low $`E_{t12}`$ values for the highest IMF multiplicities (last row, rightmost panel of figure 22). In this case, the excitation energy of the QP is low and low evaporated IMF multiplicities are expected. This observation, combined with the “hierarchy effect” and the strongly peaked $`\mathrm{cos}(\theta _{prox})`$ distributions, strongly suggests that these fragmentations are only due to entrance channel effects. For the binary break-ups (first column), the very asymmetrical break-ups (last row) are not expected for the standard fission of a quasi-Ta. Nevertheless, this is the dominant decay channel for $`M_{imf}`$=2. The second and third panels of the first column ($`M_{imf}`$=2) correspond to more symmetrical break-ups ($`Z_137`$) and the standard fission process is expected. In this case the transverse energy distributions are wider. It seems that two contributions could be considered as already suggested by the the $`\mathrm{cos}(\theta _{prox})`$ distributions. These observations are also made on the other systems.

Let us now come to the correlation between the relative velocities of the fragment $`V_{rel}`$ and $`\mathrm{cos}(\theta _{prox})`$. They are presented on figure 23 for Ta+Au collisions at 39.6 $`\mathrm{A}\mathrm{MeV}`$, on figure 24 for the U+U collisions at 24 $`\mathrm{A}\mathrm{MeV}`$ and on figure 25 for the U+C collisions at 24 $`\mathrm{A}\mathrm{MeV}`$. As in figures 20 and 21, the columns correspond to different IMF multiplicities and the rows to different values of $`Z_1`$. For the most asymmetric breakup of the Ta + Au collisions (two lowest rows for figure 23), a strong variation of $`V_{rel}`$ with $`\mathrm{cos}(\theta _{prox})`$ is seen. The value of $`V_{rel}`$ increases from 2.3 $`cm/ns`$ at $`\mathrm{cos}(\theta _{prox})`$=-1 up to $`3.5cm/ns`$ at around $`\mathrm{cos}(\theta _{prox})=0.8`$ and then decreases. The variation is weaker for the more symmetric break-ups (two first rows). This variation is also observed for the U+U collisions but its amplitude is smaller. For the U+C system (figure 25), no evolution is seen whatever the IMF multiplicity and the charge of the heaviest fragment. For the U+C system, no “hierarchy effect” was seen (see figure 18). Within our interpretation of the “hierarchy effect”, no modulation is expected for this system. On all other systems, the same correlation is observed: a modulation of $`V_{rel}`$ with $`\mathrm{cos}(\theta _{prox})`$ is seen when the “hierarchy effect” is observed. So the modulation of $`V_{rel}`$ with $`\mathrm{cos}(\theta _{prox})`$ is correlated to the observation of a “hierarchy effect”.

The decrease of $`V_{rel}`$ at the smallest angles ($`\mathrm{cos}(\theta _{prox})`$=1) is not compatible with the expected behaviour of $`V_{rel}`$ resulting from our interpretation on the “hierarchy effect”. But due to the selection of the fragments in this analysis ($`V_z>V_{c.m.}`$), the highest values of $`V_{rel}`$ can not be reached. We have tested the effect of this velocity cut on our analysis with the help of a simple simulation. For sake of simplicity, we have only verified the effect of the velocity cut for $`M_{imf}`$=2. The basic ingredients of this simulation are the following: a QP with a charge $`Z_{QP}`$, a velocity $`V_{QP}`$ and an angle $`\theta _{QP}`$ is considered. This QP splits in two fragments of charge $`Z_1`$ and $`Z_2`$, the axis of the break-up being isotropically distributed and the relative velocity between the fragments ranging from 0 cm/ns to 10 cm/ns. For each case, the event is taken into account in this analysis if both fragments have a $`V_z`$ greater than $`V_{c.m.}`$. The velocities $`\stackrel{}{V_1}`$ and $`\stackrel{}{V_2}`$ of the two fragments are calculated the following way:

$$\stackrel{}{V_1}=\stackrel{}{V_{QP}}+(1\frac{Z_1}{Z_{QP}})\stackrel{}{V_{rel}}$$
(4)
$$\stackrel{}{V_2}=\stackrel{}{V_{QP}}\frac{Z_1}{Z_{QP}}\stackrel{}{V_{rel}}$$
(5)
The first column of figure 26 corresponds to the result of the simulation; the second column shows the experimental bidimensional plots of $`V_{rel}`$ versus $`\mathrm{cos}(\theta _{prox})`$ for the Ta + Au collisions at 39.6 $`\mathrm{A}\mathrm{MeV}`$; the third column shows the same plots for the U + C collisions at 24 $`\mathrm{A}\mathrm{MeV}`$ ($`\theta _{QP}<10^{}`$). The plots corresponding to events with an IMF multiplicity equal to 2 are displayed. The rows correspond to different selections on the charge of the heaviest fragment $`Z_1`$, the uppermost row corresponding to the lowest $`Z_1`$ values and the lowermost row to the highest $`Z_1`$ values. For each plot of the simulation (leftmost column), the values of $`V_{QP}`$, $`\theta _{QP}`$ and the ratio $`Z_1/Z_{QP}`$ have been chosen according to the average experimental values for the Ta+Au collisions at 39.6 $`\mathrm{A}\mathrm{MeV}`$ for a given IMF multiplicity and for a fixed $`Z_1`$ range. The shaded areas (leftmost column) correspond to the events selected in our analysis. One can see that the velocity cut ($`V_z>V_{c.m.}`$) systematically removes the events with the highest $`V_{rel}`$ values when the fragmentation axis is aligned on the QP velocity direction. For $`\mathrm{cos}(\theta _{prox})`$=1, this effect is always present. This could explain the decrease of $`V_{rel}`$ for high $`\mathrm{cos}(\theta _{prox})`$ values observed in figures 23 and 24. This is confirmed by the bidimensional plot (second column) which was used to obtain figure 23. The effect of the velocity cut is clearly seen for the highest $`Z_1`$ values. The agreement between data and simulation is good, showing that the velocity cut limits the range of accessible $`V_{rel}`$ values. For higher $`M_{imf}`$ values, similar conclusions are obtained. Another interesting observation is that the $`V_{rel}`$ distribution for $`\mathrm{cos}(\theta _{prox})`$$`1`$ is narrow, its average value $`V_{rel}`$$`=2.3cm/ns`$ corresponds to the Viola systematics Viola  and is not affected by the velocity cut at $`V_{c.m.}`$. When $`\mathrm{cos}(\theta _{prox})`$ increases, the width of the $`V_{rel}`$ distribution and its average value increase while the velocity cut has no influence, i.e. for $`\mathrm{cos}(\theta _{prox})`$ values below 0.8. Above $`\mathrm{cos}(\theta _{prox})`$=0.8, high values of $`V_{rel}`$ cannot be reached and then its average value decreases. For the U+C system rightmost column, it can be seen that the $`V_{rel}`$ distributions are always narrow and centered around the Viola systematics value whatever the $`\mathrm{cos}(\theta _{prox})`$ value. For these collisions, our experimental cut does not affect the evolutions of $`V_{rel}`$ with $`\mathrm{cos}(\theta _{prox})`$.

The observations made in this section confirm the scenario proposed in the previous section. For the U+C system, all observations are compatible with the decay of a fully equilibrated nucleus: no modulation of $`V_{rel}`$ with $`\mathrm{cos}(\theta _{prox})`$ is seen while at the same time the “hierarchy effect” is absent or very weak. For the systems with a heavy target, the variation of $`V_{rel}`$ with $`\mathrm{cos}(\theta _{prox})`$ is observed. This indicates that a strongly deformed QP or a neck of matter is formed at the early stage of the collision, and breaks quickly into several fragments. In such a process, the incident kinetic energy is not fully damped, and the fragments keep the memory of the formation of the neck and/or deformed QP. Within this interpretation, the heaviest fragment is a remnant of the projectile. This scenario seems to occur for a wide range of system size and incident energies. For the heaviest systems, like U+U for which the fissility of the QP is high, it competes with the fission process.

## IV Conclusions

The study of the parallel velocity distributions of the fragments forward emitted as a function of their charge exhibits a “hierarchy effect”: the ranking in charge induces in average a ranking in the average parallel velocity, the heaviest fragment is the fastest and is focused in the forward direction relative to the QP recoil velocity. This “hierarchy effect” is stronger when the size of the target is large, when the fissility of the QP is limited ($`Z<80`$) and when the incident energy is high. This effect is observed for all systems, whatever the multiplicity of fragments. These observations are compatible with the formation of a neck of matter in-between the quasi-projectile and the quasi-target. The neck may be or not attached to the QP (or QT) remnant. In any case, its break-up is fast enough to keep the memory of the entrance channel.

This mechanism is predominant for asymmetric break-ups which mainly correspond to peripheral collisions. For the most peripheral collisions, the asymmetry observed for the binary break-ups is not compatible with the result of a standard fission, and for the highest multiplicities, the high focusing of the heaviest fragment at forward angles is inconsistent with the fragmentation of a fully equilibrated nucleus.

The observed variation of the fragments relative velocity with the emission angle of the heaviest fragment strenghtens the previous statement. This internal correlation study is a powerful tool to clearly establish the degree of equilibration of the studied ensemble. Up to now, the comparisons of models to data were mainly made on global observations only (size distributions, multiplicity distributions, kinetic energy distributions, and so on…). The study of such internal correlations is a more accurate tool to test the pertinence of the models.

In order to have a full understanding of the fragmentation process, the models have to reproduce the effects of the entrance channel. A first step could be to mock up these effects in effective parameters in the statistical decay approaches. It will be certainly worth to use dynamical approaches BUU ; LV ; BLV ; FMD ; QMD ; AMD ; BNV ; CNBD2002 ; Gingras2002  to test the presence of such a hierarchy effect. But in all cases, the models have to reproduce the global observations and the internal correlations as well.