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# 2MASS NIR photometry for 693 candidate globular clusters in M31 and the Revised Bologna Catalogue Tables 2, 3 and 4 are only available in electronic form at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsweb.u-strasbg.fr/cgi-bin/qcat?J/A+A/n/n

## 1 Introduction

Globular clusters (GCs) are among the oldest astrophysical objects known and they are found in galaxies of all morphological types. Thus, globular clusters systems are extensively studied to recover fundamental information on the formation and early evolution of their host galaxies (Harris, 1998a; Ashman & Zepf, 1998).

With present-day technology globular clusters can be fully resolved into stars down to below the Main Sequence (MS) Turn Off (TO) only if they reside in the neighbourhood of our own Galaxy (i.e., within $`150`$ kpc, see Buonanno et al., 1998). The evolved populations \[Red Giant Branch (RGB) and Horizontal Branch (HB)\] may be resolved in the outer regions of globulars out to $`1`$ Mpc with the Hubble Space Telescope (see Rich et al., 2002, and references therein), and a handful of bright RGB stars have been resolved by Harris et al. (1998b) in a few clusters of the galaxy NGC 5128, at $`4`$ Mpc (but see Brown et al., 2003, for the improvements achievable with the new HST-ACS instrument). Therefore, to investigate the globular cluster system of even relatively nearby galaxies we have to rely on their integrated properties, e.g., magnitudes, colors and spectral indices (Harris, 1998a).

In this framework, the study of the GC system of the Andromeda galaxy (M 31) is of special importance, since it is the only case in which the integrated properties of globular clusters, observed in conditions similar to those typical of farther galaxies, can be sensibly compared with their actual resolved stellar populations. Hence, apart from the obvious interest in the early history of the largest galaxy of the Local Group, the M 31 system is the ideal testbed to check our ability to obtain correct estimates of metallicity and ages of extragalactic globulars from their integrated colors and spectra.

The study of the M 31 GC system has a long and venerable history, starting with the first catalogues of candidates published by Hubble (1932) and Seyfert & Nassau (1945). Since then, a number of authors have contributed to the detection, classification and analysis of M 31 globulars (see, e.g. Vetesnik, 1962; Sargent et al., 1977; Crampton et al., 1985; Battistini et al., 1980, 1987, 1993; Mochejska et al., 1998; Barmby et al., 2000, 2001; Barmby & Huchra, 2001; Barmby et al., 2002a, and references therein). In addition to the lists of candidates, these studies provided a large amount of data, mainly optical colors and spectral indices (i.e., 435 entries in the catalogue by Barmby et al., 2000). Near Infrared (NIR) $`J,H,K`$ photometry is available only for $`260`$ candidate clusters in the $`J`$ and $`K`$ passbands, and just for 127 in $`H`$ from the observations by Frogel et al. (1980); Sitko (1984); Bonoli et al. (1987, 1992); Cohen & Matthews (1994); Barmby et al. (2000, 2001).

The Two Micron All Sky Survey (2MASS, Cutri et al., 2003), providing $`J,H,K`$ photometry of 99.998 % of the sky down to $`K15.5`$ (completeness $`>99`$ % for $`K14.3`$), offers for the first time the opportunity of obtaining homogeneous NIR photometry for all the candidate GCs of M 31 within the limiting magnitude of the survey.

In the present paper we exploit this opportunity, providing $`J,H,\mathrm{and}K`$ integrated magnitudes for 279 confirmed clusters 111Confirmation of the classification is usually obtained by spectroscopic measures or by resolving the object into stars (see, e.g., Federici et al., 1990, 1993; Huchra et al., 1991; Barmby et al., 2000; Racine, 1991; Racine & Harris, 1992), 406 unconfirmed candidates, and 8 objects for which the classification is controversial222Controversial objects are those that have been classified as “confirmed globulars” by some authors and as “confirmed galaxies” or stars by others.. Near-IR photometry is less sensitive to interstellar extinction with respect to the classical optical colors and provides useful complementary information that may help for instance to disentangle the age-metallicity degeneracy (see Kissler-Patig et al., 2002; Puzia et al., 2002, and references therein).

The plan of the paper is the following: in Sect. 2 we present the master list of candidate M 31 GCs we have used as a reference catalogue (Master Catalogue), and we describe how the database of existing optical and NIR photometry has been assembled from the various sources in the literature; in Sect. 3 the actual search for counterparts of the Master Catalogue objects in the 2MASS database is described and discussed; Sect. 4 illustrates the power of the optical-NIR color index $`VK`$ in the discrimination between bona fide globular clusters and background galaxies, in the range $`VK<3.0`$; in Sect. 5 the Revised Bologna Catalogue of candidate globular clusters in M 31 is presented and described. The main results of the present analysis are summarized in Sect. 6.

## 2 The Master Catalogue

A reliable and complete catalogue of M 31 globulars based on modern CCD photometry has yet to be achieved even if limited to a quite bright threshold $`V=18`$, i.e., $`M_V7`$ at the M 31 distance. This situation arises because of: (a) the large field of view covered by the M 31 GC system (more than $`9\times 9\mathrm{deg}`$ in the sky, if extended out to $`100`$kpc from the M 31 center), (b) the possible contamination by foreground stars, other objects within M 31 itself, and background galaxies (see Battistini et al., 1987, 1993, and references therein), and (c) the variable apparent size of the candidates (ranging from 2 up to 10 arcsec) often with a strong and highly variable photometric fore/background due to M 31 itself. Therefore, the available catalogues which we have assembled from different sources are necessarily incomplete and, to some extent, contaminated. Moreover, both the photometric and the spectroscopic data are generally not homogeneous.

As a first step, we compiled a master list of the known candidates that has been reported in the literature up to 2003, June. The list of the original Bologna catalogue (Battistini et al., 1987) has been implemented with (i) the lists of cluster candidates detected near the nucleus by Battistini et al. (1993) and Aurière et al. (1992), (ii) the candidates found by Mochejska et al. (1998) and, finally, (iii) the list of new candidates found by Barmby & Huchra (2001) searching M 31 HST/WFPC2 images in the HST archive.

The final database (hereafter the Master Catalogue, MC) includes 1164 entries: 337 confirmed GCs, 688 candidate GCs, 10 objects with controversial classification, 70 confirmed background galaxies, 55 confirmed stars, and 4 confirmed H II regions. These objects are spread out over an area of more than $`3\mathrm{°}\times 3\mathrm{°}`$ around the center of M 31. The positions of all the entries are taken from the respective sources. We decided to include also previous candidates whose stellar or galactic nature has been (subsequently) observationally ascertained. Information about these objects may be useful (a) to avoid their re-discovery as candidate globulars and (b) to characterize the typical population of sources that may be misclassified as M 31 globulars.

### 2.1 Optical Photometry

The available photometric measures have been secured by the various authors using different devices and techniques: CCD and photoelectric photometry, photographic plates and, for several candidates, visual photometry obtained by eye. To assemble all this material as coherently as possible we ranked the sources of M 31 GCs photometry according to the adopted technique, choosing CCD photometry whenever available. Lacking CCD photometry, photoelectric photometry was preferred to photographic photometry and the latter was preferred to eye estimates based on photographic plates. We chose to include eye estimates to provide, at least, a guide for future observations of the candidates which lack any instrumental photometry. When one cluster was present in two different sets of CCD photometry the source with the lower photometric uncertainty and/or providing the larger number of entries was preferred.

In order to obtain a Master Catalogue with photometric measures as homogeneous as possible we have taken as a photometric reference the dataset by Barmby et al. (2000, their tab. 3), that gives homogeneous $`UBVRI`$ data for 260 confirmed GC and candidates. All other catalogues considered in the present compilation have been transformed to this reference list by applying the offsets we derived from the objects in common between the considered catalogue and the list of Barmby et al. (see Macrina, 2004, for details). The derived offsets are reported in Table 1 and are in good agreement with what found by Barmby et al. (2000, see their tab. 4).

In case of duplicated CCD observations from Barmby et al. (2000) and Barmby & Huchra (2001) the average value has been adopted. The same approach has been adopted for duplicate photoelectric measures from Sharov (1973) and Sharov & Lyutyi (1983). No transformation is feasible for the $`V`$ eye magnitudes of the 132 D class objects from Battistini et al. (1980) since this data set has too few objects (15) in common with other catalogues to derive a reliable transformation. 26 objects taken from the list of Crampton et al. (1985) have no photometry from other sources, hence they lack optical photometry in the Johnson-Cousins system and the magnitudes provided by Crampton cannot be consistently transformed to the photometric reference adopted here.

Concerning the photometric errors, one has to refer to the original sources. Typical internal errors for the CCD and photoelectric magnitudes are less than 0.05 mag (0.08 in $`U`$); however, the photometry of candidates affected by a strong background in the inner M 31 regions typically has larger errors. For the photographic magnitudes the typical errors range from 0.05 up to 0.20 mag, as shown by the comparisons with the CCD data in common. For the 15 objects with both eye-estimates and CCD or photoelectric photometry, comparison of $`V`$ magnitudes suggests that the typical uncertainty of the eye-estimates is $`\pm 0.5`$ mag (Macrina, 2004).

### 2.2 Near IR Photometry

Though the observations were carried out with different setups (telescopes, filters, etc.), the existing NIR photometric data sets (Frogel et al., 1980; Sitko, 1984; Bonoli et al., 1987, 1992; Cohen & Matthews, 1994) are in agreement to within the errors (see Barmby et al., 2000, 2001). These errors are fairly large: $`0.1`$ mag in $`J`$, and $`0.2`$ mag in $`H`$ and $`K`$. Hence the $`J,H,K`$ magnitudes available before 2MASS can be considered as a virtually homogeneous set. In the compilation of the Master Catalogue, as a first step, we have therefore adopted for each object the average values of all the available measurements, obtaining $`J`$ and $`K`$ magnitudes for $`260`$ objects and $`H`$ magnitudes for 127 objects.

### 2.3 Astrometry and Identifications

The coordinates of the objects included in the MC are taken from the original sources. They were measured with slightly different reference frames and are thus affected by different internal and systematic uncertainties. For this reason, performing the cross-correlation of the MC with the 2MASS database (described in Sect. 3), we had to check several cases of objects whose identification was not straightforward (see below). This analysis led to a few corrections of the original MC that are described in the present section.

Several direct checks carried out during the preparation of HST and spectroscopic observations (see, i.e. Fusi Pecci et al., 1996; Rich et al., 2003; Barmby et al., 2002a) have confirmed that the average astrometric accuracy of the coordinates in the Battistini et al. (1987, 1993) catalogue is better than $`1\mathrm{}`$.

For all A, B and confirmed C class objects from Battistini et al. (1987) with no 2MASS counterpart within $`1\mathrm{}`$ (see below) the coordinates have been checked on the Digitized Sky Survey (DSS-2) or on HST archive WFPC2/STIS frames, when available. This last check was needed for the objects near the bulge or in regions with a very high background, which cannot be seen on the DSS-2 images. The MC coordinates have been verified also for all the objects that had $`JHK`$ photometry in the MC, but that were not found in the 2MASS database (see below). The identification of these objects has been performed directly on the available images and their listed positions has been accordingly revised.

In a few cases, we have found a discrepancy between the coordinates reported in the Battistini et al. (1987) catalogue and the corresponding finding charts. In particular, B472 is the brightest object $`18\mathrm{}`$ SE of what reported in the Battistini et al. (1987) finding chart, B453 is $`27\mathrm{}`$ NE, B450 is $`1\mathrm{}`$ SE, and B284 is $`3\mathrm{}`$ S. Moreover, the coordinates of B288 and B142 in Battistini et al. (1987) are wrong, the correct values are reported in Table 2.

In Battistini et al. (1987) there are also a few wrong cross-identifications with previous catalogues. In table VII, G162 corresponds to SH11 and G171 to SH12; as noted by Sharov & Lyutyi (1983) G162 and G171 actually are SH12 and SH11, respectively. Moreover, in table IV of Racine (1991) the object 231D-DAO61 is actually 230D-DAO61 and in table V(b) DAO95 is DAO96.

Finally, the visual check carried out on the HST WFPC2/STIS archival frames allowed a better classification of a few candidates. B123 and B196 are clearly resolved into stars by HST, hence they have been classified as confirmed globular clusters; B261 is recognized as a foreground star while B329 is a background galaxy. B445 and NB76 appear as good GC candidates, while B430 is probably a star, but the classification is not completely unambiguous in these cases.

## 3 M 31 cluster candidates in the 2MASS database

### 3.1 2MASS IR photometry of the objects

The classification of unresolved globular clusters is a very hard task. Because of the round and compact appearance of unresolved GCs at the typical resolution of ground-based images ($`1\mathrm{}`$), both distant galaxies and foreground stars can be misclassified as GCs. Given the low spatial resolution of the survey, the automated classification pipeline of 2MASS has assigned the M 31 GCs either to the Point Source Catalogue (PSC) or to the Extended Source Catalog (XSC), depending on their apparent sizes. Therefore we decided to search the objects of the MC in both catalogues.

We selected from the 2MASS All-Sky Data Release all the sources within an area of $`4\mathrm{°}\times 4\mathrm{°}`$ centered on M 31 from both the PSC and the XSC data-sets, excluding all entries flagged as low-quality or contaminated by nearby sources. A general astrometric transformation between the MC and the 2MASS catalogues was found using the many entries in common as reference. The astrometric solutions were refined in repeated iterations until a typical residual $`<1\mathrm{}`$ was achieved. The final cross-correlation between the MC and the PSC provided 597 identifications, while 179 MC objects have been cross-identified in the XSC. In both cases the identification was considered safe if a 2MASS source was found within $`1\mathrm{}`$ from the position of a MC entry (see Fig. 1). The identification of the sources found at distances larger the $`1\mathrm{}`$ from one MC entry has been checked by visual inspection and has been accepted only if there was no possible ambiguity. Note that most of the identifications with residuals larger than $`1\mathrm{}`$ regards XSC entries. Of the total of 776 identified objects, 693 are confirmed or candidate globular clusters, the remaining 83 are confirmed stars, H ii regions or galaxies333The reported number of MC objects actually identified in the 2MASS databases depends on the considered passband. For example the total number of confirmed and candidate clusters who have a couterpart in 2MASS are 693 in J, 675 in H and 620 in K; the number of objects who lacked any previous IR photometry are 529, 637 and 463 if we consider the J, H and K passband, respectively. For brevity and to avoid confusion, all over the paper we report only the numbers referring to the J band measures. The corresponding numbers in the other passbands are similar, the exact numbers can be obtained by inspecting the catalogues presented in Tab. 2, 3 and 4. More than one hundred of the confirmed or candidate GCs identified in the 2MASS databases have previous NIR photometry. In particular, 247 objects have previous $`J`$ photometry, 122 have previous $`H`$ photometry and 236 have previous $`K`$ photometry. This large set of objects in common allows a sensible comparison between the different photometries (see below). There are $`400`$ MC entries for which we cannot find a counterpart in the 2MASS catalogues. These include $`20`$ (the exact numbers depends on the considered passband) objects with pre-2MASS NIR photometry. Almost all of these are fainter than the limiting magnitude of the 2MASS survey. Finally, the MC contains 88 entries (from different sources, e.g. Battistini et al., 1987, 1993; Crampton et al., 1985; Aurière et al., 1992) that have no optical photometry. These include 7 confirmed GC, 56 GC candidates and 25 confirmed stars/galaxies/H ii regions. We provide here $`J,H,K`$ photometry from 2MASS for 30 of them, 19 of which being confirmed or candidate clusters.

### 3.2 The IR photometric system and the adopted JHK magnitudes

After a set of extensive tests of the different kind of magnitudes provided in the PSC and XSC catalogues (e.g. isophotal, Point Spread Function fitting, aperture), we decided to rely on the aperture photometry in both cases. Unfortunately, magnitudes measured with the same aperture were not available for both catalogues; hence our final choice was to use the aperture photometry within $`r=4\mathrm{}`$ for the PSC and $`r=5\mathrm{}`$ for the XSC. All the 2MASS magnitudes have then been transformed to the CIT photometric system (Frogel et al., 1978; Elias, 1982, 1983) using the color transformations provided by Carpenter (2001).

Fig. 2 shows the comparison between the 2MASS photometry and the previous NIR photometries as adopted in the MC for the sources identified in the XSC (left panels) and in the PSC (right panels). In all cases the average absolute difference is $`<0.1`$ mag and the rms scatter around the mean is $`<0.2`$ mag. No residual color effect has been detected.

There are small systematic shifts determined from Fig. 2, probably due to the difference in the adopted radius of the aperture. These have thus been applied to the 2MASS photometry to put all of the measures to the same photometric calibration adopted in the MC.

In Fig. 3 the JHK photometry of the total sample (obtained by merging the corrected magnitudes from the PSC and XSC) are compared with the previous NIR photometry from the MC. As can be seen, (a) the corrected magnitudes from both the PSC and the XSC form a homogeneous set, and (b) for the vast majority of the candidates the difference between corrected 2MASS photometry and previous photometries is less then $`\pm 0.2`$ mag in all passbands, i.e., of the order of the intrinsical uncertainties of pre-2MASS NIR measures. The few objects displaying a difference larger that $`0.5`$ mag has been checked by visual inspection of DSS images. All of them lie within $`811\mathrm{}`$ of another source of similar or larger luminosity, hence their magnitude estimates may be influenced by the contamination of the close companions. The above procedure has provided $`JHK`$ photometry for 529 objects for which no previous NIR photometry was available. In particular, the final catalogue contains homogeneous NIR data for 291 confirmed GCs, 412 candidates, 8 controversial objects, 58 confirmed galaxies, 23 confirmed stars and 3 H ii regions. In conclusion, the NIR photometric dataset of the M 31 GC candidates has been nearly tripled by the present work.

## 4 NIR-optical color-color diagrams: A powerful tool for a preliminar classification

The knowledge of integrated colors offers a wealth of information on any stellar population, and in particular, may be quite useful for classification purposes. Here we show that the available data on integrated colors may be used in many cases to discriminate between star clusters and background galaxies thanks to the large baseline provided by optical-infrared colors.

Various color-color diagrams with $`VK`$ vs. optical colors are presented in Fig. 4 where small points are confirmed M 31 globulars, and filled circles are the confirmed galaxies that are present in our Master Catalogue. These galaxies should be typical of the background galaxies that can contaminate the set of candidate M 31 GCs. In each panel of Fig. 4 (as well as in Fig. 5 below) the arrow indicates the reddening vector corresponding to $`E(BV)=0.1`$ to illustrate quantitatively the effects of the interstellar exctinction.

There are two remarkable features in Fig. 4: (1) the confirmed GCs (points) span a range of more than 3 magnitudes in $`VK`$, much larger than in optical colors (also due to the larger impact of the reddening in $`VK`$); (2) the vast majority of confirmed galaxies (filled circles) has $`VK3.0`$, while $`50`$% of confirmed globulars are bluer than this limit, reaching colors as blue as $`VK1.2`$.

Therefore the $`VK`$ colors provide a useful discriminant to separate good candidate clusters from background galaxies. This should lead to higher efficiency in observational programs aimed at assessing the classification of clusters in M 31, since it is very unlikely that a candidate having $`VK<3.0`$ could be a misclassified background galaxy. On the other hand, foreground stars that may be erroneously classified as candidate M 31 globulars span the whole range of $`VK`$ colors covered by confirmed clusters. Therefore, while the above criterion is very valuable for the galaxy/cluster discrimination, it is ineffective in the star/cluster separation.

It may also be useful to note that most of the clusters having $`VK4.0`$ lie in a region of the M 31 disk that seems to be affected by higher extinction (Barmby et al., 2000). The isolated cluster at $`VK>5.0`$ is B037. Its very red color is probably due to a color excess $`E(BV)>1.0`$ mag (in which case this may be the brightest globular of the whole M 31 system, see Barmby et al., 2002b, for discussion and references), or to contamination by a bright and cold star accidentally superposed to the cluster. The confirmed galaxy at $`VK2.75`$ is B136D (confirmed by Huchra et al., 1991), the one at $`VK1.5`$ is B390 (classified as galaxies by Racine, 1991).

Making use of the indications drawn from the plots presented in Fig. 4 for the confirmed clusters and galaxies, one can apply the above criterion to get useful hints on the nature of candidates whose classification is uncertain. In Fig. 5 we show the same color-color diagrams as in Fig. 4 for the not-yet-confirmed candidate GCs (small open circles) in our Master Catalogue and for the four controversial objects (filled squares) classified as “cluster” by some authors and as “galaxy” by others. It can be readily seen that most candidates have colors consistent with those typical of background galaxies ($`VK3.0`$), hence it can be reasonably deduced that many of them are in fact misclassified galaxies. On the other hand, 83 candidates have $`1.2VK<3.0`$ and, according to the above discussion, the contamination of this sub-sample by background galaxies should be negligible. A spectroscopic campaign on these blue candidates would probably be very rewarding in terms of confirmation of bona fide clusters per observed candidate. On the other hand, it has to be recalled that the criterion introduces an obvious bias against intrinsically red and/or highly reddened clusters, hence it cannot be considered as a suitable method to select complete samples of candidate clusters.

The controversial candidates G268, B409, G355 and B140 have been classified as galaxies by Racine (1991), based on high resolution ground based imaging, while Federici et al. (1990); Huchra et al. (1991); Perrett et al. (2002) classified them as globular clusters on the basis of spectroscopical observations. All these candidates have $`VK<3.0`$, hence their $`VK`$ colors seem to confirm the classification by Federici et al. (1990) and Perrett et al. (2002). For the other four controversial candidates not mentioned here, the controversy is between the classification as a cluster or as a star, hence the doubt cannot be resolved with the presently adopted criterion.

## 5 The Revised Bologna Catalogue

The MC described in Sect. 2, implemented with the new set of NIR magnitudes obtained from 2MASS constitutes a new version of the Battistini et al. (1987) catalogue: the Revised Bologna Catalogue of candidate GCs in M 31. The Revised Bologna Catalogue includes 337 confirmed GCs, 688 GC candidates, 10 objects with controversial classification, 70 confirmed background galaxies, 55 confirmed stars and 4 H ii regions. The whole catalogue is organized in three different tables, all of them made available at the CDS in electronic form.

Identifications and adopted coordinates are reported in Table 2, that contains the following columns:

* $`Column`$ 1: Designation derived from the object coordinates, following Barmby & Huchra (2001) (M31JHHMMSS+DDMMSS)
* $`Column`$ 2: Designation: B and BxxxD from Battistini et al. (1980, 1987), G from Sargent et al. (1977), V from Vetesnik (1962), DAO from Crampton et al. (1985), NB from Battistini et al. (1993), AU from Aurière et al. (1992), M from Mochejska et al. (1998), BH from Barmby & Huchra (2001), SH from Sharov & Lyutyi (1983), BA from Baade & Arp (1964))
* $`Column`$ 3–12: Different identifications, respectively from Battistini et al. (1987); Sargent et al. (1977); Vetesnik (1962); Battistini et al. (1993); Aurière et al. (1992); Crampton et al. (1985); Baade & Arp (1964); Sharov (1973); Mochejska et al. (1998); Barmby & Huchra (2001)
* $`Column`$ 13: Classification flag describing the nature of the entry (1: confirmed GC, 2: GC candidate, 3: controversial object, 4: confirmed galaxy, 5: confirmed H ii region, 6: confirmed star)
* $`Column`$ 14: Classification from the original papers (Battistini et al. (1987); Mochejska et al. (1998); Barmby & Huchra (2001))
* $`Column`$ 15: Spectroscopic confirmation: C - cluster, G - galaxy, S- star, H - H ii region
* $`Column`$ 16: Confirmation via high resolution imaging: C - cluster, G - galaxy, S - star, H - H ii region
* $`Column`$ 17: comments and references
* $`Column`$ 18 $`and`$ 19: RA, Dec (J2000) from the original catalogues or from DSS-2 or from HST/WFPC2 images (see Sect. 3).
* $`Column`$ 20: Sources of the adopted coordinates.

The adopted photometric data have been collected and are listed in Table 3 for all the confirmed and candidate globular clusters, and in Table 4 for all the objects confirmed to be galaxies, stars or H ii regions. The two tables have the following columns:

* $`Column`$ 1: Designation, as in Table 2
* $`Column`$ 2: Classification, as column 12 in Table 2
* $`Columns`$ 3-10: $`U,B,V,R,I,J,H,K`$ magnitudes (see Sect. 2)
* $`Column`$ 14: Sources of the adopted optical data and NIR pre-2MASS.

The entries associated to the object listed in Tab. 4 are reported at the end of Tab. 2. In this way Tab. 2 can be easily combined with Tab. 3 and Tab. 4 to obtain tables including positions and photometric properties of “candidate GC only” and “confirmed contaminant objects only”.

## 6 Summary and future prospects

We have compiled a Master Catalogue of M 31 globular cluster candidates including 1164 entries and we have searched the counterparts of the MC objects in the NIR 2MASS databases. We have found 776 2MASS counterparts, 693 of which correspond to confirmed or candidate M 31 GCs. In this way we have provided integrated $`J,H,K`$ magnitude for 529 objects for which no previous NIR photometry was available.

Moreover, we have collected and revised all the available photometries, yielding a final adopted list of $`UBVRIJHK`$ magnitudes as homogeneous as possible. The classification of a few candidates has been assessed by inspection of HST images and a few controversial cases have been reconsidered. With all the newly collected material, we have updated the original Bologna Catalogue (Battistini et al., 1987) so obtaining the Revised Bologna Catalogue (RBC). The RBC is the most comprehensive list presently available of candidate M 31 clusters, including 1035 confirmed and candidate GCs, 70 confirmed galaxies, 55 confirmed stars, and 4 H ii regions previously considered possible GC candidates, for a total of 1164 entries. The Bologna Revised Catalogue is currently in use to prepare observational programs aimed at increasing the sample of bona-fide M 31 globular clusters and to study the integrated properties of the whole globular clusters system of M 31.

It has also been shown that optical-infrared colors may be very valuable in the discrimination between background galaxies and bona fide globular clusters for $`VK<3.0`$. According to this criterion, we can extract from the RBC a sub-sample of 83 objects whose contamination by misclassified background galaxies is (probably) very low.

###### Acknowledgements.

We are very grateful to R.T. Rood for a critical reading of the original manuscript and to an anonymous Referee for her/his useful comments and suggestions. This publication makes use of data products from the Two Micron All Sky Survey, which is a joint project of the University of Massachusetts and the Infrared Processing and Analysis Center/California Institute of Technology, funded by the National Aeronautics and Space Administration and the National Science Foundation. Part of this work is based on observations made with the NASA/ESA Hubble Space Telescope, obtained from the data archive at the Space Telescope Science Institute. STScI is operated by the Association of Universities for Research in Astronomy, Inc., under NASA Contract NAS 5-26555. This work was supported by a fellowship (S.G.) from the Consorzio Nazionale Astronomia ed Astrofisica–CNAA and contributions from MIUR-COFIN and Agenzia Spaziale Italiana–ASI.


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# On the premelting features in sodium clusters

## Introduction

The early days of cluster thermodynamics were first mostly concerned with theoretical of numerical studies of simple rare-gas aggregates. Beyond the now generally accepted idea that melting in finite atomic clusters appears as a first-order transition rounded by size effects,labwhet  it was also observed in simulations that these system can exhibit dynamical coexistence,berry  a process in which the cluster fluctuates in time between its solidlike and liquidlike states.

While no experiment has yet permitted to test these predictions on the very same clusters, recent observations achieved in the group lead by Haberlandhab1 ; hab2 ; hab3  have provided valuable qualitative and quantitative information about the way sodium clusters melt, by extracting the full caloric curves from photodissociation measurements. In particular these authors reported that the melting point and the latent heat of fusion both vary strongly and nonmontonically with size.hab2  These results significantly attracted the attention of theoreticians, who since then tried to interpret or reproduce these unexpected complex variations using a variety of models.cs1 ; cs2 ; cs3 ; aguado ; manninen1 ; manninen2 ; garzon  Further evidence was also seeked in indicators, which are alternative to the caloric curves, such as the electric polarizability,kummel  the photoabsorption spectrum,moseler  or the ionization potential.manninen2

Up to now, none of the above cited theoretical works has been able to reach a fully satisfactory quantitative agreement with experiments. The situation is largely due to the expected strong interplay between geometric and electronic effects, which could be responsible for the variations of the thermodynamic quantities. However, the previous simulations have brought some clues about the relevance of the various models and potentials used to describe simple metal clusters. For instance, it was seen that the distance dependent tight-binding (TB) model developed by Poteau and Spiegelmanpoteau  overestimated melting points by more than 20 percents. This was interpreted as the consequence of the parameterization of this model, carried out on small clusters only but not on bulk properties.cs2  On the other hand, both the empirical embedded-atom model (EAM) potentialcs1 ; cs2 ; manninen2 ; garzon  and orbital-free density functionalaguado  calculations lead to a notable underestimation. Unfortunately, more realistic simulations still lack the extent of phase space sampling required for a precise computation of the melting point above 50 atoms.

## Numerical experiments

In our previous works, we concluded that melting in sodium clusters actually occurs differently in the smallest and in medium to large sizes clusters.cs1 ; cs2  While the caloric curve of the smallest clusters (having less than about 80 atoms) exhibit several features due to multiple isomerizations prior melting, the heat capacity of the larger sizes mainly has one main peak indicating melting in a non ambiguous way. This could partly explain why experimental measurements do not find such premelting features above 55 atoms, and also why they have difficulties in getting a clear, single-peak picture below this size. More recently we noticed that premelting effects could also be artefactually due to poorly converged simulations.cs3

Based on our previous results, the disagreement between experimental measurements and the results of both the TB and EAM models seemed mostly quantitative. One could hope in getting a much better agreement by suitably modifying the parameters, after including both molecular and bulk properties, possibly through allowing these parameters to become size-dependent. However, the range of sizes that was investigated by us and by others was quite limited,cs1 ; cs2 ; manninen2 ; garzon  with only very few sizes above 80. Moreover, the mediocre agreement for the latent heats of fusion lead us revisit the problem with newly available simulation methods and less ambiguous tools of analysis.

We have performed exchange Monte Carlo canonical simulationsemc  of the clusters Nan with $`55n145`$, $`n`$ being a multiple of 5 in this range, plus the following sizes $`n=59`$, 93, 127, 129–131, 133, 139, 142, and 147. The clusters are again described using the same empirical many-body EAM potential whose parameters are given in Ref. li, , and each simulation consisted of $`10^7`$ cycles following $`2\times 10^6`$ equilibration cycles for each of the 31 trajectories characterized by their temperature $`T_i=i\times 10`$ K for $`1i30`$ plus $`i=1.5`$. The starting structures for all clusters was always chosen to be the result of basin-hopping global optimization carried out with 10 sets of $`10^4`$ quenches. All were found to be based on the icosahedral motif. The absence of any different structural motif such as octahedral or decahedral for the sizes studied here is very favorable for the simulations to reach equilibrium and not fall into broken ergodicity problems, as one major cause for such difficulties precisely lies in the energy landscape having several funnels.wales38 ; neirotti  Each cluster was simulated 5 times independently, with different random seeds, and we used a hard-wall spherical container with radius $`R_{\mathrm{max}}=7n^{1/3}`$. The caloric curves were constructed from the distributions of potential energies using a multihistogram technique. In Ref. cs2, , we calculated the latent heat of melting, $`L`$, as the integral of the heat capacity minus the Dulong-Petit contribution. This lead to appreciable overestimates, mostly due to the neglect of anharmonicities. Here we proceed similarly to the experimental approach of Schmidt and coworkers,hab2  namely by fitting the low- and high-temperature parts of the internal energy as straight lines and defining $`L`$ as the gap between these lines at the melting point $`T_{\mathrm{melt}}`$. The melting point itself is defined as the temperature at which the last heat capacity peak has its maximum: in cases where there are several peaks each centered around $`T_{\mathrm{melt}}^{(k)}`$ the true melting temperature is taken as $`\mathrm{max}_k\{T_{\mathrm{melt}}^{(k)}\}`$. The low- and high-temperature parts are defined as $`T50`$ K and $`T250`$ K, respectively. Therefore, if premelting events are present between these limits, they will contribute to the latent heat.

## Results and discussion

The variations of $`T_{\mathrm{melt}}`$ and $`L`$ with size are sketched in Fig. 1 along with the latest experimental data of Schmidt and coworkers.hab3  Except for very low sizes, we first notice that the melting points computed here are significantly lower than the ones we previously reported.cs2  This is an unfortunate consequence of using the q-jumping method with un inappropriate Tsallis parameter.difres  However they are comparable to the ones obtained by Garzón and coworkers in the microcanonical ensemble.garzon  Since we expect the differences between this ensemble and the canonical ensemble to become smaller and smaller for increasing sizes, this agreement appear as a mutual confirmation of the convergence of both calculations, even though they rely on very different numerical experiments.

Interestingly, the experimental and theoretical variations of $`T_{\mathrm{melt}}`$ with size appear to be related to each other, especially if we shift the simulation data around size 120 by about 15 atoms and 70 K. This had not been noticed before, and is probably fortuitous. But it may also hide that some mechanisms causing the strong variations in the experimental results close to 140 atoms are indeed the same here, only occuring sooner.

In Fig. 1 one should also notice that the melting point at $`n=55`$ is not the highest, as clusters having 59 or 60 atoms are more resistant to an increase in temperature. However, we were not able to extract any latent heat for these sizes (nor for $`n=65`$ and 70) due to very broad heat capacity peaks. Therefore one should maybe not give too much importance to the melting points extracted from these curves.

While the melting temperatures are usually well below the experimental data (except in the vicinity of 130 atoms), the computed latent heats show a reasonable overall agreement, even though the complex variations are not as sharply seen as in the measurements of Schmidt et al.cs3  A definitive comparison would require one to extend the range of sizes. As far as latent heats are concerned, the difference between the present results and our previously published datacs2  comes nearly entirely from the different way of estimating $`L`$, which is now much closer to the experimental way.

The heat capacity curves in the range $`125n135`$ are all plotted in Fig. 2 versus temperature. Despite strong changes from one size to another, a regular evolution can be seen from 125 atoms and above this size. The heat capacity consists of two peaks, the melting (or high-temperature) peak being centered near 203 K. The smaller peak, denoted as premelting peak in the following, goes from 100 to about 180 K in a quite continuous fashion. The premelting peak is surprisingly strong, and can be clearly distinguished from the melting peak. Strikingly, it is even stronger than the melting peak itself at size 133.

To interpret these curves, we have chosen to focus on Na133, by carrying periodic quenches from instantaneous configurations extracted from the Monte Carlo simulations for all trajectories. We thus gathered nearly 14000 different isomers. Fig. 3 shows the energy of these isomers versus their rank, as well as the discrete spectrum of isomers versus the temperature of the trajectory from which they were quenched. Both graphs clearly indicate a correlation between the repartition of isomers in energy space, their number and the heat capacities. Small variations in $`C_v`$ occur below 150 K, but are hardly visible when compared to the main peaks. They are related to the first few hundreds of isomers, which involve the migration of a limited number of some of the missing atoms on the external layer of the icosahedron (the 135-atom cluster has $`I_h`$ symmetry with all vertex atoms missing).

The presence of two major peaks in $`C_v`$ is consistent with the two main increases in the number of isomers having less than a given energy. Most new isomers appearing between 150 and 190 K have their rank between 1000 and 5000 in the upper part of Fig. 3. Looking at their structure reveals that they are all still based on the two-layer icosahedron, but that the third layer is hardly recognisable. Hence this case of premelting is an extreme illustration of surface melting following preliminar surface reconstruction.doyesurf  Eventually, above 200 K the icosahedral structure is completely lost and the true (volume) melting takes place.

If now we look more closely at the results obtained for Na135, we notice that the main peak is indeed located at the same temperature as the premelting peak in Na133, and that the true melting peak of the latter cluster has been replaced by a right shoulder. Thus the same phenomena seem to be present in Na135, only with different relative magnitude. This case could be referred to as ’post-melting’.

To some extent, this progressive evolution of the premelting and melting peaks can be compared to what has been observed in small Lennard-Jones (LJ) clusters by Frantz.frantz  In these systems, a premelting peak starts appearing close to the size 31 corresponding to the competition between Mackay-type and anti-Mackay-type icosahedral structures. The premelting peak remains as the cluster size increases, and it is shifted to higher temperatures before becoming higher than the melting peak itself near the size 38.frantz  Because of the structural similarities between LJ clusters and the present sodium clusters, it is likely that the present observations express the same qualitative mechanisms. However, a significant quantitative difference can be seen in the caloric curves of LJ clusters and sodium clusters, as the melting peak is never really well resolved for van der Waals systems until it has replaced the premelting peak. Here the two peaks are of very similar widths, but their respective heights vary strongly, their total contribution to the latent heat being nearly constant.

Up to now, experimental data did not find any evidence for any pronounced premelting peak in the heat capacities of charged sodium clusters.hab1 ; hab2 ; hab3  This indicates that the present empirical potential is qualitatively unadequate to describe these systems. In particular, beyond a simple scaling of the parameters of the potential, we do not expect the use of explicit, size-dependent parameters to improve the situation notably. We repeated the above simulation for Na133 using the more realistic quantum distance-dependent tight-binding (TB) Hamiltonian described in Ref. poteau, , but we had to reduce the statistics to $`10^6`$ cycles following $`2\times 10^5`$ equilibration cycles (per trajectory) for the computation to be tractable. Even though melting points were shown to be overestimated,cs2  we also noticedcs3  that premelting effects were quite reduced using this model, in better consistency with experiments. The heat capacity computed from exchange Monte Carlo simulations is reported in the inset of Fig. 2. For this calculation we neglected the (weak) effects of nonzero electronic temperature.cs3  The starting configuration was taken as the same one as for the classical potential, but we did not find any more stable structure during the course of the simulation.

At first sight, the caloric curve looks similar to the classical result, with a clear premelting peak. However using the TB Hamiltonian has two consequences. First, the premelting peak is much lower than the melting peak, which is in agreement with our previous general observation that the empirical potential overemphasizes premelting features.cs2 ; cs3  More importantly, premelting also occurs much closer in temperature to the melting peak itself. This also suggest that premelting is not seen experimentally simply because it is too broad.

## Conclusion

In the present work, we have obtained some evidence that premelting effects in the caloric curves of sodium clusters could be present at unexpectingly large sizes. We also found that some clusters could exhibit ’post-melting’, a process in which the premelting effect is stronger than the actual melting peak. In the cases studied here, these effects seem to be associated with surface reconstruction of the third icosahedral layer, and thus seem to be of character similar to what occurs in Lennard-Jones clusters having about 35 atoms.frantz

One consequence of the above results is that explicit empirical potentials are not fully reliable for predicting melting points in small sodium clusters, not only because they do not allow one to reproduce the complex variations observed by the group of Haberland,hab2  but mostly because they exhibit prominent premelting peaks not seen in experiments.

Calculations performed using the quantum tight-binding model also predict a premelting phenomenon near 133 atoms, but the corresponding anomaly of the heat capacity is much smaller than the melting peak, as well as closer to it. In this respect, it resembles more the measurements by Schmidt et al.hab2

Even though our calculations overestimate premelting effects, they provide insight into the possible causes for the nonmonotonic variations of the melting point. In particular, they suggest that such variations may reflect premelting becoming actual melting. The discrepancies with the present work would then be ascribed to a possible merging of the premelting feature into one shoulder of the melting peak, but not necessarily on the low temperature side.

## Acknowledgments

The authors wish to thank H. Haberland for helpful discussions.


text:
# The infrared spectrum of Na0.57CoO2

## Abstract

The optical conductivity of single crystals of NaxCoO2 (for $`x`$ = 0.57) is first reported between 295 and 30 K. In the far infrared, an ”anomalous Drude” analysis leads to a carrier effective mass of 5$`\pm 1`$ electron masses. That this high value is due to strong electron-phonon coupling is suggested by the Fano distortion of a phonon at 570 cm-1. A peak at 8800 cm-1 scales with the charge transfer band of several high-$`T_c`$ cuprates by simply replacing the in-plane Cu-O bond length with that for Co-O.

preprint: NaCoO/2004

The layered oxides NaxCoO2 have attracted the attention of the scientific community after the discovery that samples with $`x`$ 0.3 become superconducting, below $`T_c`$ 5 K, after exposure to humid air.Takada  These hole-doped metals have a hexagonal structure, with the $`ab`$ planes formed by CoO2 sheets intercalated by layers of Na+ ions. Water molecules between those planes increase the lattice parameter along the $`c`$-axis from 1.09 to 1.96 nm.Takada  However, how water inclusion triggers superconductivity in NaxCoO2 is not fully understood yet. Therefore, also the investigation of non-hydrated samples is deserving a considerable research effort. NaxCoO2 is considered to be a strongly correlated system, with a Hubbard splitting $`U`$ 5 eV. The conduction band should be narrow, with an effective mass of the carriers $`m^{}7m`$,Yang  where $`m`$ is the bare electron mass. In the $`ab`$ planes, the resistivity $`\rho (T)`$ is quasi-linear with $`T`$ for $`x`$ = 0.7,Hasan  with a change of slope around 100 K, while for $`x`$ = 0.75 $`\rho (T)`$ is suggestive of a spin ordering instability below 22 K.Motohashi  For $`x`$ = 0.57, $`\rho (T)`$ follows a $`T^{3/2}`$ law in the $`ab`$ planeRivadulla1  below 175 K. Along the $`c`$ axis, it has a maximum at the same temperature.Valla  The latter behavior may be related with the growth, at low temperature, of a coherent quasiparticle peak in the density of states measured by Angle Resolved Photoemission Spectroscopy (ARPES).Valla

In the optical domain, only room-temperature Raman data are presently available to our knowledge: those of Iliev et al.Iliev  on Na0.7CoO2 and those of Lemmens et al. on NaxCoO2$`y`$H2O.Lemmens  Group theory predicts 4$`E_{1g}`$+4$`A_{1g}`$ Raman active modes. However, the spectra of dry powders show one $`E_{1g}`$ phonon at 480 cm-1 and one $`A_{1g}`$ mode at 598 cm-1. In the $`ab`$ planes of single crystals with $`x`$ 0.7, one observes a mode at 588 cm-1 with weak satellites and, in the hydrated compound, an additional peak at 470 cm-1. All these values may change considerably after sample ageing and/or surface treatment. To our knowledge, no infrared data are presently available for the system NaxCoO2. However, they might provide valuable information on the charge dynamics, complementary to that collected by ARPES and transport measurements. The present paper is aimed at filling this gap.

Our experiment was made possible by the use of mosaics of Na0.57CoO2 single crystals. They were protected from humidity by keeping them in dry air at +450C, and in a high vacuum when mounted in the cryostat. All of them were grown from the flux as described in Ref. Rivadulla1,  and were extracted from the same batch. After growth, $`x`$ resulted to be 0.57, the closest value to 0.5 that could be obtained.Rivadulla1  Ten to twelve small crystals were mounted on the sample holder. The resulting mosaic surface was approximately 2x2 mm wide. The crystal surfaces, that are excellent $`ab`$ planes as they are flux-grown, were coplanar within a few degrees. This was obtained by monitoring the reflections of a laser beam focused on the individual crystals and adjusting their positions while the glue (silver paint) was drying. The eventual contribution of the $`c`$ axis due to residual disalignment of a crystal was largely reduced by the effect of refraction, which bends the radiation wavevector toward the normal to the surface. As final check, the reflectivity of one crystal was measured at room temperature by an infrared microscope Hyperion 2000, mounted onto a Bruker IFS 66V interferometer, between 400 and 17,000 cm-1. The reference was the crystal itself after exposure to gold evaporation. The resulting $`R(\omega )`$ (solid line) is compared with that of the mosaic at the same temperature (dotted line) in the inset of Fig. 1.

The $`R(\omega )`$ of the mosaic was measured between 30 and 295 K, and between 40 and 10000 cm-1 at quasi-normal incidence (80), by a Bomem DA3 interferometer. The final alignment of the reflectivity setup was performed by remotely controlled motors, in order to compensate for the mechanical stress of the interferometer optics after the evacuation. The reference was a gold film evaporated in situ onto the sample by displacing a hot filament in front of it. The $`R(\omega )`$ thus measured is shown at different temperatures in Fig. 1. The complex optical conductivity $`\stackrel{~}{\sigma }(\omega )`$ was then obtained by standard Kramers-Kronig relations. A Hagen-Rubens extrapolation was employed below 40 cm-1, an extrapolation based on fits by Lorentzians and polynomials was used above 17,000 cm-1. An alternative extrapolation based on the reflectivityTerasaki  of NdCoO3 gave the same results within errors. As the surface of the flux-grown crystals is intrinsically $`ab`$, the $`\stackrel{~}{\sigma }(\omega )`$ obtained in this way is the optical conductivity of the CoO2 sheets of Na0.57CoO2.

The real part of $`\stackrel{~}{\sigma }(\omega )`$, $`\sigma _1(\omega )`$, is shown at two temperatures in Fig. 2. In both sets of data, the main features are a metallic conductivity in the far and mid infrared, a phonon line, and a broad absorption in the near infrared. This latter exhibits an edge around 6000 cm-1 and a well defined peak at $`\mathrm{\Delta }`$ = 8800 cm-1. This energy roughly corresponds to that (0.7 eV) of a peak observed in ARPES spectra, and assigned to Co $`t_{2g}`$-derived states.Hasan ; Yang  However, the infrared band at 8800 cm-1 can be rather attributed to charge transfer (CT) between the Co $`3d`$ orbitals and the O $`2p`$ orbitals. This assignment is supported by scaling the energy of the band of Na0.57CoO2 with that of the corresponding bands of the cuprates. In high-$`T_c`$ materials, where the Cu-O bonds of length $`d`$ are hybridized $`pd`$ and have a octahedral coordination, the CT peak energy $`\mathrm{\Delta }`$ is found to follow a law $`\mathrm{\Delta }d^7`$.Tokura ; Cooper  The same hybridization and coordination are present in NaxCoO2, despite its unit cell being hexagonal instead of tetragonal. As shown in the inset of Fig. 2, the present value of $`\mathrm{\Delta }`$ for the CoO2 sheets (where $`d_{CoO}`$ = 0.210 nm) is in excellent agreement with the prediction obtained by extrapolating the $`d^7`$ law which holds for cuprates. The latter compounds in Fig. 2 are undoped, unlike Na0.57CoO2. However, it has been shown that the energy of the charge-transfer band in La2-xSrxCuO4 is approximately independent of doping.Lucarelli

The conductivity of oxides within the charge-transfer gap has been often described in terms of an ”anomalous-Drude” model, where both the effective mass $`m^{}(\omega )`$ and the relaxation rate $`\tau ^1(\omega )`$ of the carriers are allowed to depend on frequency. Both those quantities, as well as the plasma frequency $`\omega _p`$, can be directly extractedPuchkov  from $`\stackrel{~}{\sigma }(\omega )`$. The results for Na0.57CoO2 are shown in Fig. 3. The strong phonon absorption around 570 cm-1, that will be discussed later on, does not prevent one from obtaining information on the carrier parameters. First, for $`\omega `$ 1500 cm-1, an ”anomalous Drude” regime indeed holds, where both $`m^{}/m`$ and $`\tau ^1`$ depend on $`\omega `$. There is no indication for the opening of a pseudogapPuchkov  down to 30 K, which would suggest either charge localization or pair pre-formation. Secondly, at any $`T`$, $`m^{}(\omega )/m5\pm 1`$ for $`\omega 0`$, in satisfactory agreement with the photoemission data cited above.Yang  Thirdly, below a temperature $`T_0`$ between 230 and 160 K, $`\tau ^1\omega ^{3/2}`$ (see the inset of Fig. 3). Moreover, below $`T_0`$ its low-frequency values become independent of $`T`$ within errors. This is clearly suggestive of a change in the transport properties and may be related to the crossover observed at $`T_M`$ 180 K both in the ARPES spectraValla  of Na0.57CoO2 and in its resistivity,Rivadulla1 ; Valla  which is proportional to $`T^{3/2}`$ below $`T_M`$.

The $`E_{1u}`$ optical phonon observed around 570 cm-1 deserves a detailed description. Four of such modes are predicted by group analysis but, as for Raman spectra cited above,Iliev  just one line is observed here. It can be assigned to the Co-O stretching,Sudheendra  consistently with its strong hardening for decreasing temperature (see $`\stackrel{~}{\omega }_F`$ in Table I). In the present infrared spectra, the other phonon lines, which are expected to occur at lower frequencies than the Co-O stretching, are probably shielded by the narrow free-carrier continuum in a more efficient way.

The phonon line around 570 cm-1, as shown in the inset of Fig. 4, exhibits a pronounced Fano distortion. This indicates a strong coupling between the Co-O stretching and the Drude-like continuum, which indeed has most of its spectral weight on the opposite side of the absorption minimum.Lupi98  The effect is more and more evident as $`T`$ is lowered. The observed spectrum can be accurately fitted at all temperatures by the Fano equation for the dielectric functionLupi98 ; Davis

$$ϵ_{2F}(\omega )=R\left(\frac{(q\gamma _F+(\omega \stackrel{~}{\omega }_F))^2}{\gamma _F^2+(\omega \stackrel{~}{\omega }_F)^2}1\right).$$
(1)
Therein, $`\stackrel{~}{\omega }_F`$ is the renormalized frequency of the phonon and $`\gamma `$ is its half width, which here basically measures the electron-phonon interaction strength. $`R`$ is a scale parameter which includes the transition rates, and $`q`$ is the Fano-Breit-Wigner parameter, which measures the reciprocal of the electron-phonon interaction once weighted for the density of states of the continuum.Fano61

The quantities in Eq. 1, as provided by the fit to data, are reported in Table I. One may notice that $`\gamma _F`$, which measures the electron-phonon interaction, is large and independent of temperature within the errors reported in parenthesis. On the other hand, as already mentioned, $`\stackrel{~}{\omega }_F`$ appreciably increases as $`T0`$. Also $`1/q^2`$ steadily increases for decreasing $`T`$ as shown in Fig. 4. Therein, its behavior is show to be consistent with that of the spectral weight of the coherent peak which appears in the ARPES spectra, close to the Fermi level, for $`T<`$ 200 K. Indeed, as the electron-phonon interaction $`\gamma _F`$ is $`T`$-independent in Table I, and the same holds for the matrix element of the dipolar Hamiltonian, the $`T`$-dependence of $`1/q^2`$ probes that of the density of states of the continuum at the phonon energy.

In conclusion, we have reported here the reflectivity spectra of single crystals of Na0.57CoO2 in the $`ab`$ plane. The resulting optical conductivity exhibits a near infrared peak that can be attributed to Co(3d)-O(2p) charge transfer. Indeed, it scales with that charge transfer band observed in the cuprates by simply replacing the Cu-O in-plane bond length with the Co-O bond length. In the far infrared, $`\stackrel{~}{\sigma }(\omega )`$ can be described by an anomalous Drude behavior, where the carriers have an effective mass of about 5$`m`$. Their relaxation rate varies as $`\omega ^{3/2}`$ and is independent of $`T`$, within errors, below a temperature $`T_0`$. $`T_0`$ is consistent with the crossover temperature $`T_M`$ below which either $`\rho (T)T^{3/2}`$ and a quasiparticle peak appears in the photoemission spectra of Na0.57CoO2.

Only one unshielded phonon has been observed in the present spectra, namely the transverse optical Co-O stretching mode. It exhibits a marked Fano profile, which is suggestive of a strong electron-phonon coupling. This is consistent with the high effective mass of the carriers, which therefore could be polaronic in nature. Under this assumption, the observation of the quasiparticle photoemission peak below $`T_M`$ and, here, of a $`\tau ^1`$ independent of $`T`$ below $`T_0`$, may be interpreted in terms of coherent (tunneling) propagation of large polarons. On the other hand, even if we observe a broad background in the midinfrared, which cannot be described in terms of Drude-like models, we cannot identify any clear polaronic ”shake-off” band in the present data. Systematic infrared investigations of the NaxCoO2 system as a function of doping and temperature would be needed to clearly identify the nature of the carriers.

We wish to thank F. Rivadulla for producing and characterizing the samples here measured, as well as for many valuable discussions.


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# Large-Scale Model of the Milky Way: Stellar Kinematics and Microlensing Event Timescale Distribution in the Galactic Bulge

## 1 Introduction

It is now known, from several independent lines of evidence, that the Milky Way Galaxy (MWG) is barred (e.g., Gerhard (2001)). However, a comprehensive model consistent with the main observables – luminosity distribution, stellar-kinematics, gas-kinematics, and microlensing – has so far been still missing. Recently, Bissantz & Gerhard (2002) obtained a luminosity density model for the MWG from the dust-corrected $`L`$-band COBE/DIRBE map of Spergel, et al. (1995), through a non-parametric constrained maximum likelihood deprojection. This model (hereafter: COBE-$`\rho `$ model) is consistent also with the observed magnitude distributions of clump giant stars towards several bulge fields, and with the microlensing optical depth towards the bulge derived from these stars (Popowski, et al., 2003; Afonso, et al., 2003); see also Binney, et al. (2000) and Bissantz & Gerhard (2002). Furthermore Bissantz, et al. (2003) found that the hydrodynamical gas flow in the potential of the COBE-$`\rho `$ model matches the observed gas dynamics of the inner MWG well.

The structure of the inner MWG can also be constrained by observations of stellar kinematics along fixed lines of sight (Sharples, et al. (1990) \[Sh90\]; Spaenhauer, et al. (1992) \[Sp92\]; Minniti, et al. (1992) \[Mi92\]) and by the microlensing event timescale distribution (ETD) (Alcock, et al., 2000). The ETD has been studied largely with models which assume some distribution of disk and bulge kinematics (e.g. Han & Gould (1996); Peale (1998); Méra, et al. (1998)). An exception was Zhao, et al. (1996), who used the dynamical bar model of Zhao (1996) augmented by an analytic disk model, but failed to match the long duration ($`\widehat{t}>100`$ days) tail of the ETD. In the present Letter we show that a full stellar-dynamical model based on the COBE-$`\rho `$ model is consistent with these independent data as well.

Dynamical models of the MWG have been generated using the Schwarzschild (1979) method, in which the distribution function (DF) of a galaxy is built from numerically integrated stellar orbits. Following earlier work by Zhao (1996), Häfner, et al. (2000) constructed a 22168-orbit dynamical model of the MWG. Dynamical models of the MWG have also been obtained by $`N`$-body methods (Fux, 1997). Syer & Tremaine (1996) \[ST96\] introduced a novel method for generating self-consistent dynamical models. The Syer-Tremaine (hereafter ST) method is allied to the Schwarzschild method, but, rather than superposing time-averaged observables from an orbit library, the ST method constructs a model by actively varying the weights of individual particles (orbits) as a function of time. This permits arbitrary geometry and a larger number of orbits to be used in the model building. Our dynamical model for the COBE-$`\rho `$ density in the MWG is constructed with the ST method, demonstrating its usefulness for real galaxy modeling. This Letter compares the model’s bulge kinematics and microlensing ETD with their observed counterparts.

## 2 The Syer-Tremaine method

The idea of the ST algorithm is to assign individual weights to particles of a simulation, which are then changed to reduce the deviation between the model and observations. An observable $`Y_j`$ associated to a stellar system characterized by a distribution function $`f(𝐳)`$, $`𝐳=(𝐱,𝐯)`$, can be written as $`Y_j=K_j(𝐳)f(𝐳)d^6𝐳`$, where $`K_j(𝐳)`$ is a known kernel. If this stellar system is simulated with $`N`$ particles having weights $`w_i`$ and phase space coordinates $`𝐳_𝐢`$, then we can write the observables of the simulation as $`y_j(t)=_{i=1}^Nw_i(t)K_j(𝐳_𝐢(t))`$. ST96 define the ”force of change” on the weights as

$$\frac{dw_i(t)}{dt}=\epsilon w_i(t)\underset{j}{}\frac{K_j(𝐳_𝐢)}{Z_j}\left(\frac{y_j(t)}{Y_j}1\right)$$
(1)
The small and positive parameter $`\epsilon `$ governs how rapidly the weights are pushed such that the simulation observables $`y_j(t)`$ converge towards the observables $`Y_j`$. The constants $`Z_j`$ act as normalizations. The full ST method also includes prescriptions for temporal smoothing and a maximum entropy term, to reduce fluctuations. We have implemented the ST method with the MWG disk-plane surface density as the observable (Debattista et al. in preparation). We set $`\epsilon =0.25`$, $`\alpha =0.524`$, $`\mu =0.001`$, where $`\alpha `$ and $`\mu `$ are the parameters of the temporal smoothing and the entropy terms, respectively, in the notation of ST96.

### 2.1 Simulation

Since the MWG contains a bar, our initial model also had to be barred. The simplest way to achieve this was to evolve an $`N`$-body model of an initially axisymmetric, bar-unstable, disk galaxy. The $`N`$-body simulation which produced the barred model consisted of live disk and bulge components inside a frozen halo. The frozen halo was represented by a cored logarithmic potential. The initially axisymmetric disk was modeled by a truncated exponential disk. Disk kinematics were set up using the epicyclic approximation to give Toomre $`Q=1.3`$. The disk and bulge were represented by $`4\times 10^6`$ equal-mass particles, with a mass ratio $`M_\mathrm{d}:M_\mathrm{b}=4:1`$. Further details of the setup methods and model units can be found in Debattista (2003) \[D03\]. We use the halo, disk, and bulge parameters given in Table 2 of D03, which give a flat rotation curve out to large radii.

The simulation was run on a 3-D cylindrical polar grid code (described in Sellwood & Valluri (1997)), with technical parameters exactly as in D03. The initially axisymmetric system was unstable and formed a rapidly rotating bar at $`t50`$. By $`t=160`$, the bar instability had run its course and further secular evolution of the bar was mild. The resulting system did not match the COBE-$`\rho `$ model of the MWG and needed to be evolved further with the ST code. First, however, we eightfold symmetrized the COBE-$`\rho `$ model in order to reduce the amplitude of spirals, which we did not try to reproduce. We evolved the $`N`$-body model from $`t=160`$ under the ST prescription with the fixed potential of the COBE-$`\rho `$ model plus dark matter halo. We kept the bar pattern speed at its value in the $`N`$-body model, which scales to $`56`$ $`\mathrm{km}\mathrm{s}^1\mathrm{kpc}^1`$, consistent with the MWG (Dehnen (2000); Debattista, et al. (2002); Bissantz, et al. (2003)). At $`t=240`$ (i.e. $`4`$ bar rotations), we shut off the ST algorithm and evolved the system to $`t=280`$ to assure that the particles are phase mixed.

## 3 Results: Density and Bulge Kinematics

To compare our dynamical COBE model (the COBE-Dyn model) with observations, we adopted the same viewing parameters as were used to determine the COBE-$`\rho `$ model: $`R_{}=8\mathrm{kpc},z_{}=14\mathrm{p}\mathrm{c}`$ and $`\phi _{\mathrm{bar}}=20^{}`$ (Bissantz & Gerhard, 2002). We scale the velocities in the COBE-Dyn model to the MWG by matching to the local circular velocity. We assumed that the local standard of rest has only a circular motion, with $`v_{LSR}=200`$ $`\mathrm{km}\mathrm{s}^1`$, and we adopted the values of the solar peculiar motion from Dehnen & Binney (1998).

The densities of the COBE-Dyn and COBE-$`\rho `$ models match very well, with azimuthally averaged errors smaller than $`5\%`$ out to $`R_{}`$. The largest errors ($`<15\%`$) occur in small isolated regions on the bar major-axis. In the (unconstrained) vertical direction, the disk is somewhat thicker than the MWG at $`R_{}`$, but this leads to a change in optical depth $`\tau `$ towards Baade’s window of $`<15\%`$. In the bulge region, on the other hand, the scale-height of the COBE-Dyn model matches that of the MWG very well. We compared the model’s kinematics to observations towards Baade’s window (Sh90, Sp92) and in the field at $`(l,b)=(8^{},7^{})`$ (Mi92), using the selection functions determined by Häfner, et al. (2000). Table 1 shows our results. The overall fit of our model to the observed kinematics is rather good.

## 4 The Microlensing ETD

We now show that the COBE-Dyn model is also consistent with the microlensing ETD. Alcock, et al. (2000) presented an ETD, corrected for their experimental detection efficiency, based on 99 events in 8 fields. Popowski (2002) argued that one of these fields seems biased towards long-duration events, introducing some uncertainty in the observed ETD. Here we use the full-sample Alcock et al. ETD in order that our results may be compared with previous ones. We computed the ETD with the self-consistent kinematics of the COBE-Dyn model. A microlensing event is characterized by the source distance, $`D_S`$, lens distance, $`D_L`$, the proper motion, $`v_{}`$, of the lens with respect to the line-of-sight between observer and source, and lens mass, $`M_L`$. The probability $`P(\widehat{t})`$ for observing an event duration $`\widehat{t}=2\mathrm{\Theta }_E/v_{}`$ is given by

$`P(\widehat{t}){\displaystyle \rho (D_S)D_S^{2+2\beta }\rho (D_L)D_L^2\mathrm{\Theta }_E(D_S,D_L,M_L)}`$
$`\mathrm{\Phi }(M_L)v_{}f(v_{})\delta (\widehat{t}2\mathrm{\Theta }_E/v_{})dv_{}dD_LdD_SdM_L.`$ (2)
Here $`\rho (d)`$ is the density of the MWG at distance $`d`$ from the observer along the line-of-sight to the observed field, $`\mathrm{\Phi }(M_L)`$ is the mass function (MF) of the lens population, $`\mathrm{\Theta }_E(D_S,D_L,M_L)`$ is the Einstein angle, and $`f(v_{})`$ is the distribution of $`v_{}`$. We solved the multiple integral by Monte Carlo random drawings of the parameters $`(D_S,D_L,v_{},M_L)`$ as follows: (1) To obtain the source distance ($`0D_SD_S^{\mathrm{max}}=12\mathrm{kpc}`$), we used the COBE-$`\rho `$ model, since this is less noisy than the particle realization. The probability of $`D_S`$ is $`\rho (D_S)D_S^{2+2\beta }`$ with $`\beta =1`$, to account for a magnitude cut-off (Kiraga & Paczyński, 1994). (2) The lens distance ($`0D_L<D_S`$) was selected from $`\stackrel{~}{\rho }(D_L)_0^{D_S}\rho (D_L)𝑑D_L`$, where $`\stackrel{~}{\rho }`$ is a normalized probability density distributed as in the COBE-$`\rho `$ model. (3) For the relative velocity $`v_{}`$, we used the particle distribution of the COBE-Dyn model, randomly selecting a particle at $`D_S`$ and another at $`D_L`$. The proper motions of these particles then determined $`v_{}`$. (4) The lens mass $`M_L/M_{}`$ was selected from a Kroupa (1995) MF, $`\mathrm{\Phi }(M_L)=\beta (M_L/M_{})^\gamma `$, with

$$(\gamma ,\beta )=\{\begin{array}{cc}(2.35,0.1038)\hfill & M_L^<M_L/M_{}0.35\hfill \\ (0.6,0.6529)\hfill & 0.35M_L/M_{}0.6\hfill \\ (2.35,0.2674)\hfill & 0.6M_L/M_{}M_L^>\hfill \end{array}$$
(3)
We explored varying $`M_L^<`$ and $`M_L^>`$. We obtained the ETD, shown in Fig. 1, by simulating $`10^5`$ events, and weighting each by the remaining factors in Eqn. 2. We tested our Monte Carlo integrations by reproducing one of Peale (1998)’s model ETDs.

We started with $`(M_L^<,M_L^>)=(0.075,10)`$, for which we obtained a Kolmogorov-Smirnov distance between data and model of $`D_{KS}=0.213`$. (We excluded the bin at $`\widehat{t}<3.1`$ days from the MACHO data in all such comparisons, because it appears to be too heavily affected by its large detection-efficiency correction.) To improve on this fit, we first explored the effects of uncertainties in the COBE-$`\rho `$ model. The most important of these is $`\phi _{\mathrm{bar}}`$. Setting $`\phi _{\mathrm{bar}}=30^{}`$, we found only a minor change to the ETD, in agreement with Peale (1998). Making the bar stronger, or the disk velocity dispersion outside the bar smaller did not alter the ETD substantially. Therefore we next explored variations in the MF. Like Peale (1998), we found that modest changes can improve the fit substantially. Our best fit, with $`D_{KS}=0.068`$ was obtained with $`M_L^<=0.04`$ and $`M_L^>=10`$. However, a more conservative limit is $`M_L^>=4`$, which gives $`D_{KS}=0.081`$. (If the suggestion of Popowski (2002) is correct, which would shift the ETD peak to smaller $`\widehat{t}`$, then a smaller $`M_L^>`$ would be required anyway.)

We now explore the causes of long duration (LD) events in the COBE-Dyn model; using $`(M_L^<,M_L^>)=(0.04,4)`$ as our standard model for this analysis. We start by noting, from Fig. 1, that the vast majority of sources are located in the bulge ($`6D_S10`$ kpc). This is also true for the lenses responsible for short duration events, but disk lenses become more important at longer durations; indeed, for $`\widehat{t}>25`$ days, one third of the lenses are at $`D_L<4`$ kpc. In Fig. 2 we separate the ETD into the near and distant lens sub-samples and show the heliocentric angular velocities and cumulative distributions of $`M_L`$ for both. Note first that lenses with $`M_L>0.5M_{}`$ contribute significantly to LD events in both the near and distant sub-samples. Lens mass, however, is not the full explanation of the LD events, as has been noted by previous studies, and the relative motions of lens and source in the heliocentric frame must also be considered. The kinematics of the LD sources are substantially those of a rotating triaxial bulge/bar which points almost towards the observer: thus their apparent tangential motions are largely due to the solar motion, giving $`\mathrm{\Omega }_{tan,S}205/8`$ $`\mathrm{km}\mathrm{s}^1\mathrm{kpc}^1`$. Distant lens LD events are then possible because the lenses share very similar kinematics with the sources (note that massive lenses become necessary only in the last quartile, $`\widehat{t}>60`$ days). For the nearby lens sample, LD events have a rather large spread in $`\mathrm{\Omega }_{tan,L}`$ (due both to their proximity and the velocity dispersion of the COBE-Dyn model), which together with larger $`M_L`$’s is able to produce LD events. We conclude, therefore, that there is no single cause for the long-duration events.

Standard 3-parameter fits to microlensing events are symmetric about the time of peak amplification, resulting in a degeneracy between $`M_L`$, $`v_{}`$, $`D_L`$ and $`D_S`$. One degree of degeneracy is removed by also measuring the light-curve shift due to the parallax from earth’s orbit, which gives a relation between $`v_{}`$ and $`D_L/D_S`$. These shifts are present in all events, but most go undetected because of infrequent sampling and photometric errors. Buchalter & Kamionkowski (1997) estimate a $`1\%`$ detection efficiency of parallax-shifted events for the MACHO-type setup, and much higher for second generation experiments. The light curves of such events require 5 parameters, including $`\kappa R_{}(D_L^1D_S^1)/\mathrm{\Theta }_E`$, where $`R_{}=1`$ AU. In Fig. 3, we present our predictions for the probability distribution in the $`(\kappa ,\widehat{t})`$-plane, assuming $`100\%`$ detection efficiency. These distributions are twin-peaked, with the lower peak increasingly separated from the global peak as $`M_L^<`$ decreases, as it must since $`\kappa \mathrm{\Theta }_E^1`$ while $`\widehat{t}\mathrm{\Theta }_E`$. The location of the second peak may therefore provide an observational constraint on the MF at low mass.

## 5 Conclusions

We have presented a dynamical model of the MWG constructed using the Syer-Tremaine method, constrained only by the MWG density map of Bissantz & Gerhard (2002). Although no kinematic constraints were used, the model (i) matches observed bulge kinematics in several fields and is (ii) able to reproduce the observed microlensing event timescale distribution. For the best fitting MF, the model (iii) predicts a twin-peaked probability distribution in the $`(\kappa ,\widehat{t})`$-plane, which may be observationally tested with new generations of microlensing experiments. (iv) The underlying mass model has been previously shown to match the Galactic near-infrared surface brightness as well as gas-kinematic observations. It is therefore an excellent basis for further studies of the Milky Way.

This work was supported by the Schweizerischer Nationalfonds through grant 20-64856.01.

Figure Captions

Fig. 1 The ETD of the COBE-Dyn model compared to the detection-efficiency-corrected observations of the MACHO group (histograms in all panels). Top: cumulative distribution function for the standard model, $`(M_L^<,M_L^>)=(0.04,4)`$, (solid line), the best model with $`(M_L^<,M_L^>)=(0.04,10)`$ (dotted), and a model with $`(M_L^<,M_L^>)=(0.075,10)`$ (dashed). We obtain $`D_{KS}=0.081,0.068,0.213`$, respectively, for the 3 models. Middle panel: differential distributions of these models (same line styles). (In these two panels, all model distributions have been smoothed with a kernel density estimator of bandwidth $`0.1`$.) Bottom: ETD of the $`(M_L^<,M_L^>)=(0.04,4)`$ model and its decomposition into events with: $`6D_S10`$ kpc (dotted line), $`0D_L4`$ kpc (dashed) and $`D_L>4`$ kpc (dot-dashed).

Fig. 2 Top two panels: The long duration events ($`\widehat{t}>42`$ days) in the $`(M_L^<,M_L^>)=(0.04,4)`$ model. Both are maps (on the same relative scale) in the plane of heliocentric tangential angular velocities, $`\mathrm{\Omega }_{tan,L}`$ and $`\mathrm{\Omega }_{tan,S}`$. Left: near lenses ($`D_L<4`$ kpc); right: distant ones ($`D_L>4`$ kpc). The diagonal and horizontal dashed lines indicate $`\mathrm{\Omega }_{tan,L}=\mathrm{\Omega }_{tan,S}`$ and $`\mathrm{\Omega }_{tan,S}=205/8=25.6`$ $`\mathrm{km}\mathrm{s}^1\mathrm{kpc}^1`$, respectively. Bottom: distributions of $`M_L`$ for distant (solid lines) and nearby (dashed) lenses. The different lines result from splitting into quartiles by contribution to the full ETD the distribution of events sorted on $`\widehat{t}`$. Event durations increase as the mean mass increases. The heavy curve shows the underlying mass function.

Fig. 3 Predicted probability distribution of parallax shifted events in the $`(\kappa ,\widehat{t})`$-plane, for the standard model with $`(M_L^<,M_L^>)=(0.04,4)`$. We use a smoothing kernel with $`(\delta _\kappa ,\delta _{\mathrm{log}\widehat{t}})=(0.01,0.1)`$. The stars mark the locations of secondary peaks when $`M_L^<=`$ 0.075, 0.04, 0.02 and 0.01 in order of increasing $`\kappa `$.


text:
# Two-qubit Quantum Logic Gate in Molecular Magnets

## Abstract

We proposed a scheme to realize a controlled-NOT quantum logic gate in a dimer of exchange coupled single-molecule magnets, $`[\text{Mn}_4]_2`$. We chosen the ground state and the three low-lying excited states of a dimer in a finite longitudinal magnetic field as the quantum computing basis and introduced a pulsed transverse magnetic field with a special frequency. The pulsed transverse magnetic field induces the transitions between the quantum computing basis so as to realize a controlled-NOT quantum logic gate. The transition rates between the quantum computing basis and between the quantum computing basis and other excited states are evaluated and analyzed.
PACS number(s): 03.67.Lx, 75.50.Xx, 75.10.Jm
Key words:Quantum computation, controlled-NOT gate, molecular magnets.

In recent years, quantum computation remarkably attracts the interests of the theoretical and experimental physicists because of its extensive prospects for the practical applications. With the development of the integration techniques, computational devices get smaller, eventually, the physical principles of quantum mechanics must be taken into account. The quantum algorithmsgrover ; shor  discovered show that quantum computation is more effective than classical one. Many systems are investigated theoretically and experimentally to realize quantum computing, such as trapped ionscirac , solid state NMRgershenfeld ; cory , quantum dotsbarenco2 ; loss , SQUIDaverin ; makhin  and spin clustersloss1 ; loss2 . Recently, quantum computation in molecular magnets is addressed. Leuenberger and Loss proposed a scheme to realize Grover’s algorithms in molecular magnets such as $`\text{Fe}_8`$ and $`\text{Mn}_{12}`$leuenberger .

Any quantum logic gate can be decomposed into one-qubit rotation and two-qubit controlled-NOT gate operationbarenco , so the key point for quantum computing is how to realize an arbitrary single-qubit operation gate and a two-qubit controlled-NOT gate(or controlled-phase gate), which are assembled together to realize a universal quantum computing. Realizing a two-qubit quantum logic gate in molecular magnets requires that there are interactions between different molecular particles. But for most molecular magnets such as $`\text{Fe}_8`$ and $`\text{Mn}_{12}`$, the interactions between molecules are relatively weak and have been neglected in most studies. Fortunately, the recent study of a dimerized single-molecule magnets, $`[\text{Mn}_4]_2`$, showed that intermolecular exchange interactions are not always negligiblewernsdorfer . This system is $`[\text{Mn}_4\text{O}_3\text{Cl}_4(\text{O}_2\text{CEt})_3(\text{py})_3]_2`$(called $`[\text{Mn}_4]_2`$), a member of the $`[\text{Mn}_4\text{O}_3\text{Cl}_4(\text{O}_2\text{C}\text{R})_3(\text{py})_3]_2`$ family, with $`\text{R}=\text{Et}`$. The supramolecular linkage within $`[\text{Mn}_4]_2`$ introduces exchange interactions between the $`\text{Mn}_4`$ molecules via the six C–H$`\mathrm{}`$Cl pathways and the Cl$`\mathrm{}`$Cl approach, which lead to noticeable antiferromagnetic coupling between the $`\text{Mn}_4`$ units. Each $`\text{Mn}_4`$ can be modelled as a ‘giant spin’ of $`S=9/2`$ with Ising-like anisotropy.

In this paper,we proposed a scheme to realize a controlled-NOT quantum logic gate in a dimer of exchange coupled single-molecule magnets. First, we don’t consider the transverse exchange interactions between two $`\text{Mn}_4`$ units, and choose the ground state and the three low-lying excited states as quantum computing basis. Then, we introduce an oscillating transverse magnetic field, which can induce transitions between the quantum computing basis so as to realize a controlled-NOT gate in molecular magnets. In our scheme, the two dipole-allowed transitions are at different resonance frequencies, while the oscillating magnetic field is in resonance with only one of them. Finally, we evaluate the amplitudes of transitions between quantum computing basis and the decaying rates of them due to the transverse exchange interactions.

The model– The corresponding Hamiltonian of each $`\text{Mn}_4`$ unit is given bywernsdorfer

$$H_i=DS_{zi}^2+g\mu _BB_zS_{zi},$$
(1)
where $`i=1`$ or $`2`$(referring to the two $`\text{Mn}_4`$ units of the dimer) , $`D`$ is the axial anisotropy constant, $`\mu _B`$ is the Bohr magneton, $`S_z`$ is the easy-axis spin operator, $`g`$ is the electronic g-factor, and $`B_z`$ is the applied longitudinal field. The last term in Eq.(1) is the Zeeman energy associated with an applied field. The $`\text{Mn}_4`$ units within $`[\text{Mn}_4]_2`$ are coupled by a weak superexchange via both the six C–H$`\mathrm{}`$Cl pathways and the Cl$`\mathrm{}`$Cl approach. Thus, the Hamiltonian of a dimer of exchange coupled molecular magnets, $`[\text{Mn}_4]_2`$, can be written aswernsdorfer

$`H_{dimer}=H_1+H_2+J_zS_{z1}S_{z2}+{\displaystyle \frac{J_{xy}}{2}}(S_1^+S_2^{}+S_1^{}S_2^+),`$ (2)
where $`J_z`$ and $`J_{xy}`$ are respectively the longitudinal and the transverse superexchange interaction constants, $`S_i^+`$ and $`S_i^{}`$ are the usual spin raising and lowering operators respectively.

Firstly we don’t consider the transverse exchange interaction term in Eq.(2). Then the corresponding Hamiltonian can be simplified to the form

$$H_0=H_1+H_2+J_zS_{z1}S_{z2}.$$
(3)
For this simplification, every eigenstate of $`[\text{Mn}_4]_2`$ can be labelled by two quantum numbers $`(m_1,m_2)`$ for two $`\text{Mn}_4`$ units, with $`m_1=9/2,7/2,\mathrm{},9/2`$ and $`m_2=9/2,7/2,\mathrm{},9/2`$. The corresponding eigenvalues are given by

$`E_{m_1m_2}^{(0)}=(m_1^2+m_2^2)D+(m_1+m_2)g\mu _BB_z+m_1m_2J_z,.`$ (4)
To realize a controlled-NOT gate, we introduce a pulsed time-depending transverse magnetic field $`V(t)=B_{}(t)[\mathrm{cos}(\omega t)\text{e}_x\mathrm{sin}(\omega t)\text{e}_y]`$, where $`\text{e}_x`$ and $`\text{e}_y`$ are respectively the unit vectors pointing along the $`x`$ and $`y`$ axes. Thus, we obtain the Hamiltonian due to the interactions with the transverse magnetic field asberman

$`H_{}(t)`$ $`=`$ $`{\displaystyle \underset{i}{}}g\mu _BB_{}(t)[\mathrm{cos}(\omega t)S_{xi}\mathrm{sin}(\omega t)S_{yi}]`$ (5)
$`=`$ $`{\displaystyle \underset{i}{}}{\displaystyle \frac{g\mu _BB_{}(t)}{2}}[e^{i\omega t}S_i^++e^{i\omega t}S_i^{}].`$
The pulsed transverse magnetic field rotates clockwise and thus produces left circularly polarized $`\sigma ^{}`$ photons. Absorption (emission) of $`\sigma ^{}`$ photons give rise to $`\mathrm{\Delta }m=1(\mathrm{\Delta }m=+1)`$ transitions of spin states.

A controlled-NOT gate– We choose the ground state and the three low-lying excited states in a finite longitudinal magnetic field as the basis for quantum computing, which are marked by the symbol ‘$`\times `$’ and labelled respectively by the letters ‘a,b,c’ and ‘d’ in Figure 1. These states are $`(9/2,9/2),(9/2,7/2),(9/2,9/2),(9/2,7/2)`$ in a 0.5T longitudinal magnetic field.

From the Eq.(4), we obtain the energy gaps between the quantum computing basis or between them and neighboring excited states, which are shown in Table 1. The energy gap $`E_{9/2,7/2}^{(0)}E_{9/2,9/2}^{(0)}`$ between the states (-9/2,9/2) and (-9/2,7/2) is different from others, which is important to realize a controlled-NOT gate in our scheme.

Now we consider the pulsed transverse magnetic field introduced and evaluated the transition rates between the states by considering the Hamiltonian term about the transverse magnetic field, i.e. Eq.(5), as a perturbation. Using a rectangular pulse shapes with $`B_{}(t)=B_{}`$, if $`T/2<t<T/2`$, and $`0`$ otherwise, we obtain the quantum amplitude for the transition from the state $`(l,l^{})`$ to $`(k,k^{})`$ induced by the magnetic field pulse,

$`C_{kk^{};ll^{}}`$ $`=`$ $`{\displaystyle \frac{\pi g\mu _BB_{}}{i\mathrm{}}}{\displaystyle \underset{i}{}}\left[kk^{}|S_i^+|ll^{}\delta ^{(T)}(\omega _{kk^{},ll^{}}+\omega )+kk^{}|S_i^{}|ll^{}\delta ^{(T)}(\omega _{kk^{},ll^{}}\omega )\right]`$ (6)
where $`\delta ^{(T)}(\omega )=1/2\pi _{T/2}^{+T/2}e^{i\omega t}𝑑t=\mathrm{sin}(\omega T/2)/\pi \omega `$ is the delta-function of the width $`1/T`$, ensuring overall energy conservation for $`\omega T1`$. For convenience, we denote the energy gaps between the quantum computing basis as $`\omega _1=(E_{9/2,7/2}^{(0)}E_{9/2,9/2}^{(0)})/\mathrm{}`$ and $`\omega _2=(E_{9/2,7/2}^{(0)}E_{9/2,9/2}^{(0)})/\mathrm{}`$. From the Table 1, we obtain $`\mathrm{\Delta }\omega \omega _1\omega _2=9J_z/\mathrm{}`$. In our scheme, we choose the frequency of the magnetic pulse $`\omega =\omega _1`$. Then,the transition rate $`w_{9/2,7/2;9/2,9/2}=|C_{9/2,7/2;9/2,9/2}|^2/T`$ from the states $`(9/2,9/2)`$ to $`(9/2,7/2)`$ by absorbing a $`\sigma ^{}`$ photon is

$$w_{9/2,7/2;9/2,9/2}\frac{9T(g\mu _BB_{})^2}{4\mathrm{}^2},$$
(7)
where the relations $`|\delta ^{(T)}(\omega )|^2(T/2\pi )\delta ^{(T)}(\omega )`$ and $`\delta ^{(T)}(0)=T/2\pi `$ are used. The transition rate $`w_{9/2,9/2;9/2,7/2}`$ from the states $`(9/2,7/2)`$ to $`(9/2,9/2)`$ by emitting a $`\sigma ^{}`$ photon is identical to $`w_{9/2,7/2;9/2,9/2}`$. Since the magnetic pulse frequency $`\omega `$ isn’t equal to the energy gap $`\omega _2`$ between the states (9/2,9/2) and (9/2,7/2), i.e., $`\omega _1\omega _2`$, which is shown in Figure 2, the transition rate between the two states is very small and can be negligible. From Reference wernsdorfer , the parameters $`D`$ and $`J_z`$ are chosen as $`0.72K`$ and $`0.1K`$ respectively in this paper. We insert the parameters $`T=10^8\text{s}`$ and $`B_{}=3.8\text{G}`$ into Eq.(7) giving the transition rates $`w_{9/2,7/2;9/2,9/2}=w_{9/2,9/2;9/2,7/2}=1.0\times 10^8\text{s}^1`$, while $`w_{9/2,7/2;9/2,9/2}=w_{9/2,9/2;9/2,7/2}=2.4\times 10^2\text{s}^1`$. If we set $`T=10^7\text{s}`$ and $`B_{}=0.38\text{G}`$, then the transition rates $`w_{9/2,7/2;9/2,9/2}=w_{9/2,9/2;9/2,7/2}=1.0\times 10^7\text{s}^1`$, while $`w_{9/2,7/2;9/2,9/2}=w_{9/2,9/2;9/2,7/2}=0.23\text{s}^1`$. Here the values of $`T`$ and $`B_{}`$ are chosen to guarantee $`Tw_{9/2,7/2;9/2,9/2}=1`$, *i.e.*, the transverse magnetic pulse introduced is a $`\pi `$ pulse. From the data above, we can neglect the transitions between the states $`(9/2,9/2)`$ and $`(9/2,7/2)`$ compared with that between $`(9/2,9/2)`$ and $`(9/2,7/2)`$. In addition, the pulsed transverse magnetic field can induce transitions from the states as quantum computing basis to the other excited states, which lead to the decaying of quantum computing basis. When $`T=10^8\text{s}`$ and $`B_{}=3.8\text{G}`$, the transition rates $`w_{9/2,5/2;9/2,7/2},w_{9/2,5/2;9/2,7/2}`$ and $`w_{7/2,7/2;9/2,7/2}`$ are $`4.4\times 10^1\text{s}^1,8.8\text{s}^1`$ and $`3.6\times 10^2\text{s}^1`$ respectively; when $`T=10^7\text{s}`$ and $`B_{}=0.38\text{G}`$, transition rates $`w_{9/2,5/2;9/2,7/2},w_{9/2,5/2;9/2,7/2}`$ and $`w_{7/2,7/2;9/2,7/2}`$ are $`2.5\times 10^2\text{s}^1`$, $`4.3\times 10^2\text{s}^1`$ and $`3.6\times 10^1\text{s}^1`$ respectively. These transition rates are smaller several orders than the transition rates $`w_{9/2,7/2;9/2,9/2}`$ and $`w_{9/2,9/2;9/2,7/2}`$, so they are also negligible.

From the above discussion, we know that, when introducing the special frequency transverse magnetic field, only coherent transition between the spin states $`(9/2,9/2)`$ and $`(9/2,7/2)`$ is prominent and others are negligible. So we can interpret it as Rabi oscillation of two level atom. With $`|a`$ and $`|b`$ denote the spin states $`(9/2,9/2)`$ and $`(9/2,7/2)`$ respectively, simplify the Hamiltonian as

$`H_{rabi}(t)`$ $`=`$ $`\mathrm{}\omega _a|aa|+\mathrm{}\omega _b|bb|`$ (8)
$`{\displaystyle \frac{\mathrm{}}{2}}\mathrm{\Omega }(e^{i\omega t}|ab|+e^{i\omega t}|ba|).`$
where $`\omega _a=E_{9/2,9/2}^{(0)}/\mathrm{}`$, $`\omega _b=E_{9/2,7/2}^{(0)}/\mathrm{}`$ and $`\mathrm{\Omega }=g\mu _BB_{}\mathrm{}`$ is Rabi frequency. The coherent wave function of the two states can be written in the form

$$|\psi (t)=c_a(t)e^{i\omega _at}|a+c_b(t)e^{i\omega _bt}|b.$$
(9)
From Eqs.(8) and(9), we obtain the solution

$`c_a(t)=c_a(0)\mathrm{cos}\left({\displaystyle \frac{\mathrm{\Omega }t}{2}}\right)+ic_b(0)\mathrm{sin}\left({\displaystyle \frac{\mathrm{\Omega }t}{2}}\right),`$ (10)
$`c_b(t)=c_b(0)\mathrm{cos}\left({\displaystyle \frac{\mathrm{\Omega }t}{2}}\right)+ic_a(0)\mathrm{sin}\left({\displaystyle \frac{\mathrm{\Omega }t}{2}}\right),`$ (11)
where $`c_a(0)`$ and $`c_b(0)`$ are the initial values of $`c_a`$ and $`c_b`$ respectively when $`t=0`$. From this solution, we know that, if the transverse magnetic field introduced is $`\pi `$ pulse, i.e. $`\mathrm{\Omega }t=\pi `$, we realize a NOT gate between the two states. Simultaneously, other states of computing basis do not vary.

Therefore,the pulsed magnetic field gives rise to the state transitions shown in the left column of Table 2. We choose the first $`\text{Mn}_4`$ unit as the control qubit and the second one as the target qubit. Here the quantum states $`m_1=9/2`$ and $`9/2`$ of the first $`\text{Mn}_4`$ unit correspond to the quantum logic state $`|0`$ and $`|1`$ of the control qubit respectively, while the quantum states $`m_2=9/2`$ and $`7/2`$ of the second $`\text{Mn}_4`$ unit correspond to the quantum logic state $`|0`$ and $`|1`$ of the target qubit respectively, as shown in Table 2. In fact, the transition induced by the pulsed magnetic field correspond to the transform of the the quantum computing basis as

$$U_{CNOT}=\left(\begin{array}{cccc}1& 0& 0& 0\\ 0& 1& 0& 0\\ 0& 0& 0& 1\\ 0& 0& 1& 0\end{array}\right).$$
(12)
So our scheme has realized a conditional quantum dynamics in a dimer of exchange coupled single-molecule magnets, $`[\text{Mn}_4]_2`$.

In our scheme a key point is that the frequency of the pulsed transverse magnetic field is chosen as $`\omega =\omega _1`$ instead of $`\omega =\omega _2`$. Seemingly, if we choose the quantum states $`m_1=9/2`$ and $`9/2`$ of the first $`\text{Mn}_4`$ unit as the quantum logic states $`|0`$ and $`|1`$ of the control qubit respectively and the frequency of the pulsed transverse magnetic field as $`\omega =\omega _2`$, the controlled-NOT gate can also be realized. However, this is not true. In fact, when $`\omega =\omega _2`$, the pulsed transverse field can induce the transition from the state $`(9/2,9/2)`$ to the states $`(9/2,7/2)`$ or $`(7/2,9/2)`$ by absorbing a $`\sigma ^{}`$ photon, because the states $`(9/2,7/2)`$ and $`(7/2,9/2)`$ are energy degenerate and the energy gaps $`E_{9/2,7/2}^{(0)}E_{9/2,9/2}^{(0)}`$ and $`E_{7/2,9/2}^{(0)}E_{9/2,9/2}^{(0)}`$ are identical with each other, which are shown in Table 1. Thus, if we choose $`\omega =\omega _2`$, the state $`(9/2,9/2)`$ will decay into the state $`(7/2,9/2)`$, which does not belong to the quantum computing basis.

The effects of the transverse exchange interactions– In the above discussion, we have not considered the transverse exchange interactions, i.e., the last term in Eq.(2), re-denoted as

$$H_{xy}=\frac{J_{xy}}{2}(S_1^+S_2^{}+S_1^{}S_2^+)$$
(13)
which in fact can induce the decaying of the quantum computing basis into other excited states. In the first order, $`H_{xy}`$ acts between the zeroth-order eigenvectors $`(m_1,m_2)`$ and $`(m_1\pm 1,m_21)`$. The effect of $`H_{xy}`$ on the tunnelling of the states is discussed in details in Ref.hill . We perturbatively evaluated the amplitude of the transition from the states from $`(l,l^{})`$ to $`(k,k^{})`$ as,

$`C_{kk^{};ll^{}}={\displaystyle \frac{2\pi }{i\mathrm{}}}kk^{}|H_{xy}|ll^{}\delta ^{(T)}(\omega _{kk^{},ll^{}})`$ (14)
Here the transitions from the quantum computing basis to other excited states induced by the $`H_{xy}`$ are $`(9/2,7/2)(7/2,9/2),(9/2,9/2)(7/2,7/2)`$ and $`(9/2,7/2)(7/2,5/2)`$, while transition from the state $`(9/2,9/2)`$ can not occur since the total spin of the $`\text{Mn}_4`$ unit is $`9/2`$. Since the superexchange interaction of the dimer $`[\text{Mn}_4]_2`$ is nearly isotropictiron , we set the parameter $`J_{xy}=0.1K`$. When the duration $`T`$ is infinite, $`\delta ^{(T)}(\omega _{kk^{},ll^{}})`$ in Eq.(14) becomes Dirac delta function $`\delta (\omega _{kk^{},ll^{}})`$. The energy conservation holds when the transitions happen. From Table 1, only the transition between spin states $`(9/2,7/2)`$ and $`(7/2,9/2)`$ is possible. However, if $`T`$ is finite, the energy conservation does not hold during transition due to uncertainty principle. Thus, the transition between nondegenerate states is possible if $`T`$ is finite. Because the time of quantum computing operation is finite, it is necessary to evaluate the transition rate due to exchange interaction to compare with transition induced by magnetic field. When $`T`$ is $`10^8\text{s}`$, we evaluated the transition rates $`w_{7/2,9/2;9/2,7/2}`$, $`w_{7/2,7/2;9/2,9/2}`$ and $`w_{7/2,5/2;9/2,7/2}`$ are $`8.9\times 10^{13}\text{s}^1`$, $`3.8\times 10^{21}\text{s}^1`$ and $`1.3\times 10^{20}\text{s}^1`$ respectively. If the duration $`T=10^7\text{s}`$, then $`w_{7/2,9/2;9/2,7/2}=8.9\times 10^{12}\text{s}^1`$, $`w_{7/2,7/2;9/2,9/2}=6.2\times 10^{22}\text{s}^1`$ and $`w_{7/2,5/2;9/2,7/2}=1.1\times 10^{21}\text{s}^1`$. The rates of transitions induced by the transverse exchange interactions are far smaller than that of the transitions between the quantum computing basis, so we can neglect them and do not consider their effects in our scheme.

Conclusion– We have proposed a scheme to realize a controlled-NOT quantum logic gate in a dimer of exchange coupled single-molecule magnets, $`[\text{Mn}_4]_2`$. We first neglected the transverse exchange interactions between the two $`\text{Mn}_4`$ units and obtained the spin states, and the energy spectrum. Then, we chosen the ground state and the three low-lying excited states in a finite longitudinal magnetic field as the quantum computing basis and introduced a pulsed transverse magnetic field with a special frequency, which can induce transitions between the quantum computing basis so as to realize a controlled-NOT operation. In our scheme, the magnetic pulse is a $`\pi `$ pulse, which leads to the transitions of spin states with $`\mathrm{\Delta }m=\pm 1`$. We have evaluated the transition rates induced by the transverse exchange interactions and analyzed the their effects on decaying of the states. In this paper, we have not considered the initializing, read-in and read-out of the states, which are needed to improve in technique for molecular magnets. If the measure approach of the single molecular magnet is improved, molecular magnets are promising candidates for quantum computing.

This work is in part supported by NSF of China No.10447125.