text:
# 1 Introduction

## 1 Introduction

Mathematical diffraction theory is concerned with the Fourier analysis of the autocorrelation measures of unbounded, but translation bounded, complex measures in Euclidean space, compare  and references listed there. More generally, the same question is also analyzed in the setting of locally compact Abelian groups . There are many interesting and relevant open questions connected with it, in particular how to assess the spectral type of the (positive) diffraction measure, which is the Fourier transform of the autocorrelation.

One important subclass of translation bounded measures consists of the set of discrete Dirac combs which are supported on a lattice or a subset thereof. This paper provides a characterization of the autocorrelation and diffraction measures associated to measures of this class. As an application, we derive a relation between the diffraction measures of complementary lattice subsets. Other recent (sometimes implicit) applications of this characterization include deterministic cases such as the visible lattice points or the $`k`$th power free integers  and the class of substitution lattice systems , but also a wide class of lattice gas models . The latter are presently gaining practical importance in crystallography due to the need for a better understanding of diffuse scattering, compare  and references given there.

The article is organized as follows. First, we describe the problem in the Euclidean setting and state the corresponding result in Theorem 1. The next Section then covers the step by step proof of this result. All details, or at least precise references, are given in order to make the presentation relatively self-contained and accessible also to readers with a more applied background. As general references for topological concepts and results, we use . As one application, we then compare lattice subsets with their complements, with special emphasis on the homometry problem (see Theorem 2). This is followed by an extension of Theorem 1 to the more general situation that Euclidean space $`^n`$ is replaced by a locally compact Abelian group (LCA group) $`G`$ which is Polish. An analogous result is true here, and is summarized in Theorem 3. Finally, we close with a slightly weaker result for the situation of $`\sigma `$-compact LCA groups in Theorem 4.

## 2 Euclidean lattices

Let $`\mathrm{\Gamma }`$ be a lattice in $`^n`$, i.e. the integer span of $`n`$ vectors that are linearly independent over $``$. We are interested in the weighted Dirac comb

$$\omega =\underset{t\mathrm{\Gamma }}{}w(t)\delta _t$$
(1)
where $`w:\mathrm{\Gamma }`$ is a bounded function and $`\delta _t`$ denotes the normalized point (or Dirac) measure located at $`t`$, so that $`\delta _t(\phi )=\phi (t)`$ for continuous functions $`\phi `$. Since $`\mathrm{\Gamma }`$ is uniformly discrete and $`w`$ is bounded, $`\omega `$ is a translation bounded (or shift bounded) complex measure, cf. \[7, Ch. I.1\]. By a measure, we always mean a regular (complex) Borel measure, identified with the corresponding linear functional on $`𝒦(^n)`$, the space of continuous functions of compact support. This is justified by the Riesz-Markov theorem, compare  for details. The space of measures is then equipped with the vague topology which we will use throughout.

Let us first assume that the natural autocorrelation measure of $`\omega `$ exists. It is defined with respect to an increasing sequence of balls around the origin, and denoted by $`\gamma _\omega `$. So, we assume for the moment that

$$\gamma _\omega =\underset{r\mathrm{}}{lim}\frac{\omega _r\stackrel{~}{\omega }_r}{\mathrm{vol}(B_r(0))}$$
(2)
exists as a vague limit, where $`\omega _r`$ means the restriction of $`\omega `$ to the (open) ball $`B_r(0)`$ of radius $`r`$ around $`0`$, $`\stackrel{~}{\omega }_r:=(\omega _r)\stackrel{~}{}`$, and $`\stackrel{~}{\omega }`$ is the measure defined by $`\stackrel{~}{\omega }(\phi )=\overline{\omega (\stackrel{~}{\phi })}`$ for any continuous function $`\phi `$ of compact support, with $`\stackrel{~}{\phi }(x):=\overline{\phi (x)}`$. In particular, for $`\omega `$ of (1), we have $`\stackrel{~}{\omega }=_{t\mathrm{\Gamma }}\overline{w(t)}\delta _t`$.

Since $`\mathrm{\Gamma }`$ is a lattice, the natural autocorrelation is a pure point measure of the form $`\gamma _\omega =_{z\mathrm{\Gamma }}\nu (z)\delta _z`$ with the coefficients being given by

$`\nu (z)`$ $`=`$ $`\underset{r\mathrm{}}{lim}{\displaystyle \frac{1}{\mathrm{vol}(B_r(0))}}{\displaystyle \underset{\begin{array}{c}t,t^{}\mathrm{\Gamma }_r\\ tt^{}=z\end{array}}{}}w(t)\overline{w(t^{})}`$
$`=`$ $`\underset{r\mathrm{}}{lim}{\displaystyle \frac{1}{\mathrm{vol}(B_r(0))}}{\displaystyle \underset{t\mathrm{\Gamma }_r}{}}w(t)\overline{w(tz)}`$
Here, $`\mathrm{\Gamma }_r=\mathrm{\Gamma }B_r(0)`$, and there are several variants to write $`\nu (z)`$ as a limit. For fixed $`z`$ and $`r|z|`$, the two approximations for finite radius used in (2), prior to dividing by $`\mathrm{vol}(B_r(0))`$, differ by surface contributions which are uniformly small in comparison to the bulk. To make this precise, one needs an estimate for the number of lattice points in spherical shells of thickness $`s`$ and radius $`rs`$ which is $`O(r^{n1})`$ in $`n`$ dimensions, see . Hence, the above limit does not depend on such details, and we will make use of this freedom in the Euclidean setting without further mentioning.

Since $`\mathrm{\Gamma }`$ is a lattice in $`^n`$, its density is well-defined as a limit, namely

$$\mathrm{dens}(\mathrm{\Gamma })=\underset{r\mathrm{}}{lim}\frac{|\mathrm{\Gamma }B_r(a)|}{\mathrm{vol}(B_r(0))}$$
(4)
with $`a^n`$ and $`|A|`$ denoting the cardinality of a (finite) set $`A`$. This limit exists uniformly in $`a`$, see . As a lattice, $`\mathrm{\Gamma }`$ is uniformly discrete (i.e. the minimal distance between any two distinct points is strictly positive), and the natural autocorrelation thus exists if and only if the coefficients $`\nu (z)`$ of (2) exist for all $`z\mathrm{\Gamma }`$.

So far, we explicitly assumed the existence of the natural autocorrelation as a limit, and hence its uniqueness. This is the standard situation investigated e.g. in crystallography, and it seems very adequate in view of the usual homogeneity of the systems analyzed. Mathematically, however, this assumption is not necessary, and we will thus formulate our results in a slightly more general setting.

Our key assumption is that the complex weight function $`w`$ is bounded, so that $`\omega `$ is translation bounded. This is already sufficient to ensure that all finite approximations to the autocorrelation are uniformly translation bounded, see \[14, Prop. 2.2\]. Consequently, there is always at least one vague limit point, but, in general, we might have several. To make this precise, let us define

$$\gamma _\omega ^{(r)}=\frac{\omega _r\stackrel{~}{\omega }_r}{\mathrm{vol}(B_r(0))}$$

and consider the family of autocorrelation approximants $`\{\gamma _\omega ^{(r)}r>0\}`$, which are all positive definite measures by construction. When restricted to a compact set $`K`$, the corresponding family of finite measures is precompact in the vague topology.

Let us now consider any vague limit point $`\gamma `$ of the family $`\{\gamma _\omega ^{(r)}r>0\}`$. It is then possible to select a sequence of radii $`(r_i)_i`$ such that $`\gamma _\omega ^{(r_i)}\gamma `$ vaguely as $`i\mathrm{}`$. As we will see, the proof of our main result (Theorem 1) will only depend on the existence of such a sequence, so we can formulate it as a result for each limit point.

The standard tools from Fourier analysis are also needed. The Fourier transform of a rapidly decreasing (or Schwartz) function $`\phi `$ is

$$\widehat{\phi }(x)=_^ne^{2\pi ixy}\phi (y)dy$$

where $`xy`$ is the standard Euclidean scalar product in $`^n`$. From here, we take the usual route to the Fourier transform of measures that are, at the same time, tempered distributions, see \[23, Ch. IX.1\] or \[25, Ch. 7\] for general background and  for our conventions. An alternative approach, without any reference to Schwartz functions, could follow \[7, Ch. I.4\] and employ the positive definiteness of $`\gamma _\omega `$ which guarantees the existence of $`\widehat{\gamma }_\omega `$.

We call a Borel set $`A`$ regular, if $`A`$ has Lebesgue measure $`0`$, and say that a measure $`\mu `$ is supported on a regular Borel set $`A`$, if $`\mu `$ and $`\mu |_A`$, the restriction of $`\mu `$ to $`A`$, are identical as measures on $`^n`$. The central result can now be phrased as follows.

###### Theorem 1

Let $`\mathrm{\Gamma }`$ be a lattice in $`^n`$ and $`\omega `$ a weighted Dirac comb on $`\mathrm{\Gamma }`$ with bounded complex weights. Let $`\gamma _\omega `$ be any of its autocorrelations, i.e. any of the limit points of the family $`\{\gamma _\omega ^{(r)}r>0\}`$. Then the following holds.

$`(1)`$ The autocorrelation $`\gamma _\omega `$ can be represented as

$$\gamma _\omega =\mathrm{\Phi }\delta _\mathrm{\Gamma }=\underset{x\mathrm{\Gamma }}{}\mathrm{\Phi }(x)\delta _x$$

where $`\mathrm{\Phi }:^n`$ is a bounded continuous positive definite function that interpolates the autocorrelation coefficients $`\nu (x)`$ as defined at $`x\mathrm{\Gamma }`$. Moreover, there exists such a $`\mathrm{\Phi }`$ which extends to an entire function $`\mathrm{\Phi }:^n`$ with the additional growth restriction that there are constants $`C,R0`$ and $`N`$ such that $`|\mathrm{\Phi }(z)|C(1+|z|)^N\mathrm{exp}(R|\mathrm{Im}(z)|)`$ for all $`z^n`$.

$`(2)`$ The Fourier transform $`\widehat{\gamma }_\omega `$, also called a diffraction measure of $`\omega `$, is a translation bounded positive measure that is periodic with the dual lattice $`\mathrm{\Gamma }^{}=\{uuv\text{ for all }v\mathrm{\Gamma }\}`$ as lattice of periods. Furthermore, $`\widehat{\gamma }_\omega `$ has a representation as a convolution,

$$\widehat{\gamma }_\omega =\varrho \delta _\mathrm{\Gamma }^{},$$

in which $`\varrho `$ is a finite positive measure supported on a fundamental domain of $`\mathrm{\Gamma }^{}`$ that is contained in the ball of radius $`R`$ around the origin.

Remarks: The interpolating function $`\mathrm{\Phi }`$ is not unique. It can be changed by adding any positive definite continuous (entire) function which vanishes on $`\mathrm{\Gamma }`$. Also, the positive measure $`\varrho `$ depends on the choice of the fundamental domain of $`\mathrm{\Gamma }^{}`$. As soon as the latter is fixed (as a regular Borel set, say, to avoid pathologies with singular versus continuous parts), $`\varrho `$ is unique. This is so because $`\widehat{\gamma }_\omega `$ is $`\mathrm{\Gamma }^{}`$-periodic and thus defines a unique measure on the factor group $`^n/\mathrm{\Gamma }^{}`$, which, in turn, gives rise to a unique measure $`\varrho `$ on the fundamental domain chosen.

A rather natural fundamental domain of $`\mathrm{\Gamma }^{}`$ can be constructed from the Voronoi cell of $`\mathrm{\Gamma }^{}`$, which is a polytope, namely the set of all points of $`^n`$ which are not farther apart from the origin than from any other point of $`\mathrm{\Gamma }^{}`$. It is the intersection of finitely many closed half-spaces and hence a zonotope. A fundamental domain emerges from it by removal of certain boundaries, starting with the $`(n1)`$-boundaries, then the $`(n2)`$-boundaries, and so on down to the 0-boundaries. Due to the lattice structure of $`\mathrm{\Gamma }^{}`$, these boundaries always come in translation pairs, one member of which is removed. What remains, is a regular Borel set $`E`$ which is a true fundamental domain of $`\mathrm{\Gamma }^{}`$, i.e. the $`\mathrm{\Gamma }^{}`$-translates of $`E`$ form a partition of $`^n`$. Its existence is vital for the above statement because $`\varrho `$ may contain point measures.

The radius $`R`$ in the above growth estimate can be taken as the radius of the circumsphere of the fundamental domain of $`\mathrm{\Gamma }^{}`$ chosen. This follows from the Paley-Wiener theorem for distributions with compact support \[25, Thm. 7.23\]. If a fundamental domain is constructed on the basis of the Voronoi cell of $`\mathrm{\Gamma }^{}`$, then its circumradius $`R`$, the covering radius of $`\mathrm{\Gamma }^{}`$, is minimal among all fundmanental domains of $`\mathrm{\Gamma }^{}`$.

If there is only one limit point to the family $`\{\gamma _\omega ^{(r)}r>0\}`$, we are in the standard situation of crystallography, where the homogeneity of the systems makes this a very natural assumption. In this case, Theorem 1 simply refers to the autocorrelation.

The above mentioned question of the spectral type of $`\widehat{\gamma }_\omega `$ is now obviously reduced to that of the spectral type of $`\varrho `$. The latter is a finite positive measure and admits the unique decomposition

$$\varrho =(\varrho )_{pp}+(\varrho )_{sc}+(\varrho )_{ac}$$

with respect to Lebesgue measure, which is the natural reference measure in this context. As usual, $`pp`$, $`sc`$ and $`ac`$ stand for pure point, singular continuous and absolutely continuous, see \[23, Sec. I.4\] for details.

The result of Theorem 1 is not really restricted to Dirac combs. If $`h`$ is a (continuous) $`L^1`$-function, say, and $`\omega `$ a Dirac comb of the above type, then $`h\omega `$ is a well-defined translation bounded measure, with autocorrelation $`\gamma =(h\stackrel{~}{h})\gamma _\omega `$ and diffraction measure $`\widehat{\gamma }=|\widehat{h}|^2\widehat{\gamma }_\omega `$ by the convolution theorem. This can be considered as a situation where $`h`$ describes a more realistic profile of the scatterers (e.g. atoms), and Theorem 1 can then be applied to $`\gamma _\omega `$ and $`\widehat{\gamma }_\omega `$. Convolution is also a key ingredient to tackle the problem of diffraction at high temperature, compare .

Various applications were already mentioned in the Introduction. Also, the case that $`\varrho =(\varrho )_{pp}`$ can now be analyzed in more detail, and a set of necessary and sufficient conditions will be given in . Arrangements of scatterers where $`\widehat{\gamma }_\omega `$ is a pure point measure are often called pure point diffractive. These cases are of particular interest because they include perfect crystals, but also several aperiodic lattice substitution systems, see  for details.

## 3 Proof of Theorem 1

The key idea is to use an appropriate regularization of the point measure $`\omega `$ of (1) for the construction of the function $`\mathrm{\Phi }`$ and the measure $`\varrho `$. It relies on the existence of a properly converging sequence of approximating measures. We will employ Ascoli’s Theorem to construct a (Lipschitz) continuous interpolation of the autocorrelation coefficients of (2), and a combination of Bochner’s Theorem with the convolution property of the Fourier transform to conclude on the existence of the measure $`\varrho `$.

Let $`cC_c^{\mathrm{}}`$ be a non-negative bump function with compact support contained in $`B_\epsilon (0)`$ where $`\epsilon >0`$ is at most half the packing radius of $`\mathrm{\Gamma }`$ (the technical reason for this restriction will become clear below). Let $`c(0)=c_0`$ be the maximal value of $`c`$, so that $`0c(x)c_0`$ for all $`x^n`$. Such a function, which is also called an approximate identity, can be constructed as follows, compare \[18, p. 168\]. Start from $`\varphi (x)=\mathrm{exp}\left(|x|^2/(|x|^21)\right)`$ for $`|x|<1`$ and $`\varphi (x)=0`$ otherwise. This is a $`C^{\mathrm{}}`$-function with support in the closed unit ball, with $`\varphi (0)=1`$. Now, set $`c(x)=c_0\varphi (x/\epsilon )`$. Clearly, $`0c(x)c_0`$, the support is in the closed ball of radius $`\epsilon `$, and $`c`$ is integrable, i.e. $`c_1<\mathrm{}`$. Also, $`(c\stackrel{~}{c})(0)=_^nc(x)\stackrel{~}{c}(x)dx=c_2^2<\mathrm{}`$, and, for fixed $`\epsilon >0`$, we can always adjust $`c_0`$ so that $`c_2^2=1`$. We henceforth assume that such a function $`c`$ is given.

Recall that a function $`c`$ is (globally) Lipschitz, with Lipschitz constant $`L_c<\mathrm{}`$, if $`|c(x)c(y)|L_c|xy|`$ for all $`x,y^n`$, and $`L_c`$ is the smallest number with this property. In particular, $`c`$ is then uniformly continuous.

###### Lemma 1

A non-negative bump function $`cC_c^{\mathrm{}}`$ is Lipschitz. Furthermore, also $`\stackrel{~}{c}`$ and $`c\stackrel{~}{c}`$ are Lipschitz, with $`L_{\stackrel{~}{c}}=L_c`$ and $`L_{c\stackrel{~}{c}}c_1L_c`$.

Proof: It is clear that $`c`$ is Lipschitz because it is smooth and has compact support, so $`L_csup_{x^n}\left|\mathrm{grad}(c(x))\right|<\mathrm{}`$. Since $`c`$ is a real function, we have $`\stackrel{~}{c}(x)=\overline{c(x)}=c(x)`$, so that $`L_c=L_{\stackrel{~}{c}}`$ is obvious. Finally, consider

$`\left|(c\stackrel{~}{c})(x)(c\stackrel{~}{c})(y)\right|`$ $`=`$ $`\left|{\displaystyle _^n}c(z)\left(\stackrel{~}{c}(xz)\stackrel{~}{c}(yz)\right)dz\right|`$
$``$ $`{\displaystyle _^n}c(z)\left|\stackrel{~}{c}(xz)\stackrel{~}{c}(yz)\right|dz`$
$``$ $`L_c|xy|{\displaystyle _^n}c(z)dz=c_1L_c|xy|`$
which establishes the assertion. $`\mathrm{}`$

Fix a radius $`r>0`$ and set $`\mathrm{\Gamma }_r=\mathrm{\Gamma }B_r(0)`$. Let $`\omega _r=_{t\mathrm{\Gamma }_r}w(t)\delta _t`$ be the weighted Dirac comb of $`\mathrm{\Gamma }_r`$. Define $`f_r=c\omega _r`$, so that

$$f_r(z)=\underset{t\mathrm{\Gamma }_r}{}w(t)c(zt).$$
(5)
This is a continuous function, as is $`\stackrel{~}{f}_r`$. A simple calculation then shows that $`f_r\stackrel{~}{f}_r=(c\stackrel{~}{c})(\omega _r\stackrel{~}{\omega }_r)`$ which is the continuous positive definite function

$$\left(f_r\stackrel{~}{f}_r\right)(z)=\underset{u,v\mathrm{\Gamma }_r}{}w(u)\overline{w(v)}\left(c\stackrel{~}{c}\right)(zuv).$$
(6)
Due to the small support of $`c`$ (recall that $`\epsilon `$ is at most half the packing radius of $`\mathrm{\Gamma }`$), and hence that of $`c\stackrel{~}{c}`$, most terms of the double sum vanish, and it effectively collapses to a single sum. In particular, if $`z=t`$ is in the lattice, $`\left(c\stackrel{~}{c}\right)(tuv)`$ is either 0 or 1 by construction. In fact, for $`u\mathrm{\Gamma }`$, the value 1 is taken precisely for $`v=tu`$. This is a consequence of the above choice of $`\epsilon `$, and also motivates it, a posteriori.

Let us now define $`g_r=\frac{1}{\mathrm{vol}(B_r(0))}f_r\stackrel{~}{f}_r`$. Then it is clear from the above that $`g_r(t)\nu (t)`$ as $`r\mathrm{}`$ for all $`t\mathrm{\Gamma }`$. We have thus constructed a family of continuous positive definite functions $`\{g_rr>0\}`$ that pointwise converges to the autocorrelation coefficients for all $`t\mathrm{\Gamma }`$. We now have to check whether it will result in a continuous interpolation.

###### Lemma 2

The family $`\{g_rr>0\}`$ is uniformly Lipschitz, hence in particular equi-continuous, and uniformly bounded.

Proof: The function $`f_r`$ of (5), for any $`r>0`$, is a finite linear combination of Lipschitz functions and hence Lipschitz, by Lemma 1. With $`W:=sup_{t\mathrm{\Gamma }}|w(t)|`$, we can estimate the Lipschitz constant of $`f_r`$ as $`L_{f_r}|\mathrm{\Gamma }_r|WL_c`$ since the support of $`c`$ is so small that no two bumps in $`f_r`$ overlap. Lemma 1 then gives $`L_{f_r\stackrel{~}{f}_r}f_r_1L_{f_r}`$, and with $`f_r_1Wc_1`$ we obtain

$$L_{f_r\stackrel{~}{f}_r}|\mathrm{\Gamma }_r|W^2c_1L_c<\mathrm{}.$$

Consequently, also $`g_r`$ is Lipschitz, and we have

$$L_{g_r}\frac{|\mathrm{\Gamma }_r|}{\mathrm{vol}(B_r(0))}W^2c_1L_c.$$

The first factor on the right hand side is the number of lattice points in a ball of radius $`r`$ divided by its volume. This is known  to be

$$\frac{|\mathrm{\Gamma }_r|}{\mathrm{vol}(B_r(0))}=\mathrm{dens}(\mathrm{\Gamma })+𝒪(r^1)\text{as }r\mathrm{}$$
(7)
from which the uniform Lipschitz condition follows, and hence also the equi-continuity of the family $`\{g_rr>0\}`$.

Similarly, consider $`g_r=(c\stackrel{~}{c})\frac{\omega _r\stackrel{~}{\omega }_r}{\mathrm{vol}(B_r(0))}`$ which is a continuous function composed of non-overlapping little bumps. Consequently, using (2) and (2) and observing that $`c\stackrel{~}{c}_{\mathrm{}}=c_2^2=1`$ (due to our choice of $`c_0`$), we see that

$$\left|g_r(z)\right|g_r_{\mathrm{}}\frac{|\mathrm{\Gamma }_r|}{\mathrm{vol}(B_r(0))}W^2$$

from which, again with (7), one obtains equi-boundedness. $`\mathrm{}`$

Lemma 2 allows us to use Ascoli’s Theorem, see \[18, Cor. III.3.3\] for a version that covers our situation (note that $`^n`$ is only locally compact, but $`\sigma `$-compact, i.e. it can be covered by a countable family of compact sets). In particular, no matter whether we start from the entire family $`\{g_rr>0\}`$ or from a sequence $`\left(g_{r_i}\right)_i`$ (as needed for the case that we have several autocorrelations), there is a (sub)sequence of radii, $`(r_j)_j`$, such that, as $`j\mathrm{}`$, the $`g_{r_j}`$ converge compactly to some function $`g`$ which is then bounded and continuous. Since the family is actually equi-uniformly continuous, convergence is globally uniform. As a limit of positive definite functions, $`g`$ is still positive definite. Moreover, it is also (globally) Lipschitz, and $`g(t)=\nu (t)`$ for all $`t\mathrm{\Gamma }`$ by construction. So far, we have established:

###### Proposition 1

Let $`\mathrm{\Gamma }`$ be a lattice in $`^n`$ and $`\omega `$ the Dirac comb of $`(\text{1})`$, with bounded complex weights. Let $`\gamma _\omega `$ be any of its $`(`$natural$`)`$ autocorrelation measures, the latter defined as the limit of a suitable sequence $`\left(\gamma _\omega ^{(r_i)}\right)_i`$ of approximants, with $`(r_i)_i`$ an increasing, unbounded sequence of radii. Then, $`\gamma _\omega `$ admits a representation of the form

$$\gamma _\omega =g\delta _\mathrm{\Gamma }$$

where $`\delta _\mathrm{\Gamma }=_{t\mathrm{\Gamma }}\delta _t`$ is the Dirac comb of $`\mathrm{\Gamma }`$ and $`g`$ is a bounded, positive definite Lipschitz function on all of $`^n`$. $`\mathrm{}`$

Now, we can invoke Bochner’s Theorem \[23, Thm. IX.9\] which tells us that $`\widehat{g}`$, the Fourier transform of $`g`$, is a finite positive measure (our above construction was crucial to ensure this). On the other hand, $`\widehat{\delta }_\mathrm{\Gamma }`$ is translation bounded, wherefore $`\widehat{g}\widehat{\delta }_\mathrm{\Gamma }`$ is well defined \[7, Prop. 1.13\], and it is a tempered measure. This allows us to (backwards) employ the convolution theorem, compare \[7, Prop. 4.10\]:

$$\widehat{\gamma }_\omega =\widehat{g}\widehat{\delta }_\mathrm{\Gamma }=\mathrm{dens}(\mathrm{\Gamma })\widehat{g}\delta _\mathrm{\Gamma }^{}$$
(8)
where the second step uses the identity $`\widehat{\delta }_\mathrm{\Gamma }=\mathrm{dens}(\mathrm{\Gamma })\delta _\mathrm{\Gamma }^{}`$, known as Poisson’s summation formula for lattice Dirac combs, see \[7, Ex. 6.22\] or .

###### Proposition 2

The diffraction measure $`\widehat{\gamma }_\omega `$ of $`(\text{8})`$ is $`\mathrm{\Gamma }^{}`$-periodic. It can thus alternatively be represented as

$$\widehat{\gamma }_\omega =\varrho \delta _\mathrm{\Gamma }^{}$$

where $`\varrho `$ is a bounded positive measure that is supported on a fundamental domain of $`\mathrm{\Gamma }^{}`$ which we may choose to be bounded.

Proof: The $`\mathrm{\Gamma }^{}`$-periodicity of $`\widehat{\gamma }_\omega `$ is obvious from the convolution formula in (8). Also, it is a standard result that each lattice in $`^n`$ has a fundamental domain inside the Voronoi cell of $`\mathrm{\Gamma }^{}`$ that is a Borel set, $`E`$ say (the construction of such a set was described in the Remark following Theorem 1). The translates $`t+E`$ for $`t\mathrm{\Gamma }^{}`$ then form a disjoint partition of $`^n`$, and we have

$$\widehat{\gamma }_\omega =\underset{t\mathrm{\Gamma }^{}}{}\widehat{\gamma }_\omega |_{t+E}$$

where $`\widehat{\gamma }_\omega |_{t+E}`$ is the restriction of $`\widehat{\gamma }_\omega `$ to the set $`t+E`$. But periodicity tells us that $`\widehat{\gamma }_\omega |_{t+E}=\widehat{\gamma }_\omega |_E\delta _t`$, and the assertion follows with $`\varrho :=\widehat{\gamma }_\omega |_E`$. $`\mathrm{}`$

To complete the proof of Theorem 1, it remains to go back to the autocorrelation, i.e.

$$\gamma _\omega =\stackrel{ˇ}{\varrho }\stackrel{ˇ}{\delta }_\mathrm{\Gamma }^{}=\mathrm{\Phi }\delta _\mathrm{\Gamma }$$

where we have

$$\varrho =\mathrm{dens}(\mathrm{\Gamma })\widehat{\mathrm{\Phi }},$$

again by Poisson’s summation formula. The nice properties of the function $`\mathrm{\Phi }`$ claimed in Theorem 1 are now a direct consequence of the Paley-Wiener Theorem, see \[23, Thm. IX.12\] or \[25, Thm. 7.23\], because $`\varrho `$ is by construction a positive measure with compact support. This also concludes the proof of Theorem 1. $`\mathrm{}`$

Remark: The above proof employed the Lipschitz property of the bump functions $`c`$. Alternatively, using (6) and the smallness of the support of $`c`$ (and hence also of that of $`c\stackrel{~}{c}`$), one can derive that

$$\left|g_r(z)g_r(z^{})\right|\frac{|\mathrm{\Gamma }_r|}{\mathrm{vol}(B_r(0))}W^2\underset{x}{sup}\left|\left(c\stackrel{~}{c}\right)(zx)\left(c\stackrel{~}{c}\right)(z^{}x)\right|$$

for all $`z,z^{}`$ sufficiently close. This inequality implies equi-continuity of the family $`\{g_rr>0\}`$ without reference to any Lipschitz property. This results in a slightly weaker version of Proposition 1, with $`g`$ being a bounded, positive definite continuous function on all of $`^n`$ which need not be Lipschitz.

## 4 Complementary lattice subsets

A particularly interesting situation emerges in the comparison of a lattice subset $`S\mathrm{\Gamma }`$ with its complement $`S^{}=\mathrm{\Gamma }S`$. Here, the Dirac combs to be compared are $`\omega =\delta _S=_{xS}\delta _x`$ and $`\omega ^{}=\delta _S^{}`$. Note that the Dirac comb of (1), when specialized to $`w1`$, results in an autocorrelation with coefficients

$$\nu _S(z)=\underset{r\mathrm{}}{lim}\frac{|S(z+S)B_r(0)|}{\mathrm{vol}(B_r(0))}=\mathrm{dens}\left(S(z+S)\right)$$

for all $`z^n`$, provided the limits exist. This can easily be derived from (2) and the comments following it.

Next, recall that two point sets are called homometric if they share the same (natural) autocorrelation. This is an important concept in crystallography, both in theory and practice, because homometric sets cannot be distinguished by diffraction .

###### Theorem 2

Let $`\mathrm{\Gamma }`$ be a lattice in $`^n`$, and let $`S\mathrm{\Gamma }`$ be a subset with existing $`(`$natural$`)`$ autocorrelation coefficients $`\nu _S(z)=\mathrm{dens}\left(S(z+S)\right)`$. Then the following holds.

$`(1)`$ The autocorrelation coefficients $`\nu _S^{}(z)`$ of the complement set $`S^{}=\mathrm{\Gamma }S`$ also exist. They are $`\nu _S^{}(z)=0`$ for all $`z\mathrm{\Gamma }`$ and otherwise, for $`z=t\mathrm{\Gamma }`$, satisfy the relation

$$\nu _S^{}(t)\mathrm{dens}(S^{})=\nu _S(t)\mathrm{dens}(S).$$

$`(2)`$ If, in addition, $`\mathrm{dens}(S)=\mathrm{dens}(\mathrm{\Gamma })/2`$, then the sets $`S`$ and $`S^{}=\mathrm{\Gamma }S`$ are homometric.

$`(3)`$ The diffraction spectra of the sets $`S`$ and $`S^{}`$ are related by

$$\widehat{\gamma }_S^{}=\widehat{\gamma }_S+\left(\mathrm{dens}(S^{})\mathrm{dens}(S)\right)\mathrm{dens}(\mathrm{\Gamma })\delta _\mathrm{\Gamma }^{}.$$

In particular, $`\widehat{\gamma }_S^{}=\widehat{\gamma }_S`$ if $`\mathrm{dens}(S^{})=\mathrm{dens}(S)`$.

$`(4)`$ The diffraction measure $`\widehat{\gamma }_S^{}`$ is pure point if and only if $`\widehat{\gamma }_S`$ is pure point.

Proof: In what follows, each term involving a density is to be viewed as the limit along a fixed increasing and unbounded sequence of radii. Since $`\mathrm{\Gamma }`$ is the disjoint union of $`S`$ and $`S^{}`$, $`\mathrm{\Gamma }=S\dot{}S^{}`$, we get $`\mathrm{dens}(S^{})=\mathrm{dens}(\mathrm{\Gamma })\mathrm{dens}(S)`$ and the natural density of $`S^{}`$ exists because $`\mathrm{dens}(S)=\nu _S(0)`$. Since $`S^{}\mathrm{\Gamma }`$, we also have $`\nu _S^{}(z)=0`$ whenever $`z\mathrm{\Gamma }`$.

So, let $`z=t\mathrm{\Gamma }`$ from now on. Now observe that $`\mathrm{\Gamma }(t+\mathrm{\Gamma })=\mathrm{\Gamma }`$ and thus, using $`\mathrm{\Gamma }=S\dot{}S^{}`$, we obtain

$`\mathrm{dens}(\mathrm{\Gamma })`$ $`=`$ $`\mathrm{dens}\left(\mathrm{\Gamma }(t+\mathrm{\Gamma })\right)`$
$`=`$ $`\nu _S^{}(t)+\nu _S(t)+\mathrm{dens}\left(S(t+S^{})\right)+\mathrm{dens}\left(S^{}(t+S)\right).`$
Since $`S^{}=\mathrm{\Gamma }S`$, it is easy to verify that

$`\mathrm{dens}\left(S^{}(t+S)\right)`$ $`=`$ $`\mathrm{dens}\left(\mathrm{\Gamma }(t+S)\right)\mathrm{dens}\left(S(t+S)\right)`$
$`=`$ $`\mathrm{dens}(S)\nu _S(t)`$
because $`(t+S)\mathrm{\Gamma }`$ and $`\mathrm{dens}(t+S)=\mathrm{dens}(S)`$. Similarly,

$$\mathrm{dens}\left(S(t+S^{})\right)=\mathrm{dens}(S)\nu _S(t)$$

by first shifting and then using the previous formula. Since $`\nu _S(t)`$ is a real positive definite function, we have $`\nu _S(t)=\nu _S(t)`$, and obtain

$$\mathrm{dens}(\mathrm{\Gamma })=2\mathrm{dens}(S)+\nu _S^{}(t)\nu _S(t)$$

from which the first assertion follows with $`\mathrm{dens}(\mathrm{\Gamma })=\mathrm{dens}(S)+\mathrm{dens}(S^{})`$.

If $`\mathrm{dens}(S)=\mathrm{dens}(\mathrm{\Gamma })/2`$, then $`\mathrm{dens}(S^{})=\mathrm{dens}(S)`$ and we obtain $`\nu _S^{}(z)=\nu _S(z)`$, for all $`z`$, by the first assertion. This settles assertion (2).

Since $`S\mathrm{\Gamma }`$, its autocorrelation is $`\gamma _S=_{t\mathrm{\Gamma }}\nu _S(t)\delta _t`$, and analogously for $`S^{}`$, the complement set in $`\mathrm{\Gamma }`$. From the first assertion, we then infer

$$\gamma _S^{}=\gamma _S+c\delta _\mathrm{\Gamma }$$

with $`c=\mathrm{dens}(S^{})\mathrm{dens}(S)`$. Assertion (3) now follows from taking the Fourier transform and applying Poisson’s summation formula to the lattice Dirac comb $`\delta _\mathrm{\Gamma }`$.

Finally, the difference between $`\widehat{\gamma }_S^{}`$ and $`\widehat{\gamma }_S`$ in the third assertion is a multiple of $`\delta _\mathrm{\Gamma }^{}`$ which is a uniform lattice Dirac comb and hence a pure point measure, whence the last claim is obvious. $`\mathrm{}`$

In , it was shown that the set of visible lattice points is pure point diffractive. The last assertion of Theorem 2 then tells us that their complement, the set of invisible points, also is pure point diffractive. Similarly, the set of $`k`$-th power free integers, a subset of $``$, has pure point diffraction , so does then its complement, the set of integers divisible by the $`k`$-th power of some integer $`2`$. This indicates that many more pure point diffractive point sets of independent interest exist, and a general criterion based on the almost periodicity of the autocorrelation is derived in .

## 5 Generalizations

Our above derivation, with little modification, can also be carried through in the case that $`^n`$ is replaced by an arbitrary locally compact Abelian group $`G`$ which is $`\sigma `$-compact and metrizable. As such, $`G`$ is certainly Hausdorff, but also Polish, see the Corollary in \[8, Ch. IX.6.1\]. In particular, we may assume $`G`$ to be equipped with a metric $`d`$ which induces the topology of $`G`$ and with respect to which $`G`$ is complete. This class contains all groups of the form $`^n\times ^m\times H`$ with $`n,m0`$ and $`H`$ compact and metrizable, which are (up to isomorphism) the so-called metrizable compactly generated LCA groups. We assume $`G`$ to be equipped with an appropriately normalized Haar measure $`\theta _G`$, compare \[11, Ch. 2.5\]. In particular, we assume $`\theta _G(G)=1`$ if $`G`$ is a compact group.

A lattice $`\mathrm{\Gamma }`$ is now a discrete (hence closed) subgroup of $`G`$ such that $`G/\mathrm{\Gamma }`$ is compact (this is the appropriate generalization of our previous definition in the Euclidean setting). The Dirac comb $`\omega `$ of (1) is well defined, and it is translation bounded (or shift bounded) if and only if the function $`w`$ is bounded. Note that $`\omega `$ is then a finite complex measure if $`G`$ is compact. The (open) ball of radius $`r`$ around $`a`$ is

$$B_r(a)=\{xGd(x,a)<r\},$$

but the autocorrelation $`\gamma _\omega `$ of the Dirac comb $`\omega `$ can, in general, no longer be defined as in Eq. (2), because balls in general groups $`G`$ can have rather weird properties. So, even with $`\mathrm{vol}(B_r(0)):=\theta _G(B_r(0))`$, the limit in (2) might be meaningless. There is no problem for compact $`G`$, though: one can simply write $`\gamma _\omega =\omega \stackrel{~}{\omega }`$ because $`\theta _G(G)=1`$ in this case, so that existence and uniqueness of the autocorrelation are automatic. This is clear since all sums involved are actually finite.

We overcome the general difficulty by employing the concept of an averaging sequence which, at the same time, also constitutes a restricted (monotone increasing) van Hove sequence, see  for details. To explain this, recall that an LCA group $`G`$ is $`\sigma `$-compact if and only if a countable family

$$𝒰=\{U_ii\}$$
(9)
of relatively compact open sets exists with $`U_1\mathrm{}`$, $`\overline{U_i}U_{i+1}`$ for all $`i`$, and $`_iU_i=G`$, see \[22, Thm. 8.22\]. In particular, $`0<\theta _G(U_i)<\mathrm{}`$ for all $`i`$. We call such a family $`𝒰`$ an averaging sequence. It also constitutes a van Hove sequence, if one extra property is satisfied which guarantees that the surface/bulk ratio becomes sufficiently negligible in the limit $`i\mathrm{}`$. To formalize the latter, we introduce

$$^KU=\left((\overline{U}+K)U\right)\left((GUK)\overline{U}\right)$$

for an open set $`U`$ and any compact set $`K`$ in $`G`$. Here, we use the convention $`A\pm B:=\{x\pm yxA,yB\}`$, with $`\mathrm{}\pm B=\mathrm{}`$. The set $`^KU`$ can, cum grano salis, be seen as a ‘thickened’ version of the boundary of $`U`$. Then, the final condition is that

$$\underset{i\mathrm{}}{lim}\frac{\theta _G(^KU_i)}{\theta _G(U_i)}=\mathrm{\hspace{0.33em}0}$$
(10)
for all compact $`KG`$. The existence of such averaging sequences of van Hove type in $`\sigma `$-compact LCA groups is shown in .

Let us assume that a family $`𝒰=\{U_ii\}`$ has been given which also constitutes a van Hove sequence. Since $`\mathrm{\Gamma }`$, as a lattice, is a special case of a regular model set, we can then conclude from \[26, p. 145\] that the density of $`\mathrm{\Gamma }`$ exists,

$$\mathrm{dens}(\mathrm{\Gamma })=\underset{i\mathrm{}}{lim}\frac{|\mathrm{\Gamma }U_i|}{\theta _G(U_i)},$$
(11)
and that the limit is independent of the van Hove sequence chosen. This is the correct analogue of the statement (4) for lattices in $`^n`$. If we now define $`\omega _i=\omega |_{U_i}`$ and, similarly, $`\stackrel{~}{\omega }_i=(\omega |_{U_i})\stackrel{~}{}`$, the analogue of Eq. (2) would read

$$\gamma _\omega =\underset{i\mathrm{}}{lim}\frac{\omega _i\stackrel{~}{\omega }_i}{\theta _G(U_i)}$$
(12)
provided the limit exists.

In this case, the autocorrelation is always a pure point measure of the form $`\gamma _\omega =_{z\mathrm{\Gamma }}\nu (z)\delta _z`$ with the coefficients $`\nu (z)`$ now being given by

$$\nu (z)=\underset{i\mathrm{}}{lim}\frac{1}{\theta _G(U_i)}\underset{\begin{array}{c}t,t^{}\mathrm{\Gamma }U_i\\ tt^{}=z\end{array}}{}w(t)\overline{w(t^{})},$$
(13)
again with the simplification that $`\nu (z)=_{t\mathrm{\Gamma }}w(t)\overline{w(tz)}`$ for $`G`$ compact. Usually, the more interesting cases of Dirac combs will occur for groups $`G`$ that are locally compact, but not compact, such as $`^n`$.

At this point, let us state the analogue of Theorem 1 in this more general setting.

###### Theorem 3

Let $`\mathrm{\Gamma }`$ be a lattice in a Polish LCA group $`G`$, and let $`\omega =_{t\mathrm{\Gamma }}w(t)\delta _t`$ be a Dirac comb on $`\mathrm{\Gamma }`$ with bounded complex weights. Let an averaging sequence $`𝒰=\{U_ii\}`$ be given which constitutes a monotone increasing van Hove sequence, and assume that the corresponding autocorrelation measure $`\gamma _\omega `$ of $`(\text{12})`$ exists. Then we have:

$`(1)`$ The autocorrelation measure $`\gamma _\omega `$ admits the representation

$$\gamma _\omega =g\delta _\mathrm{\Gamma }$$

where $`g`$ is a bounded, positive definite Lipschitz function on $`G`$ which interpolates the autocorrelation coefficients $`\nu (t)`$, $`t\mathrm{\Gamma }`$.

$`(2)`$ The Fourier transform $`\widehat{\gamma }_\omega `$ is a translation bounded positive measure on the dual group $`\widehat{G}`$ which is periodic with lattice of periods $`\mathrm{\Gamma }^{}`$, the dual lattice of $`\mathrm{\Gamma }`$. It can be represented as

$$\widehat{\gamma }_\omega =\varrho \delta _\mathrm{\Gamma }^{}$$

with a finite positive measure $`\varrho `$ that is supported on a totally bounded and measurable fundamental domain of $`\mathrm{\Gamma }^{}`$.

Proof: The argument is very similar to the proof in Section 3, wherefore we only describe the changes needed.

Lemma 1 needs a replacement because the concept of a smooth bump function makes no sense in general. Instead, we can employ a different kind of Lipschitz function as follows. Choose $`\epsilon >0`$ so that $`B_\epsilon (0)B_\epsilon (t)=\mathrm{}`$ for all $`t\mathrm{\Gamma }\{0\}`$. Such an $`\epsilon `$ clearly exist because $`G`$ is Hausdorff and our metric induces the topology of $`G`$. If we set $`A=GB_\epsilon (0)`$, which is a closed set, then $`0A`$ and thus $`d(0,A)\epsilon >0`$, where $`d(x,A)=inf_{yA}d(x,y)`$ is the distance of $`x`$ from $`A`$. We can now define

$$c(x)=\frac{c_0d(x,A)}{d(0,A)}.$$
(14)
One has $`c(x)0`$, $`c(0)=c_0`$ and $`c(x)=0`$ for all $`xA`$, so $`c`$ is nontrivial (if $`c_00`$) and supported on $`B_\epsilon (0)`$.

###### Lemma 3

The function $`c`$ of $`(\text{14})`$ is Lipschitz, with Lipschitz constant $`L_c=c_0/d(0,A)`$. The functions $`\stackrel{~}{c}`$ and $`c\stackrel{~}{c}`$ als also Lipschitz, with $`L_{\stackrel{~}{c}}=L_c`$ and $`L_{c\stackrel{~}{c}}c_1L_c`$.

Proof: The Lipschitz property of $`d(x,A)`$, with Lipschitz constant $`1`$, is stated in \[8, Prop. IX.2.3\], see  for an explicit proof. The remainder of the proof is that of Lemma 2, with $`^n`$ and Lebesgue measure replaced by $`g`$ and Haar measure, respectively. $`\mathrm{}`$

Since both $`c`$ and $`c\stackrel{~}{c}`$ are integrable w.r.t. the Haar measure $`\theta _G`$, the construction of a family of approximating functions $`\{g_ii\}`$, relative to the sequence $`𝒰`$, is now possible, in complete analogy to above.

With this modification, Lemma 2 still holds. For its proof, we only need that the density of lattice points of $`\mathrm{\Gamma }`$ in $`G`$ exists and that, if $`G`$ is not compact, $`|\mathrm{\Gamma }U_i|/\theta _G(U_i)`$ converges to it as $`i\mathrm{}`$. This follows from (11). We can then proceed as before: since we assume $`G`$ to be $`\sigma `$-compact, we have Ascoli’s Theorem at our disposal. Consequently, we obtain the following modification of Proposition 1.

###### Proposition 3

Let $`\mathrm{\Gamma }`$ be a lattice in a Polish LCA group $`G`$ and let $`\omega `$ be the Dirac comb of $`(\text{1})`$, with bounded complex weights. Let $`\gamma _\omega `$ be an autocorrelation measure which is assumed to exist as the limit of a sequence $`\{\gamma _\omega ^{(i)}i\}`$ of approximants with respect to a given averaging sequence $`𝒰=\{U_ii\}`$. Then, $`\gamma _\omega `$ admits a representation of the form

$$\gamma _\omega =g\delta _\mathrm{\Gamma }$$

where $`g`$ is a bounded, positive definite Lipschitz function on all of $`G`$. $`\mathrm{}`$

Next, we need some results from harmonic analysis in the setting of LCA groups, see \[7, Ch. I.4\] or \[11, Ch. 2.8\] for a suitable summary. We denote the dual group by $`\widehat{G}`$ and assume it is equipped with a matching Haar measure, $`\theta _{\widehat{G}}`$ (a suitable normalization of it is suggested by the Fourier inversion formula, see \[11, Ch. 2.8.7\]). We can now, once more, invoke Bochner’s Theorem \[7, Thm. 4.5\]: since $`\gamma _\omega `$ is a positive definite measure by construction, its Fourier transform is a uniquely determined translation bounded positive measure on $`\widehat{G}`$, denoted by $`\widehat{\gamma }_\omega `$.

To make complete sense out of Eq. (8), we have to say what the dual lattice is and how Poisson’s summation formula works. Each $`k\widehat{G}`$ defines a (continuous) character on the group $`G`$, $`k,x`$, which replaces $`\mathrm{exp}(2\pi ikx)`$ from above. Then,

$$\mathrm{\Gamma }^{}=\{k\widehat{G}k,x=1\text{ for all }x\mathrm{\Gamma }\}$$

and $`\mathrm{\Gamma }^{}`$ (which is called $`\mathrm{\Gamma }^{}`$ in ) is the annihilator of the closed subgroup $`\mathrm{\Gamma }G`$ in the dual group $`\widehat{G}`$, compare \[11, Ch. 2.9.1\]. We have $`\mathrm{\Gamma }^{}=(G/\mathrm{\Gamma })\widehat{}`$ and $`\widehat{\mathrm{\Gamma }}=\widehat{G}/\mathrm{\Gamma }^{}`$, see \[11, Thm. 2.9.1\], so that with $`\mathrm{\Gamma }`$ also $`\mathrm{\Gamma }^{}`$ is a lattice because the dual of a compact group is discrete and vice versa \[11, Thm. 2.8.3\]. Moreover, we can interpret $`G/\mathrm{\Gamma }`$ and $`\widehat{G}/\mathrm{\Gamma }^{}`$ as (measurable) fundamental domains of the lattices $`\mathrm{\Gamma }`$ and $`\mathrm{\Gamma }^{}`$. We now get, in complete analogy to before, the general Poisson summation formula

$$\widehat{\delta }_\mathrm{\Gamma }=a\delta _\mathrm{\Gamma }^{}$$
(15)
where $`a`$ is a constant which depends on the density of $`\mathrm{\Gamma }`$ and on the relative normalization of $`\theta _G`$ and $`\theta _{\widehat{G}}`$, see \[11, Ch. 9.9\] for details. So, the following modification of Proposition 2 holds in our more general setting.

###### Proposition 4

Under the assumptions of Proposition 3, the corresponding diffraction measure $`\widehat{\gamma }_\omega `$ exists and is $`\mathrm{\Gamma }^{}`$-periodic. It can be represented as

$$\widehat{\gamma }_\omega =\varrho \delta _\mathrm{\Gamma }^{}$$

where $`\varrho `$ is a bounded positive measure, supported on a fundamental domain of $`\mathrm{\Gamma }^{}`$ which we may choose to be bounded. $`\mathrm{}`$

Finally, we have to combine Propositions 3 and 4 which completes the proof of Theorem 3. $`\mathrm{}`$

Remark: Similar to the situation in Theorem 1, the assumption on the existence of the autocorrelation as a limit is not essential. If $`\gamma _\omega ^{(i)}:=\omega _i\stackrel{~}{\omega }_i/\theta _G(U_i)`$, the uniform translation boundedness of the $`\gamma _\omega ^{(i)}`$ implies the existence of at least one limit point, $`\gamma `$ say. We can then choose a subfamily $`\{U_{i_j}j\}`$ such that $`\gamma _\omega ^{(i_j)}\gamma `$ vaguely, as $`j\mathrm{}`$, and we thus obtain the corresponding results for each vague limit point $`\gamma `$ of $`\{\gamma _\omega ^{(i)}i\}`$ separately, by applying Theorem 3 to $`\omega `$ together with this averaging subsequence.

Finally, if one needs even more generality, one can employ the Remark at the end of Section 3, which remains valid in this more abstract setting if elements of $`𝒰`$ are used instead of balls, and start with a suitable continuous function $`c`$ of sufficiently small support. If $`G`$ is an LCA group (which includes $`G`$ being Hausdorff in our terminology) and $`\sigma `$-compact, we obtain

###### Theorem 4

Let $`G`$ be a $`\sigma `$-compact LCA group $`(`$not necessarily Polish$`)`$, and let the other assumptions be as in Theorem 3. Then, the first statement of Theorem 3 is still true after the modification that $`g`$ is merely continuous $`(`$not necessarily Lipschitz$`)`$, while the second statement remains unaltered. $`\mathrm{}`$

### Acknowledgments

It is my pleasure to thank Robert V. Moody, Peter A. B. Pleasants, and Martin Schlottmann for a number of clarifying discussions, and the Department of Mathematical Sciences of the University of Alberta (Edmonton, Canada) for hospitality during a stay in summer 2000, where part of this work was done. I also thank an anonymous referee for a number of suggestions to improve the results. It was also supported by the German Research Council (DFG).


format: text

text:
# Spin, charge and orbital ordering in La0.5Sr1.5MnO4

\[

## Abstract

We have analyzed the experimental evidence of charge and orbital ordering in La0.5Sr1.5MnO4 using first principles band structure calculations. Our results suggest the presence of two types of Mn sites in the system. One of the Mn sites behaves like an Mn3+ ion, favoring a Jahn-Teller distortion of the surrounding oxygen atoms, while the distortion around the other is not a simple breathing mode kind. Band structure effects are found to dominate the experimental spectrum for orbital and charge ordering, providing an alternate explanation for the experimentally observed results.

\]

In recent times there has been a resurgence of interest in the manganites as a result of the wide range of physical properties that they exhibit. In some of the doped compounds, there is a real space ordering of the charge carriers in certain orbitals, resulting in orbital ordering (OO) and sometimes charge ordering (CO). As the magnetic and transport properties are closely correlated with the orbital and charge degrees of freedom, there have been intense efforts - both experimental and theoretical - to clarify the microscopic mechanisms giving rise to such exotic phenomena. While techniques such as electron microscopy and neutron scattering have been traditionally used to detect CO as well as magnetic ordering, the direct observation of OO has been difficult. Murakami et al. performed pioneering experiments on LaMnO3  and La0.5Sr1.5MnO4  and were successfully able to detect OO. The technique they used exploited the anisotropy of the x-ray scattering tensor at an absorption edge, thereby making the intensity of the scattered x-rays sensitive to the valence electron distribution.

La0.5Sr1.5MnO4 is a layered manganite with an average valence of 3.5 at each Mn site. In the high temperature phase, above the CO temperature, all Mn-O bond lengths within the ab plane are equal . Neutron scattering studies by Sternlieb et al.  indicated a real space ordering of two distinct Mn sites below 217 K, with the two sites identified as Mn3+ and Mn4+ sites. The intensity variation observed at the two sites was interpreted as arising from a 1% breathing mode-like movement of the oxygen atoms in the ab plane towards one set of Mn atoms, identified as the higher valent Mn4+ sites. Later experiments by Murakami et al.  used the anisotropy of the x-ray scattering tensor to show that the Mn sites form a pattern of alternating Mn3+-Mn4+ sites in the ab plane, with both CO and OO taking place at the same temperature, 217 K. They claimed that the charge modulation between the two Mn sites is not small, but corresponds to as much as an integral charge fluctuation between neighboring Mn sites. However, if this is the case, strong correlations are necessary to localize charge carriers. Surprisingly, however, certain other spectroscopic properties  of this system can be easily explained by a single particle approach.

The contrasting experimental evidence where one set of spectroscopic data could be easily explained by an effective single particle approach, while another set implied the importance of strong correlations in the system prompted us to perform a detailed analysis of the electronic structure using the density-functional pseudopotential framework. Apart from providing a microscopic mechanism for the observed orbital and charge-ordering in this system, our results have important implications on recent anomalous x-ray scattering experiments on Pr1-xCaxMnO3 , LaSr2Mn2O7  and NaV2O5 .

The details of the computational method are described elsewhere , and we only mention minimum additional aspects. The cutoff energy for the plane wave expansion of the eigen state is 20 Ry, being smaller than the value of 30.25 Ry in our usual calculations because of the large unit cell in the present calculation. The k-point mesh used is 4x4x2. The generalized gradient approximation (GGA) was used for the exchange functional . The alloying effects of (La0.5Sr1.5) at the A-site of the lattice are treated within the virtual crystal approximation .

The Mn spins order below 110 K forming one-dimensional ferromagnetic zigzag chains in the ab plane coupled antiferromagnetically to each other, known as the CE-type magnetic ordering. As the exchange splitting is large (about 3 eV), the amplitude for electrons to hop from a zig-zag chain of parallel spins (indicated by thick solid lines in Fig. 1a) to the neighboring chain is small. Hence the electronic structure is governed by these one-dimensional chains. Considering a single chain, it was shown  that the anisotropic hopping between the Mn $`d`$ orbitals could explain the OO at the two Mn sites. We have performed ab-initio calculations considering the complete 3-dimensional Immm structure . Similar to the findings in ref. , we also found the kind of OO that is observed experimentally. Choosing the x and y axes as shown in Fig. 1, we found that while the $`d_{3x^2r^2}`$ orbital was preferentially occupied on atom 1, the $`d_{3y^2r^2}`$ orbital was preferentially occupied on atom 3. These results can be understood within the framework of a simple nearest neighbour tight-binding model involving the $`e_g`$ orbitals: $`d_{3x^2r^2}`$ and $`d_{y^2z^2}`$ on atom 1, $`d_{3y^2r^2}`$ and $`d_{z^2x^2}`$ on atom 3 as well as $`d_{3z^2r^2}`$ and $`d_{x^2y^2}`$ on atoms 2 and 4 as used in Ref. . While the $`d_{3x^2r^2}`$ orbital at Mn(1) and $`d_{3y^2r^2}`$ orbital on Mn(3) hybridize with both $`e_g`$ orbitals on atoms 2 and 4, the $`d_{y^2z^2}`$ on Mn(1) and $`d_{z^2x^2}`$ on Mn(3) do not. The eigenvalue spectrum of such a simple model, consists of two bonding bands, energetically separated from four non-bonding bands, with the antibonding bands at higher energies. As the average valence of Mn is 3.5, there are two electrons in the $`e_g`$ orbitals of the 4 Mn atoms comprising the chain. Hence the two bonding bands which have dominantly $`d_{3x^2r^2}`$ character on atom 1 and $`d_{3y^2r^2}`$ character on atom 3 are occupied. Thus, the one-dimensional chains which are a consequence of the magnetic structure drive the OO within these calculations. However, the difficulty in approaching the problem this way is that the Immm structure exists only above the CO/OO temperature and there are extensive evidence in the literature suggesting a symmetry lowering below the ordering transition. However, the details of the crystal structure of this compound is shrouded in controversy. It was suggested  that the structure, within the charge ordered state, is Cmmm with lattice constants equal to $`\sqrt{2}`$ a, $`\sqrt{2}`$ a, c where a and c are the cell dimensions of the basic Immm cell. More recent work by Larochelle , however, indicate that the structure is Ammm or one of its two subgroups Am2m or A222, with the lattice parameters being $`\sqrt{2}`$a, 2$`\sqrt{2}`$ a, and c. None of the structural investigations have been able to provide the atom positions, particularly for the oxygen sites, owing to the large unit cell and the existing data quality . This work however suggests certain possible distortions of the oxygens, though not in agreement with ref. . In view of such uncertainities, we have optimised the structure of this system using ab-initio band structure calculations. The structure that we find (see Fig. 1) is P21/m with lattice parameters $`\sqrt{2}`$a, 2$`\sqrt{2}`$a and c. The lattice parameters as well as the space group that we have obtained are the same as in ref. , if the virtually negligible ($``$ 0.015 Å) displacements of the Mn4+ atoms shown in Fig 1 are ignored.

On optimizing the internal coordinates, the system exhibited different distortions of the MnO6 octahedra associated with different Mn atoms. The direction of displacement of the oxygen atoms in the ab-plane is indicated by the arrows shown in Fig. 1b, though the oxygen atoms have been left out of the figure for added clarity. The Mn site, Mn(3), showing $`d_{3y^2r^2}`$ OO lowered its energy by an elongation of the Mn-O bonds in the y-direction. This kind of distortion can be understood easily within the framework of crystal-field effects. A tetragonal distortion of a MnO6 octahedron resulting in an elongation of the Mn-O bondlengths in the y-direction, lowers the bare energy of the $`d_{3y^2r^2}`$ orbital. Thus, the sites Mn(1) and Mn(3) behave like Mn3+ species, sustaining a Jahn-Teller (JT) like distortion of the surrounding oxygens in two mutually perpendicular directions, giving rise to the orbital ordering. As a consequence, the oxygen atoms surrounding the sites labelled Mn(2) and Mn(4) sustain distortions with the oxygen atoms along the x-axis being displaced in one direction and the ones along the y-axis being displaced in another direction, as shown in the figure, in contrast to the suggestion in ref.  where all four oxygen atoms surrounding the Mn4+ site move closer to the Mn atom. We found the kind of distortion suggested in that work to have a higher energy. The sites Mn(2) and Mn(4) have been identified as Mn4+ sites in the literature and we retain that nomenclature, although within our calculations the charge difference between the so-called Mn3+ and Mn4+ species is negligible.

While our calculations suggest different distortions of the surrounding oxygens about the Mn3+ and Mn4+ sites, the actual magnitude of the distortion is fairly small . The underestimation of the magnitude of the JT distortion by these first-principles approaches is well-known, though these methods do get the nature of distortions correctly. An example of this is LaMnO3 where the nature of distortion was correctly predicted, while the magnitude of the theoretical JT distortion was found to be half of the experimental value . We simulated the neutron diffraction pattern using the optimized coordinates as well as the coordinates assuming a Jahn-Teller distortion equal to what is found in LaMnO3. The simulated diffraction patterns were nearly identical, indicating the difficulty of determining the oxygen positions with any precision from such measurements. Therefore the enhanced distortion of the oxygen octahedra are not inconsistent with the structural data available so far. We in fact hope that the present theoretical considerations will help in the future structural investigations. It is also significant that with optimized JT distortion, the correct ground state magnetic order cannot be reproduced for LaMnO3 . The situation seems to be the same in the present case, where the CE type antiferromagnetic state is more stable than the ferromagnetic state only with the enhanced JT distortion, consistent with earlier observations . Hence in the subsequent analysis, we have extrapolated the magnitude of the JT distortion to the value observed in LaMnO3.

The experiments of Murakami et al.  analyzed the energy dependence of the OO superlattice reflection across the Mn K absorption edge. The strong energy dependence was interpreted as arising from a splitting of $``$ 5 eV between the 4$`p_x`$ and 4$`p_y`$ PDOS at the sites Mn(1) and Mn(3) which show OO. While the 4$`p_x`$ states were suggested to be 5 eV lower than the 4$`p_y`$ on one Mn atom, the order was reversed on the other Mn atom. Theoretically there are two contrasting interpretations possible for such a splitting. Ishihara and Maekawa  argued in the context LaMnO3 that the splitting in the Mn 4$`p`$ states induced by the intraatomic $`pd`$ Coulomb interaction produces such a strong tensor character of the scattering form factor. However, it was pointed out  that as the 4p states are extended, the suggested $`p`$-$`d`$ Coulomb interaction strength is unphysically large and the splitting in the 4$`p`$ states is actually caused by the JT distortion, though Coulomb interactions, particularly within the Mn 3$`d`$ manifold, may have important consequences for other properties in such systems. These suggestions are consistent with an earlier analysis of transition metal $`K`$-edge XAS in Fe and Co oxides .

In Fig. 2 we plot the Mn 4$`p_x`$ and 4$`p_y`$ partial densities of states (DOS) in the energy range 10-20 eV above the Fermi level, projected onto the Mn site (Mn(1)) showing $`d_{3x^2r^2}`$ ordering. A splitting of $``$ 3 eV is clearly visible, with the 4$`p_x`$ states located at lower energies. The order is reversed at the other Mn site (Mn(3)) which shows $`d_{3y^2r^2}`$ ordering. Thus, our results on La0.5Sr1.5MnO4 are consistent with the suggestion  in the context of LaMnO3 that the JT distortion to be not only the driving force for the orbital ordering, but also responsible for the specific experimental effect of the pronounced tensor character of the form factor via the splitting of the 4$`p`$ partial DOS.

Strong enhancement in the intensity at the energy corresponding to the absorption edge of Mn3+ was observed at the CO superlattice reflection.  These results suggested the presence of a second Mn atom in the system, with its absorption edge 4 eV higher than that for the Mn3+ atoms. As the absorption edge for Mn4+ atoms lies $``$4 eV above the absorption edge for Mn3+ atoms, they claimed that this was a direct evidence of an ordering of the two charge species - Mn3+ and Mn4+ in this system. From the present calculations, we find that as the environment for the Mn3+-like sites is different from the environment for the Mn4+-like sites, there is a substantial modification in the Mn 4$`p`$ PDOS, though the net charge associated with these two sites, 4.53 at Mn 1 and 3, and 4.51 at Mn 2 and 4, are almost identical. Hence, the modifications at the so-called CO superlattice reflection cannot be interpreted on the basis of a substantial difference in the charge state of the two inequivalent sites. Interestingly, our results for the electronic structure at these two sites provide a natural explanation for the observed results. With the x- and y-axis defined in Fig. 1 we have the 4$`p_x`$ states at Mn3+(1) at lower energies compared to the Mn 4$`p_x`$ states at Mn4+ site (Fig. 3). As a result we have an intensity maximum at the CO superlattice reflection. If the axes are rotated by 45 degrees, one finds that the Mn 4$`p_x^{}`$ states at Mn3+(1) and those at the Mn4+ site almost coincide (inset in Fig. 4). This results in a minimum in the intensity. A similar angular dependence is also observed at the OO superlattice reflection. Our reinterpretation is supported by recent experiments on Nd0.5Sr0.5MnO3  which also found a similar angular dependence of the intensity at a CO superlattice reflection.

In conclusion, we have carried out an analysis of the experimental observation for orbital and charge orderings in La0.5Sr1.5MnO4. Our results indicate the presence of two Mn species with very different environments. One of the Mn species has a JT distortion of the oxygens surrounding that atom and hence, in this sense, behaves like an Mn3+ species. The distortions around the so-called Mn4+ atoms are different from the simple breathing mode distortion suggested earlier. Extrapolating the magnitude of the JT distortion around the Mn3+ to equal the value observed in LaMnO3 is necessary to obtain the correct description of the ground magnetic state. Further, the energy dependence at the orbital ordering as well as the charge ordering superlattice reflections can be explained by the distortions of the MnO6 octahedra. The present results establish that no real-space substantial charge ordering needs to be invoked in this system in order to explain the experimentally observed results; instead band structure effects are responsible for the dependence of the superlattice intensities on the energy and the orientation. The above interpretation is consistent with the observation that both charge ordering as well as the orbital ordering show the same temperature dependence. As the origin of the intensity variation observed at both reflections is the same, namely the lattice distortions, our results explains why the charge ordering as well as the orbital ordering transition occur over the same temperature range in this system.

The authors acknowledge Dr. Solovyev and Dr. Fang for valuable discussions and comments. The present work is partially supported by NEDO.


text:
# Neutron-Capture Element Abundances and Cosmochronometry

## 1. Introduction

The dominant isotopes of elements with atomic numbers (Z $`>`$ 30) are synthesized in neutron bombardment reactions during late stellar evolution. Some of the heaviest of these so-called neutron-capture ($`n`$-capture) elements are radioactively unstable but long-lived on astrophysically interesting (many Gyr) time scales. In principle, abundance analyses of old, metal-poor stars that compare radioactive to stable $`n`$-capture elements can be used to determine the age of the Galactic halo. But there are practical difficulties in applying this idea to most halo stars. In this brief review we focus on studies of $`n`$-capture elements relevant to cosmochronometry, discussing in turn general $`n`$-capture abundance trends with metallicity, detailed distributions of these elements in a few very well-observed stars, and possible new initiatives to improve the use of $`n`$-capture elements in the description of early Galactic nucleosynthesis.

## 2. Overall n-Capture Abundance Trends with Metallicity

Abundances of $`n`$-capture elements vary respect to those of the Fe-peak by several orders of magnitude from star to star. This “scatter” is most apparent in the lowest metallicity regimes. The onset metallicity of the $`n`$-capture scatter is poorly established, but at least for stars with \[Fe/H\] $`<`$ –2, the total range in \[$`<n`$-capture$`>`$/Fe\] is $`\pm `$1.5 dex (e.g., Gilroy et al. 1988, McWilliam et al. 1995, Ryan et al. 1996, Burris et al. 2000). (Here, \[$`<n`$-capture$`>`$/Fe\] stands for abundance ratios \[Sr/Fe\], \[Ba/Fe\], \[La/Fe\], etc.) The abundance scatter is far greater than that ascribable to uncertainties in the observed stellar spectra, atomic data, or model atmosphere parameters. The variation is clearly seen in published spectra of very metal-poor stars (e.g. Figure 16, McWilliam et al. 1995; Figure 3, Burris et al. 2000; Figure 1, Westin et al. 2000). This provides direct evidence that local nucleosynthesis events added to an early Galactic halo ISM that remained poorly mixed on time scales corresponding to the formation of stars with metallicities as high as \[Fe/H\] $``$ –2.

Abundance ratios among the $`n`$-capture elements in very metal-poor stars are distinctly non-solar. Spite & Spite’s (1979) high resolution spectroscopic investigation of a few bright metal-poor stars provided the first convincing observational evidence of this phenomenon. In the metallicity domain 0 $`>`$ \[Fe/H\] $`>`$ –2, the surveys cited above have shown that the ratio \[Ba/Eu\] $``$ 0, but by \[Fe/H\] $``$ –3 this ratio has declined to $``$–1. Barium is synthesized most efficiently via slow neutron captures (the $`s`$-process) while europium is predominantly created via rapid neutron captures (the $`r`$-process). Thus observed low \[Ba/Eu\] values in the most metal-poor stars suggest (e.g. Truran 1981) that $`r`$-process products comprise most of the $`n`$-capture abundances at lowest metallicities. This supports the notion that $`n`$-capture element production in the early Galaxy should have been from very short-lived, high mass stars that generate large neutron fluxes during their death throes. Products of the $`s`$-process come from longer-lived ($`>`$ $``$108 yr) low-to-intermediate mass stars. The evident lack of $`s`$-process contributions at \[Fe/H\] $``$ –3111 Here we do not consider the so-called CH stars, ones that exhibit extremely large overabundances of C and of $`n`$-capture elements evidently created via the $`s`$-process (Norris et al. 1997a,b; Hill et al. 2000). Most such stars are binaries, undoubtedly victims of mass transfer from higher-mass former AGB companions. These nucleosynthesis events eventually lead to the buildup of $`s`$-process levels in the Galaxy, but contribute little at lowest metallicities. argues for a very rapid buildup of Galactic metallicity to this level from first onset of star formation.

Less discussed is the lack of good correlation between abundances of heavier (Z $``$ 56) and lighter (Z = 38–40; Sr-Y-Zr) $`n`$-capture elements. While the heavier elements appear to be $`r`$-process in origin, the lighter elements cannot be fit by the main $`s`$-process or $`r`$-process or their combination. Instead, it may require a complicated admixture of the weak $`s`$-process and the $`r`$-process to reproduce the Sr-Y-Zr abundance ratios in well-observed very metal-poor stars (e.g., Cowan et al. 1995). Moreover, Wasserburg et al. (1996) have argued that the solar-system $`r`$-process distribution results from two different sources or sites – one for the lighter and one for the heavier $`n`$-capture elements. It is also not yet fully understood why the abundances of the Sr-Y-Zr group correlate much more closely with Fe-peak abundances than do the heavier $`n`$-capture abundances, although it might suggest a role for the weak $`s`$-process operating in massive stars early in the history of the Galaxy. The lighter $`n`$-capture elements will be considered again in the next section.

## 3. $`n`$-Capture Element Distributions in Well-Observed Halo Stars

To thoroughly examine the details of $`n`$-capture abundances in metal-poor stars it is necessary to detect many elements over the entire Z = 31–92 element range. This in turn requires identification of stars with \[$`<n`$-capture$`>`$/Fe\] $``$ +0.5, in order to maximize the spectroscopic contrast between the strengths of $`n`$-capture and Fe-peak absorption features. The few known extremely $`n`$-capture-rich metal-poor stars subjected to detailed abundance scrutiny have been serendipitous discoveries, e.g. HD 115444 (Griffin et al. 1982; Westin et al. 2000), CS 22892-052 (McWilliam et al. 1995; Sneden et al. 2000a, and references therein), and now CS 31082-001 (Cayrel et al. 2001). Much attention has been given to CS 22892-052, and in Figure 1 we summarize the results of Sneden et al. This figure also adds revised abundance determinations from the same observed spectra for elements with new transition probability and hyperfine structure data: La (Lawler et al. 2001a), Ce (Biémont et al. 2000), Tb (Lawler et al. 2001b), and Dy (Wickliffe et al. 2000). The CS 22892-052 abundances are compared with scaled solar-system $`r`$-process, $`s`$-process, and total abundance distributions.

Three features stand out in the plots of Figure 1. First, the scaled solar $`r`$-process distribution almost perfectly fits the observed abundances of the 18 heavier (Z $`>`$ 56) stable $`n`$-capture elements; the other two solar-system distributions fail by large margins. While the “solar total” curve appears to hold promise in comparison to the observed abundances, normalizing the curve to Eu or Dy yields a mismatch by 0.5–0.9 dex in the Ba–Ce group. Second, among the long-lived radioactive elements, the observed abundance of Th (Z = 90) falls below the “solar $`r`$-process” curve, as does the observed upper limit to the abundance of U (Z = 92). Thus $`if`$ these elements were originally synthesized in the same proportions with respect to the lighter stable $`n`$-capture elements that occurred prior to solar system formation, then CS 22892-052 is substantially older than the solar system, and in fact its $`n`$-capture elements were synthesized $``$15 Gyr ago (e.g., Cowan et al 1999). Third, none of the solar system abundance distributions provide satisfactory matches to the lighter (38 $``$ Z $``$ 48) $`n`$-capture element abundances of this star.

The excellent agreement between observed abundances of the heavier stable elements and the “solar $`r`$-process” is not confined to CS 22892-052. It is repeated in each of the few ultra-metal-poor stars (\[Fe/H\] $`<`$ –2.5) studied in comparable detail (Westin et al. 2000; Johnson & Bolte 2001). Note in particular the halo giant BD+17 3248. This star has a nearly pure $`r`$-process signature among the $`n`$-capture elements, but with \[Fe/H\] $``$ –2.0, it is the highest metallicity example of very $`r`$-process enriched material. It will be of great interest to explore further the \[Fe/H\] $`>`$ –2 domain to discover at what metallicity the influence of individual $`r`$-process synthesis events are lost in the general Galactic $`n`$-capture element buildup.

Recently Cayrel et al. (2001; see also their contribution to this conference volume) have discovered that the UMP star CS 31082-001 (\[Fe/H\] $``$ –3) may have even larger $`n`$-capture element overabundances than does CS 22892-052. Most interesting is their detection of $`many`$ transitions of Th II and the strongest U II line; the combined abundances of two radioactive elements (with different half-lives) suggests to them that the “age” of the $`n`$-capture elements in this star is $``$13 Gyr. Their ongoing study of this star finds an $`observed`$ \[Th/Eu\] ratio that is much larger than in CS 22892-052 (Sneden et al. 2000a), HD 115444 (Westin et al. 2000), several other halo stars (Johnson & Bolte 2001) and in globular cluster stars (Sneden et al. 2000b). This higher abundance ratio in CS 31082-001 would imply a young age comparable to the solar system, obviously inconsistent with this star’s metallicity and halo membership. This may indicate something unusual about the abundances in CS 31082-001, or it may indicate that the production ratio of \[Th/Eu\] is not single-valued and may lead to inconsistencies in age determinations (e.g., Goriely & Clerbaux 1999). It is clear that many more Eu and Th abundances need to be determined for halo stars, in order to make some sense of this issue.

Finally, consider the non-conformity of CS 22892-052 abundances in the 38 $``$ Z $``$ 48 domain to any of the scaled solar system curves. Previous studies have indicated that the abundances of Sr–Zr did not fall on the same curve as the heavier elements, but this is the first case where elements between Z = 40–50 have been detected. The difference between the lighter and heavier $`n`$-capture element abundance distributions in CS 22892-052 (as shown in Figure 1) has been explained as the superposition of two distinct $`r`$-process events (Wasserburg & Qian 2000), or perhaps resulting from different regions of the same neutron-rich jet of a core-collapse supernova (Cameron 2001) that are responsible for synthesizing the lighter and heavier $`n`$-capture elements. The breakpoint between the two r-process signatures is predicted to occur near Ba, as observed in CS 22892-052. However, there has been no success thus far in fitting the individual abundances in this star, although the entire set of $`n`$-capture abundances in just CS 22892-052 has been used to constrain nuclear mass models and theoretical $`r`$-process predictions (Cowan et al. 1999). Further, since knowledge of the 41 $``$ Z $``$ 48 elements is confined so far to just CS 22892-052, what is most needed now are abundances of the lighter $`n`$-capture elements in more stars.

## 4. Some Future Prospects

The link between $`n`$-capture elemental abundances and Galactic time scales lies with the long-lived cosmochronometer elements. So far, ratios of Th and U to each other and to other elements do not yield a consistent answer for the age of the Galactic halo when the observed abundances of a (very) few stars are compared to zero-age predictions for them. The \[Th/Eu\] ratios in CS 22892-052 and HD 115444 suggest ages of $``$15 Gyr, while that of CS 31082-001 yields $``$4 Gyr. But the \[Th/U\] ratio of this star pushes the age back to $``$13 Gyr. Johnson & Bolte (2001) find that the ages of their five stars with detected Th II features can range from 11-15 Gyr, depending on assumptions about initial Th/Eu production ratios. Clearly both further theoretical (e.g. Cowan et al. 2001) and observational efforts are needed on this problem. Extensive $`n`$-capture abundance distributions should be derived in at least $``$30 very low metallicity stars, to discover what is the normal abundance level of the radioactive chronometer elements in the Galactic halo.

Probably no other $`absolute`$ Galactic time scale information can be deduced from $`n`$-capture elements in metal-poor stars. But recent improvements in stellar spectroscopic and laboratory atomic data permit renewed attack on an unsolved $`relative`$ time scale question: what is Galactic metallicity at which major contributions from $`s`$-process nucleosynthesis began to generally influence the halo ISM? Most $`s`$-process synthesis is associated with the AGB phases of intermediate-to-low mass stars, $``$ $`<`$ 8$`_{}`$, whose evolutionary time scales are $``$ $``$108 yr. Metallicity regimes with little or no detectable $`s`$-process contributions are those resulting from the first waves of Galactic nucleosynthesis that happened on faster time scales. The approximate \[Fe/H\] indicating a general rise in the $`s`$-process should tell us how much the first nucleosynthesis burst contributed to overall Galactic metallicity.

This question has usually been empirically addressed by trying to find the metallicity domain for substantial movement in \[Ba/Eu\] ratios from the $`r`$-process-dominated value of $``$–0.9 at \[Fe/H\] $``$ –3 toward the solar-system $`r+s`$ value of $``$0.0 that appears to be complete by \[Fe/H\] $``$ –1.5. With such data, Gilroy et al. (1988) suggested that the onset of major Galactic $`s`$-process occurred at \[Fe/H\] $``$ –2.3, while Burris et al. (2000) argue that this may happen at \[Fe/H\] $``$ –2.8. At present it is impossible to narrow this metallicity down to better than somewhere in the range –3 $``$ \[Fe/H\] $``$ –2.

This situation may never change, because large observed star-to-star scatter exists in \[Ba/Eu\] ratios at all Galactic halo metallicities. The scatter may be intrinsic to the stars, or it may simply be an artifact of abundance analyses. The problem lies in basic atomic structure. Unlike the first ions of neighboring rare earth elements, Ba II has a structure that in cool stellar atmospheres gives rise to only five very strong transitions from lower energy levels in the visible spectral range. All other Ba II transitions are very weak ones from higher excitation levels. Significant hyperfine and isotopic splitting exists for the strong low excitation lines, and Ba has 5 stable isotopes whose relative abundances are synthesized in different proportions under the $`r`$\- and $`s`$-processes; estimates of these proportions becomes part of the abundance derivation process (e.g. Magain 1995, Sneden et al. 1996). Abundances of Ba also are very sensitive to values of microturbulent velocity assumed in the analyses. All in all, it is difficult to believe \[Ba/Eu\] ratios in most metal-poor stars to better than an uncertainty of $`\pm `$0.2 dex, and this is inadequate to map out the metallicity evolution of the $`s`$\- and $`r`$-processes.

Fortunately other (Z $``$ 56) elements have very different abundances resulting from the two $`n`$-capture events, and in particular \[La/Eu\] and \[Ce/Eu\] have $`r`$-/$`s`$-process sensitivities nearly equal to that of \[Ba/Eu\] (e.g., see Figure 1 of Sneden et al. 2001). Both La II and Ce II have much more favorable atomic structures than does Ba II, and these elements have one very dominant isotope each. McWilliam (1997) advocated abandoning the use of \[La/Eu\] in favor of \[Ba/Eu\] (see his Figure 10). But the data depicted in that diagram still has significant scatter. Johnson & Bolte (2001) argue from better data that observed \[La/Eu\] ratios indicate $`r`$-process dominance in stars as metal-rich as \[Fe/H\] $``$ –1.5. Now, armed with higher resolution, higher S/N spectra and employing the new atomic data of Lawler et al. (2001a), we are beginning a large-sample survey of \[La/Eu\] in metal-poor stars. Excellent line-by-line abundance agreement is seen for La II in the Sun, CS 22892-052, and BD+17 3248 (Sneden et al. 2001) and in Figure 2 we show the run of \[La/Eu\] with \[Fe/H\] for a few very metal-poor but $`n`$-capture-rich stars. The small star-to-star scatter in \[La/Eu\] at lowest metallicities is so far very encouraging, but the sample is very small. When this survey is completed we hope to be able to tell with far greater certainty the metallicity at which the $`s`$-process makes substantial contributions to most stars’ $`n`$-capture abundances, and hence be able to tell how fast the Galaxy may have increased its Fe-peak metallicity before the deaths of the first intermediate-mass stars.

### Acknowledgments.

Our work on $`n`$-capture elements in halo stars has been a collaborative effort over many papers, and we appreciate our Co-authors for their contributions over the years. Emile Biémont, Rica French, Jennifer Johnson, Jennifer Simmerer, and Craig Wheeler are thanked for helpful discussions. We are happy to acknowledge that this research has been supported by various NSF grants to the authors.

## References

Burris, D. L., Pilachowski, C. A., Armandroff, T. A., Sneden, C., Cowan, J. J., & Roe, H. 2000, ApJ, 544, 302

Cameron, A. G. W. 2001, Nuc. Phys. A, in press

Cayrel, R., Hill, V., Beers, T. C., Barbuy, B., Spite, M., Spite, F., Plez, B., Andersen, J., Bonifacio, P., Francois, P., Molaro, P., Nordstrom, B., & Primas, F. 2001, Nature, 409, 691

Cowan, J. J., Burris, D. L., Sneden, C., McWilliam, A., & Preston, G. W. 1995, ApJ, 439, L51

Cowan, J. J., McWilliam, A., Sneden, C., Burris, D. L., & Preston, G. W. 1997, ApJ, 480, 246

Cowan, J. J., Pfeiffer, B., Kratz, K.-L., Thielemann, F.-K., Sneden, C., Burles, S., Tytler, D., & Beers, T. C. 1999, ApJ, 521, 194

Cowan, J.J., Sneden, C., & Truran, J. W. 2001, in Cosmic Evolution, ed. E. Vangioni-Flam and M. Cassé, (Singapore: World Scientific Publishing), in press

Gilroy, K. K., Sneden, C., Pilachowski, C. A., & Cowan, J. J. 1988, ApJ, 327, 298

Goriely, S., & Clerbaux, B. 1999, A&A, 346, 798

Griffin, R., Gustafsson, B., Viera, T., & Griffin, R. 1982, MNRAS, 198, 637

Hill, V., Barbuy, B., Spite, M., Spite, F., Cayrel, R., Plez, B., Beers, T. C., Nordstr m, B., & Nissen, P. E. 2000, A&A, 353, 557

Johnson, J. A., & Bolte, M. 2001, ApJ, in press

Lawler, J. E., Bonvallet, G., & Sneden, C. 2001a, ApJ, in press

Lawler, J. E., Wickliffe, M. E., Cowley, C. R., & Sneden, C. 2001b, submitted

Magain, P. 1995, A&A, 297, 696

McWilliam, A. 1997, ARA&A, 35, 503

McWilliam, A., Preston, G. W., Sneden, C., & Searle, L. 1995, AJ, 109, 2757

Norris, J. E., Ryan, S. G., & Beers, T. C. 1997a, ApJ, 488, 350

Norris, J. E., Ryan, S. G., & Beers, T. C. 1997b, ApJ, 489, L169

Palmeri, P., Quinet, P., Wyart, J.-F., & Biémont, E. 2000, Phys. Scr., 61, 323

Ryan, S. G., Norris, J. E., & Beers, T. C. 1996, ApJ, 471, 254

Sneden, C., Cowan, J.J., & Truran, J. W. 2001, in Cosmic Evolution, ed. E. Vangioni-Flam and M. Cassé, (Singapore: World Scientific Publishing), in press

Sneden, C., Cowan, J. J., Ivans, I. I., Fuller, G. M., Burles, S., Beers, T. C., & Lawler, J. E. 2000a, ApJ, 533, L139

Sneden, C., Johnson, J., Kraft, R. P., Smith, G. H., Cowan, J. J., Bolte, M. S. 2000b, ApJ, 536, L85

Sneden, C., McWilliam, A., Preston, G. W., Cowan, J. J., Burris, D. L., & Armosky, B. J. 1996, ApJ, 467, 819

Spite, M., & Spite, F., 1978, A&A, 67, 23

Truran, J. W. 1981, A&A, 97, 391

Wasserburg, G. J., Busso, M., & Gallino, R. 1996, ApJ, 466, 109

Wasserburg, G. J., & Qian, Y.-Z. 2000, ApJ, 529, L21

Westin, J., Sneden, C., Gustafsson, B., & Cowan, J. J. 2000, ApJ, 530, 783

Wickliffe, M. E., Lawler, J. E., & Nave, G. 2000, JQSRT, 66, 363


text:
# 1999 Quadrantids and the lunar Na atmosphere

## 1 Introduction

Evidence of a lunar atmopshere has been sought since the dawn of the telescopic era, but none was found until in situ measurements by the Apollo missions revealed the presence of He and Ar, both of solar origin, and possibly CH4, CO, CO2, and N2 (Hodges 1974). Discovery from the ground of Na \[Potter & Morgan 1985\] and K \[Potter & Morgan 1986\] in Mercury’s atmosphere renewed interest in observing the lunar atmosphere from Earth, since both atmospheres are believed to be generated by similar mechanisms, though at different rates. Their atmospheres are continuosly lost and repopulated under the influence of the interplanetary medium, and are known as transient atmospheres. There are four candidate source mechanisms for such atmospheres: desorption and sputtering by solar photons; chemical sputtering by the solar wind and by energetic particles from the Earth’s magnetosphere; micrometeoroid impacts; and thermal desorption. The sink mechanisms are: Jeans escape; escape due to solar radiation pressure; ionization by the solar wind; and photoionization. The latter is the dominant sink mechanism for lunar Na, with proposed lifetimes of 15 or 47 hr at 1 AU (cf. Cremonese et al. 1997). The expected energy distribution, characteristic temperature and spatial distribution of each source mechanism is given by Smyth & Marconi (1995).

Lunar Na and K were discovered in 1988 (Potter & Morgan 1988; Tyler et al. 1988). Many observations using different techniques have been made to address the origin and evolution of this atmosphere, at present thought a combination of sputtering by solar photons and meteoroid impacts (Cremonese & Verani 1997, Sprague et al. 1998) or of chemical sputtering by solar wind ions and photosputtering \[Potter & Morgan 1998\] is proposed. For a comprehensive overview see Stern (1999). Similar Na atmospheres are present around Jupiter’s moons Io \[Brown 1974\] and Europa \[Brown & Hill 1996\], but the source mechanism for these is believed to be sputtering by heavy ions in the Jovian magnetosphere. Na is a good tracer of such thin atmospheres because of the ease with which its strong emission can be observed.

Wide-angle imaging has shown that in the region between 1 and 10 lunar radii, about 15% of the Na atmosphere is due to micrometeor impacts \[Flynn & Mendillo 1995\]. Spectroscopic observations of the inner region of the atmosphere show that meteor impacts have an effect which is spatially anisotropic, and which is variable on short timescales (Cremonese & Verani 1997; Sprague et al. 1998). In 1991, Hunten, Kozlowski & Sprague published the results of a 3-day campaign of observations, during which the Na abundance increased by 60% at 80 south, while that at the equator remained unchanged. They suggested that the cause may have been a meteor shower, undetected by radar or by other measurements, impacting near the south pole of the Moon. In 1998 Verani et al. reported a set of high-resolution spectra taken 4.5 days before the maximum of the 1995 Leonids, with the same observational technique used for the observations reported here, as described in Cremonese & Verani (1997) and in Sprague et al. (1992). They found significant enhancements of the brightness and temperature (scale-height) of the Na atmosphere compared with previous observations at similar lunar phase and local solar zenith angle. Since the impact-generated component of the atmosphere has the highest expected temperature \[Smyth & Marconi 1995\], the measured increase in temperature may be associated with increased meteor activity during the Leonids.

A similar enhancement was detected during the maximum of the 1997 Leonids, at Mount Lemmon and Asiago observatories \[Hunten et al. 1998\]. These measurements appear to be confirmed by observations taken with a different technique during the night of the 1998 Leonids maximum \[Smith et al. 1999\]. The authors reported the detection of a region of neutral Na emission in the direction of the antisolar/lunar point in the 3 nights around new moon phase (18-20 November 1998), suggesting as the most likely cause the detection of the tail of the Moon’s atmosphere, i.e. its escaping component, driven outwards by solar radiation pressure. A model of these results \[Wilson et al. 1999\] indicates an increase of a factor of 2 or 3 in the amount of Na escaping during the peak of the Leonids.

Despite these observations, many issues remain to be resolved before one can conclude with certainty that meteor showers are responsible for the observed enhancements. In fact the lunar atmosphere shows time variations, the nature of which is not fully understood (Sprague et al. 1998; Smith et al. 2000). A measurement of enhanced Na emission from the Moon during a meteor shower other than the Leonids would strongly support the hypothesis that these showers are an important source of the transient Na atmosphere, both on the Moon and on other solar-system bodies with thin atmospheres. In terms of mass flux (g cm-2 s-1), the Quadrantids are the most intense meteor stream; in fact if we compare the mass flux of the meteor streams and the mass flux of the sporadic meteoroids reported in Table 3, we can see the micrometeoritic flux could increase up to 30% - 50% during the Quadrantids. From this point of view, this stream gives a good opportunity to test the impact mechanism; we therefore observed the lunar atmosphere during the 1999 Quadrantid meteor shower.

## 2 Observations

The observations were made in the early mornings of 3 and 4 January 1999 with the Utrecht Echelle Spectrograph of the William Herschel Telescope on La Palma (dispersion 0.053 Å pixel-1). Both nights were photometric. The Moon was full on Jan 2, at 02:49. The Sun was quiet. The diameter of the magnetotail is about 52 Earth radii at the Moon’s orbit \[Reiff & Reasoner 1975\], which means that the Moon was inside the magnetotail on the first night of the observations (phase angle = 14o). On the second night (phase angle = 26o) the Moon was near the predicted position of the magnetopause, and thus its location with respect to magnetotail and magnetosheath is uncertain.

The maximum of the Quadrantids was predicted on the night Jan 3/4, with radiant at $`\alpha =`$ 230, $`\delta =`$ +49. The right ascensions of the Moon at 0h UT on 3 and 4 January 1999 were respectively 115 and 129, so the shower fell on the Moon’s western limb (cf. Fig. 1). The slit of the spectrograph, 150 arcsec long and 1 arcsec wide, was oriented perpendicular to the lunar limb, and observations were made at various positions along the limb (Table 1) to investigate changes in the Na emission with distance from the sub-radiant point. Exposure time were typically 500 sec. The first 50 arcsec from the surface had to be discarded due to the strong scattered moonlight; the spatial coverage was then augmented placing two fields end-to-end. For details of the data reduction and analysis see Cremonese et al. (1992) and Verani et al. (1998).

The full moon prevented reliable visual measurements of the intensity of the shower at the Earth, but 50-MHz radar observations made at Toyokawa Meteor Observatory, Aichi, Japan, revealed an activity five times higher than sporadic on Jan 3, between 20 and 24 UT, with a maximum of 235 events hr-1, in good agreement with the observations of the 1997 and 1998 showers \[Suzuki 2000\]. In addition, the MLT Dynamics Group of the University of Wales (V. S. Howells and H. R. Middleton private communication) used the radar station at Aberystwyth, UK, detecting a maximum on January 4, with activity two to three times higher than the preceding and following nights. These observations suggest that the 1999 Quadrantids were at least as active as in previous years.

## 3 Discussion

The data were interpreted using Chamberlain’s model of the exosphere \[Chamberlain & Hunten 1987\], correcting the barometric density with an appropriately adjusted partition function for the escaping and balistic components (cf. Sprague et al. 1992). The results of the observations are shown in Table 1. There are no significant differences between the measurements made on Jan 3 and Jan 4, and none between measurements made in directions towards the radiant and in other directions. The lack of any observed change between the first and second nights could also indicate that there were no significant changes due to the Moon’s exit from the magnetotail; if indeed that took place. While the differences between sputtering by magnetospheric and solar wind particles are still not fully understood, our observations are consistent with the dominant source mechanism being sputtering by solar radiation, which will be isotropic around the limb at full moon (Mendillo & Baumgartner 1995; Mendillo, Baumgartner & Wilson 1999).

In Table 2 we compare measurements of the lunar Na atmosphere made by other authors, at full moon phase or at similar local solar zenith angle with those reported here during the Quadrantids. The brightness and temperature we measured during the Quadrantids are in good agreement with most of the measurements made when there was no meteor shower, i.e. the 1999 Quadrantids had no detectable effect on the lunar Na atmosphere.

These results may indicate that meteor impacts could have significant influence on the Moon’s atmosphere only under particular conditions, so that the detected difference in the effects of the two streams may be due to physical differences between the two streams. In fact the production of gas after an impact depends on various factors, including the velocity, mass, and composition of the impactors. The two streams differ in many parameters (cf. Table 3), the impact velocity being one of the greatest: the mean impact velocity of the Leonids (orbiting the Sun in the opposite direction to the Earth and Moon) is 70.7 km s-1, much higher than that of the Quadrantids (41.0 km s-1).

O’Keefe & Ahrens (1977) have found that the amount of gas generated by an impact is proportional to the factor S=($`\rho _m`$/$`\rho _t`$)(v/cp)2, where v is the impact velocity, $`\rho _m`$ and $`\rho _t`$ are respectively the density of the projectile and of the target, and cp is the bulk sound velocity in the target. Starting from this model, Morgan, Zook & Potter (1988) calculated the amount of gas produced by impacts having impactor-target densities ratio of 1 and sound speed in the target of 7.44 km/s (estimated for Mercury’s regolith components). They found that a negligible amount of gas is produced at velocities below 23 km/s (less than the mass of the projectile); at progressive velocities this amount increases, becoming proportional to v2, i.e. to the kinetic energy, for velocities higher than 44 km/s, (cf. fig. 6 therein). In our case (cometary grains into lunar regolith) the density ratio is $``$ 1 (0.7 - 3 g/cm3 vs 2.3 - 2.7 g/cm3), so the threshold velocity should be higher than the ones previously reported (up to 45 km/s). Cintala (1992) in a model of high-velocity micrometeoroid impacts in the regolith, also found that vapour production increases with impact velocity. This model suggests that a difference of a factor 2 for the impact velocity yields a factor of almost 3 in the amount of material melted, and a factor of more than 4 in the amount of target material vaporised.

The effects of high-velocity impacts have also been investigated in the laboratory (Eichhorn 1978), using a variety of materials for the targets and for the impactors. The impact velocities ranged from 3 to 15 km/s, and the masses from 10-14 to 10-9 g with a size of few microns; both ranges are unfortunately lower than the typical ones for the Leonids and Quadrantids. This experiment shows that the temperature of the generated gas increases with the impact velocity (this could explain the enhancement of the temperature of the Na atmosphere during the Leonids). These results seem to confirm also the theoretical prediction of a low vapor production for such impact velocities, as the mass of gas produced is less than twice the mass of the impactor body. On the other hand, Schultz (1996) found that the vaporization increases with the square (or even higher power) of the velocity, even for velocities of 3-10 km/s, inconsistent with the hypothesis of a “threshold” velocity. The mean kinetic energies delivered per unit area and time by the Leonids (after 1994) and Quadrantids are of the same order of magnitude, so the different impact velocities of the two streams may be responsible for the observed differences only if the threshold velocity is real.

Different chemical compositions of the streams may affect the composition, e.g., the Na abundance, of the gas produced. Spectroscopic measurements of the airglow were made during the Leonid shower (Chu 2000, Nagasawa 1978), suggesting a higher content of Na in Leonids with respect other meteoroids. Moreover, Borovicka et al. (1999) found in their spectroscopic observations of the Leonid meteors that smaller meteoroids tend to be poorer in Na than larger ones, and a similar behaviour was found for the Perseids. Šimek (1986) investigated the mass distribution of five meteor streams (Geminids, Quadrantids, Perseids, Leonids, and Giacobinids) and of the sporadics observed with the radar. In his results he found an absence of larger particles in the Quadrantids (and also in the sporadics). These results suggest that the Na content of the Quadrantids is lower than that of the Leonids. Finally, age could also play a role in depleting the content of volatiles in Quadrantids meteoroids. The Quadrantids are much older than the Leonids, being created 7500 (Babadzhanov & Ibrunov 1992) or 500 years ago (Jenniskens 1997). In addition, because the Quadrantids have a shorter orbital period (5.3 years, vs 33 years for the Leonids), they have passed close to the Sun more often, resulting in greater evaporation of volatile elements, such as Na, leaving the meteoritic particles depleted in these elements.

## 4 Conclusions

No enhancement of the Na emission from the lunar atmosphere was detected during the Quadrantids meteor shower. This contrasts with the reported enhancements seen during at least three of the Leonids showers. As a possible explaination we suggest the differences in the physical and chemical parameters of the two streams, as widely explained in the previous section. To investigate this hypothesis new measurements of hypervelocity impacts with a velocity range resembling the one for the meteor showers and on a target more closely approximating the the lunar regolith, or accurate modelling of such impacts, are required. Measurements of the chemical composition of the meteoroids are also required, as well as new observations of the lunar atmosphere during other major meteor streams. For these reasons we believe that is not possible at the moment to understand under which conditions the impact mechanism can generate a significative amount of gas in the lunar atmosphere.

## 5 Acknowledgements

We are grateful to the referee, A. Fitzsimmons, for valuable comments and suggestions, and to J. Geiss and to S. Håland for useful discussions. Barbieri acknowledges support from ASI; Mendillo acknowledges support from the NASA Planetary Astronomy Program. The WHT is operated on the island of La Palma by the Isaac Newton Group in the Spanish Observatorio del Roque de los Muchachos of the Instituto de Astrofisica de Canarias.