text:
# A new catalogue of ISM content of normal galaxies.

## 1 Introduction

Different surveys have been conducted thus far to establish if galaxies can be characterized by a canonical gas content that may vary significantly along the Hubble sequence (early-type versus late-type objects) and/or depend on the particular environment (isolated versus strongly interacting galaxies) (Knapp et al. 1989; Bregman et al. 1992; Casoli et al. 1998; Fabbiano et al. 1992; Burstein et al. 1997; Beuing et al. 1999). A global study of the ISM content in galaxies requires a multi-wavelength approach: far infrared (FIR) observations at 60 and 100 $`\mu `$m trace the warm dust content, while those at 140-200 $`\mu `$m the cold dust; mm lines of carbon monoxide (CO) and the 21cm line of HI must be used to infer the molecular and atomic gas content, respectively: the X-ray wave-band is used to study the hot gas component. However, results obtained from previous surveys have strong biases due to poor statistics (uneven coverage along the Hubble sequence) and, also, due to the inclusion of galaxies which are known to be ‘peculiar’. As an example, the selection of candidate galaxies to be observed in CO surveys have been typically based on Far Infrared Luminosity (FIR) criteria. This often favors the inclusion of ‘peculiar’ galaxies in surveys and introduces a bias against ‘normal’ systems.

In this work we present a new catalogue describing the Interstellar Medium (ISM) content in a sample of 1916 ‘normal’ galaxies. A first preliminary version of this catalogue was used by Bettoni et al. (2001) (Paper I) as a reference in their study of the gas content of gas-accreting galaxies. First of all, this requires the adoption of a non-obvious definition for ‘normality’. In this work we will consider a galaxy to be ‘peculiar’, hence to be excluded from the catalogue, if it has any sign of perturbed morphology due to a recent or ongoing interaction like tidal tails, bridges, warps or disk lopsidedness. Furthermore, with our definition of normal galaxy, we also exclude from this catalogue any galaxy having any sign of peculiar kinematics, revealed by the presence of polar rings, counterrotating cores/disks or other decoupled components. With this definition, we do not exclude in principle galaxies belonging to groups or clusters: here, a ‘normal’ galaxy is not necessarily an ‘isolated’ galaxy, but rather a dynamically relaxed stable system. Nuclear activity is far from universal among galaxies, although most galaxies are known to host super-massive black holes in their nuclei. We purposely include active galaxies in our sample, considering that activity may represent just an episodic stage in the evolution of normal galaxies that appear as globally unperturbed, and therefore fitting our requirements.

The ISM catalogue has been compiled making use of several sources available in the literature. All values have been re-scaled using a common distance reference taken from the Catalogue of Principal Galaxies (PGC). We derive mean values for the ISM content along the Hubble sequence, using a survival analysis method that properly takes into account upper limits. The various gas content estimators have been normalized using both the galaxy absolute blue luminosity LB and the size D$`{}_{25}{}^{}{}_{}{}^{2}`$. The latter allows the direct comparison of our results with those of previous works that used either LB (Bregman et al. 1992) or D$`{}_{25}{}^{}{}_{}{}^{2}`$ (Casoli et al. 1998) to derive canonical mean values for galaxies of different Hubble types.

The new catalogue significantly improves the statistics of previous reference catalogues. This is especially relevant in the case of early type galaxies: compared to previous studies, our sample improves the number of early-type galaxies included by a factor $`>`$3 (from ellipticals to lenticulars). This catalogue is intended to be used in future studies as a reference for the ISM content in normal galaxies. The catalogue can be accessed on line and is also available at the Centre des Données Stellaires (CDS).

## 2 Data compilation

### 2.1 The data search

We searched in the literature for the different available papers (both survey papers and those dealing with case-by-case studies (Knapp et al. 1989; Roberts et al. 1991; Casoli et al. 1998; Fabbiano et al. 1992; Burstein et al. 1997; Beuing et al. 1999)) and collected all the published data on the different tracers of ISM in galaxies. This produced a preliminary list of more than 3400 candidate galaxies. From this list, all the systems having an acknowledged peculiarity had to be excluded. In addition, we found 148 galaxies, included in this preliminary compilation, that are listed in the Veron et al. (2000) catalogue of active galaxy nuclei (AGN). For the reasons explained above, we decided to include these galaxies in our sample, although they will be discussed separately.

### 2.2 Discarded types of galaxies

We considered all the systems belonging to at least one of the following categories to be globally peculiar and we therefore removed them from our sample:

1) Interacting and disturbed galaxies. They are mainly listed in the Arp (1966), Arp & Madore (1987) and Vorontsov-Velyaminov (1959) catalogues and appear to be interacting with a close object or have an evident sign of distortion in their disks/spheroids. This category includes 1422 galaxies, i.e., the bulk of the systems we discarded to build this compilation.

2) Polar ring galaxies. Some galaxies appear to host polar- or very inclined- rings of gas and/or stars. In this category of peculiar galaxies we find ellipticals (Bertola & Galletta 1978; Hawarden et al. 1981) such as NGC 5128 and disk galaxies (Schweizer et al. 1983; Whitmore et al. 1990) as NGC 4650A. These decoupled components betray a passed accretion episode. The origin of polar rings is connected to an interaction or merging between a galaxy and a ‘donor’ source which may be another galaxy or intergalactic gas. The ISM content of polar rings has been discussed in Paper I. We found 51 polar ring galaxies, which were removed from our catalogue.

3) Galaxies with counterrotation. Counterrotating galaxies have a significant amount of their gas and/or stars (Galletta 1996; Bettoni et al. 2001) rotating in opposite direction with respect to the majority of the stars. Similarly to the case of polar rings, the counterrotation phenomenon is also considered to be linked with interaction or merging episodes. Sixty galaxies were discarded due to the presence of stellar- or gas- counterrotating components.

### 2.3 The final sample

After exclusion of all the systems belonging to one of the three categories enumerated above, the final sample of normal galaxies includes 1916 objects. The data presented in this catalogue have been collected from the following sources:

* FIR observations, at 60 and 100 $`\mu `$m from Knapp et al. (1989) catalogue and the Lyon-Meudon Extragalactic Database (LEDA) (Paturel et al. 1997). These references furnish the bulk of the FIR data used here: 992 detections and upper limits from Knapp et al. (1989) and 711 from LEDA. In the latter case, both the 60 $`\mu `$m and 100 $`\mu `$m fluxes (S60 and S100) are available in the raw data, kindly provided by G. Paturel. Many of the galaxies (346) are also listed in Roberts et al. (1991). Additional IR data for 81 galaxies have been extracted from the NASA/IPAC extragalactic database (NED) and Lavezzi et al. (1999) (30 galaxies).
* CO(1–0) observations for 175 galaxies have been taken from a long list of published papers. We extracted data also from Roberts et al. (1991) (58) and from the references listed in Casoli et al. (1998), including 299 galaxies studied in previous works.
* HI data, 855 from LEDA (Paturel et al. 1997), 277 from Roberts et al. (1991), and 251 from various sources, including (Casoli et al. 1998) and NED.
* X-ray data from papers based on observations made with the Einstein (Fabbiano et al. 1992; Burstein et al. 1997) and the ROSAT (Beuing et al. 1999) missions. They furnish 290, 683 and 247 values respectively, with many galaxies in common. A more recent revision of these data for 343 galaxies has been presented by O’Sullivan et al. (2001).

For each galaxy we also collected the distance, the blue luminosity and the size. To standardize the information contained in our catalogue we decided to use the morphological classification, distances, sizes and optical luminosities derived from a single source: the LEDA archive. These data were used to normalize the values of FIR and X-ray luminosities as well as the atomic and molecular gas masses. More precisely, we have extracted the following items for each galaxy: PGC number, morphological type and related numerical parameter $`t`$, distance modulus and absolute magnitude. The distance moduli are mainly derived from redshifts, corrected for Virgocentric inflow and adopting Ho=70 km s-1 Mpc-1. When redshift was not available, we used the photometric distance modulus, if present in LEDA. Information lacking in LEDA for some galaxies was completed using the ADS bibliographic archive, the NED database or the SIMBAD service of the Strasbourg Centre of Donnée Stellaire (CDS). Finally, the very few galaxies having no classification in the literature were classified by us looking at the optical images extracted from NED.

The luminosity function and the distribution of morphological types are shown in Fig. 1. The distribution of morphological types has two maxima for ellipticals and lenticulars. However, the rest of morphological types are equally represented in the catalogue with similar percentages. Altogether, spirals and irregulars (t$``$0) represent 40% of our sample. In Fig. 1 galaxies hosting AGN are represented with dark shaded histograms. At first sight, their mean blue luminosity is slightly above the average value for the whole sample; on the other hand, the morphological type distribution of AGN is more weighted by spiral galaxies compared to the whole sample.

## 3 Data processing

### 3.1 Mass estimates

We have estimated total gas masses and/or luminosities following standard procedures (e.g. see Roberts et al. (1991)). The number of detections and upper limits in our sample are listed in Table 2. In the following formulae, the distance $`d`$ is always in Mpc.

From the value of the IR fluxes at 60 and 100 $`\mu `$m we estimated the dust temperature (K):

$$T_d=49\times (S_{60}/S_{100})^{0.4}$$

The corresponding warm dust mass, in solar units, follows from the expression:

$$LogM_d=2.32+LogS_{100}+2Logd+Log(exp(\frac{144.06}{T_d})1)$$

Where $`S_{100}`$ is in mJy. When data for a single galaxy were available in several catalogues, we compared the mass values and the data quality, and derived accordingly in Table 1 a weighted mean value.

HI gas masses were derived mainly from 21 cm fluxes $`S_{21}`$ or from the m21 magnitudes of LEDA. From individual papers giving HI masses only, we have scaled the published values to the adopted galaxy distance. ¿From m21, we used the expression:

$$LogM_{HI}=5.370.4(m_{21c}17.4)+2Logd$$

while if S21, in Jy km s-1, was available we used the formula:

$$LogM_{HI}=5.37+LogS_{21}+2Logd$$

Similarly, we have produced mean values when data from different sources were simultaneously available. When both upper limits and detections were available only detections have been used to compute mean values. Moreover, when several upper limits were available, only the lowest value has been adopted.

The data needed to derive the molecular gas content have been taken from various sources (see Appendix A). The formula used to derive molecular gas masses from CO(1–0) line fluxes ($`S_{CO}`$ in Jy km s-1) is:

$$LogM_{mol}=4.17+2Logd+LogS_{CO}$$

We implicitly assume a constant CO/H2 conversion factor $`\chi `$ = $`N(H_2)/I_{CO}`$= 2.3 $`\times `$ 1020 mol/K km s-1 (Strong 1988); $`M_{mol}`$ includes the helium mass fraction by multiplying the H2 mass by 1.36. When only mass values were available in the consulted references, these have been scaled to the distances assumed here. As discussed in paper I, a source of uncertainty for the estimates of Mmol comes from the undersampling of some of the sources mapped in CO. However the majority of CO observations considered here sample fairly well the emission in the inner galaxy disks. As we expect the bulk of CO emission to come precisely from these regions, the derived Mmol should be taken as a meaningful lower limit for the total molecular gas mass. A variation of the CO-H2 conversion factor–$`\chi `$–can neither be excluded and may be caused by the different metallicities or physical conditions for molecular gas among the galaxies in the sample. Before any further improvement can be envisaged we will assume the above derived values as a good estimate of the molecular gas masses.

X-ray emission in galaxies may derive from diffuse gas and/or from discrete sources. This means that the mass estimate of hot gas strongly depends on the prevalent mechanism at work in a particular galaxy. Hence, mass estimates cannot be described by a simple formula. We thus decided to use the X-ray luminosities, instead of the masses, to describe the canonical X-ray yield for galaxies in our sample. A discussion of the differences existing in literature data on X-ray observations with different telescopes has been made by Beuing et al. (1999).

We have 325 detections and 626 upper limits among the inactive galaxies; and 84 detections and 29 upper limits from galaxies indicated in the Veron et al. (2000) catalogue as AGN (139) or containing quasars (6) or BL Lac (3).

To avoid zero-order biases we have normalized the gas masses and luminosities using two different normalization factors: the total blue luminosity–LB-and the square of the linear diameter measured at 25 mag arcsec-2D$`{}_{25}{}^{}{}_{}{}^{2}`$. These parameters are available for all the 1916 galaxies of our sample. The absolute blue magnitudes (from LEDA catalogue) are corrected for dust absorption and cosmological reddening. The global correction is also a function of the type (Paturel et al. 1997); the correction factor increases toward later types.

The mean value of $`Log\text{L}\text{B}/\text{D}{}_{25}{}^{}{}_{}{}^{2}`$, derived for the galaxies in our sample is:

$$Log\text{L}\text{B}/\text{D}{}_{25}{}^{}{}_{}{}^{2}=0.013t+7.6$$

with LB/D$`{}_{25}{}^{}{}_{}{}^{2}`$in L/kpc2 with an rms of $`\pm `$0.3 (1$`\sigma `$). As we shall see in the following paragraphs, this relatively low slope produces similar trends in the M/LB and M/D$`{}_{25}{}^{}{}_{}{}^{2}`$ mean ratios derived in this work.

### 3.2 Stability of the results.

In principle, M/LB and M/D$`{}_{25}{}^{}{}_{}{}^{2}`$ ratios do not depend at all on the adopted distance of the galaxy. This makes our results insensitive to the specific value of the Hubble constant adopted. However, distances and magnitudes are affected differently by the corrections for the Virgocentric motion and by the galactic and internal absorptions. Hence, M/LB and M/D$`{}_{25}{}^{}{}_{}{}^{2}`$ may change significantly. Since the first approach to this catalogue was published by Bettoni et al. (2001), the LEDA database has been modified, because the stored data are continuously being updated. In addition to these changes, a significant amount of new data from other sources have been included in the new catalogue.

While these changes forced us to recalculate all the ratios, this allowed us to test the stability of our results. Comparing the data extracted from this database in different dates in the last two years, we found that the 90% of the Log M/LB and the 98% of the Log M/D$`{}_{25}{}^{}{}_{}{}^{2}`$ values calculated from these different data extractions differ by less than 1$`\sigma `$, with no variation larger than 2$`\sigma `$. Within these ranges we expect our conclusions to be stable.

### 3.3 Derivation of mean ratios: Log $`M/D^2`$–Log $`M/L`$

In order to define the mean content of each tracer according to the type, we made use of survival analysis methods (see Feigelson & Nelson 1999), applied to the different ensembles of M/LB and M/D$`{}_{25}{}^{}{}_{}{}^{2}`$ data. This analysis tool properly takes into account both detections and upper limits (UL) in order to derive representative averages. The mean values are derived and shown in the following Tables, binned according to the morphological type code. This method also allows a more direct comparison of our data with that from literature.

Survival analysis (Feigelson & Nelson 1999) programs are part of several packages of data analysis, such as IRAF, and may be applied when a number of upper or lower limit values are available together with values from detections. Making use of the Kaplan-Meier estimator, we derived, for each $`t`$, mean values of mass/light and mass/area ratios and the corresponding standard deviations. When all the galaxies considered within an interval of $`t`$ are detected, these values coincide with that from arithmetic means. On the contrary, the method cannot be applied when both upper and lower limits are present, for instance when considering the mass ratios (e.g. Mmol/MHI). In such a case, we present ratios of mean values.

### 3.4 Description of the full version of the catalogue.

All the data of this catalogue are listed in Table 1, which is only available in digital form. The first page is shown in Table 1 of this paper, as an illustration of the on-line catalogue format. The columns are: (1) the PGC identifier and (2) the galaxy name, (3) the numerical type code $`t`$ (de Vaucouleurs et al. 1991; Paturel et al. 1997), (4) this column indicates the presence of nuclear activity (Veron et al. 2000) with the letter ‘a’, (5) the adopted distance $`d`$ (in Mpc), (6) the logarithm of the total blue luminosity LB in solar units, (7) the logarithm of the linear size $`D_{25}`$ in kpc corresponding to the 25 mag arcsec-2 isophote. The values for each tracer (dust, HI, molecular gas, X-ray) span four columns: the first two are mass vs. LB and the next two are mass vs. area, defined as D$`{}_{25}{}^{}{}_{}{}^{2}`$. Values corresponding to detections of a galaxy in the corresponding tracers are in the first and in the third columns while upper limits are in the second and fourth columns. All masses and luminosities are in solar units. Following this scheme, the following columns contain: Log Mdust/LB detections (col. 8) and upper limits (col. 9), Log Mdust/D$`{}_{25}{}^{}{}_{}{}^{2}`$ detections (col. 10) and upper limits (col. 11), Log MHI/LB detections (col. 12) and upper limits (col. 13), Log MHI/D$`{}_{25}{}^{}{}_{}{}^{2}`$ detections (col. 14) and upper limits (col. 15), Log Mmol/LB detections (col. 16) and upper limits (col. 17), Log Mmol/D$`{}_{25}{}^{}{}_{}{}^{2}`$ detections (col. 18) and upper limits (col. 19), Log LX/LB detections (col. 20) and upper limits (col. 21), Log LX/D$`{}_{25}{}^{}{}_{}{}^{2}`$ detections (col. 22) and upper limits (col. 23). References for the gas masses are listed in the last column (24). The reference codes are given in the Appendix.

This table contains all the essential information compiled for this catalogue. This compilation is intended to serve as a template for future studies on the gas content in selected types of galaxies.

## 4 Analysis of main results

Tables 26 give the normalized mean gas contents–Log $`M/D^2`$ and Log $`M/L_B`$– and the detection rates for the galaxies of the sample, as a function of the Hubble type. The galaxies are identified according to the numerical code $`t`$ (RC3 morphological type). Some types have two numerical codes: elliptical galaxies span the types -5 and -4; S0-a the types -1 and 0 and Sc galaxies fill the types 5 and 6; all the remaining galaxy types are identified by a single code. Note that the code 5.00 also includes spiral galaxies with ambiguous classification (type S?). In our sample there are only 7 galaxies falling into this category.

### 4.1 Detection rates

As far as detection rates are concerned, we have found the following trends:

* The detection rate of elliptical galaxies in X-ray wavelengths from our data is 1.3–4 times higher than that of late-type galaxies. As expected, the percentage of X-ray detections for spirals increases by 10% if AGN galaxies are included in the sample.
* On the other hand, compared with ellipticals, both CO and HI detections are $``$4 times more common in disk galaxies (note however that $``$40% of type t=-5 ellipticals have been detected in CO or HI). This high detection rate in spirals reflects the higher cold gas content of disk galaxies. The dust detection roughly follows the HI detection rates.

### 4.2 Comparison with previous work

Bregman et al. (1992) and Casoli et al. (1998) have previously addressed the study of the ISM content in galaxies and its variation along the Hubble sequence. Both groups based their study on two samples of 467 (Bregman et al. 1992) and 582 (Casoli et al. 1998) galaxies, compiled and processed according to different criteria. Our catalogue improves by a significant factor ($``$3–4) the overall statistics of previous samples. The most significant improvement corresponds to the left branch of the Hubble sequence: compared to previous works, the number of early-type galaxies (t $`<0`$) with firm detections processed for this catalogue is $`>`$3 times larger.

Bregman et al. (1992) analyzed their sample using other non-parametric tests, based on rank, to study the variation of the mean gas content with morphological type. The estimated averages were normalized to the galaxy blue luminosity. Their results indicate that the mean content of atomic gas (in M/LB scale) decreases by two orders of magnitude from early-type spirals (Sa) to ellipticals (E). A similar result is obtained for the mean content of molecular gas. Altogether, these results underlined that ellipticals have a neutral gas content significantly lower than lenticulars (see Fig. 2). The sample of Bregman et al. (1992) has only 7 (35) firm detections in CO (HI) for galaxies spanning the lenticular-elliptical range.

The scenario depicted by Casoli et al. (1998) seems at odds with Bregman et al. (1992)’s results, however. Casoli et al. (1998) used a survival analysis method and normalized their data by D$`{}_{25}{}^{}{}_{}{}^{2}`$. According to Casoli et al. (1998), the atomic mean gas content shows little variation going from elliptical to lenticular galaxies (see upper panel of Fig. 2). Within the same type range, the molecular gas content varies by less than one order of magnitude: i.e., significantly less than shown by Bregman et al. (1992). Casoli et al. (1998) excluded from their sample galaxies in cluster environments, tagged as HI-deficient. This might explain why, in contrast to Bregman et al. (1992), Casoli et al. (1998) find no significant trend for the HI content. The sample of Casoli et al. (1998) has 11 (13) firm detections in CO (HI) for galaxies spanning the lenticular-elliptical range.

These two scenarios might only be reconciled if the mean LB/D$`{}_{25}{}^{}{}_{}{}^{2}`$ ratios were seen to strongly depend on morphological type in the ‘conflicting’ range: ellipticals would need to be much fainter, by at least two orders of magnitude, with respect to S0 of comparable sizes. As it has been discussed in Sect. 3.1, the estimated trend of $`Log\text{L}\text{B}/\text{D}{}_{25}{}^{}{}_{}{}^{2}`$ is much smoother, however; this is confirmed by the similar trends obtained using either M/LBor M/D$`{}_{25}{}^{}{}_{}{}^{2}`$as gas content indicators.

The strong disagreement between these two studies should be attributable to their poor statistics. This is probably the reason why our estimates of the neutral gas content match neither of previous claims in this range. As it is shown in Table 2, the present catalogue is based on 31 CO detections and 132 HI detections within the range of early type galaxies (ellipticals to lenticulars). Our results, normalized with respect to LB and D$`{}_{25}{}^{}{}_{}{}^{2}`$ both indicate a similar trend: a moderate one order of magnitude decrease of the mean neutral gas content (atomic and/or molecular) going from S0 to E galaxies.

It is worth noting that, in contrast to Casoli et al. (1998), we found that the Mmol/MHI ratio is roughly constant along the Hubble sequence, except for the latest type systems (Sd and Irr) where this ratio decreases by one order of magnitude. Early-type galaxies and early spirals possess $``$40% of their neutral gas content in the molecular phase, while late-type spirals and irregulars have $``$90% of their neutral gas content in atomic form. In Fig. 3, we plotted our data together with values derived by Casoli et al. (1998).

### 4.3 AGN versus non-active galaxies

We have found no significant differences in the neutral gas content between galaxies hosting AGNs and those considered as non-active. For this reason, the mean data in Tables 3-4 do not distinguish between active and inactive galaxies, even if it is possible to identify both categories of galaxies in our catalogue.

In our database there are 20 active galaxies that are more luminous than Log LX/LB=-2, while most of the remaining galaxies have values between -2 and -4. Apart from the overluminous galaxies, the mean ratios LX/LB and LX/D$`{}_{25}{}^{}{}_{}{}^{2}`$ show an almost flat trend going from elliptical galaxies to Sa and a slowly decreasing trend for later types (Fig. 4). In Table 6 we publish the mean values obtained by both including and excluding AGN.

## 5 On-line access

We have presented a catalogue devoted to study the ISM content in a sample of normal galaxies. The catalogue has been compiled based on previous catalogues with the addition of a significant volume of new data. This is intended to serve as a reference defining the canonical gas content of ’normal’ galaxies along the Hubble sequence. The latest version of the catalogue is available at http://dipastro.pd.astro.it/galletta/ismcat/. The number of galaxies included, 1916 systems, is 3–4 times higher than previous studies, and fills a gap currently existing in the ISM studies of cold gas for early-type galaxies. All the catalogue data have been homogenized and reduced to the same distance scale and can be accessed as a single text list, formatted in columns, or consulted at CDS. Upon request, it can be obtained from the authors as an Excel-formatted database.

## 6 Acknowledgments

The authors thanks Dr. D. Hogg, for the useful comments to this work.

This research made use of Vizier service (Ochsenbein, Bauer, & Marcout 2000), the SIMBAD database (operated at CDS, Strasbourg, France), the NASA/IPAC Extragalactic Database (NED) (which is operated by JPL, California Institute of Technology, under contract to NASA) and NASA’s Astrophysics Data System Abstract Service (mirrored in CDS of Strasbourg). The authors would like to thank Dr. G. Paturel for kindly making the LEDA database’s FIR raw data available and Dr. F. Ochsenbein for the changes made to the Vizier’s query form on our request. GG made use of funds from the University of Padova (Fondi 60%-2002).

## 7 Appendix A: References to Table 1

| reference | Source of data | ISM |
| --- | --- | --- |
| code |  | tracer |
| 1a | Andreani, Casoli & Gerin (1995) | HI |
| 1b | Andreani, Casoli & Gerin (1995) | CO |
| 2 | Beuing et al. (1999) | X |
| 3 | Boselli et al. (1995) | CO |
| 4 | Bregman et al. (1992) | CO |
| 5 | Burstein et al. (1997) | X |
| 6a | Casoli et al. (1991) | HI |
| 6b | Casoli et al. (1991) | CO |
| 7 | Casoli et al. (1998) | CO |
| 8 | Fabbiano et al. (1992) | X |
| 9 | Gerin & Casoli (1994) | CO |
| 10a | Horellou, Casoli & Dupraz (1995) | HI |
| 10b | Horellou, Casoli & Dupraz (1995) | CO |
| 11 | Knapp et al. (1989) | IR |
| 12a | Lavezzi et al. (1999) | IR |
| 12b | Lavezzi et al. (1999) | HI |
| 12c | Lavezzi et al. (1999) | CO |
| 13a | Paturel et al. (1997) | IR |
| 14a | NASA/IPAC Extragalactic Database (NED) | IR |
| 14b | NASA/IPAC Extragalactic Database (NED) | HI |
| 14c | NASA/IPAC Extragalactic Database (NED) | CO |
| 15 | Nishiyama & Nakai (2001) | CO |
| 16 | O’Sullivan et al. (2001) | CO |
| 17a | Roberts et al. (1991) | IR |
| 17b | Roberts et al. (1991) | HI |
| 17c | Roberts et al. (1991) | CO |
| 17d | Roberts et al. (1991) | X |
| 18a | Sage 1993 | HI |
| 18b | Sage 1993 | CO |
| 19 | Van Driel et al. (2000) | HI |
| 20a | Welch & Sage (2003) | HI |
| 20b | Welch & Sage (2003) | CO |
| 21 | Wiklind, Combes & Henkel (1995) | CO |
| 22 | Young et al. (1995) | CO |


format: text

text:
# The Fate of Non-Radiative Magnetized Accretion Flows: Magnetically-Frustrated Convection

## 1 Introduction

Stellar dynamical measurements indicate a black hole with mass $`M_{\mathrm{BH}}=2.4\times 10^6M_{}`$ (Genzel et al., 1997; Ghez et al., 1998) at the location of Sgr A\* in the galactic center. Apart from its origin, a puzzling aspect of this object – and others like it in nearby galaxies – is its low X-ray luminosity, given the gaseous environment. High resolution X-ray imaging (Baganoff et al., 2001) shows hot gas with temperatures $`T=2`$ keV at densities near $`n_e=130\mathrm{c}\mathrm{m}^3`$ within 1” of Sgr A\*. In Bondi (1952)’s theory, gas within the gravitational region of influence (Bondi radius)

$$r_B\frac{GM_{\mathrm{BH}}}{c_s^2}0.03\mathrm{pc}$$
(1)
falls inward, approaching free-fall. This scale is barely resolved by Chandra at the galactic center. The natural mass accretion rate is of order $`4\pi \lambda r_B^2\rho c_s`$ if the background density is $`\rho `$; $`\lambda =0.25`$ for a monatomic gas dominated by thermal (as opposed to magnetic) pressure. If matter is converted into radiation at an efficiency $`\eta `$ by the black hole, the luminosity $`L2\times 10^{40}(\eta /10\%)`$ erg/s. Reported instead (Baganoff et al., 2001) is a source, potentially the hole, with a luminosity of $`2.4\times 10^{33}`$ erg/s – $`10^7`$ times fainter than this estimate. Even the advection of thermal energy across $`r_B`$ at the Bondi rate would incur $`2\times 10^{36}`$ erg/s, exceeding the observations by three orders of magnitude. Because Bondi assumed spherical adiabatic flow of an ideal gas, many factors may be at work in this immense discrepancy.

First, the flow could be incredibly sporadic and we may have caught it in an off moment. However, the dynamical time $`r_B/c_s`$ is only $`50`$ years, comparable to the history of radio observations and only a few times longer than the X-ray observations.

Second, it had been suggested (as in the ADAF model of Narayan & Yi, 1994) that fluid can accrete at the Bondi rate without radiating ($`\eta 10\%`$), which might be possible if electrons coupled to protons only by Coloumb collisions. However, observations of linear submillimeter polarization (Bower, 2000) are interpreted (Melia et al., 2000) to imply an accretion rate far below Bondi’s prediction. Moreover, Bondi-rate influx of electron thermal energy alone would exceed limits by $`10^{2.7}`$.

Third, Bondi accretion passes through a sonic point only if the effective adiabatic index is smaller than $`5/3`$. Gas with $`\gamma _{\mathrm{eff}}=5/3`$ accretes subsonically at all radii, and if $`\gamma _{\mathrm{eff}}>5/3`$ then quasi-hydrostatic settling flow is expected, becoming sonic just above the Schwarzschild radius $`r_{\mathrm{Sch}}`$ (Begelman, 1978). Monatomic gas with $`\gamma =5/3`$ has $`\gamma _{\mathrm{eff}}>5/3`$ if viscous or magnetic dissipation generates heat (which is not radiated) during inflow (Cowie et al., 1978; Scharlemann, 1981). Therefore, rapid inflow of the Bondi or ADAF type is unstable to motions that reverse the inflow of some fluid elements – potentially reducing $`\dot{M}_{\mathrm{BH}}`$ far below the Bondi estimate. The ADIOS model of Blandford & Begelman (1999) posits axial outflows cancelling the equatorial inflow. Similarly, the CDAF model of Quataert & Gruzinov (2000) invokes a rotating convecting atmosphere surrounding the hole. Igumenshchev & Narayan (2002, hereafter IN) and Gruzinov (2001) discuss a similar, nonrotating, convecting flow (§3).

Fourth and fifth, rotation and magnetic fields can both strongly affect the flow and interact with one another and with other physical effects in non-trivial ways.

If the angular frequency is $`\mathrm{\Omega }_B`$ at the Bondi radius, conservation of angular momentum would bring it into orbit at a Kepler radius $`r_K\mathrm{\Omega }_B^2r_B^3/c_s^2`$. If cooling permits the formation of a thin disk, this signals the onset of efficient radiation ($`\eta 10\%`$ as used above). If angular momentum transport is weak, however, this can be a limiting step in accretion. Nayakshin (2003) has recently suggested a cold disk onto which the hot flow condenses, accreting sporadically with a long duty cycle. The disk of stars inferred by Levin & Beloborodov (2003) could have arisen this way. Recall, however, condensation onto this disk would exceed constraints if it emitted X-rays.

Similarly, magnetic fields can grow in strength as they are dragged inward by the flow. Accretion will shear embedded fields to become radial. An initial field, whether uniform or tangled (Shapiro, 1973), will be stretched toward the split-monopole (hedgehog) configuration in which $`B^2r^4`$ (e.g., IN), incurring a centrally divergent energy. Although radial fields exert no net force, this configuration is unstable and unattainable (Zeldovich & Novikov, 1971). Instead, inflow can stall at a magnetic turnaround radius $`r_{\mathrm{mag}}GM/v_A(r_{\mathrm{mag}})^2`$, where $`v_A(r)`$ is the Alfvén velocity. Mass inflow will be limited by the rate of magnetic energy dissipation via reconnection, by interchange instabilities, or by inflow along open field lines.

This contrasts with the widely-held picture of magnetic fields enhancing accretion through angular momentum transport, either via turbulent stresses (Balbus & Hawley, 1991) or via magnetocentrifugal winds (Blandford & Payne, 1982). Also, if fields are generated locally through convection or magnetorotational instability, then they are limited in strength to partial equipartition with kinetic energy. Fields strengthened by inflow can reach equipartition with the gravitational potential, which can be a larger value (§2.1).

We pause here to note the critical importance of the density profile in the phenomenology and viability of models; see also Quataert (2003) and Gruzinov (2001). An atmosphere with $`\rho r^n`$ and, generically, $`Tr^1`$, has a bolometric free-free luminosity $`Lr^3\rho ^2T^{1/2}r^{(54n)/2}`$ (or for a single frequency, $`L_\nu r^3\rho ^2T^{1/2}r^{7/22n}`$), so long as $`T3`$ keV. Thus profiles with $`n>5/4`$ (or $`n>7/4`$) suffer a singularity in the bolometric (or single-frequency) luminosity. If $`n<5/4`$, emission is dominated at outer radii; this is consistent with the small contrast in Chandra images.

Similarly, the thermal time varies as $`T^{1/2}/\rho r^{n1/2}`$ whereas the inflow time $`r/v=4\pi r^3\rho /\dot{M}_{\mathrm{BH}}r^{3n}`$. Thus, flows with $`n<7/4`$ are dynamically nonradiative. Finally, the local Bondi accretion rate varies as $`r^2\rho c_sr^{3/2n}`$: flows with $`n<3/2`$ accrete at $`\dot{M}\dot{M}_B(R_B/R_{\mathrm{Sch}})^{3/2n}`$.

Hydrostatic models are characterized by a polytropic index $`n=1/(\gamma _{\mathrm{eff}}1)`$, which describes the correlation between density and pressure $`p\rho ^{\gamma _{\mathrm{eff}}}=\rho ^{1+1/n}`$. In a Keplerian potential, $`\rho r^n`$ as used above. When $`\gamma _{\mathrm{eff}}=5/3`$, both hydrostatic and Bondi-like (e.g., ADAF) flows have $`n=3/2`$, shallow enough to be advective but too steep to avoid the luminosity constraint. To force a shallower density profile requires additional pressure, either through rotation, magnetic fields, or an entropy inversion. The latter is convectively unstable.

CDAFs pass this test by achieving $`n=1/2`$ in a combination of rotational, turbulent, and thermal support. However, the Quataert & Gruzinov (2000) model requires the inward angular momentum transport due to buoyant convection to exceed the outward transport due to magnetic fields. This may be possible for fields due solely to magnetorotational instability (Narayan et al., 2002), but it is unlikely a property of field strengthened by shear in inflow.

More seriously, any model invoking rotational support is plagued by outer boundary conditions. Outside $`r_B`$ one expects solid-body rotation on radial shells, implying low specific angular momentum ($`j`$) near the axis. Sufficiently low-$`j`$ gas can fall directly within the innermost stable orbit; this comprises a fraction $`(r_S/r_K)^{1/2}`$ of the total. If $`j`$ is somewhat higher, fluid falls inward to its own Kepler radius and shocks; the resulting pressure gradients drive a quadrupolar outflow of low-$`j`$ material along the equator. This has been observed in nonmagnetic simulations by Proga & Begelman (2003) and by us. It could be avoided if the inner boundary supplied a strong jet that interfered with axial accretion, as occurs in protostars (Matzner & McKee, 2000), but suggestions of such behavior in Chandra images are recent and tentative (Morris et al., 2002). Similarly, models that invoke rotational support to stem accretion require that rotational support remains important all the way out to $`r_B`$ – implying an asymmetry to the X-ray images which is not observed.

How can gas establish the flattened density profile required for low-luminosity accretion, while being fed low-angular-momentum, lightly magnetized ($`\beta >10`$ for $`B<1`$ mG) material at $`r_B`$? IN and Gruzinov (2001) offer a solution to this conundrum (§3); our simulations suggest a different answer.

## 2 Simulations

In order to further explore the interaction between infall, rotation, magnetic fields, and buoyancy, we conduct MHD simulations with 14003 zones arrayed in a uniform Cartesian grid, the largest MHD simulations to date. These were performed on the CITA McKenzie cluster: 512 Pentium-4 Xeon processors running at 2.4 GHz (Dubinski et al., 2003). At this resolution, each full dimensional sweep corresponding to two timesteps took 40 seconds. The code (Pen et al., 2003) is based on a 2nd order accurate (in space and time) high resolution Total-Variation-Diminishing (TVD) algorithm. It explicitly conserves the sum of kinetic, thermal and magnetic energy; hence magnetic dissipation (at the grid scale) heats gas directly. No explicit resistivity or viscosity is added, and reconnection and shocks occur through the solution of the flux conservation laws and the TVD constraints. Magnetic flux is conserved to machine precision by storing fluxes perpendicular to each cell face.

Inner boundary conditions are imposed on a cube of width 24 grid cells. Interior to the largest inscribed sphere within this cube, gravitational forces are turned off. At the end of each time step magnetic fields in the cubical region are relaxed to the vacuum solution, permitting rapid reconnection in the interior zone. The Alfvén speed is matched to the circular speed at the surface of this region by the removal of matter, and the sound speed is matched to the same value by the adjustment of temperature. The pressure of this matter is always smaller than that of infalling material, and we never observe spurious outflows.

Whereas many prior simulations have started with a disklike, rotation dominated geometry and no low-$`j`$ material, we wished to investigate the potential role of axial infall. We attempt to separate generic physical effects from artefacts of boundary conditions. This is challenging, since the energy available at the center of the simulation is always larger than in any other region. Results may depend sensitively on the choice of inner boundary, and it is not feasible to simulate directly from $`r_B`$ to $`r_{\mathrm{Sch}}`$. We search instead for scaling relations connecting these radii, bearing in mind the possibility of strong reactions such as outflows from an unresolved inner region.

For this reason, and since we are interested primarily in the effect of external parameters, most of our runs have worked inward from the Bondi radius. Simulations far inside $`r_B`$ elucidate local phenomena, but cannot easily be matched to their exterior environment. At each step, the outer 20 grid cells are replaced with the values from the initial conditions to enforce the continued inflow of new material. We avoid threading the outer boundary with any magnetic flux by adding flux lines to the fluid inside a region 1/2–3/4 of the box size, with an admixture of random field loops and large loops that thread the whole box. (Most of the energy is in the coherent loops.) We maintain a mean value $`\beta =10`$ in the flux generation region. To estimate $`r_{\mathrm{mag}}`$, we assume $`Br^2`$ as in the split-monopole. This gives $`r_{\mathrm{mag}}100`$ grid cells. The estimate is not rigorous: fields are added in a cubical region; rotation changes the shearing rate, and $`Br^2`$ is not perfectly achieved.

To avoid immediate energetic feedback from the central regions due to the initial conditions, we start with an empty interior (an evacuated sphere of half the box radius), and let matter fall in. We then watch the evolution away from Bondi to draw conclusions about the fate of the flow. In grid units, box length is 1400, and $`GM=700`$. We set $`c_s(r=\mathrm{})=1`$, and $`\rho (r=\mathrm{})=1`$. The Bondi radius was set at $`r_B=700`$, touching the closest box edge. The simulations ran successfully for 6000 time steps to $`t=650`$, or 1.5 free fall times from $`r_B`$. At that point, magnetic fields squeezed out along the midplane to the outer boundary, leading to numerical instabilities.

With a resolution of $`10^{2.85}`$ radial zones, of which $`10^{1.51}`$ is used for central and outer boundary conditions, we have 1.34 decades of scale in which to arrange the Kepler radius $`r_K`$ and the magnetic turnaround radius $`r_{\mathrm{mag}}`$. We have performed runs that are initially rotationally supported ($`r_{\mathrm{mag}}<r_K`$) and purely rotationally supported ones ($`r_{\mathrm{mag}}=0`$), as well as magnetized but nonrotating initial conditions ($`r_K=0`$). The fluid is initialized with solid body rotation on shells, and constant specific angular momentum on cones of constant polar angle. The production simulation (fig. 1) chose $`r_K=336`$, $`r_{\mathrm{mag}}=100`$. To further break any discrete symmetries, the velocity field was modulated at the 5% level at multipoles up to $`l=2`$.

These simulations differ from previous ones in two important ways. First, magnetic and viscous dissipation occur only at the grid scale (or inner boundary); no enhanced diffusivity or viscosity is applied. Second, we break the alignment usually assumed between magnetic and rotational symmetry axes. This was accomplished by introducing large-scale flux loops, misaligned with respect to the rotational axis, that are dragged toward the central object.

### 2.1 Results

Simulations were run about one dynamical time at $`r_B`$. Although this does not give us any handle on the long-term evolution of the flow once its inner behavior begins to alter the conditions outside $`r_B`$, it does yield a picture of how the inner flow responds – for many inner dynamical times – to initial and boundary conditions. A snapshot of the resulting magnetic field structure is shown in 1, and various stresses balancing gravity are plotted versus radius in figure 2.

At this point in the simulation, a central hydrostatic region supported by gas pressure – not rotation or magnetic fields – has grown outward. Within the region plotted in figure 2, $`\rho r^n`$ for $`n0.72`$ also, $`Pr^{1.51}`$ (so that $`Tr^{0.79}`$, whereas $`r^1`$ was expected), and magnetic pressure $`P_{\mathrm{mag}}10^{1.5}P`$. Gas pressure gradients dominate magnetic stresses by a factor $`10`$; Reynolds stresses, including rotation and inflow, are smaller still (and switch direction). Rotation is roughly one tenth the Kepler rate, despite that the entire region is a factor of two inside the initial $`r_K`$. The ratio of Alfvén to inflow velocities is similarly $`10`$, indicative of magnetic braking.

In contrast to Bondi and ADAF-type flows, inflow is very subsonic; correspondingly, the mass accretion rate is strongly suppressed relative to Bondi’s estimate. However, the accretion rate does agree with the Bondi rate derived from conditions at the inner boundary. This state is not rotationally-supported like the CDAF. It resembles in some ways the “CDBF” of IN and Gruzinov (2001); but see §3 for differences.

To test the role of magnetic fields in the clogged inflow, we suddenly turned the magnetic fields off, and evolved the fluid for a dynamical time. The flow returned to Bondi’s solution.

## 3 Physical Interpretation

The fluid can be modelled as one in quasi-hydrostatic equilibrium with a polytropic index $`\gamma _{\mathrm{eff}}2.25`$. Since the adiabatic index is $`\gamma =5/3`$, this represents a strongly superadiabatic state. In the usual description of entropy-driven convection, this can only occur when convective velocities approach the sound speed, which, in a power-law atmosphere, is roughly free-fall.

Saturation at a constant Mach number is a feature of Quataert & Gruzinov (2000)’s CDAF model and the CDBF model of IN, both of which have $`n=1/2`$ and fall within class II of Gruzinov (2001)’s classification of self-similar nonradiative flows. This slope is clearly flat enough to satisfy all of the observational constraints discussed in §1. The value of $`n=1/2`$ derives from assuming a positive convective luminsoity $`L_{\mathrm{conv}}`$ – i.e., that the gravitational energy released bubbles out through the flow rather than being dragged inward (as it is in Bondi and ADAF flows). If $`c_s`$ scales with the Kepler speed $`v_K`$, then $`L_{\mathrm{conv}}r^2\rho v_K^3r^{1/2n}`$, where $``$ is the turbulent Mach number. Constancy of $`L_{\mathrm{conv}}`$, required by steady state, implies $`r^{n1/2}`$. If $`n>1/2`$, $``$ rises outward until it saturates at $`1`$; thereafter, $`n=1/2`$.

Our simulation shows $`n=0.72`$ and mildly subsonic convective motions: $`0.4`$ – not increasing outward at $`r^{0.22}`$ as implied by the above argument. This has prompted us to calculate the total flow ($`L_{\mathrm{conv}}`$) of magnetic, thermal, and gravitational energy. We find it to be inward and small: $`L_{\mathrm{conv}}0.04\times (4\pi r^2\rho v_K^3)`$.

How can subsonic convection persist in the presence of strong superadiabatic gradients? And, how can the net flow of energy be inward despite the existence of convective motions? Since the detailed treatment of magnetic field structures is the only physical effect distinguishing our final state from ordinary gaseous convection, the simulation results must represent a state of magnetically-frustrated convection in which magnetic shear stresses oppose buoyant motions. This is verified by the equipartition between magnetic stresses and buoyant stresses (variations of $`\rho g`$ at fixed $`r`$) seen in figure 2. Correspondingly, kinetic energy is suppressed by a factor of three compared to the free energy available in density fluctuations (variations of $`\rho GM/r`$ at fixed $`r`$). For further corroboration we note an anticorrelation between magnetic and buoyant stresses (cross-correlation coefficient -0.2) and also the relaxation to Bondi flow when fields were removed. An analogy to magnetic frustration is low-Reynolds-number convection, in which viscosity slows or halts buoyancy. (That said, energy inflow may be a feature of our inner boundary conditions – a question for further study.)

The coincidence in slope between gas and magnetic pressures most likely arises from the growth of magnetic fields to balance buoyancy: since buoyancy scales with gas pressure in the presence of a strong superadiabatic gradient, so must the magnetic stress.

One can discuss the plausible scenarios of the global gasdynamics of the Sgr A\* region. In addition to the ambient gas, stellar winds may inject a larger mass flux into the region than would be lost by even ideal Bondi accretion (Quataert et al., 1999). If the natural accretion rate is sufficiently slow, the injected mass could conceivably push the ambient gas outwards. Similarly, the cooling time at the Bondi radius is approximately $`10^5`$ years, and on this time scale matter has to either flow in, or be pushed out.

## 4 Conclusions

We have presented a new picture of the hot plasma in the vicinity of the galactic center black hole based on the results of new very large three dimensional MHD simulations. We find that the code produces results consistent with observational constraints, including boundary conditions and total luminosity. Fluid remains in quasi-static equilibrium supported primarily by thermal pressure, with a radial density profile $`\rho r^{0.72}`$ in reasonably spherical symmetry. This implies a significant entropy inversion; we believe buoyancy is impeded by subdominant magnetic fields.

A distinguishing feature of the flow is that energy is advected inward, despite convection, albeit quite slowly compared to the local estimate $`4\pi r^2\rho (r)v_K(r)^3`$. The same is true of central regions of Bondi flow, where $`\dot{E}=\dot{M}c_s(r>t_B)^2/(\gamma 1)`$. Unlike Bondi, the $`\dot{M}`$ is also much slower than the dynamical accretion rate.

This feature provides a point of contrast with related suggestions for the Sgr A\* flow: CDAF (Quataert & Gruzinov, 2000) and CDBF (IN), both of which obey $`\rho r^{1/2}`$ and contain different levels of rotational support. The $`1/2`$-law in these models is a consequence of a positive outward convective luminosity, plus the saturation of convective motions at constant Mach number (see § 3 and Gruzinov, 2001). However, the density profile is essentially unconstrained when $`\dot{E}`$ and $`\dot{M}`$ (as well as the angular momentum flux $`\dot{J}`$) are all effectively zero (Gruzinov, 2001, his class-IV flow).

The influx of energy also provides a method of distinguishing magnetically-frustrated flows from the other models even if the central density profile cannot be probed. In CDAFs and CDBFs, energy must be convected outward and will heat gas outside the Bondi radius at a rate comparable to $`\dot{M}c_s^210^3L_{}`$. If present, effects of this heating on the hot gas surrounding the hole may be visible. On the other hand, winds from massive stars in the same volume may overwhelm inward advection.

Blandford & Begelman (1999) criticize ADAFs on the basis that they possess a positive Bernoulli function ($`>0`$), and that this predisposes them to outflow (realized in their ADIOS model). Note however that $``$ is positive (though small) in Bondi flow, where it is set by the external pressure; however, no outflow develops. We find $`>0`$ in the magnetically-frustrated flow as well. We do observe upwelling, but it takes the form of an overall quadrupolar circulation with inflow along the axis and outflow along the equator. There is no indication that this upwelling becomes supersonic at any radius.

We speculate that non-radiative MHD flows are in general very inefficient at accreting. The corollary is that accretion only occurs when the cooling time is short.

This research was funded by NSERC, by the Canadian Foundation for Innovation, and by the Canada Research Chairs program (for CDM). We thank Phil Arras, David Ballantyne, Robert Fisher, Chris McKee, and an anonymous referee for comments.


text:
# Ferroelectric Mott-Hubbard phase in organic conductors.

## I Ferroelectricity in organic conductors.

The family of quasi one-dimensional organic superconductors (the Bechgard - Fabre salts $`(TMTSF)_2X,(TMTTF)_2X`$) demonstrates, at low temperatures $`T`$, transitions to almost all known electronic phases, see jerome . At higher $`T=T_{ao}`$, usually there is also a set of weak structural transitions of the ‘anion orderings’ (AOs) which are slight arrangements of chains of counterions $`X`$ anions . At even higher $`TT_0`$, also other ‘structurless’ transitions lawersanne  were observed sometimes in the $`TMTTF`$ subfamily but they were not explained and left unattended. Recently their mysterious nature has been elucidated by discoveries of the huge anomaly in the dielectric susceptibility $`\epsilon `$ prl ; nad  (see Fig. 1) and of the charge disproportionation (CD) seen by the NMR brown . The new displacive instability and the usual ‘orientational’ AOs seem to be independent, as proved by finding their sequence in $`(TMTTF)_2ReO_4`$ nad .

The phase transition was interpreted prl  as the least expected one: to the Ferroelectric (FE) state, which was proved by the clear-cut fitting of the anomaly in $`\epsilon (T)`$ to the Curie law (see the figure in prl ). The FE transition is followed by a fast formation, or the steep increase, of the conductivity gap $`\mathrm{\Delta }`$ (see the Fig.2) with no signs of a spin gap formation. Hence we deal with a surprising FE version of the Mott-Hubbard state which usually was associated rather with magnetic orderings. The FE transition in $`(TMTTF)_2X`$ is a very particular, bright manifestation of a more general phenomenon of the CD, which already has been predicted in seo-97  and now becomes recognized as a common feature of organic and some other conductors fukuyama .

The anomalous diverging polarizability is coming from the electronic system, even if ions are very important to choose and stabilize the long range $`3D`$ order. Thus the theory prl  suggests that the collective singular contribution $`\epsilon (\omega _p/\mathrm{\Delta })^2/|T/T_01|`$ ($`\omega _p`$ is the metallic plasma frequency) develops upon the already big intergap contribution $`(\omega _p/\mathrm{\Delta })^210^3`$ which is also seen as the background at the Fig.1. Typical plots at the Fig.1 demonstrate very sharp (even in the $`\mathrm{log}`$ scale !) FE peaks, while the anti-FE case of $`X=SCN`$ shows a smoother maximum. At the subsequent Ist order AO transition in the case of $`X=ReO_4`$, $`\epsilon `$ drops down which might be caused by the increase of $`\mathrm{\Delta }`$ seen at the conductivity plot at the Fig.2. Finally the IInd order spin- Peierls transition in the case of $`X=PF_6`$ shows up only as a shoulder. All that seems to collaborate towards a consistent picture.

Already within the nonperturbed crystal structure at $`T>T_0`$, the tiny dimerization of bonds by anions $`X`$ provokes the dielectrization SB-VY , see more references in brazov-01 . The counting of the mean electronic occupation changes from $`1/2`$ per molecule to $`1`$ per their dimer which opens (according to Dzyaloshinskii & Larkin, Luther & Emery) the route to the Mott-Hubbard insulator. At $`T<T_0`$ the CD adds more to the charge gap $`\mathrm{\Delta }`$ which is formed now by *joint effects of alternations of bonds and sites*. The conductivity $`G`$ plots at the Fig.2 show this change by kinks at $`T=T_0`$ turning down to much higher activation energies at low $`T`$. The steepness of $`G`$ just below $`T_0`$ reflects the growth of the CD contribution to the gap $`\sqrt{T_0T}`$, see below.

None of these two perturbations changes the unit cell of the zigzag stack which basically contains two molecules, hence $`q_{}=0`$ ($`𝐪=(q_{},q_{})`$ is the CD wave vector). Their sequence lifts the mirror and then the inversion symmetries which must lead to the on-stack electric polarization. By a good fortune, the 3D pattern of the CD appears in two, anti-FE and FE, forms: i) antiphase between stacks, $`q_{}0`$ which allows for its structural identification anions  (found only for $`X=SCN`$); and ii) inphase ($`𝐪=0`$ hence the ‘structurless’ character) which is the macroscopic FE state typically observed today nad . Both types are the same paramagnetic insulators (the MI phase of SB-VY ) as we can see in Fig.2 and in other examples nad ; also their CD shows up similarly in the NMR splitting brown .

## II Symmetry breakings and emergence of solitons.

The microscopic theory for the ”combined Mott-Hubbard state” prl  accounts for two ‘orthogonal’ contributions, $`U_b`$ and $`U_s`$, to the Umklapp scattering of electrons which come from two symmetry breaking effects: the built-in nonequivalence of bonds and the spontaneous one of sites matv . The appearance of $`U_s`$ is regulated by a single parameter $`\gamma `$ ($`\gamma _\rho `$ of SB-VY , $`K_\rho `$ of today’s convention) which collects all information about electronic interactions. The spontaneous CD $`U_s0`$ requires that $`\gamma <1/2`$, far enough from $`\gamma =1`$ for noninteracting electrons. The magnitude $`|U_s|`$ is determined by a competition between the electronic gain of energy and its loss $`U_s^2`$ from the lattice deformation and charge redistribution. The $`3D`$ ordering of signs $`U_s=\pm |U_s|`$ discriminates between the FE and anti-FE states.

While the earliest theoretical approach seo-97  applies well to a generic CD, here the pronouncedly $`1D`$ electronic regime calls for a special treatment prl  which also needs to be well suited for the FE transition. It is done in terms of electronic phases $`\phi `$ and $`\theta `$ defined as for the CDW order parameters $`\mathrm{exp}(i\phi )\mathrm{cos}\theta `$) such that $`\phi ^{}/\pi `$ and $`\theta ^{}/\pi `$ count local concentrations of the charge and the spin. Beyond the energies of charge and spin polarizations $`(\mathrm{}v_F/\gamma )(\phi ^{})^2`$ and $`\mathrm{}v_F(\theta ^{})^2`$, there is the commensurability energy

$$H_U=U_s\mathrm{cos}2\phi U_b\mathrm{sin}2\phi =U\mathrm{cos}(2\phi 2\alpha )$$

where $`U=\sqrt{U_s^2+U_b^2}`$ and $`\mathrm{tan}2\alpha =U_b/U_s`$. The gap $`\mathrm{\Delta }`$ is related to the total Umklapp amplitude $`U`$ via its renormalized value $`UU^{}\mathrm{\Delta }^2/\mathrm{}v_F`$.

For a given $`U_s`$, the ground state is doubly degenerate between $`\phi =\alpha `$ and $`\phi =\alpha +\pi `$ which allows for phase $`\pm \pi `$ solitons with the energy $`\mathrm{\Delta }`$ which are the charge $`\pm e`$ spinless particles, the (anti)holons observed in conductivity at both $`TT_0`$. Also $`U_s`$ itself can change the sign between different domains of ionic displacements. Then the electronic system must also adjust its ground state from $`\alpha `$ to $`\alpha `$ or to $`\pi \alpha `$. Hence the FE domain boundary $`U_sU_s`$ requires for the phase $`\alpha `$-solitons of the increment $`\delta \phi =2\alpha `$ or $`\pi 2\alpha `$ which will concentrate the non integer charge $`q=2\alpha /\pi `$ or $`12\alpha /\pi `$ per chain. Below $`T_0`$, the $`\alpha `$ solitons must be aggregated into domain walls teber  which motion might be responsible for the observed frequency dispersion of $`\epsilon `$, and indeed it is more pronounced bellow $`T_0`$, see nad . But well above $`T_0`$ they can be seen as individual particles, charge carriers. Such a possibility requires for the fluctuational $`1D`$ regime of growing CD. It seems to be possible sometimes in view of a strong increase of $`\epsilon `$ at $`T>T_0`$ even for the anti-FE case of the $`X=SCN`$ which signifies the growing single chain polarizability before the 3D interactions come to the game.

The subsequent AO of the tetramerization in $`(TMTTF)_2ReO_4`$ exhorts upon electrons a CDW type effect thus adding the energy $`\mathrm{\Delta }_\sigma ^2\mathrm{cos}(\phi \beta )\mathrm{cos}\theta `$ (the shift $`\beta `$, the mixture of bond- and site CDWs, reflects the lack of the inversion symmetry below $`T_0`$). It lifts the continuous $`\theta `$ invariance thus opening the spin gap $`\mathrm{\Delta }_\sigma `$ growing below $`T_{ao}`$. Moreover it lifts even the discrete $`\phi \phi +\pi `$ invariance of $`H_U`$ thus prohibiting the $`\pi `$ solitons. But the joint invariance ($`\phi \phi +\pi ,\theta \theta +\pi `$) is still present giving rise to *combined topological solitons*. They are composed by the charge $`e`$ core (with $`\delta \phi =\pi `$ within the length $`\mathrm{}v_F/\mathrm{\Delta }`$) which is supplemented by longer spin $`1/2`$ tails of the $`\theta `$ soliton ($`\delta \theta =\pi `$ within the length $`\mathrm{}v_F/\mathrm{\Delta }_\sigma `$). These are the particles seen at the conductivity plot of the Fig.2 below $`T_{ao}`$.

## III Comparison, perspectives.

By now the revaluation concerns definitely only the $`TMTTF`$ subfamily. The $`TMTSF`$ compounds are highly conductive which today does not allow for difficult experiments either with the low frequency $`\epsilon `$ or with the small NMR splitting. Nevertheless the transition may be their, just being hidden or existing in a fluctuational regime like for stripes in High-$`T_c`$ cuprates. When it is confirmed, then the whole picture of intriguing abnormal metallic state jerome  will be revised. The signature of the FE CD state may have been already seen in optical experiments optics . Indeed the Drude like peak appearing within the pseudogap can be interpreted now as the optically active mode of the FE polarization; the joint lattice mass will naturally explain its surprisingly low weight. Vice versa, the FE mode must exist in $`TMTTF`$ compounds, which identification is the ultimate goal. (Being overdamped near $`T_0`$, this mode must grow in frequency following the order parameter as $`\epsilon ^{1/2}`$ which can yield about two orders of magnitude at low $`T`$.) Even the optical pseudogap itself optics , being unexpectedly big for $`TMTSF`$ compounds with their less pronounced dimerization of bonds, can be largely due to the hidden spontaneous dimerization of sites.

A popular interpretation optics  for optics of $`TMTSF`$ compounds neglects the dimerization and relies upon the more generic 4- fold commensurability effects originating higher order (8 particles) Umklapp processes. They give rise to the energy $`U_4\mathrm{cos}4\phi `$ which stabilization would require for ultra strong $`ee`$ repulsion corresponding to $`\gamma <1/8`$ in compare to our moderate constraint $`\gamma <1/2`$. While not excluded in principle, this mechanism does not work in $`TMTTF`$. We saw that even small increments of the dimerization just below $`T_0`$ immediately transfer to the activation energy.

Finally recall also numerical studies which have been performed in response to new discoveries. Usually they pass the test for the CD but they may fail in finding the FE; e.g. the nonpolar(1100 type ordering has been claimed mazilo , rather than the necessary 1010 one.

In conclusion, new events call for a revision of the existing picture and suggest new experimental and theoretical goals. The world of organic metals becomes polarized and disproportionated.

Acknowledgements. This work was partly supported by the RFFI grant N 02-02-17263, the INTAS grant 2212, and by the twinning CRTBT –IRE grant N 98-02-22061. S.B. acknowledges the hospitality of the ISSP, Tokyo University.


text:
# No spin-statistics connection in nonrelativistic quantum mechanics

## Abstract

We emphasize that there is no spin-statistics connection in nonrelativistic quantum mechanics. In several recent papers, including Phys. Rev. A 67, 042102 (2003), quantum mechanics is modified so as to force a spin-statistics connection, but the resulting theory is quite different from standard physics.

It has been known for many years that there is a spin-statistics connection in relativistic quantum field theory \[1-4\] but not in nonrelativistic quantum mechanics wightman2 . However, several recent papers \[6-8\] have led to some confusion regarding the second point.

Let us first remind ourselves why there is no spin-statistics theorem in nonrelativistic quantum mechanics. The essential reason is that the restrictions that imply a spin-statistics connection in relativistic field theory are no longer meaningful in nonrelativistic physics. For example, Weinberg’s textbook weinberg  provides a relatively simple and physical proof based on microcausality, or the requirement that commutators associated with observable quantities vanish for spacelike separations. In nonrelativistic physics, causality is still a meaningful requirement, but microcausality is not, because there is no longer a light cone. This proof then does not apply in the nonrelativistic case, and the same is true of the other proofs based on Lorentz invariance.

There are nonrelativistic wavefunctions for either $`N`$ fermions or $`N`$ bosons with any spin (0, 1/2, 1, 3/2, …). For example, a basis function with the form

$$\mathrm{\Psi }(𝐫_1,𝐫_2)=\left(\varphi _1\left(𝐫_1\right)\varphi _2\left(𝐫_2\right)\varphi _1\left(𝐫_2\right)\varphi _2\left(𝐫_1\right)\right)/\sqrt{2}$$
(1)
is acceptable for spin-zero fermions, where $`\varphi `$ is a simple scalar. More generally, a basis function with the form

$`\mathrm{\Psi }(𝐫_1,𝐫_2,\mathrm{},𝐫_N)`$ $`=`$ $`𝒜{\displaystyle \underset{i=1}{\overset{N}{}}}\psi _i\left(𝐫_i\right)\text{ , fermions}`$ (2)
$`=`$ $`𝒮{\displaystyle \underset{i=1}{\overset{N}{}}}\psi _i\left(𝐫_i\right)\text{ , bosons}`$ (3)
is appropriate for $`N`$ particles with any spin. Here $`𝒜`$ or $`𝒮`$ represents antisymmetrization or symmetrization of the product (with insertion of the correct normalization factor). Each $`\psi `$ is a function corresponding to the desired spin $`s`$; for example, $`\psi `$ is a $`2`$-component spinor if $`s=1/2`$. A nonrelativistic field theory can then be constructed in the usual way, having fermions or bosons with any spin fetter . The field operator consistently transforms as both a field and a quantum operator wightman2 .

According to Ref. 6, on the other hand, (1) is not an acceptable wavefunction. This conclusion was reached because quantum physics was modified by adding an unusual constraint: In the words of Ref. 6, “The approach used here is based on the requirement that the point $`\{𝐫_1,𝐫_2\}`$ in the configuration space for two identical spinless particles is the same point as $`\{𝐫_2,𝐫_1\}`$.” But this requirement implies that the wavefunction must return to its original value when $`(𝐫_1,𝐫_2)`$ is transformed to $`(𝐫_2,𝐫_1)`$:

$$\mathrm{\Psi }(𝐫_2,𝐫_1)=\mathrm{\Psi }(𝐫_1,𝐫_2).$$
(4)
I.e., the two-particle wavefunction is only allowed to acquire the $`+`$ sign appropriate for bosons, and is forbidden to acquire the $``$ sign appropriate for fermions. It is this requirement that forbids spin-zero fermions with the wavefunction (1). In Ref. 6, therefore, the spin-statistics connection is simply imposed by fiat.

Essentially the same philosophy was used in Refs. 7 and 8. In the words of Ref. 7, “we must identify the points $`𝐫`$ and $`𝐫`$, since these correspond to complete interchange of the particles (positions and spins) and so are indistinguishable.” (Here $`𝐫=𝐫_2𝐫_1`$ is the relative coordinate.) They then conclude that

$$|\mathrm{\Psi }\left(𝐫\right)=|\mathrm{\Psi }\left(𝐫\right)$$
(5)
where $`|\mathrm{\Psi }\left(𝐫\right)`$ specifies the state of the two particles. ($`|\mathrm{\Psi }\left(𝐫\right)`$ is a $`\left(2s+1\right)^2`$ dimensional vector, since there are $`\left(2s+1\right)`$ components for a single particle.)

With a standard basis for the spins, (5) is untenable, so further alteration of quantum theory is required. The authors of Ref. 7 write the state of the two particles as

$$|\mathrm{\Psi }\left(𝐫\right)=\underset{M}{}\mathrm{\Psi }_M\left(𝐫\right)|M\left(𝐫\right)$$
(6)
where the spin basis functions are not standard, but instead are modified to have a position dependence. This ultimately implies that

$$\pm \mathrm{\Psi }\left(𝐫\right)=\left(1\right)^{2s}\mathrm{\Psi }\left(𝐫\right)$$
(7)
where $`\mathrm{\Psi }`$ is the vector with components $`\mathrm{\Psi }_M`$. The upper sign holds for bosons and the lower sign for fermions. (See (3.4) of Ref. 7 and the discussion below this equation.) Then $`2s`$ must be even for bosons and odd for fermions. However, this result can be traced back to the assumption (5). Again, in the simplest case $`s=0`$, fermions have clearly been banished at the outset.

If one does not impose the unusual constraint (4) or (5), nonrelativistic bosons are allowed to have any spin (0, 1/2, 1, 3/2, …) and the same is true of nonrelativistic fermions.


text:
# Hexacyanometalate Molecular Chemistry : Trinuclear CrNi2 Complexes; MicroSQUID Magnetisation Studies of Intermolecular Interactions

## Abstract

Three different CrNi2 complexes were synthesized. They differ from each other by the nature of the terminal ligand and of the counter anion : \[Cr(CN)4\[CN-Ni(tetren)\]2\]Cl, that crystallizes in two different crystallographic systems and \[Cr(CN)4\[CN-Ni(dienpy2)\]2\](ClO4). The ground state spin value is 7/2 for the three systems (ferromagnetic interaction between chromium(III) and nickel(II) ions). The magnetisation of the three CrNi2 complexes was measured using an array of micro-SQUIDs in a temperature range between 0.04 K and 7 K, under a magnetic field up to 1 T. The three samples present a three dimensional magnetic ordering. The correlation between the structure and the intermolecular coupling is analysed in terms of steric hindrances of the terminal ligand, orientation of the molecules in the unit cell (canted structure) and crystal symmetry.

1. Introduction

The search for new polynuclear molecules displaying high spin ground state and anisotropy raises the interest of synthetic chemists 1 ; 2 ; 3 ; 4 ; 5 ; 6  and physicists 7 ; 8 ; 9  involved in the field of molecular magnetism 10 ; 11 . These anisotropic high spin molecules exhibit original magnetic properties such as single molecule magnet behaviour 12 ; 13 ; 14 ; 15 ; 16 ; 17  (long relaxation time for the magnetisation below a so-called blocking temperature, $`T_B`$) or magnetic quantum tunnelling effect 18 ; 19 . Our research approach is devoted to the synthesis of such complexes in order to get single molecule.

In order to understand the single molecule magnet (SMM) behaviour, it is important to remind that a phenomenological Hamiltonian correlated to a spin state diagram might describe all polynuclear complexes. In presence of a uniaxial anisotropy, a zero-field splitting is observed which splits the ground state in 2S + 1 levels. The activation energy of the anisotropy barrier, $`E_a`$, between the spin states $`M_S`$ = S, is a direct function of D (uniaxial anisotropy) and S (ground state spin value), $`E_a`$ = $`DS^2`$. To obtain a single molecule magnet i.e. to avoid a rapid relaxation process, the spin as well as the absolute value of the anisotropy have to be as high as possible and D has to be negative so that the state of highest $`M_S`$ lies below in energy. The exchange coupling J between two spin carriers has to be important to well separate the ground state from the first excited states. The intermolecular interaction, $`J_{inter}^{^{}}`$, plays also an essential role: it has to be negligible, necessary condition to avoid a three-dimensional magnetic ordering and to observe the properties of an isolated nanoscale object. Very few examples of clusters responding to all these criteria have been described in the literature, among them Mn12 14 ; 15 ; 20 , Fe8 21  and Mn4 9  are reference compounds.

To obtain anisotropic high spin molecules, we developed a step by step synthetic strategy based on the coupling reaction of polycyanometalate precursors (viewed as Lewis bases) and mononuclear complexe of transition metal ions with a polydentate ligand, leaving a unique accessible position only (as Lewis acids) 22 ; 23 ; 24 . Starting with hexacyanometalate precursors, this strategy allows to obtain : i) isotropic high spin molecules such as CrCu6 (S = 9/2), CrNi6 (S = 15/2) and CrMn6 (S = 27/2) 24 ; ii) complexes with various structural anisotropy but low ground state spin, for instance CoNi (S = 1), CoNi3 (S = 1) and CoNi5 (S = 1) or even singlets CoNi2 (S = 0) and CoNi6 (S = 0) 25 ; iii) anisotropic high spin molecules like CrNi (S = 5/2), CrNi2 (S = 7/2), CrNi3 (S = 9/2) and CrNi5 (S = 13/2) 25 ; 26 ; 27 . In the present paper, different CrNi2 complexes (\[Cr(CN)4\[CN-Ni(L)\]2\], L being a polydentate ligand) are investigated below 2K in order to search a potential single molecule magnet behaviour or to evaluate the intermolecular magnetic exchange interaction. After presenting briefly the structural parameters of the various complexes, we discuss the low temperature magnetic properties on oriented single crystals and evaluate the main parameters involved in the intermolecular exchange interaction which induces the three-dimensional ordering at very low temperature (See also Ref. 28 ; 29 ; 30 ).

2. CrNi2 complexes, presentation and structure

Five different \[Cr(CN)4\[CN-Ni(L)\]2\]+ complexes, abbreviated as CrNi2 in the following, have been isolated and characterised, including by single crystal X-ray diffraction. The compounds differ from each other by the nature of the polydentate ligand, L, \[tetraethylenepentamine (tetren), tris(2-aminoethyl)-N,N,N$`^{^{}}`$-ethyldiamine (trenen) and bis(2-pyridylmethyl) - N, N$`^{^{}}`$ \- diethylenetriamine (dienpy2)\] or by the nature of the counter anions (tetrafluoroborate, chloride or perchlorate). The magnetic studies (4-300K) indicate in all cases a ferromagnetic intramolecular interaction between the chromium and the nickel spin carriers, as predicted for orthogonal magnetic orbitals and a S = 7/2 value for the ground state. The intramolecular exchange coupling value, JCrNi, varies from + 4.5 cm-1 to + 10 cm-1 according to the distortion of the Cr-CN-Ni unit and especially to the change in the C - N - Ni angle. The uniaxial anisotropy, D, computed from fitting of the susceptibility data, is around - 0.3 cm-1. High-field EPR experiments are in progress in order to determine precisely the anisotropy factor. The synthesis, the characterisation, the magnetic properties and magneto-structural correlation studies of these species are presented elsewhere 24 .

Three of the five complexes are involved in the present study: i) \[Cr(CN)4\[CN-Ni(tetren)\]2\]Cl, noted CrNi2(tetren) that crystallizes in two different crystallographic systems: monoclinic, space group = P21/c and orthorhombic, space group = Pbc21, named 1 and 1 respectively ; ii) \[Cr(CN)4\[CN-Ni(dienpy2)\]2\](ClO4) that crystallizes in the monoclinic system, space group = C2/c, noted CrNi2(dienpy2) or 3. This compound is formed with a bulky ligand that influences the intermolecular distance and the intermolecular exchange coupling. The two cationic complexes are presented in figure 1. The CrNi2(tetren) monoclinic system 1, forms pink distorted hexagonal crystals. The hexagonal face corresponds to the (1 0 0) crystallographic plane. The three others faces are the (-1-1 1), (1-1-1) and (1 1-1) planes. In the crystal, the molecules are aligned in a two-dimensional sheet, parallel to the (1 0 0) plane. The planes are separated by the counter anions, Cl- and water molecules that form a network of hydrogen bonds. In each plane, the molecules are crystallographically equivalent but present two different orientations. The shorter intermolecular Cr-Cr, Cr-Ni and Ni-Ni distances are 8.50, 6.23 and 7.50 Å respectively. The shortest distance between two nearest molecules is less that 3.08 Å, corresponding to the distance between a free cyanide ligand on the central chromium and a nitrogen atom of the tetren ligand. Even if this distance appears slightly too long for a hydrogen bond, it can account for a possible pathway for intermolecular exchange interaction. For all the (1 0 0) planes, the direction of the molecular Ni-Cr-Ni axis forms a 36 angle with the a axis.
The CrNi2(tetren) orthorhombic system, 1, crystallises also as hexagonal plates. The two dimensional molecular arrangement is exactly the same than in compound 1. The shortest intermolecular Cr-Cr, Cr-Ni and Ni-Ni distances are 8.55, 6.29 and 7.50 Å respectively. Only differs the crystallographic plane of the hexagonal face, which is (0 0 1) and the molecular orientation from one plane to another. Instead of having the same orientation, the molecules are aligned in chevrons, with an angle of 90 between the molecular Ni-Cr-Ni axes. As in the previous case, the chloride ions and the hydrogen bond network formed by the water molecules separate the molecular layers.

Finally, the crystals obtain from the CrNi2(dienpy2) system, 3, are red-pink parallelepipeds that belong to the monoclinic system. The molecules are aligned in a two dimensional arrangement and the planes are separated by the ClO4-counterions. The orientations of the molecules in the crystal are very similar to the one observed in compound 1. Despite the facts that the dienpy2 ligand, due to the presence of pyridine rings, is more bulky than the tetren ligand and that the perchlorate is bigger than chloride, the intermolecular distances in 3 are only slightly longer than in complexes 1 and 1. The shorter intermolecular Cr-Cr, Cr-Ni and Ni-Ni distances are 9.17, 6.84 and 8.56 Å respectively. This is due to p-p interaction and to hydrogen bonds between two free cyanides through a water molecule.

3. CrNi2 complexes, magnetic behaviour

The magnetisation versus applied field was recorded on single crystals of the three CrNi2 using an array of micro-SQUIDs 31 . Different from a classical SQUID magnetometer where the flux coupling between sample and SQUID is made by using a pick up coil, a micro-SQUID magnetometer allows a much better flux coupling since the sample is placed directly on the SQUID loops. The sensitivity achieved with our device is 10-17 emu, that is ten orders of magnitude better than a traditional SQUID magnetometer 32  The sensitivity is smaller when the sample is much larger than the micro-SQUID. The high sensitivity of the magnetometer allows to study single crystals with dimensions from 10 to 500 $`\mu `$m. The magnetometer works in a temperature range between 0.035 and 10 K, in applied fields up to 1.4 T with sweeping rates as high as 1 T s-1 and a field stability better than a microtesla. The field can be applied in any direction of the micro-SQUID plane by separately driving three orthogonal coils. In order to ensure a good thermalisation, the crystal is fixed by using Apiezon grease.

Here we report on the observation of canted ferromagnetic structure for the three different compounds of CrNi2 with the same ground state spin 7/2. First we analyse the hysteresis loops of compound 1. Second, we correlate the structure with the magnetic behaviour. Third, we conclude with a comparison between the magnetisation data of the three crystals in order to establish if the intermolecular coupling is sensisitive to small variations of the structure: terminal ligands or crystal symmetry.

We used the micro-SQUID to measure magnetisation hysteresis loops at different temperatures and different field sweep rates and also the magnetic susceptibility below 7 K. A single crystal was placed on the SQUID array with the (100) plane parallel to the SQUID plane. The hysteresis loops are independent on the field sweep rate, suggesting that either resonant quantum tunnelling is hindered by intermolecular interactions or is much faster than the time scale of the micro-SQUID technique.

The magnetisation loops measured for different directions of the applied field in the (100) plane, proved that the magnetic behaviour is not isotropic in the plane. We have chosen two symmetry directions in the (100) plane which present distinct magnetic behaviour. The first direction is along the projection in the (100) plane of the bisecting line of two Ni - Cr - Ni molecular directions, showed to be an easy axis of magnetization. The second direction perpendicular to the first one, showed to be a hard axis of magnetization. The corresponding magnetizations versus applied field curves are presented in figure 2(a, b). In the first orientation (figure 2a), the magnetization is reversed from the negative saturation value to the positive saturation value in zero field. When increasing the temperature, the saturation magnetization decreases, but the zero field slope remains constant below 0.6 K. This is confirmed by the magnetic susceptibility measured in this direction (see figure 3a).

A fit to a Curie-Weiss law gives a positive Curie-Weiss constant of +0.6 K. Both results are typical of a system with ferromagnetic intermolecular coupling leading to long range ferromagnetic ordering. However, when the field is applied perpendicular to the easy axis of magnetization (second direction above), hysteresis loops (figure 2b) and susceptibility measurements (figure 3b) suggest an antiferromagnetic intermolecular coupling. This is established by the hysteresis loop shapes and the negative Curie-Weiss constant (-0.25 K).

The magnetic behaviour can be explained using the crystallographic structure. The CrNi2 compound, 1, presents an uniaxal anisotropy with a small ferromagnetic exchange interaction between the molecules. The central chromium ions of the molecules define the (100) planes (figure 1), which are separated from each other by a water and halide layer (figure 4). There might be weak antiferromagnetic interactions via hydrogen bonds between the planes but that are not clearly established. There are two different orientations of the molecules centred in the same (100) plane. The angle between the two directions is 64; the angle between each direction and (100) plane is 36.

The magnetic moments have therefore two orientations corresponding to the two orientations of the molecules. The micro-SQUID magnetometer is sensitive only to the in plane component of the magnetization, in this case to the projected magnetisation into the (100) plane. The projection coupling of magnetic moments can be decomposed into two independent contributions: a net ferromagnetic coupling along the bisecting line of two moments and a net antiferromagnetic one perpendicular to this direction. The magnetization measured along the bisecting line of two moments (figure 5a) is sensitive only to the net ferromagnetic component (the antiferromagnetic one is perpendicular to the direction of magnetic field, that is insensitive to field variation). The two moments are reversed at the same time near zero field.

Perpendicular to the bisecting line (figure 5c) only the net antiferromagnetic component of the couple is sensitive to the magnetic field. When the field increases (respectively decreases), one of the spins flips in order to align the couple with the maximum of the ferromagnetic component parallel to the field. For any other orientation, the behaviour is a mixture of the two limiting cases. At zero field we recover the projection of the ferromagnetic component of the couple on the field direction. When the field increases one of magnetic moment flips and the couple changes; the ferromagnetic projections on the field direction increase.

Measured in similar conditions, compounds 1 and 3 shows the same behaviour (figure 6). The field amplitude of the antiferromagnetic plateau for compound 1 is lower than for compound 1 and higher than for compound 3 in good agreement with the estimation of exchange interaction constant and with the fact that the molecules are closer in compound 1 than in compound 3. This points out the necessity to use bulkier ligands to reduce the intermolecular interaction. Other studies are in progress to better understand the correlation between the crystallographic structure and the magnetic behaviour in other directions of space.

4. Conclusions

The two different orientations of molecules in the crystals together with the intermolecular exchange interactions make CrNi2 a model system for canted ferromagnetic structures. It is established that the intermolecular coupling is sensitive to small variations of the structure such as the crystal symmetry or the steric hindrance of the terminal ligand. Our study allows to better understanding the synthetic parameters that have to be tuned in order to minimise intermolecular exchange interactions, necessary condition to get single molecule magnets. The ligand, as well as the counter anions has to be as bulky as possible. To isolate the high spin molecules, it is also conceivable to dilute the molecules in a diamagnetic or a paramagnetic matrix. Preliminary results performed on the CrNi2(tetren) compound co-crystallised in presence of CoNi2(tetren) complex, viewed as an ordered paramagnetic medium indicate the validity of such a strategy, which is beyond the scope of the present communication.