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# Utilizing the World Wide Web as an Encyclopedia: Extracting Term Descriptions from Semi-Structured Texts

## 1 Introduction

Reflecting the growth in utilization of machine readable texts, extraction and acquisition of linguistic knowledge from large corpora has been one of the major topics within the natural language processing (NLP) community. A sample of linguistic knowledge targeted in past research includes grammars \[Kupiec and Maxwell, 1992\], word classes \[Hatzivassiloglou and McKeown, 1993\] and bilingual lexicons \[Smadja et al., 1996\]. While human experts find it difficult to produce exhaustive and consistent linguistic knowledge, automatic methods can help alleviate problems associated with manual construction.

Term descriptions, which are usually carefully organized in encyclopedias, are valuable linguistic knowledge, but have seldom been targeted in past NLP literature. As with other types of linguistic knowledge relying on human introspection and supervision, constructing encyclopedias is quite expensive. Additionally, since existing encyclopedias are usually revised every few years, in many cases users find it difficult to obtain descriptions for newly created terms.

To cope with the above limitation of existing encyclopedias, it is possible to use a search engine on the World Wide Web as a substitute, expecting that certain Web pages will describe the submitted keyword. However, since keyword-based search engines often retrieve a surprisingly large number of Web pages, it is time-consuming to identify pages that satisfy the users’ information needs.

In view of this problem, we propose a method to automatically extract term descriptions from Web pages and summarize them. In this paper, we generally use “Web pages” to refer to those pages containing textual contents, excluding those with only image/audio information. Besides this, we specifically target descriptions for technical terms, and thus “terms” generally refer to technical terms.

In brief, our method extracts fragments of Web pages, based on patterns (or templates) typically used to describe terms. Web pages are in a sense semi-structured data, because HTML (Hyper Text Markup Language) tags provide the textual information contained in a page with a certain structure. Thus, our method relies on both linguistic and structural description patterns.

We used several NLP techniques to semi-automatically produce linguistic patterns. We call this approach “NLP-based method.” We also produced several heuristics associated with the use of HTML tags, which we call “HTML-based method.” While the former method is language-dependent, and currently applied only to Japanese, the latter method is theoretically language-independent.

Our research can be classified from several different perspectives. As explained in the beginning of this section, our research can be seen as linguistic knowledge extraction. Specifically, our research is related to Web mining methods \[Nie et al., 1999, Resnik, 1999\].

From an information retrieval point of view, our research can be seen as constructing domain-specific (or task-oriented) Web search engines and software agents \[Etzioni, 1997, McCallum et al., 1999\].

## 2 Overview

Our objective is to collect encyclopedic knowledge from the Web, for which we designed a system involving two processes. As with existing Web search systems, in the background process our system periodically updates a database consisting of term descriptions (a description database), while users can browse term descriptions anytime in the foreground process.

In the background process, depicted as in Figure 1, a search engine searches the Web for pages containing terms listed in a lexicon.

Then, fragments (such as paragraphs) of retrieved Web pages are extracted based on linguistic and structural description patterns. Note that as a preprocessing for the extraction process, we discard newline codes, redundant white spaces, and HTML tags that our extraction method does not use, in order to standardize the layout of Web pages.

However, in some cases the extraction process is unsuccessful, and thus extracted fragments are not linguistically understandable. In addition, Web pages contain some non-linguistic information, such as special characters (symbols) and e-mail addresses for contact, along with linguistic information. Consequently, those noises decrease extraction accuracy.

In view of this problem, we perform a filtering to enhance the extraction accuracy. In practice, we use a language model to measure the extent to which a given extracted fragment can be linguistic, and index only fragments judged as linguistic into the description database.

At the same time, the URLs of Web pages from which descriptions were extracted are also indexed in the database, so that users can browse the full content, in the case where descriptions extracted are not satisfactory.

In the case where a number of descriptions are extracted for a single term, the resultant description set is redundant, because it contains a number of similar descriptions. Thus, it is preferable to summarize descriptions, rather than to present all the descriptions as a list.

For this purpose, we use a clustering method to divide descriptions for a single term into a certain number of clusters, and present only descriptions that are representative for each cluster. As a result, it is expected that descriptions resembling one another will be in the same cluster, and that each cluster corresponds to different viewpoints and word senses.

Possible sources of the lexicon include existing machine readable terminology dictionaries, which often list terms, but lack descriptions. However, since new terms unlisted in existing dictionaries also have to be considered, newspaper articles and magazines distributed via the Web can be possible sources. In other words, a morphological analysis is performed periodically (e.g., weekly) to identify word tokens from those resources, in order to enhance the lexicon. However, this is not the central issue in this paper.

In the foreground process, given an input term, a browser presents one or more descriptions to a user. In the case where the database does not index descriptions for the given term, term descriptions are dynamically extracted as in the background process. The background process is optional, and thus term descriptions can always be obtained dynamically. However, this potentially decreases the time efficiency for a real-time response.

Figure 2 shows a Web browser, in which our prototype page presents several Japanese descriptions extracted for the word “deeta-mainingu (data mining).” For example, an English translation for the first description is as follows:

> data mining is a process that collects data for a certain task, and retrieves relations latent in the data.

In Figure 2, each description uses various expressions, but describes the same content: data mining is a process which discovers rules latent in given databases. It is expected that users can understand what data mining is, by browsing some of those descriptions. In addition, each headword (“deeta-mainingu” in this case) positioned above each description is linked to the Web page from which the description was extracted.

In the following sections, we first elaborate on the NLP/HTML-based extraction methods in Section 3. We then elaborate on noise reduction and clustering methods in Sections 4 and 5, respectively. Finally, in Section 6 we investigate the effectiveness of our extraction method by way of experiments.

## 3 Extracting Term Descriptions

### 3.1 NLP-based Extraction Method

The crucial content for the NLP-based extraction method is the way to produce linguistic patterns that can be used to describe technical terms. However, human introspection is a difficult method to exhaustively enumerate possible description patterns.

Thus, we used NLP techniques to semi-automatically collect description patterns from machine readable encyclopedias, because they usually contain a significantly large number of descriptions for existing terms. In practice, we used the Japanese CD-ROM World Encyclopedia \[Heibonsha, 1998\], which includes approximately 80,000 entries related to various fields.

Before collecting description patterns, through a preliminary study on the encyclopedia we used, we found that term descriptions frequently contain salient patterns consisting of two Japanese “bunsetsu” phrases. The following sentence, which describes the term “X,” contains a typical bunsetsu combination, that is, “X toha” and “de-aru”:

* X toha Y de-aru (X is Y).111Although “de-aru” itself is not a bunsetsu phrase, we use bunsetsu phrases to refer to combinations of several words.

In other words, we collected description patterns, based on the co-occurrence of two bunsetsu phrases, as in the following method.

First, we collected entries associated with technical terms listed in the World Encyclopedia, and replaced headwords with a variable “X.” Note that the World Encyclopedia describes various types of words, including technical terms, historical people and places, and thus description patterns vary depending on the word type. For example, entries for historical people usually contain when/where the people were born and their major contributions to the society.

However, for the purposes of our extraction, it is desirable to use entries solely associated with technical terms. We then consulted the EDR machine readable technical terminology dictionary, which contains approximately 120,000 terms related to the information processing field \[Japan Electronic Dictionary Research Institute, 1995\], and obtained 2,259 entries associated with terms listed in the EDR dictionary.

Second, we used the ChaSen morphological analyzer \[Matsumoto et al., 1997\], which has commonly been used for much Japanese NLP research, to segment collected entries into words, and assign them parts-of-speech. We also developed simple heuristics to produce bunsetsu phrases based on the part-of-speech information.

Finally, we collected combinations of two bunsetsu phrases, and sorted them according to their co-occurrence frequency, in descending order. However, since the resultant bunsetsu co-occurrences (even with higher rankings) are extraneous, we supervised (verified, corrected or discarded) the top 100 candidates, and produced 20 description patterns. Figure 3 shows a fragment of the resultant patterns and their English glosses. In this figure, “X” and “Y” denote variables to which technical terms and sentence fragments can be unified, respectively.

Here, we are in a position to extract sentences that match with description patterns, from Web pages retrieved by the search engine (see Figure 1). In this process, we do not conduct morphological analysis on Web pages, because of computational cost. Instead, we first segment textual contents in Web pages into sentences, based on the Japanese punctuation system, and use a surface pattern matching based on regular expressions.

However, in most cases term descriptions consist of more than one sentence. This is especially salient in the case where anaphoric expressions and itemization are used. Thus, it is desirable to extract a larger fragment containing sentences that match with description patterns.

In view of this problem, we first use linguistic description patterns to briefly identify a zone, and sequentially search the following fragments relying partially on HTML tags, until a certain fragment is extracted:222Although we use HTML tags to identify appropriate text fragments, we call the method described in this section NLP-based method, in a comparison with the method in Section 3.2 that relies solely on HTML tags.

1. paragraph tagged with `<P>...</P>` (or `<P>...<P>` in the case where `</P>` is missing),
2. itemization tagged with `<UL>...</UL>`,
3. $`N`$ sentences identified with the Japanese punctuation system, where the sentence that matched with a description pattern is positioned as near center as possible, where we empirically set $`N=3`$.

### 3.2 HTML-based Extraction Method

Through a preliminary study on existing Web pages, we identified two typical usages of HTML tags associated with describing technical terms.

In the first usage, a term in question is highlighted as a heading by way of `<H>...</H>`, `<B>...</B>` or `<DT>` tag, and followed by its description in a short fragment. In the second usage, terms that are potentially unfamiliar to readers are tagged with the anchor `<A>` tag, providing hyperlinks to other pages (or a different position within the same page) where they are described.

The crucial factor here is to determine which fragment in the page is extracted as a description. For this purpose, we use the same rules described in Section 3.1. However, unlike the NLP-based method, in the HTML-based method we extract the fragment that follows the heading and the position linked from the anchor. However, in the case where a term in question is tagged with `<DT>`, we extract the following fragment tagged with `<DD>`. Note that `<DT>` and `<DD>` are inherently provided to describe terms.

The HTML-based method is expected to extract term descriptions that cannot be extracted by the NLP-based method, and vice versa. In fact, in Figure 2 the third and fourth descriptions were extracted with the HTML-based method, while the rest were extracted with the NLP-based method.

## 4 Language Modeling for Filtering

Given a set of Web page fragments extracted by the NLP/HTML-based methods, we select fragments that are linguistically understandable, and index them into the description database. For this purpose, we perform a language modeling, so as to quantify the extent to which a given text fragment is linguistically acceptable.

There are several alternative methods for language modeling. For example, grammars are relatively strict language modeling methods. However, we use a model based on $`N`$-gram, which is usually more robust than that based on grammars. In other words, text fragments with lower perplexity values are more linguistically acceptable.

In practice, we used the CMU-Cambridge toolkit \[Clarkson and Rosenfeld, 1997\], and produced a trigram-based language model from two years of Mainichi Shimbun Japanese newspaper articles \[Mainichi Shimbun, 1994 1995\], which were automatically segmented into words by the ChaSen morphological analyzer \[Matsumoto et al., 1997\].

In the current implementation, we empirically select as the final extraction results text fragments whose perplexity values are lower than 1,000.

## 5 Clustering Term Descriptions

For the purpose of clustering term descriptions extracted using methods in Sections 3 and 4, we use the Hierarchical Bayesian Clustering (HBC) method \[Iwayama and Tokunaga, 1995\], which has been used for clustering news articles and constructing thesauri.

As with a number of hierarchical clustering methods, the HBC method merges similar items (i.e., term descriptions in our case) in a bottom-up manner, until all the items are merged into a single cluster. That is, a certain number of clusters can be obtained by splitting the resultant hierarchy at a certain level.

At the same time, the HBC method also determines the most representative item (centroid) for each cluster. Then, we present only those centroids to users.

The similarity between items is computed based on feature vectors that characterize each item. In our case, vectors for each term description consist of frequencies of content words (e.g., nouns and verbs identified through a morphological analysis) appearing in the description.

## 6 Experimentation

### 6.1 Methodology

We investigated the effectiveness of our extraction method from a scientific point of view. However, unlike other research topics where benchmark test collections are available to the public (e.g., information retrieval), there are two major problems for the purpose of our experimentation, as follows:

* production of test terms for which descriptions are extracted,
* judgement for descriptions extracted for those test terms.

For test terms, possible sources are those listed in existing terminology dictionaries. However, since the judgement can be considerably expensive for a large number of test terms, it is preferable to selectively sample a small number of terms that potentially reflect the interest in the real world.

In view of this problem, we used as test terms those contained in queries in the NACSIS test collection \[Kando et al., 1999\], which consists of 60 Japanese queries and approximately 330,000 abstracts (in either a combination of English and Japanese or either of the languages individually), collected from technical papers published by 65 Japanese associations for various fields.333http://www.rd.nacsis.ac.jp/~ntcadm/
index-en.html

This collection was originally produced for the evaluation of information retrieval systems, where each query is used to retrieve technical abstracts. Thus, the title field of each query usually contains one or more technical terms. Besides this, since each query was produced based partially on existing technical abstracts, they reflect the real world interest, to some extent. As a result, we extracted 53 test terms, as shown in Table 1. In this table, we romanized Japanese terms, and inserted hyphens between each morpheme for enhanced readability.

Note that unlike the case of information retrieval (e.g., a patent retrieval), where every relevant document must be retrieved, in our case even one description can potentially be sufficient. In other words, in our experiments, more weight is attached to accuracy (precision) than recall.

For the search engine in Figure 1, we used “goo,”444http://www.goo.ne.jp/ which is one of the major Japanese Web search engines. Then, for each extracted description, one of the authors judged it correct or incorrect.

### 6.2 Results

Out of the 53 test terms extracted from the NACSIS collection, for 44 terms goo retrieved one or more Web pages. Among those 44 test terms, our method extracted at least one term description for 27 terms, disregarding the judgement. Thus, the coverage (or applicability) of our method was 61.4%. In Table 1, the third column denotes the number of Web pages identified by goo. However, goo retrieves contents for only the top 1,000 pages.

Table 1 also shows the number descriptions judged as correct (the column “#C”), the total number of descriptions extracted (the column “#T”), and the accuracy (the column “A”), for both cases with/without the trigram-based language model.

Table 1 shows that the NLP/HTML-based methods extracted appropriate term descriptions with a 63.5% accuracy, and that the trigram-based language model further improved the accuracy from 63.5% to 67.9%. In other words, only two descriptions are sufficient for users to understand a term in question. Reading a few descriptions is not time-consuming, because they usually consist of short paragraphs.

We also investigated the effectiveness of clustering, where for each test term, we clustered descriptions into three clusters (in the case where there are less than four descriptions, individual descriptions were regarded as different clusters), and only descriptions determined as representative by the HBC method were presented as the final result. We found that 66.7% of descriptions presented were correct ones. In other words, users can obtain descriptions from different viewpoints and word senses, maintaining the extraction accuracy obtained above (i.e., 67.9%).

However, we concede that we did not investigate whether or not each cluster corresponds to different viewpoints in a rigorous manner.

For the polysemy problem, we investigated all the descriptions extracted, and found that only “korokeishon (collocation)” was associated with two word senses, that is, “word collocations” and “position of machinery.” Among the three representative descriptions for “korokeishon (collocation),” two corresponded to the first sense, and one corresponded to the second sense. To sum up, the HBC clustering method correctly identified polysemy.

## 7 Conclusion

In this paper, we proposed a method to extract encyclopedic knowledge from the World Wide Web.

For extracting fragments of Web pages containing term descriptions, we used linguistic and HTML structural patterns typically used to describe terms. Then, we used a language model to discard irrelevant descriptions. We also used a clustering method to summarize extracted descriptions based on different viewpoints and word senses.

We evaluated our method by way of experiments, and found that the accuracy of our extraction method was practical, that is, a user can understand a term in question, by browsing two descriptions, on average. We also found that the language model and the clustering method further enhanced our framework.

Future work will include experiments using a larger number of test terms, and application of extracted descriptions to other NLP research.

## Acknowledgments

The authors would like to thank Hitachi Digital Heibonsha, Inc. for their support with the CD-ROM World Encyclopedia, Makoto Iwayama and Takenobu Tokunaga for their support with the HBC clustering software, and Noriko Kando (National Institute of Informatics, Japan) for her support with the NACSIS collection.


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# On the Structure of Low Lying 0⁺ Excited States of Pt isotopes.

## Abstract

The description of the of nuclei energy spectra of 0+ states has been done involving the degree of their collectivity as a systematics parameter. Within the framework of this approach the parameter of the collectivity is mainly determined by pairs of particles placed on single ”effective” level and coupled to monopole bosons. Holshtein-Primakoff transformation of these monopole bosons leads to clear physical explanation of the structure of $`0^+`$ states in terms of ”ideal bosons”.

The results may be helpful both for experimentalists and theorists in their investigations of low-lying states structure and transition probabilities.

The great amount of experimental data for energy spectra and transition probabilities evokes the necessity of simplified description that can be easily used by experimentalists for explaining the collective properties of states and their systematics. There are many investigations dedicated to the $`E0`$ and $`E2`$ transition probabilities and analyzing the 0+ spectra in different nuclei . For instance in the rare - earth region the values of the $`B(E2;2_{K^\pi =0_2^+}^+>0_{g.s.}^+)`$and$`B(E2;2_{K^\pi =0_2^+}^+>4_{g.s.}^+)`$ transitions as a function of neutron number change drastically for different isotopes . In this paper we study the low-energy 0$`^+`$spectra of 194Pt and 196Pt within the framework of simplified pairing vibrational model using Holstein-Primakoff transformation .

As the description of the structure of the 0+ nuclear states in terms of pair configurations continues to be of great interest both for theorists and experimentalists we define the Hamiltonian in terms of monopole phonon operators:

$$\begin{array}{cc}R_+^j=\hfill & \frac{1}{2}\underset{m}{}(1)^{jm}\alpha _{jm}^{}\alpha _{jm}^{}\begin{array}{cc}R_{}^j=\hfill & \frac{1}{2}\underset{m}{}(1)^{jm}\alpha _{jm}\alpha _{jm},\hfill \end{array}\hfill \\ & \begin{array}{cc}R_0^j=\hfill & \frac{1}{4}\underset{m}{}(\alpha _{jm}^{}\alpha _{jm}\alpha _{jm}\alpha _{jm}^{}),\hfill \end{array}\hfill \end{array}$$
(1)
where $`\alpha _{jm}^{}`$,$`\alpha _{jm}`$ are the nucleons creation and annihilation operators.

Let us consider the Hamiltonian for $`N`$ particles placed on ”effective” single level j in terms of the operators $`R_+^j`$,$`R_{}^j`$, $`R_0^j`$ :

$`H`$ $`=`$ $`\alpha R_+^jR_{}^j+\beta R_0^jR_0^j+{\displaystyle \frac{\beta \mathrm{\Omega }^j}{2}}R_0^j`$ (2)
$`\mathrm{\Omega }^j`$ $`=`$ $`{\displaystyle \frac{2j+1}{2}}`$
Later in our calculations of the $`0^+`$states energies of $`{}_{}{}^{194,196}Pt`$ isotopes we take $`\mathrm{\Omega }^j=6`$ that corresponds to $`h\frac{11}{2}`$ proton system shell model level.

The operators (1) satisfy the commutation relations :

$$[R_0^j,R_\pm ^j]=\pm R_\pm ^j[R_+^j,R_{}^j]=2R_0^j$$
(3)
In order to simplify the notations further we will omit the indices$`j`$.

Let us now present this Hamiltonian in terms of ”ideal” boson creation and annihilation operators $`[b,b^{}]=1;[b,b]=[b^{},b^{}]=0`$ , using the Holstein-Primakoff transformation  for the operators $`R_+`$, $`R_{}`$ and $`R_0`$ :

$$\begin{array}{ccc}R_{}=\sqrt{2\mathrm{\Omega }b^{}b}b& R_+=b^{}\sqrt{2\mathrm{\Omega }b^{}b}& R_0=b^+b\mathrm{\Omega }\end{array}$$
(4)
The transformations ( 4 ) conserve the commutation relations ( 3) between $`R_+`$, $`R_{}`$ and $`R_0`$ operators. Thus for the Hamiltonian (2) in terms of the new boson creation and annihilation operators ”ideal bosons” $`b^+,b`$ we have:

$$H=Ab^{}bBb^{}bb^{}b$$
(5)
where :

| $`A=\alpha (2\mathrm{\Omega }+1)\beta \mathrm{\Omega }`$ |
| --- |
| $`B=`$ $`\alpha \beta `$ |

(6)
The energy of any monopole excited state $`|n=\frac{1}{\sqrt{n!}}(b^+)^n|0;`$where $`b|0=0`$can be written as:

$$E_n=n\left|Ab^{}bBb^{}bb^{}b\right|n0\left|Ab^{}bBb^{}bb^{}b\right|0=AnBn^2$$
(7)
If we analyze the behavior of the experimental 0+\- state energies using the notation $`n`$ \- as a systematic parameter for the corresponding 0+\- states after minimizing Chi-square values by permutation of $`n`$ we find that the distribution of the $`0^+`$ states energies as function of $`n`$ can be presented by simple formula:

$$E_n=AnBn^2$$
(8)
We see that the Hamiltonian (2) provides the same energy spectrum as spectrum ( 8 ). Also one can check that similar behavior possess all the $`0^+`$ state energy spectra in nuclei of rare-earth region.

The parameters of the approach which we have used are presented in figure 1 along with the experimental and calculated 0+state distributions . The calculated energies are distributed in bell form because of the anharmonic terms in the Hamiltonian (5) and often the lowest 0$`^+`$states have much more collective structure ( bigger $`n`$ ) than the states with higher energies. In the framework of this simple model we can predict that additional 0+states should exist. We indicate these predicted states by ”?” in the figure 1. Thus it may be interesting to measure $`E0`$ transition probabilities in these nuclei and especially in $`{}_{}{}^{194}Pt`$nucleus from one phonon 0+ state with energy 0.6 MeV to the ground state, and in $`{}_{}{}^{196}Pt`$nucleus from one phonon 0+ state with energy 0.57 MeV to the ground state, in 188Os from one phonon 0$`^+`$state - 0.75 MeV to the ground state and in 158Er from one phonon 0+ state - 1.2 MeV to the ground state. We point out again that this is only a prediction produced by one simple model.

Let us consider the simplest transition operator that can be written within the framework of our model :

$$\widehat{E}_0=x(R_++R_{})=x(b^{}\sqrt{2\mathrm{\Omega }b^{}b}+\sqrt{2\mathrm{\Omega }b^{}b}b)$$
(9)
Then in this approach the non-vanishing transition matrix elements are:

$$\begin{array}{c}n\left|\widehat{E}_0\right|n+1=n+1\left|\widehat{E}_0\right|n=\\ \\ x\frac{1}{\sqrt{(n+1)!n!}}0\left|b^n\sqrt{2\mathrm{\Omega }b^{}b}(b^{})^n\right|0+\\ \\ x\frac{1}{\sqrt{(n+1)!n!}}0\left|b^n\sqrt{2\mathrm{\Omega }b^{}b}b^{}b(b^{})^n\right|0\end{array}$$
(10)
Using the commutation relations between the operators $`[b^n,(b^{})^m]`$ :

$$[b^n,(b^{})^m]=\{\begin{array}{c}\underset{l=0}{\overset{n1}{}}\frac{m!}{(mn+l)!}\left(\begin{array}{c}n\\ l\end{array}\right)(b^{})^{mn+l}b^lnm\\ \\ \underset{l=0}{\overset{m1}{}}\frac{n!}{(nm+l)!}\left(\begin{array}{c}m\\ l\end{array}\right)(b^{})^lb^{nm+l}nm\end{array}$$
(11)
for matrix elements (10) we have:

$$\begin{array}{c}n+1\left|\widehat{E}_0\right|n=x\frac{1}{\sqrt{(n+1)!n!}}n\left|\sqrt{2\mathrm{\Omega }b^{}b}\right|n+\\ \\ x\frac{n}{\sqrt{(n+1)!n!}}n\left|\sqrt{2\mathrm{\Omega }b^{}b}\right|n=\\ \\ x\sqrt{2\mathrm{\Omega }n}\sqrt{n+1}=n\left|\widehat{E}_0\right|n+1n0\end{array}$$
(12)
It is suitable to consider the ratio between nuclear matrix elements: $`\rho ^2n\left|\widehat{E}_0\right|n+1^2`$ entering in $`E0`$ transition probabilities:

$$F(n,k)=\frac{n\left|\widehat{E}_0\right|n+1^2}{k\left|\widehat{E}_0\right|k+1^2}=\frac{(2\mathrm{\Omega }n)(n+1)}{(2\mathrm{\Omega }k)(k+1)}$$
(13)
because it does not depend on any additional parameters. Here we proposed that $`x`$ does not change with changing the transition energy $`\mathrm{\Delta }E=E_0(n+1)E_0(n)`$

$`F(n,k)`$ for isotopes under consideration ($`\mathrm{\Omega }=6`$) and $`n=1,2,3,4,5`$ is presented in figure 2. The curves in figure 2. indicate that $`k\left|\widehat{E}_0\right|k+1^2`$ in the region of $`k=38`$ are about four times larger than the $`0\left|\widehat{E}_0\right|1^2`$ values.

Experimental data about the rotational bands in deformed nuclei show that the dependence of the energy on angular momentum$`L`$ is qualitatively similar for the ground band and the bands constructed on any excited $`0^+`$ state . So in the first approximation one may consider the rotational bands constructed on different excited $`0^+`$states without including the band head structure. Nevertheless the influence of $`0^+`$ states structure on the rotational spectra must be included in order to explain the small quantitative differences in rotational bands with different $`0^+`$ band heads as well as transition probabilities, for instance the peculiarities in $`B(E2;2_{K^\pi =0_n^+}^+>0_{g.s.}^+)`$. This investigation is in successful progress. Furthermore the results of this paper may be helpful for more sophisticated analysis of the collective structure of the low-lying nuclear states. Having in mind the results of this paper one can estimate directly the degree of collectivity ( number of bosons ) of any 0+ excited state.

I would like to thank S. Pittel, M.Stoitsov, S. Dimitrova, A. Aprahamian, A. Georgieva and P. Terziev for fruitful discussions and help.

This work has been supported in part by the Bulgarian National Foundation for Scientific Research under project $`\mathrm{\Phi }`$ \- 809.

Captions to the figures.

Figure 1. The comparison of calculated distribution of $`0^+`$ state energies as a function of number of phonons $`n`$ with experiment. Experimental data are taken from tables

Figure 2. Ratio $`F(n,k)`$ (13) for different $`n`$.


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# Monte Carlo simulation of abnormal grain growth in two dimensions

## 1 Introduction

The grain growth processes occurring in polycrystalline materials submitted to an annealing treatment are usually classified into two types. The first type corresponds to a self-similar coarsening process and is called normal grain growth. It is characterised by a uniform increase of the grain size with a time-invariant distribution function. The second type is called abnormal grain growth and is characterised by the coarsening of a few grains at the expense of the surrounding matrix. In such conditions, the self-similar aspect of the coarsening process is lost. In addition, one also distinguishes a particular kind of abnormal grain growth, which is sometimes called "drastic" abnormal grain growth. In this last case, a few grains can invade the whole microstructure during an annealing treatment. The final size of these grains can be two orders of magnitude larger than the grain size of the surrounding matrix grains and, in some cases, a single crystal is eventually obtained. Such heterogeneous microstructures may be highly detrimental to mechanical properties and it is particularly important to avoid their occurrence during the thermo-mechanical processing of fine-grained materials.

Different mechanisms have been proposed to explain abnormal grain growth. A small prestrain can promote the onset of anomalous grain growth by a mechanism of critical strain annealing. In this case, a critical deformation is needed for the growth of a few grains that will consume all the others, the driving force being the energy stored in the deformed grains by dislocation networks. This mechanism has been reproduced with the help of Monte Carlo simulations and fully discussed by Rollettt et al.111A. D. Rollett, D. J. Srolovitz, M. P. Anderson and R. D. Doherty, Acta Metall. 40 (1992) 3475.  Capillary forces, which induce a reduction of the total grain boundary energy, can also be responsible for abnormal grain growth. In this case, normal grain growth of the matrix grains is inhibited by either a texture effect or by the presence of second phase particles. The former situation is well documented. It is characterised by an anisotropy of the grain boundary energy and mobility, as these last quantities depend on the relative misorientation of the grains. Monte Carlo simulations have been performed on textured grain aggregates by Rollett et al.222A.D. Rollett, D.J. Srolovitz and M.P. Anderson, Acta Metall. 37 (1989) 1227.  and Grest et al.333G. S. Grest, M. P. Anderson, D. J. Srolovitz and A. D Rollettt, Scripta Metall. 24 (1990) 661.  and were found in good agreement with the analytical approach proposed by Wörner et al.444C. H. Wörner, S. Romero and P. M. Hazzledine, J. Mater. Res. 6 (1991) 1773.  However, situations are met in equiaxed polycrystals, where no texture is evidenced either after a prestrain or after a further heat treatment, so that this mechanism cannot be involved.

The present study was motivated by the observation of abnormal grain growth in several nickel base superalloys for high temperature applications produced by powder metallurgy techniques.555M. Soucail, M. Marty and H. Octor, Scripta Metall. 34 (1996) 519. , 666R. Messina, M. Soucail, T. Baudin and L.P. Kubin, J. Appl. Phys. 84 (1998) 6366.  The microstructure of these alloys is made up principally of an austenitic $`\gamma `$ matrix, exhibiting no significant texture and hardened by several families of L12 ordered $`\gamma ^{}`$ precipitates. The composition of these two phases is based on Ni3Al, with significant amounts of other elements like Co, Cr and Ti. Moderate or drastic abnormal grain growth was found to occur during heat treatments performed above the $`\gamma ^{}`$ solvus (typically at 1205$`\mathrm{°}`$C). In such conditions, the only precipitates that remain stable in the alloy are incoherent oxy-carbide particles, which are preferentially located at the previously existing precipitate boundaries with a volume fraction of about 0.1%. These particles should effectively play the role of obstacles to grain boundary migration, due to their small diameter (about 100 nm) and spacing, and should normally impede normal as well as abnormal grain growth. The models by Hillert777M. Hillert, Acta Met. 13 (1965) 227.  and Andersen et al.888I. Andersen, Ø. Grong and N. Ryum, Acta Metall. 43 (1995) 2689.  refer to such a situation and are frequently invoked to explain the experimental results. However, numerical simulations have not up to now been able to check the predictions of these models.999D. J. Srolovitz, G. S. Grest and M. P. Anderson, Acta metall. 33 (1985) 2233.

Monte Carlo simulations were carried out in a model material consisting of an equiaxed, fully recrystallized and isotropic grain structure containing a fine dispersion of stable precipitates. A few useful definitions are briefly recalled in Part 2, where, in addition, the bases of the Monte Carlo simulation are outlined. The numerical results obtained in the absence or presence of thermally activated unpinning of grain boundaries from precipitates are reported in part 3. These results are discussed in part 4.

## 2 Numerical model

The numerical procedure used in the present work is similar to the one employed in previous studies.101010M. P. Anderson, D. J. Srolovitz, G. S. Grest and P. S. Sahni, Acta Metall. 32 (1984) 783. ,111111D. J. Srolovitz, M. P. Anderson, G. S. Grest and P. S. Sahni, Acta Metall. 32 (1984) 1429.  It is described in detail elsewhere.121212M. Soucail, R. Messina, A. Cosnuau and L. P. Kubin, Mater. Sci. Eng. A 271 (1999) 1. , 131313R. Messina, Doctoral thesis, University Paris-Sud, (1998) Orsay.  Use is made of a two-dimensional triangular lattice, with periodic boundary conditions. To each lattice site Si is associated a crystallographic orientation, represented by a number Q ranging between 1 and 1000. A grain is defined as an ensemble of adjacent sites having same orientation. The initial microstructure is obtained by distributing at random the crystallographic orientations on the lattice sites, which results in an initial microstructure containing grains of uniform size and of dimension one lattice site.

The particles are represented by fixed sites having a particular orientation, Si= 0. In two dimensions, and for incoherent particles, the pinning force is entirely determined by the line tension of the grain boundaries.141414E. Nes, N. Ryum and O. Hunderi, Acta Metall. 33 (1985) 11.  Thus, the interfacial particle-matrix energy is assimilated the grain boundary energy per unit length J. In the initial microstructure the particles are distributed at random with a surface fraction f whose value is 0.5, 1 or 2%. In what follows, we focus on the simulation results obtained with f = 2%.

The Hamiltonian H of the system is written

$$H=\frac{1}{2}J\underset{i=1}{\overset{N}{}}\underset{j=1}{\overset{nn}{}}\left(1\delta _{S_iS_j}\right),$$
(1)
where $`\delta `$ is the Kronecker symbol and J is a constant, assuming that the microstructure is made up of an equiaxed and non-textured polycrystal containing large-angle boundaries with isotropic energy. The sum is taken over all nearest neighbours (nn). The evolution of the microstructure is simulated with the help of a Monte Carlo scheme. A site is chosen at random and its orientation is randomly changed to one of the other (Q-1) orientations. If the resulting total variation in energy, $`\mathrm{\Delta }`$H, is negative or null, the reorientation is accepted. If the change in energy is positive, the reorientation is accepted with the Boltzmann probability

$$P=exp\left(\frac{\mathrm{\Delta }H}{kT}\right)$$
(2)
As the Hamiltonian only includes the grain boundary energy, the only driving force for grain growth included in the simulation is a capillary force. The time scale of the simulation is assimilated to the Monte Carlo Step (MCS), i.e., to the time corresponding to one reorientation attempt on all the sites that do not contain a particle. A first set of simulations, performed at the absolute zero of temperature, will be presented in the next section. The case of non-zero temperatures is also considered, since the thermally activated unpinning of grain boundaries from particles is a plausible event at high temperature.

According to the two dimensional models of Hillert7 and Andersen et al.8, a necessary condition for obtaining abnormal grain growth is the pre-existence of grains of size larger than the average size of the matrix grains. We define by $`D_{ab}`$, $`\overline{D}`$ and $`\overline{D}_{lim}`$ the initial diameter of the future abnormal grain, the current mean diameter of the matrix grains and the stagnant (i.e., final) value of $`\overline{D}`$, respectively. The results of the models can then be expressed in terms of two reduced parameters, the diametrical size advantage, $`D_{ab}/\overline{D}`$, and $`\overline{D}/\overline{D}_{lim}`$ the degree of matrix pinning. The criteria for abnormal grain growth are written as follows :

$$\frac{dD_{ab}}{dt}>0$$
(3)
and

$$\frac{d}{dt}\frac{D_{ab}}{\overline{D}}>0.$$
(4)
Eq. (3) simply expresses that the large grain must grow, while Eq. (4) expresses the condition that it must grow faster than the matrix grains. This last condition destroys the self-similarity of the coarsening process, which characterises normal grain growth. However, As was shown numerically by Srolovitz et al.9, the pre-existence of large grains is not a sufficient condition to obtain abnormal grain growth and one must consider, in addition, the influence of the particles on the growth process. Their effect is essentially to reduce the local curvature of the matrix grains and, therefore, their capillary driving force. As a consequence, a large grain may, then, be submitted to a driving force larger than that of the matrix grains and grow at a sufficient rate to fulfil the second criterion for abnormal growth \[Eq. (4)\].

In the present simulations, a large test grain with a pseudo-circular shape and an adjustable diameter is initially introduced into a matrix structure. The latter may have an average initial grain size $`\overline{D}_o`$ of one site, or may have been previously subject to a sequence of uniform growth in order to increase its initial degree of pinning. The initial value of the size advantage,$`\left(D_{ab}/\overline{D}\right)_o`$ is fixed to a value of about 3, except if stated otherwise. This initial value is implemented within a minor error due to the discrete nature of the simulation. Because the growing grains sometimes exhibit irregular shapes, it is convenient to monitor their growth by measuring their area. As a consequence, we make use in what follows of a reduced area advantage, $`A_{ab}/\overline{A}`$, and a reduced area degree of pinning, $`\overline{A}/\overline{A}_{lim}`$. These two quantities are obviously identical to the equivalent diameters squared.

## 3 Results

### 3.1 Mechanical approach (T = 0 K)

In a first step, we consider a pure mechanical approach (T = 0 K) and investigate the role of the pinning degree of the matrix grains on the coarsening process of a large test grain. The stagnant matrix grain size is known from a previous simulation study12 on Zener pinning, i.e., on the pinning of uniformly growing grains in the presence of precipitates.151515C. S. Smith, Trans. metall. Soc. A.I.M.E. 175 (1948) 15.  Fig. 1(a) shows the evolution with time of the mean grain size of a polycrystal containing a surface fraction f = 2% of particles. The driving force for grain growth in the presence of particles is provided by the grain boundary curvature, which decreases with increasing time and mean grain size. A steady pinned configuration is obtained after a certain amount of time, when the driving force becomes insufficient to overcome the Zener drag. As was shown recently, such a steady state can also be obtained by a deterministic approach.161616D. Weygand, Y Bréchet and J. Lépinoux, Acta Metall. 47 (1999) 961.  The stagnant microstructure corresponding to the conditions of Fig. 1(a) is represented in Fig. 1(b).

A potentially anomalous grain with an initial reduced size advantage $`(D_{ab}/\overline{D})_03`$ is then inserted into matrix structures with various degrees of pinning. The evolution with time of the area Aab of the test grain and of the reduced area advantage, $`A_{ab}/\overline{A}`$, are shown in Figs. 2(a) and (b), respectively. Here and in what follows, the surface fraction of particles is f = 2%.

The ratio $`A_{ab}/\overline{A}`$ increases monotonically with time and further saturates, provided that the initial degree of pinning is sufficiently large. Hence, the test grain can grow abnormally only if the matrix grains are not too far from their limit size. When the initial degree of pinning is small and the matrix grains are highly mobile, no abnormal grain growth occurs because the size advantage of the large grain gradually vanishes during the growth process. Figure 3 shows a sequence of microstructural evolution leading to abnormal grain growth. One can notice that the matrix has not evolved significantly in comparison to the large grain.

The initial pinning degree of the matrix grains is now fixed to a value ($`\overline{D}/\overline{D}_{lim}`$)o and the initial size advantage of the large grain is varied. Figs. 4(a) and (b) show the evolution of the area Aab and of the reduced area advantage, $`A_{ab}/\overline{A}`$, of the large grain for different values of the initial size advantage. The large grain grows when the size advantage is beyond a certain critical value and shrinks otherwise \[cf. Fig. 4(a)\]. The growth is abnormal in the sense of equation 4 when the initial size is above a second critical value \[cf. Fig. 4(b)\], which is larger than the first one (cf. Fig. 6, below). This confirms an assumption of the analytical models,7,8 according to which the pre-existence of a large grain is necessary for abnormal grain growth to occur.

The size of the test grain saturates after a certain amount of time and the whole microstructure is then immobilised by Zener pinning. The large grain becomes pinned after the matrix grains, since it has a larger driving force governing its growth. Fig. 5 shows a sequence of microstructural evolution starting with an initially pinned microstructure, $`\overline{D}_o=\overline{D}_{lim}`$, and an initial size advantage $`\left(D_{ab}/\overline{D}\right)_o=6`$. This situation approximately corresponds to the one studied by Srolovitz et al.,9 where no abnormal grain growth was observed. In Fig. 3, one can see that several unpinning events have occurred on the boundary of the test grain before it became fully stabilised. In contrast, no unpinning occurs in the sequence of Fig. 5, although the size advantage is larger. The boundary of the abnormal grain moves until it reaches the nearest particles. Then, it adopts a minimum energy configuration with straight segments of boundaries between the pinning particles.

The previous results are synthesised in Fig. 6, which shows a map of the different types of behaviour obtained, viz. abnormal grain growth, grain growth but no abnormal growth and grain shrinkage, as a function of the initial values of the reduced size advantage and pinning degree. This diagram confirms that for abnormal grain to occur, the initial relative size ($`D_{ab}/\overline{D}`$)o must be within a certain range of values whose upper bound is about 4. This suggests that the condition of Eq. (4), according to which the growth rate of the large grain must be larger than that of the matrix grains, is more difficult to fulfil when the initial size advantage is too large. The reason can be better understood by expressing the second condition for abnormal grain growth \[Eq. (4)\] as follows :

$$\frac{dD_{ab}}{dt}\mathrm{/}\frac{d\overline{D}}{dt}>\frac{D_{ab}}{\overline{D}}.$$
(5)
One can see from Eq. (5) that with a larger initial size advantage, a larger growth rate of the test grain is required to fulfil the criterion. Srolovitz et al.9 concluded from their simulations that abnormal grain growth is not possible in equiaxed materials containing particles when the only driving force is of capillary nature. However, this conclusion was reached from a study involving too large size advantages and we see from the present results that an intermediate domain can be defined where abnormal grain growth is, indeed, possible.

Finally, the type of abnormal grain growth that has been obtained so far can be considered as moderate, but certainly not as drastic (cf. for instance Fig. 3). The objective of the next sections is to understand in which conditions the present simulation can reproduce the experimental observations of drastic abnormal growth.

### 3.2 Thermal unpinning

As drastic grain growth is experimentally a high temperature feature, it may be necessary to account for the possibility of a thermally activated detachment of the grains from the pinning particles. Such an effect was already studied analytically by Gore et al.171717M. J. Gore, M. Grujicic, G. B. Olson and M. Cohen, Acta Metall. 37 (1989) 2849.  and with the help of extensive Monte Carlo simulations by Miodownick et al.,181818M. Miodownik, E. A. Holm and G. N. Hassold, Scripta Metall. 42 (2000) 1173.  in the case of homogeneous grain growth in the presence of pinning particles.

In our simulation, such a mechanism can be achieved by allowing site re-orientations, which involve the unpinning of a grain boundary and lead to an increase of the energy of the system, to be conditionally accepted with a Boltzmann probability. Thus, in this first step, it is simply assumed that the reduced energy J/kT is not too large, so that the unpinning probability is significant. Site reorientations involving no pinning events are treated in a purely mechanical manner (T = 0 K). The initial microstructure consists of structure of pinned grains, like the one of Fig. 2. A single test grain test is introduced in the pinned microstructure and from the beginning of the simulation, the temperature is set to a non-zero value.

Fig. 7 shows the evolution of a large test grain as a function of the reduced temperature. Abnormal grain growth is never obtained within the range of reduced temperatures considered here, 0.2 J/k \< T \< 0.6 J/k. In addition, an apparently paradoxical behaviour is obtained. The higher the temperature, the earlier the size advantage, $`D_{ab}\mathrm{/}\overline{D}`$, starts decreasing. Indeed, one may expect a priori that the size advantage should increase with time, all the more as temperature increases. The interpretation of this particular behaviour is postponed to the discussion part. Finally, Fig. 8 shows a typical microstructural evolution at a temperature T = 0.4 J/k. Similar results, not shown here, were obtained with other values of the particle volume fraction, 0.5% and 1%, as well as with other values of the particle size (3 and 7 sites).13 As will be discussed in the next section, the reason for the absence of abnormal growth stems from the too rough treatment of the unpinning events.

### 3.3 Selective thermal unpinning

The discrete simulation attributes the same activation energy for unpinning to the small and the large grains. However, it is important to have in mind in mind, that in conditions favourable for abnormal grain growth, the small grains are subject to a smaller capillary driving force than the large ones. Hence the corresponding activation energy should be increased accordingly. As the present simulation is not refined enough to describe the local configurations of the pinned grain boundaries and include this effect, the difference in energy barrier between the large and small grains is incorporated into the Metropolis criterion in a very simplified manner. The method employed is illustrated by Fig. 9. Between two pinning events, the boundaries of the test grain evolve according to the capillary force i.e., the local curvature, and its motion is not thermally activated. When the boundary is pinned by a particle, the probability for thermal unpinning is considered. For the small grains, the probability for thermal unpinning is assumed negligible and only mechanical unpinning can occur. This rather crude procedure may seem to drive the final result but, as discussed in the next part, it can be justified in physical terms.

Fig. 10 shows the evolution of the reduced area $`A_{ab}\mathrm{/}\overline{A}`$ of the abnormal grain as a function of time and for different reduced temperatures. Drastic abnormal grain growth does occur above a critical temperature Tc $``$ 0.2 J/k and qualitatively follows an Arrhenius type of behaviour. Fig. 11 shows the microstructural evolution at T = 0.3 J/k of a polycrystal containing a large circular grain, initially introduced in a pinned matrix structure. In such conditions, an initial size advantage of about 3 is sufficient for the large grain to invade the whole microstructure. Similar results, not reported here, were obtained with other values of the particle surface fraction (0.5% and 1%). It was also checked that such a strong abnormal grain growth occurred with two other particle sizes, 3 and 7 sites. This type of behaviour strongly contrasts with the moderate growth of the large grain obtained in the absence of selective unpinning. Below T = 0.2 J/k, this drastic abnormal growth behaves as a transient process. The whole microstructure, including the large grain, becomes eventually pinned when the driving force is no longer sufficient to overcome the Zener drag.

## 4 Discussion

In the present study, the pre-existence of a large grain has systematically been assumed and an initial size advantage was confirmed to be a necessary condition for obtaining abnormal grain growth. The presence of these large grains can be explained as follows. The thermo-mechanical treatment induces a weak primary recrystallization, thus generating a few fresh grain embryos. The latter may further grow at the expense of the deformed matrix grains. For this process to occur, it is sufficient to slightly predeform the material close to a critical deformation value.13,191919C. Antonione, F. Marino, G. riontino, and M. C. Tabasso, J. Mater. Sci. 12 (1977) 747.  The driving force for this primary recrystallization step is, then, provided by the stored energy accumulated during the prestrain. When this driving force is exhausted, the coarsening process can only continue under the influence of the capillary driving force.

A second condition for abnormal grain growth is that the mobility of the matrix grain boundaries must be sufficiently reduced by pinning effects. This allows the large grain to outgrow the surrounding matrix grains. When the matrix grain boundaries are too mobile, i.e. when $`\overline{D}/\overline{D}_{lim}`$ is small, the large grain may grow but not in an abnormal manner. This situation is similar to the one encountered in the absence of precipitation, when a large grain is introduced in a matrix governed by normal grain growth. It has been shown both analytically202020C. V. Thompson, H. J. Frost and F. Saepen, Acta metall. 35 (1987) 887.  and numerically,9 that such a large grain becomes rapidly incorporated into the steady-state distribution function characterising normal grain growth. Therefore, a significant initial perturbation is necessary in order to destabilise the uniform growth process.

The map of coarsening behaviour shown in Fig. 6 agrees well, in qualitative terms, with the predictions of the model by Andersen et al.8 In both cases, an upper limit is predicted for the initial size advantage leading to abnormal grain growth. Such a feature is absent from the classical model of Hillert.7 Indeed, Hillert’s approach is a pure mean-field model, whereas the approach by Andersen et al.8 combines a mean-field aspect with a local aspect. The latter is associated with a fine description of the geometry of the interface between the large grain and the surrounding matrix grains. The mean-field aspect resides in the assimilation of the matrix grain structure to a regular honeycomb structure, as first proposed by Gladman.212121T. Gladman, Proc. R. Soc. A 294 (1966) 298.

It is interesting to compare the present results with those obtained in the absence of particles with anisotropic materials, i.e., with anisotropic grain boundary energy and/or mobility. In the case of a mobility advantage and a constant grain boundary energy, simulations2,3 as well as the model by Wörner et al.4 show that abnormal grain growth also occurs within a range of values of the initial size advantage. Quite generally, a factor has to inhibit normal grain growth, which can be provided by local pinning, textural effects or surface energy anisotropy.

As drastic abnormal coarsening is not obtained within a pure mechanical approach, an attempt was made in section 3.2 to account for thermal effects. The physical idea consists in taking into account thermal detachment and noting that this later should be easier when the driving force for grain boundary motion is larger. This was simply performed by treating the unpinning of the grain boundaries from the second phase particles via the Metropolis criterion. As a result, it was found that the tendency to abnormal grain growth was not enhanced but reduced, even at elevated reduced temperatures (cf. Fig. 8). The obvious reason for this unphysical behaviour is that the abnormal grain and the matrix grains are able to pinch off the particles with the same probability, since the activation energy is not indexed on the local driving force due to the discrete lattice structure. As a result, the advantage provided by the particles to the large grain, due to the reduction of the average curvature radius of the small grains, is destroyed. Indeed, in a more realistic (continuous) approach, the thermally activated unpinning of the grain boundaries should be easier for the abnormal grains, due to their larger mean curvature, than for the small matrix grains.17,21,222222C. H. Wörner and A. Olguin, Scripta Metall. 28 (1992) 1.  A similar behavior was observed for all particle sizes (1, 3 and 7 sites). This is in agreement with theory since, in 2D, the maximal pinning force is written $`F_{pin}=2\gamma _l`$, where $`\gamma _l`$ is the grain boundary line tension, and does not depend on the particle size.14 In contrast, one has $`F_{pin}\gamma _sr`$ in 3D, where $`\gamma _s`$ is the grain boundary surface tension and r is the average radius of the particles.14 This explains why in recent 3D simulations the pinning and unpinning properties of a single grain boundary were found to strongly depend on the particle size.232323M. Miodownik, J. W. Martin and A. Cerezo, Phil. Mag. A79 (1999), 203.

The present procedure leading to drastic abnormal grain growth may seem a bit rough. Restricting thermal activation to the pinning sites that involve the boundaries of the large grain indeed favours the growth of the latter. However, although this method may be considered as an ad hoc one, it is not devoid of physical meaning. It simply consists of replacing a continuum energy spectrum that is distributed over two rather different populations by two average characteristic states. It is possible to verify that this method does not oversimplify too much the dependence of the energy barrier on the driving force. For this purpose, one specific grain of the pinned matrix was selected and allowed to thermally pinch off the particles. As can be seen from Fig. 12, this grain does not grow faster than the surrounding matrix at a temperature T = 0.3J/k, while in the same conditions the dimension of the large grain significantly increases (cf. Fig. 11). This result shows that the dependence of the energy barrier on the driving force of a specific grain is well reproduced in a qualitative manner. It also illustrates in a qualitative way how the coupled effect of a critical size and non-zero temperature is needed to trigger true anomalous grain growth.

Wörner and Olguin22 have shown that thermal unpinning becomes significant for particle sizes smaller than about 100 nm, low particle volume fractions (smaller than 0.3%) and sufficiently high annealing temperatures (about 1000$`\mathrm{°}`$C). These values are quite consistent with the experimental ones in the case of a nickel-based superalloy  (cf. part 1). In such conditions and with a grain boundary energy of typically 1.5 J/m2, the energy barrier is estimated to about 0.6 eV for the abnormal grain. The ratio kT/J should then be about 0.2, which is within the range investigated in the present study. Experimentally, abnormal growth is obtained after annealing at 1205 $`\mathrm{°}`$C for 4 hours. For longer annealing times, the drastic coarsening process is such that one single grain invades the whole microstructure, as is also the case in the present simulation.

## 5 Conclusion

The simulation of abnormal grain growth in polycrystalline aggregates has yielded the main following results, that are qualitatively independent of the particle surface fraction within the range investigated in the present study.

1. The moderate growth of a test grain under the effect of capillary forces can be effective in polycrystalline materials with equiaxed grains containing stable particles.

2. The simulations confirm that two interdependent reduced parameters, the reduced abnormal grain size and the reduced matrix mean grain size, govern the occurrence of this growth process.

3. For moderate grain growth to occur, the initial size advantage of the "abnormal" grain has to lye between an upper and a lower bound. In addition, the matrix grain boundaries must be sufficiently pinned by second phase particles. These results are in good agreement with the recent model by Andersen et al.8

4. True abnormal grain growth in an equiaxed and isotropic matrix containing stable particles can be described as resulting from a thermally activated unpinning process. It is still conditioned by an initial size advantage and is enhanced by the effect of the capillary driving force on the large grain.

FIGURE CAPTIONS

FIG. 1. a) - Evolution of the mean grain area $`\overline{A}`$ (number of sites) with Monte Carlo Step number, for a microstructure containing an area fraction of particles f = 2%.

b) - The corresponding pinned microstructure.

FIG. 2. Evolution with time of a test grain, for a fixed size advantage $`\left(A_{ab}/\overline{A}\right)_0=\left(D_{ab}/\overline{D}\right)_0^210`$, and for different values of the initial degree of matrix pinning, $`\overline{D}_0/\overline{D}_{lim}`$, given in the insert. a) - Absolute area, Aab. b) \- Reduced area, $`A_{ab}/\overline{A}`$.

FIG. 3. A typical microstructure exhibiting abnormal grain growth. The initial conditions are $`\left(D_{ab}/\overline{D}\right)_0=3`$ and $`\overline{D}_0/\overline{D}_{lim}=0.9`$.

FIG. 4. Evolution of the area of the test grain for a fixed degree of pinning of the matrix grains, $`\overline{D}_0/\overline{D}_{lim}=0.9`$ and for various values of the relative size of the test grain, $`D_{ab}/\overline{D}_0`$, given in the insert. a) - Absolute area, Aab. b) \- Reduced area, $`A_{ab}/\overline{A}`$.

FIG. 5. Microstructural evolution of a large grain (with initial size advantage $`\left(D_{ab}/\overline{D}\right)_0=6`$) embedded in an initially pinned polycristal ($`\overline{D}_0/\overline{D}_{lim}=1`$). No abnormal grain growth occurs.

FIG. 6. Map of the behaviour of the test grain in a plot of size advantage $`\left(D_{ab}/\overline{D}\right)_0`$ vs. pinning degree ($`\overline{D}_0/\overline{D}_{lim}`$). The three types of behaviour observed are abnormal grain growth (AGG), grain growth (GG) and grain shrinkage (GS).

FIG. 7. Thermal unpinning. Evolution of the reduced area advantage, $`\overline{A}_{ab}\mathrm{/}\overline{A}`$, for different values of the temperature T, expressed in units of J/k. The initial size advantage of the large grain is about 3.

FIG. 8. Microstructural evolution in conditions where thermal unpinning of the grain boundaries from the precipitates is effective (T = 0.4 J/k). The initial size advantage of the large grain (in the centre of the simulation) is about 3. No abnormal grain growth is observed.

FIG. 9. Schematic procedure for simulating the thermally activated unpinning of the boundaries of the abnormal grain. Three types of sites are particularised. Sites P contain a particle, sites L belong to the large abnormal grain and site S to a small grain. A Boltzmann reorientation is accepted only if the considered site belongs to a small grain and is simultaneously adjacent to a particle and to the abnormal grain.

FIG. 10. Evolution of the relative size, $`A_{ab}/\overline{A}`$, of the abnormal grain for different temperatures. Thermally activated unpinning is restricted to the boundaries of the abnormal grain. The initial size advantage of this grain is 3.

FIG. 11. Microstructural evolution in the case of selective thermal unpinning (T = 0.3 J/k). The initial size advantage of the large grain is about 3. True abnormal grain growth is observed.

FIG. 12. Effect of the thermally activated grain boundary unpinning on a particular matrix grain (in grey). The temperature is T = 0.3 J/k and the initial microstructure is similar to the one of Fig. 2. No significant evolution of this grain is observed.


text:
# Experimental Signatures of Anomaly Induced DCC Formation

## Abstract

We discuss characteristic experimental signatures related to the formation of domains of disoriented chiral condensate (DCC) triggered by the axial anomaly in relativistic heavy ion collisions. We predict that the enhancement of the fraction of neutral pions compared to all pions depends on the angle of emission with respect to the scattering plane and is concentrated at small transverse momentum and small rapidity in the center-of-mass frame. The anisotropy with respect to the reaction plane is also observable in the inclusive photon distribution.

preprint: KUNS-1748,TMUP-HEL-0018,DUKE-TH-01-206

The experimental search for domains of disoriented chiral condensate (DCC)  in high-energy heavy-ion collisions is under way. The first results were negative , but this may be due to a variety of experimental limitations, such as beam energy, pion momentum range, and event selection. In two previous papers, we demonstrated that the axial anomaly may enhance the formation of DCC domains in non-central nuclear collisions . Here we present an important new result concerning the observational characteristics of DCC’s created by the anomaly mechanism. We show that they will exhibit a very specific property, in that the ratio of neutral to charged pions will depend on the angle of emission with respect to the nuclear scattering plane.

The anomaly mechanism for the creation of DCC domains is based on the effective interaction $`_{\mathrm{int}}=(\alpha /\pi f_\pi )\stackrel{}{E}\stackrel{}{B}\varphi ^0`$ . In non-central relativistic heavy ion collisions this interaction generates a (classical) source for the neutral pion field $`\pi ^0`$ in the form of an almost instantaneous “kick”. The short duration of the anomalous interaction, of the order of collision time, begs the question whether the use of the effective pion field is justified, or whether the electromagnetic field should rather be microscopically coupled to the quark degrees of freedom. In response, we recall that the anomaly term precisely describes the low-energy limit of the interaction between on-shell photons and the quarks in the neutral pseudoscalar channel. The short time scale of the anomalous interaction is effectively taken into account by using an uniformly “kicked” initial field configuration in our previous treatment in refs. .

For far off-shell photons, the coupling is suppressed by a form factor , but this effect is expected to be small here, because the coherent nuclear electromagnetic field corresponds to nearly on-shell virtual photons. Furthermore, we only consider the effect of the anomalous interaction on pion field modes with momenta far below the chiral symmetry-breaking scale $`\mathrm{\Lambda }_{\mathrm{ch}}1`$ GeV. Finally, the temperature dependence of the anomalous electromagnetic interaction of the neutral pion  needs to be considered. Strictly speaking, the anomaly provides a temperature-independent source term for the dynamics of the axial current $`j_5^\mu `$. As the temperature approaches the critical temperature $`T_c`$ for chiral symmetry breaking, the axial current is less and less dominated by single-pion excitations. Accordingly, the pion coupling to two photons decreases and vanishes at $`T_c`$ . In principle, the treatment of the anomaly term should be based on the full dynamics of the axial current, rather than the pion field alone. However, since we are interested in the effects of the interaction at very early times (the “anomaly kick” occurs before thermalization) and at late times (after the assumed rapid quench to conditions below the QCD critical temperature), where the axial current is again dominated by the dynamics of the pion field, the treatment in terms of the low-energy effective interaction appears to be a plausible first approximation.

We now turn to our original question of the possible characteristic signatures of the DCC formation triggered by the anomaly effect. We here focus on the (previously ignored) correlation between the ion scattering plane and the $`\pi ^0/\pi `$ ratio. Due to the linear dependence of the electromagnetic invariant $`\stackrel{}{E}\stackrel{}{B}`$ on the impact parameter, the chiral anomaly generates a “kick” on the collective pion field only in collisions with a nonzero impact parameter . In these non-central collisions one can use collective flow patterns of the produced hadrons to define a collision plane on an event-by-event basis . We choose the $`x`$-$`z`$ plane as the collision plane, taking the $`z`$-direction along the beam axis, and the $`y`$-axis normal to the collision plane. Because $`\stackrel{}{E}\stackrel{}{B}`$ is an odd function of $`y`$, the anomaly term has a characteristic dependence on the momentum component normal to the collision plane, $`k_y`$, rather than on the momentum components $`k_x`$ and $`k_z`$.

Therefore, one would expect that the coherent pion field excitation due to the anomaly kick would result in the preferential emission of pions with values of $`k_y`$ that are small (reflecting the spatial coherence of the source) but nonzero. In fact, there should be no effect of the kick at all to pions with $`k_y=0`$, since $`_{\mathrm{}}^{\mathrm{}}𝑑y\stackrel{}{E}\stackrel{}{B}=0`$ for a fixed $`x`$ and $`z`$. This argument remains valid also beyond perturbation theory because of the coherence of the source. Following the procedure outlined in Section IV. E of ref. , we have evaluated the $`\pi ^0/\pi `$ ratio as a function of the azimuthal angle $`\varphi `$ around the beam axis. The direction $`\varphi =0^{}`$ coincides with our choice of the $`x`$-axis. According to the above, we expect an increase in the $`\pi ^0/\pi `$ ratio for emission near the angles $`\varphi =90^{}`$ and $`\varphi =270^{}`$.

In order to test this hypothesis, we have generated 1000 events following the procedure described in ref. . The anomaly kick parameter $`a_n`$ defined in ref.  has been taken to be 0.1. The size of the anomaly kick expected in Au + Au collisions at $`\sqrt{s}=200`$ GeV/A at the Relativistic Heavy Ion Collider (RHIC) at Brookhaven National Laboratory is of this order. We did calculations both for an infinitely extended system with $`R_0=\mathrm{}`$ and for a finite system with $`R_0=5`$ fm in the transverse direction, where $`R_0`$ is defined in eq. (22) of ref.  and represents the transverse extension of the system. The other parameters are the same as those used in ref. . Our results are shown in Figs. 1 and 2, presenting the dependence of the ratio $`n_{\pi ^0}/n_\pi `$ of low momentum pions ($`|\stackrel{}{k}|<250`$ MeV) as a function of the azimuthal angle $`\varphi `$. The three different curves represent the results at different times: $`\tau =1`$ fm (initial time, solid line), $`\tau =6`$ fm (dashed line), and $`\tau =11`$ fm (dash-dotted line).

The angular distributions clearly show the expected behavior. As described in our earlier work, the $`\pi ^0/\pi `$ ratio is overall enhanced for the low momentum pions (see Fig. 20 of ref. ), but the enhancement exhibits strong peaks near $`\varphi =90^{}`$ and $`\varphi =270^{}`$, i.e. for emission normal to the scattering plane. The directional peak structure somewhat diminishes with time, but clearly survives until the final moments in our calculations. The magnitude of the effect and the width of the peaks depend on the size of the region affected by the coherent excitation, indicating that the spatially coherent source term provided by the axial anomaly is an essential ingredient of the effect.

The predicted azimuthal anisotropy of the $`\pi ^0/\pi `$ ratio provides a clear, and most likely unique, signature of DCC domain formation triggered by the chiral anomaly. Its detection relies on the ability to determine the orientation of the collision plane by means of collective flow patterns in the distribution of emitted particles. At high energies, the flow in the central rapidity region exhibits an elliptical (or quadruple) distribution in the azimuthal angle $`\varphi `$ . This effect has been observed in Pb+Pb collisions at the CERN-SPS  and has recently also been confirmed for Au+Au collisions at RHIC . Both elliptical flow and the anomaly effect are characteristic for collisions with a nonzero impact parameter and absent in central collisions.

Another characteristic signature for anomaly induced DCC formation would be the strong $`Z`$-dependence of the low-$`k_y`$ enhancement, which should serve as a confirmation of the electromagnetic nature of the anomaly effect. To reveal this dependence, we repeated the simulation with $`R=5`$ fm for three different values of $`Z`$, expressed as three different values of the kick amplitude $`a_n`$. The results are shown in Fig. 3, presenting the dependence of the ratio $`Rn_{\pi ^0}/n_\pi `$ of low momentum pions ($`|\stackrel{}{k}|<250`$ MeV) as a function of the azimuthal angle $`\varphi `$. $`\tau `$ is fixed at 11 fm. The three different curves of $`R`$ represent the results at different $`a_n`$: 0.05 (dashed line), 0.1 (solid line), and 0.2 (dash-dotted line).

If we fit the peak value of $`R`$ by using the function $`c+b(a_n)^\alpha `$ we obtain $`\alpha 1.8`$. Since $`a_n`$ scales as $`Z^2`$, our simulation indicates that the $`Z`$-dependence of the anomaly effect is roughly consistent with $`Z^4`$ dependence. Assuming that the directional dependence of the neutral-to-charged pion ratio is observed, it will be interesting to study the $`Z`$-dependence of this effect. Here we note only that, in practice, the $`Z`$-dependence will be partially obscured by the unavoidable dependences on various other experimental parameters, e.g. the nuclear radii, the impact parameter, and the initial energy density, which all vary with nuclear size. These factors must be taken into account in the interpretation of the experimental data.

An important phenomenological question is whether the anisotropy of the neutral pion distribution gives rise to an anisotropy of the inclusive photon distribution. If this were the case, its experimental observation would be greatly simplified, as it would not be necessary to reconstruct the $`\pi ^0`$ distribution from two-photon coincidences. In the high-multiplicity environment of relativistic heavy-ion collisions, such a reconstruction is only possible on a statistical basis. We have therefore, calculated the azimuthal dependence of the inclusive photon distribution resulting from the calculated neutral pion distribution. The result, shown in Fig. 4 for photons with $`0<k_T<500`$ MeV, clearly shows that the azimuthal anisotropy persists in the photon yield. Most of the anisotropy is due to photons with momentum $`k_T<250`$ MeV.

In conclusion, we have shown that model simulations in the framework of the linear sigma model predict that the $`\pi ^0/\pi `$ ratio shows an enhancement for pions emitted perpendicular to the scattering plane when the formation of DCC domains is aided by the chiral anomaly. The effect is most pronounced at low, but non-vanishing transverse pion momenta and at intermediate heavy ion impact parameters, and for collisions of heavy nuclei. The anisotropy is also observable in the inclusive photon spectrum from the decaying neutral pions.

Acknowledgments: B.M. wishes to thank the Japan Society for the Promotion of Science for support which made his visit to Tokyo Metropolitan University possible. H.M. thanks the MIT Center for Theoretical Physics for its warm hospitality. This work was supported in part by a grant from the U. S. Department of Energy (DE-FG02-96ER90945), and by Grants-in-Aid for Scientific Research No. 11640271 and No. 12640285, the Japan Society for the Promotion of Science.


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# Orbital polarons and ferromagnetic insulators in manganites

## I Introduction

The interplay between the magnetic and electric properties of $`R_{1x}A_x`$MnO3 ($`R`$ is a trivalent rare-earth ion and $`A`$ is a divalent alkaline-earth ion) has been extensively studied in the light of basic physics as well as their technological importance.  La/Sr and La/Ca based compounds La1-xSrxMnO3 and La1-xCaxMnO3 are metallic below the Curie temperature for 0.15 $`<`$ $`x`$ $`<`$ 0.5. While the transport properties of the La/Sr system with $`x`$ = 0.3 are well described by the conventional double exchange theory,  the La/Ca system ($`x`$ $``$ 0.3) shows the colossal magnetoresistance (CMR) behavior which cannot be explained by the double exchange mechanism.  Neutron diffraction and x-ray absorption measurements of the La/Ca system indicate that the small magnetic polarons, in which spins are ferromagnetically aligned, play a role in the CMR effect.  Recently, it was suggested that phase separation between the ferromagnetic metal (FM) region and the antiferromagnetic insulator (AFI) region is essential for the CMR behavior  and, actually, the coexistence of the FM and AFI clusters has been observed in La/Ca.  On the other hand, Pr1-xCaxMnO3 is insulating for all $`x`$; it has the AFI phase for 0.3 $`<`$ $`x`$ $`<`$ 0.5 and the ferromagnetic insulator (FI) phase for 0.1 $`<`$ $`x`$ $`<`$ 0.3  although the structural details are still not elucidated.  It has been reported that in the Pr/Ca system, while the magnetic moments are almost ferromagnetically aligned for $`x`$ $``$ 0.2, they are canted for $`x`$ $``$ 0.1 and 0.3, namely, near the boundary between the AFI and FI phases.  Recently, it has been found that the La/Sr system of 0.10 $`<`$ $`x`$ $`<`$ 0.15 exhibits a FI behavior at low temperature and may have charge and orbital ordering.  This all raises a question as to the origin of the FI phase in the Pr/Ca system with $`x0.2`$ while the La/Sr system with similar hole concentrations are ferromagnetic metals.

In this work, we study a charge and orbitally ordered state which can be viewed as an orbital polaron lattice and which produces the fully polarized FI state for $`x`$ = 1/4. Hartree-Fock (HF) calculations on $`d`$-$`p`$-type lattice models show that the magnetic coupling between the orbital polarons is actually ferromagnetic and support this idea. We also shortly discuss the evolution from the FI state at $`x`$ = 1/4 to the AFI state at $`x`$ = 1/2 in Pr1-xCaxMnO3 as well as the relationship between the orbital polarons and the small ferromagnetic polarons observed in La1-xCaxMnO3.

## II Orbital Polaron

First, let us explain the basic idea underlying the concept of orbital polarons (see also ref.). Since the electronic configuration of Mn3+ in $`R`$MnO3 is $`t_{2g}^3e_g^1`$, in an octahedral coordination, there exists double orbital degeneracy and a strong Jahn-Teller effect. On the other hand, the $`e_g`$ orbitals are empty in Mn4+. When one dopes $`R`$MnO3 with holes, namely, puts Mn4+ ions in the background of the Mn3+ ions, the $`e_g`$ orbitals of all the Mn3+ site surrounding the Mn4+ site tend to be directed towards it as displayed in Fig. 1. Such an orbital orientation occurs for two reasons. One is simply steric: oxygen ions sitting in between the Mn ions move towards the Mn4+ site and, consequently, the MnO6 octahedra of the neighboring Mn3+ sites are elongated along the axis pointing to the Mn4+ site. Another factor is that the orbital occupation helps to optimize the covalency between the Mn3+ and Mn4+ sites: the $`e_g`$ orbitals directed towards Mn4+ site allow for maximal Mn-O-Mn hopping. An important consequence of such an orbital ordering is that, according to the Goodenough-Kanamori rules, the exchange interaction between the Mn3+ and Mn4+ in this cluster is ferromagnetic. Thus one can treat this object simultaneously as a lattice (both breathing-type and Jahn-Teller-type) polaron, a ferromagnetic polaron, and an orbital polaron.

For $`x`$ = 1/4, one can expect a very natural type of ordering of these polarons shown in Fig. 2. In this polaron lattice, the orbital polarons form a body-centered cubic lattice which have two such polarons per unit cell. Therefore, one can divide the orbital polaron lattice into two sublattices which are simple cubic lattices labeled as $`A`$ and $`B`$. In Fig. 2, the shaded (open) circles and orbitals indicate the Mn4+ and Mn3+ sites in sublattice $`A`$ ($`B`$). In each sublattice, since the neighboring orbital polarons share the Mn3+ sites, the coupling between them is very strong and ferromagnetic. On the other hand, it is not trivial whether the coupling between the neighboring orbital polarons belonging to the different sublattices is ferromagnetic or antiferromagnetic. In order to see whether the magnetic coupling between sublattices $`A`$ and $`B`$ is ferromagnetic or not and to check the stability of this ordered structure (which is actually a form of charge ordering (CO)), we performed HF calculation on the perovskite-type lattice model with the Mn 3$`d`$ and O 2$`p`$ orbitals under the lattice distortion shown in Fig. 1.

## III Model Hartree-Fock Calculation

We employ the multi-band $`d`$-$`p`$ model with 16 Mn and 48 oxygen sites in which full degeneracy of Mn 3$`d`$ orbitals and the O 2$`p`$ orbitals are taken into account. In this model, the intra-atomic Coulomb interaction between the 3$`d`$ electrons is considered in terms of Kanamori parameters $`u`$, $`u^{}`$, $`j`$ and $`j^{}`$. The charge-transfer energy $`\mathrm{\Delta }`$ is defined by $`ϵ_d^0ϵ_p+nU`$, where $`ϵ_d^0`$ and $`ϵ_p`$ are the energies of the bare 3$`d`$ and 2$`p`$ orbitals and $`U`$ ($`=u20/9j`$) is the multiplet-averaged $`dd`$ Coulomb interaction. The transfer integrals between Mn 3$`d`$ and O 2$`p`$ orbitals are given in terms of Slater-Koster parameters $`(pd\sigma )`$ and $`(pd\pi )`$ and those between the O 2$`p`$ orbitals are expressed by $`(pp\sigma )`$ and $`(pp\pi )`$. Here, the ratio $`(pd\sigma )`$/$`(pd\pi )`$ is -2.16. $`\mathrm{\Delta }`$, $`U`$, and $`(pd\sigma )`$ for $`R`$MnO3 are 4.0, 5.5, and -1.8 eV, respectively, which are deduced from the photoemission studies  and ab-initio band-structure calculations.  $`(pp\sigma )`$ and $`(pp\pi )`$ are fixed at -0.60 and 0.15 for the undistorted lattice, which are close to the values widely used for various 3$`d`$ transition-metal oxides.

The $`t_{2g}`$-$`t_{2g}`$ antiferromagnetic coupling is correctly captured by the present method which can reproduce the $`A`$-type AFI state for LaMnO3 and the $`G`$-type AFI state for LaCrO3.  When the lattice is distorted, the transfer integrals are scaled using Harrison’s prescription. In this model calculation, $`\mathrm{\Delta }`$ is the most important parameter and the other parameters are not sensitive to the calculated result. Since $`\mathrm{\Delta }`$ typically has an error bar of $`\pm `$ 1 eV, we have performed calculations for $`\mathrm{\Delta }`$ = 2.0 and 6.0 eV and confirmed that our conclusion is not changed. In this work, the magnitude of the distortion is given by the ratio $`(d_ld_s)/d`$ where $`d_s`$ is the Mn-O bond length at the Mn4+ site and $`d_l`$ is the longest Mn-O bond at the Mn3+ site. $`d=(d_l+d_s)/2`$ is the Mn-O bond length before the lattice distortion is included. Please note that ($`dd\sigma `$), ($`dd\pi `$), and ($`dd\delta `$) between the Mn 3$`d`$ orbitals have been neglected. This is because, in the perovskite structure, the shortest distance between the Mn ions is approximately 2$`d`$ ($``$ 4 $`\AA `$) and that, using the Harrison’s relation,  ($`dd\sigma `$), ($`dd\pi `$), and ($`dd\delta `$) are $``$ -0.08, 0.04, and -0.01 eV which are very small compared to ($`pd\sigma `$) and ($`pd\pi `$). Therefore, the effective $`d`$ band width mainly arises from ($`pd\sigma `$) and ($`pd\pi `$) in the perovskites.

In Fig. 3, the energy difference between the ferromagnetic state and the AFI state, where the two sublattices are antiferromagnetically coupled, is plotted for $`x`$ = 1/4 as a function of the distortion of the oxygen octahedron $`(d_ld_s)/d`$. The postulated distortion compatible with the orbital polaron is justified by the fact that the AFI state with the orbital polaron exists as a meta-stable solution even without the lattice distortion. Without the lattice distortion, the FM state is lower in energy than the AFI state. The distortion larger than 0.075 opens a band gap for the ferromagnetic state and induces the FM to FI transition. As plotted in Fig. 3, the magnitude of the band gap increases monotonically with the lattice distortion exceeding the critical one $`0.065`$. The magnitude of the charge ordering, namely, the difference of the occupation between the Mn3+ and Mn4+ sites ($`\mathrm{\Delta }N_d`$) also increases with the lattice distortion ($`\mathrm{\Delta }N_d`$ $``$ 0.7 for $`(d_ld_s)/d`$ = 0.1).

The FI state found here is exactly the orbital polaron lattice shown in Fig. 2. Interestingly, under the lattice distortion, the FI state is still lower in energy than the AFI state. This indicates that the magnetic coupling between two orbital polarons in different sublattices is also ferromagnetic. In the FI state, the oxygen between the two Mn3+ sites has hole concentration of $``$ 0.2 which is as large as that in the oxygen between the Mn3+ and Mn4+ sites. Namely, the holes at the Mn4+ site are partially transferred to the oxygen between the two Mn3+ sites and make the Mn3+\- Mn3+ coupling ferromagnetic. Therefore, the Mn3+\- Mn3+ coupling at $`x`$ = 1/4 is different from that at $`x`$ = 0. In this case, once the band gap opens due to the lattice distortion, the energy difference between the FI and AFI states is not sensitive to the magnitude of the distortion. Here, it should be noted that the FM state without lattice distortion is homogeneous and metallic, indicating that the lattice distortion is essential to stabilize the orbital polarons and realize the CO FI state. The orbital polaron lattice, namely, the FI state with the polaron-type charge and orbital ordering might be responsible for the FI phase found in Pr1-xCaxMnO3 for 0.1 $`<`$ $`x`$ $`<`$ 0.3.  In the La/Sr system, the lattice distortion is suppressed and the orbital polaron is not formed. On the other hand, in the Pr/Ca system, the lattice distortion is favored and the orbital polaron lattice would be stabilized.

## IV Comparison between charge orderings at $`x`$ = 1/8, 1/4 and 1/2

The charge and orbital ordering in the $`xy`$-plane of the orbital polaron lattice is shown in Fig. 4(a) for $`x`$ = 1/4. One can visualize it as the orbital zigzags constructed from the $`3x^2r^2`$/$`3y^2r^2`$ orbitals and the Mn4+ sites which are arranged in a staggered way, so that the neighboring zigzags (shown by the thick solid and broken lines ) meet at the Mn4+ sites. In the $`CE`$-type AFI state for $`0.3<x<0.5`$,  the non-crossing zigzag is stabilized by the Jahn-Teller distortion at the Mn3+ site  and the charge and orbital ordering along the zigzags  is shown in Fig. 4(b). Thus this orbital ordering is quite different from the one suggested above for $`x`$ = 1/4. It would be interesting to see how the orbital polaron lattice for $`x`$ = 1/4 evolves to the $`CE`$-type AFI state with charge and orbital ordering for $`x`$ = 1/2 which consists of non-crossing orbital zigzag: via continuous flipping of ”broken” zigzags of Fig. 4(a) or as a first order phase transition with eventual phase separation into ”1/4”-like and ”1/2”-like phases.

It is instructive to describe the difference between two FI states which the model HF calculations give for Pr3/4Ca1/4MnO3 (this work) and for La7/8Sr1/8MnO3.  The calculations for $`x`$ = 1/8 show that some ferromagnetic states with orbital and charge modulations are stable even without a lattice distortion. The predicted FI state with charge and orbital ordering for La7/8Sr1/8MnO3 has the hole-rich and hole-poor planes alternating along the $`z`$-axis. Since the orbital ordering in the hole-poor plane is essentially the same as that in LaMnO3, a small amount of lattice distortion can open a band gap.  The calculated results qualitatively agree with the experimental facts that La1-xSrxMnO3 of $`x`$ = 1/8 is a FI state with orbital ordering but does not have substantial lattice distortion.  On the other hand, at $`x`$ = 1/4, the homogeneous FM state is very stable and no FI state with orbital and charge modulations is obtained unless a large lattice distortion is included. In the FI state obtained for Pr3/4Ca1/4MnO3, the large lattice distortions of the Jahn-Teller and breathing type are required to open a band gap. Pr3/4Ca1/4MnO3 can be insulating probably because the large buckling of the Mn-O-Mn bonds ( $`\mathrm{}`$ Mn-O-Mn $``$ 155 ) reduces the band width of the $`e_g`$ band and allows the oxygen ions to relax easily. In this sense, the FI state in La7/8Sr1/8MnO3 is in the weak coupling limit and is different from the FI state for Pr3/4Ca1/4MnO3 which requires the strong electron-lattice coupling. La3/4Sr1/4MnO3 however remains a ferromagnetic metal because the straight Mn-O-Mn bonds make the bandwidth relatively large and increase the frequency of the Mn-O stretching mode.

It is expected that the electron-lattice coupling increases in going from the La/Sr to La/Ca to Pr/Ca systems. This is consistent with the fact that the $`CE`$-type AFI state becomes stable in going from La1/2Sr1/2MnO3 to La1/2Ca1/2MnO3 to Pr1/2Ca1/2MnO3. Therefore, it is reasonable to speculate that the orbital polarons still exist in metallic La3/4Ca1/4MnO3 but cannot form a lattice to realize the FI phase because the electron-lattice coupling in La3/4Ca1/4MnO3 is not strong enough compared to Pr3/4Ca1/4MnO3. Actually, small ferromagnetic polarons are observed in La1-xCaxMnO3  and their size is comparable to that of the orbital polaron shown in Fig. 1. The tendency to form orbital polarons discussed above may play a role in the phase separation.  In particular, the important role of lattice distortion which follows from our results (see Fig. 3) may in principle help to explain the large scale phase separation observed in ref. : In different degree of lattice distortion in different parts of the sample may stabilize respectively the homogeneous metallic phase in one of them and the CO insulating state in another, the charge densities in them being (almost) equal.

At the end of this section, let us discuss possible limitation of the present calculation. First, we cannot exclude the possibility that other lattice distortions would stabilize some charge and orbital orderings which are not considered here. For example, the Jahn-Teller distortion of LaMnO3-type would stabilize the charge and orbital ordering similar to that predicted for $`x`$=1/8 . With the hole-poor plane having the orbital ordering of LaMnO3, the hole-rich plane would have the hole concentration $`x`$ = 1/2 and may have the $`CE`$-type state. However, it is not clear whether such layered structure would support a ferromagnetic state or not. Second, the Pr 4f orbitals are not included in the present model. It is possible that the Pr 4$`f`$-O 2$`p_\pi `$ band accommodates some holes and, consequently, the effective hole concentration in the Mn 3$`d`$-O 2$`p_\sigma `$ band is reduced. In order to check this possibility, one should study a model with the Pr 4$`f`$ orbitals in future.

## V Conclusion

In conclusion, the model HF calculation indicates that orbital polarons, in which the orbitals of Mn3+ sites are directed towards the Mn4+-like site and the spins are ferromagnetically aligned, are stabilized by the breathing-type and Jahn-Teller-type lattice distortions and that the magnetic coupling between these polarons is ferromagnetic. At $`x`$ = 1/4, they form a body-centered cubic lattice (a form of charge ordering), which can be also viewed as a staggered arrangement of the orbital zigzags. Further theoretical and experimental studies are required in order to check whether the proposed structure is realized in Pr3/4Ca1/4MnO3, and in general to clarify the importance of the orbital polarons and their relation to the CMR effect and to the phase separation.

## Acknowledgement

The authors are grateful to J. Hill, Y. Tomioka and Y. Tokura for informing us of their preliminary results on Pr3/4Ca1/4MnO3 and for useful discussion. They would like to thank the kind hospitality of Lorentz Center, University of Leiden, where this work was initiated. This work was supported by the Nederlands Organization for Fundamental Research of Matter (FOM) and by the European network on Oxide Spin Electronics (OXSEN).