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# Detection of DCO+ in a circumstellar disk

## 1 Introduction

Disks around pre-main sequence stars are the likely sites of the formation of planetary systems (e.g., Beckwith 1999). Part of the gas and dust from the collapsing protostellar envelope settles into this disk, where it may undergo a complex chemistry before incorporation into planets and icy bodies. Tracing this chemistry is a key goal of molecular astrophysics, not only to establish a chemical inventory prior to planet formation but also as a probe of the dynamical processes in disks such as radial and vertical mixing (e.g., Aikawa et al. 1999, Markwick et al. 2002). Moreover, the abundances and excitation of the molecules provide unique insight into the physical structure of disks such as their temperature and density profiles (Dutrey et al. 1997, van Zadelhoff et al. 2001).

Deuterated molecules are a particularly interesting probe of the temperature history of interstellar and circumstellar gas. It is well known that the abundances of deuterated molecules in cold pre-stellar cores and protostellar envelopes are enhanced by orders of magnitude over the elemental \[D\]/\[H\] abundance ratio of $`1.5\times 10^5`$ through fractionation (e.g., Watson 1976, Millar et al. 1989). In particular, at temperatures below $``$50 K, the reaction

$$\mathrm{H}_3^++\mathrm{HD}\genfrac{}{}{0pt}{}{\genfrac{}{}{0pt}{}{}{}}{\genfrac{}{}{0pt}{}{}{}}\mathrm{H}_2\mathrm{D}^++\mathrm{H}_2+232\mathrm{K}$$
$`(1)`$
is driven strongly in the forward direction (e.g., Pagani et al. 1992). H2D+ can subsequently transfer a deuteron to the abundant CO molecule

$$\mathrm{H}_2\mathrm{D}^++\mathrm{CO}\mathrm{DCO}^++\mathrm{H}_2$$
$`(2)`$
leading to DCO+/HCO+ ratios of order 0.01. Such high ratios have indeed been observed in interstellar clouds (e.g., Guélin et al. 1977, Wootten et al. 1982, Butner et al. 1995, Williams et al. 1998) and in protostellar regions (van Dishoeck et al. 1995, Loinard et al. 2000, Shah & Wootten 2001, Parise et al. 2002). Deuterium fractionation can also occur through reactions of atomic deuterium on the surfaces of interstellar grains (Tielens 1983), but this is thought to affect primarily molecules which are formed on grains such as H2CO and CH3OH. The DCO+/HCO+ ratio can thus serve as a clear measure of the importance of low-temperature gas-phase deuterium fractionation processes. Moreover, this ratio is enhanced if the main destroyer of H$`{}_{}{}^{+}{}_{3}{}^{}`$, —i.e., CO—, is depleted onto grains, since reaction (1) then becomes an important H$`{}_{}{}^{+}{}_{3}{}^{}`$ removal route in addition to recombination with electrons, enhancing H2D+ even more (Brown & Millar 1989, Stark et al. 1999, Caselli et al. 1999). Thus, the DCO+/HCO+ ratio can also trace the level of depletion.

We present here the first detection of the DCO+ ion in a circumstellar disk, using the James Clerk Maxwell Telescope (JCMT). Together with observations of the HCO+ ion and its optically thin isotope H13CO+, an accurate DCO+/HCO+ ratio is derived. This ratio is subsequently compared with that found in the envelopes of deeply embedded protostars — the precursor material of disks —, and with those observed in solar system objects, in particular comets — the remnant material of disks.

## 2 Observations

The DCO+ $`J`$=5–4 rotational line at 360.169 GHz was observed with the JCMT111The James Clerk Maxwell Telescope is operated by the Joint Astronomy Centre in Hilo, Hawaii, on behalf of the Particle Physics and Astronomy Research Council in the United Kingdom, the National Research Council of Canada and the Netherlands Organization for Scientific Research. on Mauna Kea, Hawaii. The dual polarization receiver B3 was used in single-sideband mode. The backend was the Digital Autocorrelator Spectrometer (DAS) set at a resolution of $``$0.15 km s-1. The observations were taken in beam-switching mode with a throw of 180′′. The same set-up was used to observe the HCO+ and H13CO+ $`J`$=4–3 lines at 356.734 and 346.998 GHz, respectively. The antenna temperatures were converted to main-beam temperatures using a beam efficiency of 62%, calibrated from observations of planets by the telescope staff. The flux calibration was checked against bright sources with well-determined fluxes for different lines and was generally found to agree within 10%. The data were reduced and analyzed in the SPECX and CLASS data reduction packages.

The DCO+ search focussed on the disk around TW Hya, an isolated T Tauri star (K8Ve) which is part of a young group of stars at a distance of only $``$56 pc (Webb et al. 1999). Its age is estimated to be $``$7–15 Myr, somewhat older than most classical T Tauri stars, but its large lithium abundance and H$`\alpha `$ equivalent width are indicative of continued active disk accretion at a rate of $`10^8`$ M yr-1 (Kastner et al. 2002). TW Hya is surrounded by a nearly face-on disk of $`2\times 10^2`$ M (Wilner et al. 2000), which has been imaged recently in scattered light with the Hubble Space Telescope (Krist et al. 2000). The extent of the disk in the scattered light is $``$200 AU, corresponding to a 3.6′′ radius at 56 pc. Since this size is small compared with the $``$13′′ beam size of the JCMT at 360 GHz, the data suffer from beam dilution. Thus, long integration times of typically 2–4 hrs were needed to detect the weak lines reported here.

The DCO+ and HCO+ observations are part of a larger survey for molecular lines from disks, which will be reported in Thi et al. (2003).

## 3 Results

In Figure 1, the HCO+, H13CO+ and DCO+ spectra toward TW Hya are presented. All three lines are clearly detected at the same velocity, $`V_{\mathrm{LSR}}`$=3.0$`\pm `$0.1 km s-1. The lines are very narrow, $`\mathrm{\Delta }V0.6`$ km s-1, and do not show the characteristic double-peak profile of a rotating disk, consistent with the nearly face-on orientation. The lack of detection of the 12CO 3–2 line at 30′′ offset positions demonstrates that the molecular emission is indeed associated with the disk and not due to any remnant cloud material in the vicinity (Thi et al. 2003). The critical densities of the observed HCO+ and DCO+ lines are at least $`10^6`$ cm-3, further assuring that only the dense gas in the disk is probed. The integrated line intensities are summarized in Table 1.

Molecular column densities and abundances can be derived from the observed line strengths under different assumptions. In general, the emerging lines from interstellar gas are a complex function of abundance, excitation and radiative transfer effects. In circumstellar disks, where strong chemical gradients can exist in both vertical and radial directions, the interpretation of spatially unresolved data is particularly uncertain. However, since the main interest of this study is in the DCO+/HCO+ ratio, the analysis can be considerably simplified if it is assumed that DCO+ and HCO+ occupy roughly the same regions of the disk. Moreover, since the densities in disks are generally high in the regions where these molecules exist ($`>10^6`$ cm-3) (van Zadelhoff et al. 2001), the excitation can be assumed to be in local thermal equilibrium to first order. A single excitation temperature of 25 K is adopted in the following analysis. Finally, both the H13CO+ and DCO+ lines are assumed to be optically thin. The observed line intensity ratio of HCO+/H13CO+ of $``$7 compared with the optically thin ratio of $``$60 clearly indicates that the main isotope HCO+ $`J`$=4–3 line is optically thick.

The inferred column densities for a 200 AU radius disk are included in Table 1. For an assumed gas + dust disk mass of $`2\times 10^2`$ M, the beam-averaged HCO+ abundance is $`2\times 10^{11}`$, derived from the optically thin H13CO+ line assuming LTE excitation at 25 K (see Thi et al. 2003 for details). This is significantly lower than the typical HCO+ abundance of $`10^910^8`$ in dark clouds (e.g., Ohishi et al. 1992) and some protostellar envelopes (e.g., Schöier et al. 2002). Most of the observed emission is thought to originate from the warm intermediate layer of the disk just below the surface where the HCO+ abundance reaches a few $`\times 10^{10}`$ (e.g., Aikawa et al. 2002, Willacy & Langer 2000). The molecules are significantly depleted in the cold midplane of the disk where the bulk of the mass resides . For the TW Hya disk, observations of CO and other species indicate depletions up to a factor of 100 in the midplane (van Zadelhoff et al. 2001).

## 4 Discussion

The inferred column densities imply a beam-averaged DCO+/HCO+ abundance ratio of 0.035 $`\pm `$ 0.015, assuming a \[12C\]/\[13C\] isotopic ratio of 60 (see Table 1). The error bar reflects the observational uncertainties. The DCO+/HCO+ value is more than three orders of magnitude higher than the elemental \[D\]/\[H\] ratio of $`1.5\times 10^5`$, illustrating that strong deuterium fractionation occurs in disks.

Models of the deuterium fractionation in disks have been calculated by Aikawa & Herbst (1999, 2001) and Aikawa et al. (2002), with the latter models using a realistic 2-dimensional (2D) temperature and density structure of a flaring disk. The models include a detailed gas-phase chemistry network with freeze-out onto grains, but do not contain an active grain-surface chemistry. The resulting DCO+/HCO+ abundance is found to decrease with decreasing radius from $`0.1`$ at 400 AU to $`<0.01`$ at $`<`$50 AU, owing to the increasing temperature in the inner disk. The DCO+/HCO+ ratio also decreases with height in the outer disk, because of the higher temperatures in the upper layers. Close to the midplane where strong CO freeze-out occurs, the DCO+/HCO+ ratio reaches high values, but this region contributes negligibly to the observed emission due to the much lower overall abundances. Time-dependent effects appear to play a minor role, although results for disks as old as 10 Myr have not been published. Overall, the observed DCO+/HCO+ ratio of 0.035$`\pm `$0.015 averaged over the entire TW Hya disk appears consistent with these models.

Roberts et al. (2002) show that the model results for molecular clouds are lowered by a factor of a few if updated rate coefficients for reaction (1) are used. Since the main processes affecting the DCO+/HCO+ ratio in disks, namely low-temperature gas-phase reactions and freeze-out of CO on grains, are the same as those in clouds, similar effects are expected for disk models using updated rate coefficients.

Only few other measurements of deuterated molecules in disks have been reported. Qi (2001) and Kessler et al. (2003) searched for DCN and HDO in several disks using the Owens Valley Millimeter Array but obtained mostly upper limits. The inferred DCN/HCN ratio of $`<0.002`$ is much lower than that for DCO+/HCO+ found here.

Table 2 summarizes the observed DCO+/HCO+ and DCN/HCN ratios in different environments. It is seen that the DCO+/HCO+ ratio in the TW Hya disk is comparable to that found in cold dark cores where freeze-out has been observed (e.g., L1544), testifying to the low temperatures in disks. Indeed, DCO+/HCO+ ratios as high as 0.035 are difficult to produce in models which do not include CO depletion (Roberts et al. 2002). It is higher than that found in most protostellar envelopes, where heating has affected a larger fraction of the material resulting in higher temperatures and less CO freeze-out.

Because comets spend much of the time since their formation in the cold outer region of the Solar System, they are likely to contain the most primitive record of solar nebula material. No DCO+ is observed in comets, but DCN/HCN has been measured. In cold clouds and protostellar envelopes, the observed DCN/ HCN ratios are often comparable to the DCO+/HCO+ ratios (see Table 2), even though they involve different fractionation reactions. The most pristine material originating from below the comet surface and emanating in jets shows very high DCN/HCN ratios comparable to those seen in cold dark clouds and in the TW Hya disk. The upper surface layers which evaporate to produce the coma have significantly lower ratios, indicative of processing in the solar nebula.

The similarity of the deuterium fractionation ratios in cold clouds, disks and pristine cometary material suggests that the gas spends most of its lifetime at low temperatures and is incorporated into the disks before the envelope is heated, i.e., before the Class I stage. Alternatively, the DCO+/HCO+ ratio may be reset in disks by low-temperature gas-phase chemistry. Comparison of D/H ratios of molecules which enter the disk in the gas phase (such as HCO+) and those which are likely incorporated as ices (e.g., H2CO, CH3OH) can distinguish between these scenarios. Also, spatially resolved data can further test the models, since the high ratios observed here probe largely the outer disk.

The data presented in this paper are at the limit of the capabilities of current observational facilities. The Atacama Large Millimeter Array (ALMA) will be essential to provide high-resolution measurements of D/H ratios in disks down to comet- and planet-forming regions.

###### Acknowledgements.

Astrochemistry in Leiden is supported by a Spinoza grant from the Netherlands Organization of Scientific Research (NWO). WFT thanks PPARC for a post-doctoral grant to UCL.


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# Absence of orbital-selective Mott transition in Ca2-xSrxRuO4

## Abstract

Quasi-particle spectra of the layer perovskite Sr2RuO4 are calculated within Dynamical Mean Field Theory for increasing values of the on-site Coulomb energy $`U`$. At small $`U`$ the planar geometry splits the $`t_{2g}`$ bands near $`E_F`$ into a wide, two-dimensional $`d_{xy}`$ band and two narrow, nearly one-dimensional $`d_{xz,yz}`$ bands. At larger $`U`$, however, the spectral distribution of these states exhibit similar correlation features, suggesting a common metal-insulator transition for all $`t_{2g}`$ bands at the same critical $`U`$.

Sr2RuO4 has attracted considerable interest during the recent years because of a variety of fascinating properties. It exhibits unconventional p-wave superconductivity maeno ; phystoday  and is in fact the only known layered perovskite without copper that becomes superconducting in the absence of doping. The ground state is non-magnetic whereas the volume perovskite SrRuO3 is a strong ferromagnet. Substitution of Sr with Ca makes Sr2RuO4 undergo a transition to an antiferromagnetic Mott insulator nakatsuji ; cao . In contrast, doping with La leads to a ferromagnetic instability accompanied by a breakdown of Fermi-liquid behavior kiku . Spin fluctuations in Sr2RuO4 are believed to have both ferromagnetic and antiferromagnetic components mazin . Moreover, inelastic neutron scattering data indicate a soft phonon mode associated with in-plane rotations of oxygen octahedra braden . Clearly Sr2RuO4 is close to structural and magnetic instabilities. Substitution of Sr by the smaller Ca ions also causes a crystallographic distortion consisting of tilting and rotation of oxygen octahedra. These modifications reduce the effective hopping between Ru $`4d`$ orbitals via O $`2p`$ levels. The resulting narrowing of the $`4d`$ bands is believed to be the driving mechanism for the metal-insulator transition observed in Ca2-xSrxRuO4 for $`x=0.2`$ nakatsuji ; cao ; anisimov .

The layer perovskite Sr2RuO4 can be regarded as a prototype of a strongly correlated, highly anisotropic multi-orbital transition metal oxide with coexisting wide and narrow bands near the Fermi level. Due to the planar crystal structure the partially filled $`t_{2g}`$ bands separate into a two-dimensional $`d_{xy}`$ band with a van Hove singularity (vHs) just above $`E_F`$ lda , and two nearly one-dimensional $`d_{xz,yz}`$ bands. In the single-particle picture these bands do not hybridize for symmetry reasons. Local electron-electron interactions in the Ru $`4d`$ shell, however, are strong and according to angle-resolved photoemission spectra pes  the on-site Coulomb energy lies between the single-particle band widths of the $`d_{xz,yz}`$ and $`d_{xy}`$ bands: $`W_{xz,yz}<U<W_{xy}`$ liebsch . Thus, although correlations primarily affect the narrow $`d_{xz,yz}`$ bands, multi-orbital interactions also influence the wider $`d_{xy}`$ bands, in particular its singularity above $`E_F`$. Recent quasi-particle calculations liebsch  based on the Quantum Monte Carlo (QMC) Dynamical Mean Field Theory (DMFT) vollhardt ; georges ; pruschke  showed that on-site correlations give rise to a charge transfer from the narrow bands to the wider $`d_{xy}`$ band and to a red-shift of the van Hove singularity to within approximately 10 meV of $`E_F`$. Thus, doping with a few % La moves the Fermi level through the $`d_{xy}`$ singularity, thereby causing deviations from Fermi liquid behavior kiku .

At the surface of Sr2RuO4, a $`\sqrt{2}\times \sqrt{2}`$ lattice reconstruction driven by a soft phonon mode involving rotations of O octahedra reduces the effective $`dd`$ hopping matzdorf . As a result of the slightly narrower width of the $`d_{xy}`$ band in the first layer the van Hove singularity is shifted below $`E_F`$, converting the $`\gamma `$ sheet at the Fermi surface from electron-like to hole-like. Thus, photoemission spectra reveal a superposition of bulk bands with $`E_{vHs}>E_F`$ and surface bands with $`E_{vHs}<E_F`$ shen . The bulk bands are then consistent with the Fermi surface derived from de Haas-van Alphen measurements dHvA .

To investigate the metal-insulator transition induced by iso-electronic substitution of Sr with Ca, Anisimov et al. anisimov  recently performed DMFT calculations for Sr2RuO4 for increasing values of the local Coulomb repulsion $`U`$. While in reality the transition is driven by a distortion of O octahedra, giving rise to a narrowing of the Ru $`4d`$ band without any significant increase in $`U`$, these authors argued that a qualitative understanding of the Mott transition can be achieved by increasing $`U`$ and ignoring the modifications of the density of states due to the structural transition. This picture is very interesting from a conceptual point of view since in the anisotropic $`t_{2g}`$ configuration $`U`$ is comparable at first to $`W_{xz,yz}1.3`$ eV and subsequently to $`W_{xy}3.5`$ eV. A remarkable result of these calculations were two successive Mott transitions for the $`d_{xz,yz}`$ and $`d_{xy}`$ bands, implying an intermediate region of $`U`$ or, equivalently, of Ca concentration, where the narrow bands exhibit an excitation gap while the wide band is still metallic. Only at still larger $`U`$ a gap appeared for the entire $`t_{2g}`$ complex.

To study this unusual electronic structure in greater detail we have extended our previous DMFT calculations for Sr2RuO4 liebsch  to larger values of the on-site Coulomb energy. Surprisingly, we find a behavior that differs fundamentally from the one reported in Ref. anisimov . For small $`U`$, the $`d_{xy}`$ and $`d_{xz,yz}`$ quasi-particle spectra indeed have quite different shapes owing to their predominantly two- versus one-dimensional electronic structure, respectively. As $`U`$ increases, however, these spectral distributions begin to resemble one another, with only minor differences in the weight and shape of the coherent peak near $`E_F`$ and of the lower and upper Hubbard bands. Our results therefore suggest that for sufficiently large $`U`$ the correlated electronic structure within the $`t_{2g}`$ shell dominates the one-electron hopping. As a consequence, one common metal-insulator transition exists at an intermediate critical value of $`U`$ between those of the isolated $`d_{xz,yz}`$ and $`d_{xy}`$ bands. The reason for the discrepancy between the two approaches is not clear at present, but could be related to the fact that in Ref. anisimov  the quantum impurity problem was treated within the non-crossing approximation (NCA) nca ; zoelfl  whereas we use the more accurate Quantum Monte Carlo method georges .

Fig. 1 shows the tight-binding fit to the LDA band structure of Sr2RuO4 lda  in the vicinity of $`E_F`$ and the density of states. In the bulk the $`d_{xy}`$ vHs is about 50 meV above $`E_F`$. All three bands are approximately 2/3 filled. The non-symmetric shape of the two-dimensional $`\rho _{xy}(\omega )`$ is caused by second-neighbor Ru-Ru hopping terms. The $`d_{xz,yz}`$ densities are dominated by one-dimensional hopping along the Ru rows.

To take account of local Coulomb interactions we calculate the quasi-particle spectra within the multi-orbital QMC-DMFT approach liebsch ; held . Since the $`d_{xy}`$ and $`d_{xz,yz}`$ bands do not hybridize, the self-energy is diagonal in orbital space. In the DMFT the elements $`\mathrm{\Sigma }_i`$ ($`i=xy,xz,yz`$) are functionals of the bath Green’s functions $`𝒢_i^1=G_i^1+\mathrm{\Sigma }_i`$, where the local $`G_i`$ is given by

$$G_i(i\omega _n)=_{\mathrm{}}^{\mathrm{}}𝑑\omega \frac{\rho _i(\omega )}{i\omega _n+\mu \mathrm{\Sigma }_i(i\omega _n)\omega }$$
(1)
and $`\mu `$ is the chemical potential. Most QMC calculations were done for $`\beta =8`$ with 64 time slices and several runs using $`2x10^5`$ sweeps. In the low temperature calculations for $`\beta =40`$ 128 time slices were used, with up to $`5x10^4`$ sweeps. The quasi-particle density of states $`N_i(\omega )=\mathrm{Im}G_i(\omega )/\pi `$ is obtained via maximum entropy reconstruction jarrell .

As shown in Ref. liebsch , the angle-resolved photoemission spectra of Sr2RuO4 can qualitatively be represented by quasi-particle distributions for local Coulomb and exchange energies $`U=1.2`$ eV, $`J=0.2`$ eV. The $`d_{xy}`$ and $`d_{xz,yz}`$ spectra then look like moderately deformed versions of their respective single-particle densities of states. For instance, the lower van Hove singularity of the $`d_{xz,yz}`$ bands near $`1`$ eV is broadened and shifted to about $`0.5`$ eV. Larger Coulomb energies would yield too small binding energies for this spectral feature. This result is consistent with the fact that on-site Coulomb energies for $`4d`$ transition metals are smaller than for $`3d`$ metals. The $`d_{xy}`$ vHs is also shifted and lies only about 10 meV above $`E_F`$. Both bands show very low spectral weight in the energy region of the Hubbard peaks. The effective masses calculated within the QMC-DMFT for these Coulomb energies also agree with experiment.

We now increase the on-site Coulomb energy in order to explore the metal-insulator transition for this anisotropic multiband system. To illustrate the effect of the different widths of the $`t_{2g}`$ subbands on the quasi-particle spectra we show first in Fig. 2 the results for hypothetical three-fold degenerate bands consisting either of $`d_{xy}`$ or $`d_{xz,yz}`$ character. The total filling is 4 as in actual Sr2RuO4. For $`U=3.0`$ eV the wide $`d_{xy}`$ band is dominated by the strong quasi-particle peak at $`E_F`$. Since $`U<W_{xy}`$ it is only moderately affected by correlations and shows only weak shoulders in the range of the Hubbard bands. On the other hand, since $`U>>W_{xz,yz}`$ the narrow band derived from the $`d_{xz,yz}`$ density of states exhibits clear signs of a Mott transition. The upper and lower Hubbard peaks are the dominant spectral features. Because of the finite temperature used in the QMC-DMFT calculation, the remaining quasi-particle peak at $`E_F`$ obscures the gap between the Hubbard bands. Nevertheless, according to the temperature dependence of similar features found in one-band systems georges ; bulla  the value of $`U`$ used in the spectra shown in Fig. 2 should be very close to the critical value for a metal-insulator transition within the $`d_{xz,yz}`$ bands.

The quasi-particle spectra for the actual $`t_{2g}`$ bands of Sr2RuO4 are shown in Fig. 3 (a) for the same on-site energies. Evidently, as as result of the strong inter-orbital Coulomb and exchange interactions both $`d_{xy}`$ and $`d_{xz,yz}`$ spectral distributions have nearly lost their original density of states character and look remarkably similar: with coherent peaks at $`E_F`$ and upper and lower Hubbard bands of about the same intensity, position and shape. These spectra suggest a common Mott transition for the $`t_{2g}`$ bands at a value of $`U`$ only slightly larger than 3 eV. We point out that the local correlations for $`U=3`$ eV induce a charge transfer of about 0.05 electrons from the narrow $`d_{xz,yz}`$ bands to the $`d_{xy}`$ band. This would imply that the $`d_{xy}`$ van Hove singularity has shifted below $`E_F`$ and that the $`\gamma `$ sheet of the Fermi surface is hole-like rather than electron-like as observed in de Haas-van Alphen measurements dHvA . This supports our previous choice of a smaller $`U`$ for the actual Sr2RuO4 $`t_{2g}`$ bands liebsch .

Fig. 3 (b) illustrates the effect of increasing the exchange energy to $`J=0.7`$ eV. In order to keep the average Coulomb energy $`\overline{U}`$ unchanged $`U`$ is increased to 4 eV. (For a $`t_{2g}`$ complex $`\overline{U}`$ coincides with the inter-orbital Coulomb energy $`U^{}=U2J`$ anisimov . Thus, $`\overline{U}=2.6`$ eV in Figs. 3 (a) and (b).) Although the $`d_{xy}`$ and $`d_{xz,yz}`$ spectra are not quite as similar as in Fig. 3 (a), they have coherent and incoherent peaks of about the same intensity. Only the positions of these features are shifted. Extrapolation to lower temperatures does not seem to be quite as straightforward as in the previous case. Nevertheless, qualitatively both $`d_{xy}`$ and $`d_{xz,yz}`$ spectra are equally correlated and therefore also suggest a common Mott transition.

Judging from the results discussed so far for $`U`$ in the critical region it does not seem likely that upon lowering the temperature the $`d_{xy}`$ and $`d_{xz,yz}`$ spectra would begin to lose their similarity again and diverge towards two separate Mott transitions. To test this behavior we have performed multiband QMC-DMFT calculations at about 300 K which are computationally much more costly. Fig. 4 shows the $`d_{xy}`$ and $`d_{xz,yz}`$ quasi-particle distributions for $`U=3.0`$ eV, $`J=0.2`$ eV. The peak near $`E_F`$ exhibits a fine structure which is the remnant of the upper and lower edge singularities of the $`d_{xz,yz}`$ bands. The $`d_{xy}`$ spectrum also reveals this structure as a result of the strong orbital interactions. The important point is that both $`d_{xy}`$ and $`d_{xz,yz}`$ spectra are similarly correlated: the coherent peak has about the same weight and the upper Hubbard bands are almost identical. The main difference is that the lower Hubbard $`d_{xz,yz}`$ satellite is split off from the main peak by a gap while the $`d_{xy}`$ satellite lies in the lower tail of the $`d_{xy}`$ density of states and therefore forms a continuum with the main peak. Leaving aside the uncertainties caused by the maximum entropy reconstruction, such a gap does not imply that the spectral weight at the Fermi level vanishes at a different $`U_{\mathrm{crit}}`$ or $`T_{\mathrm{crit}}`$ than in the case of the $`d_{xy}`$ states. On the contrary, the comparable strength of the coherent peaks indicates that the $`d_{xy}`$ and $`d_{xz,yz}`$ bands undergo a common Mott transition.

The above results differ qualitatively from the ones obtained by Anisimov et al. anisimov . The NCA in principle should be applicable also to multiband materials. On the other hand, even in one-band cases it is known to be unreliable in certain situations and even violate Fermi-liquid behavior georges ; held ; pruschke . It would be desirable to perform numerical renormalization group calculations for this system at very low temperatures. Unfortunately, multiband calculations within this scheme are computationally not yet within reach.

In summary, we have used the QMC-DMFT to calculate quasi-particle spectra of Sr2RuO4 in the range of on-site electron-electron interactions appropriate for a possible metal-insulator transition. Qualitatively, increasing $`U`$ might be a way to simulate the reduced $`t_{2g}`$ band width caused by distortions of O octahedra when Sr is replaced by Ca. At low Coulomb energies, the spectral distributions of the $`d_{xy}`$ and $`d_{xz,yz}`$ bands differ strongly because of the planar geometry of this perovskite material. Despite this anisotropy, at sufficiently large $`U`$ these spectra resemble one another in the sense that they are equally strongly affected by local correlations. In particular, they exhibit similar upper and lower Hubbard bands and a coherent peak of similar strength. These results suggest that there is a common Mott transition for the $`t_{2g}`$ complex, in contrast to the squential orbital-selective Mott transitions found in Ref. anisimov . Thus, in the critical region of $`U`$ local Coulomb interactions appear to dominate the anisotropic one-electron hopping.

Acknowledgement: I like to thank A. Bringer, R. Bulla, O. Gunnarsson, A. Kampf, J. Keller, Th. Pruschke, and D. Vollhardt for useful discussions. I also thank A.I. Lichtenstein for the QMC-DMFT code.


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# Two more years of GRB optical afterglows

## 1. Introduction: what happened in the past two years

I will summarize here the discoveries accomplished during the past two years in the optical domain and concerning the Gamma-Ray Burst (GRB) afterglow phenomenon, along with the information carried by these detections.

I start by briefly listing, in a (not too tight) chronological order, what in my opinion are the technical and instrumental landmarks in the GRB field since October 2000. First, by the end of 2000, HETE-2 became fully operational and started delivering fast GRB triggers; meanwhile, the GRB community began making wider use of robotic telescopes (among them ROTSE, LOTIS, BOOTES, BART, KAIT, Palomar 48-inch, Mount Stromlo 50-inch, RAPTOR). In parallel, afterglow searches were performed also by applying new techniques such as the color-color diagram (Rhoads 2001) or the image subtraction (Alard 2000) methods. On April 2002 the Mars Odyssey spacecraft joined the InterPlanetary Network (IPN), making this satellite network active and efficient again for GRB localizations after the end of the NEAR mission on February 2001. The bad news of this two-year period is the end of BeppoSAX operative life on April 30, 2002, exactly six years after its launch. A happy appendix is however the successful launch, on October 17, 2002, of INTEGRAL, which will be able to provide real-time arcmin-sized GRB localizations.

## 2. The new discoveries

In this section I will review the main characteristics of the Optical Transients (OTs) discovered in the period October 2000 - September 2002, along with a GRB, exploded in March 2000, which can potentially be very interesting and for which a comprehensive study was published only very recently. I will also briefly mention the new OT discoveries occurred after the end of this Workshop and before the proceedings submission deadline (January 2003). In the following I will denote with $`\alpha `$ and $`\beta `$ the time decay and spectral indices of the afterglow emission, respectively, according to the common notation $`F(t,\nu )t^\alpha \nu ^\beta `$.

GRB000313. This short/hard GRB was detected by BATSE only, thus it had not an accurate localization. Nevertheless, within the 3$`\sigma `$ BATSE error box, an object (Fig. 1, left) of magnitude $`I`$ = 9.4$`\pm `$0.1 was detected by BOOTES about 4 minutes after the GRB. Subsequent observations showed that neither an optical afterglow, nor a host down to a limiting magnitude $`R`$ 24.5 were detected at the position of the transient. If this was indeed the optical counterpart of this GRB, the early light curve had a decay index $`\alpha >`$ 2.2, similar to the decay observed in the optical flash of GRB990123 (Akerlof et al. 1999). Thus, BOOTES may have caught the first optical flash associated with a short/hard GRB. The absence of an afterglow and of a host would suggest that indeed short/hard GRBs occur in low-density environments outside their hosts. A detailed study on this GRB can be found in Castro-Tirado et al. (2002).

GRB001007. This GRB was detected by the IPN and its OT was characterized by a very fast ($`\alpha `$ 2) light curve decay. Its non-detection in LOTIS data suggested a possible early break in the light curve. The spectral and temporal behaviour of the OT were plausibly modeled assuming a collimated emission. The host galaxy was detected at $`R`$ 24.8 and presented an irregular shape. More information is available in Castro-Cerón et al. (2002).

GRB001011. The OT of this GRB localized by BeppoSAX was the first to be found with the color-color diagram technique (Rhoads 2001) extended to the infrared data, and later confirmed by its fading. It showed a time decay with $`\alpha `$ 1.3 and was located in a host with $`R`$ 25.4. Further details on the discovery of this OT can be found in Gorosabel et al. (2002a).

GRB010222. This GRB, one of the best shots by BeppoSAX, was accompanied by a relatively bright OT with three absorption systems in the spectrum at redshifts 0.927, 1.155 and 1.475 (Jha et al. 2001; Masetti et al. 2001). Its light curve underwent an achromatic break (with the exception of the $`K`$ band; Fig. 1, right) $``$0.7 days after the GRB, while the broadband spectrum suggested that the cooling frequency $`\nu _\mathrm{c}`$ was in the UV domain $``$1 day after the prompt event (Masetti et al. 2001). No significant polarization was detected (Björnsson et al. 2002). A possible further light curve break was found by Fruchter et al. (2001a) $``$10 days after the GRB. No unanimous interpretation of the fireball shape, physics and emission mechanisms at play in this OT was reached: subrelativistic transition (Masetti et al. 2001), continuous energy injection (Björnsson et al. 2002), low electron distribution index $`p`$ (Sagar et al. 2001) were invoked to explain the OT behaviour. High-resolution spectra indicated that the GRB environment was not particularly dense (Mirabal et al. 2002); this result is at variance with the findings of Masetti et al. (2001) and Savaglio et al. (2003).

GRB010921. This was the first GRB detected by HETE-2 for which an OT was found, and the first OT found by means of image subtraction technique (Price et al. 2001); it would have probably been overlooked if this method was not applied. It was at redshift $`z`$ = 0.451 (Price et al. 2001) and its light curve showed two breaks: one within 1 hour (Park et al. 2001) and the other about 35 days (Price et al. 2002a) after the GRB. Indication for spherical fireball expansion and for substantial absorption in the host were found (Price et al. 2001). Any underlying supernova (SN), if present, was at least 1.3 mag fainter than SN1998bw (Price et al. 2002a).

GRB011211. The OT of this BeppoSAX GRB was located at $`z`$ = 2.14 (Fruchter et al. 2001b). The light curve showed a break $``$2 days after the GRB and fluctuations which could be due to circumburst medium (CBM) inhomogeneities on a scale of tens of AUs; observations are consistent with the OT emission being produced by a fireball expanding in a homogeneous medium (Holland et al. 2002). The OT was not polarized (Covino et al. 2002a).

GRB020305. This was the second OT detected following an HETE-2 alert. It showed decay and spectral indices $`\alpha `$ 1.3 and $`\beta `$ 1, respectively (Lee et al. 2002), and the presence of a host was reported (Ohyama et al. 2002; Gorosabel et al. 2002b). Further observations can be found in Yoshida et al. (these proceedings).

GRB020322. The OT of this BeppoSAX GRB was one of the dimmest ones detected up to now: 8 hours after the GRB it was already at magnitude $`R`$ 23.3 (Bloom et al. 2002a; Fig. 2, left) and was very likely discovered only thanks to the arcsecond-sized position available through the XMM-Newton detection of the X–ray afterglow (Ehle et al. 2002). A possible break around $``$1 day after the GRB was detected in its optical light curve (Burud et al. 2002).

GRB020331. The HETE-2 ‘Easter GRB’ was associated with a very slowly decaying OT ($`\alpha `$ 0.6; Fox et al. 2002). This was possibly due to the contamination of the underlying host (Dullighan et al. 2002). However, Castro-Cerón et al. (these proceedings) reported a flattening and a possible subsequent restart of the (slow) decay occurring $``$1 week after the GRB, which would suggest that this behaviour might be intrinsic and not due to the host contribution.

GRB020405. The OT of this IPN GRB, at a redshift $`z`$ = 0.69 (Masetti et al. 2002; Price et al. 2002b), showed a bump in the light curve between 10 and 20 days after the GRB: this was interpreted by Price et al. (2002b) as due to an underlying SN. Besides, the OT was possibly highly polarized ($`P`$ 10%; Bersier et al., 2002; however, see the review by Covino in these proceedings). A fairly complete spectrophotometric and polarimetric study of this GRB, along with an alternative interpretation of the optical light curve bump, can be found in Masetti et al. (these proceedings).

GRB020410. One of the last BeppoSAX localizations allowed the detection of an OT, for the first time ever, by means of HST (Fruchter et al. 2002c; Fig. 2, right). This was possible thanks to the very accurate (20<sup>′′</sup> in radius) X–ray afterglow position by BeppoSAX so that the entire error box could be fitted in the HST-WFPC2 field of view. Comparison with ground-based observations showed that the OT light curve underwent a break; however, the possibility that this was actually a high-$`z`$ SN cannot be excluded (Fruchter et al. 2002c).

GRB020813. This was one of the brightest GRB detected by HETE-2 up to now. Its OT showed two absorption systems in its spectrum, at redshifts 1.122 and 1.254 (Price et al. 2002c). A marked light curve break was detected $``$1 day after the GRB (Bloom et al. 2002b), while a flattening, most likely due to the presence of the host, was observed at late times (Gorosabel et al. 2002). For the first time in the case of an OT, a very high resolution spectrum was acquired (Fiore et al. 2002). Optical polarization, possibly variable, was also detected (Barth et al. 2003; Covino et al. 2002b; Rol et al., these proceedings).

Other OTs. After the end of the meeting, and before the submission deadline (January 15, 2003), the OTs of three more GRBs (021004, 021211 and 030115, all localized by HETE-2) were detected. The fast localizations of 021004 and 021211 allowed the detection, by means of robotic telescopes, of the corresponding OTs within the first minutes after the GRB trigger: the emission was in both cases interpreted as the tail of the optical flash simultaneous with the GRB itself (Kobayashi & Zhang 2003; Wei 2003). The OT of GRB021004 was quite bright and well sampled; observations suggest a clumpy CBM (e.g. Lazzati et al. 2002). GRB021211 was instead associated with a quite faint OT (Fox et al. 2003) and, possibly, an even fainter OT was found for GRB030115 (Masetti et al. 2003) at the position of the infrared afterglow (Levan et al. 2003).

A controversial case is that of the HETE-2 X–ray flash XRF020903. In its error box a decaying optical source showing a SN-like bump after $``$30 days was detected at $`z`$ = 0.25 (Soderberg et al. 2002). Thus, were this indeed the OT of XRF020903, it would be the first optical counterpart ever detected for an XRF; moreover, its behaviour would not substantially differ from that of GRB OTs, in spite of their different high-energy prompt event characteristics. Alternatively, an AGN interpretation for this OT was given (Gal-Yam 2002); recent HST observation showed however that the variable object is in a complex of interacting galaxies, but not at the center of any of them (Levan et al. 2002).

I intentionally did not mention the OTs of GRB011121 and GRB020124: they will be discussed in these proceedings by Greiner, Zeh et al. and Price.

## 3. Summary: the lessons we (hopefully) learnt

The discoveries of new OTs during the past two years increased our knowledge (and in some cases our uncertainties) on the behaviour and emission mechanisms of GRB afterglows in the optical. We found that OTs show no “preference” in their expansion geometry, fireball evolution or environmental characterstics.

Thanks to the availability of accurate (arcmin-sized) real-time GRB alert and to the increasing number of fast-response robotic telescopes, we are getting closer and closer to see the OT behaviour in its very first phases. Recent observations are moreover suggestive of a noteworthy point: there indeed seems to be wide a spread in the OT brightnesses and this might, at least partially, explain the ‘dark’ optical afterglow conundrum. That is, quite likely some of them are actually intrinsically ‘dim’ OTs, rather than obscured or high-$`z`$ ones.

Also, evidence for late-time bumps in the OT light curves is growing. These are customarily associated with the emerging contribution of a SN exploded at, or around, the time of the GRB; however, this behaviour is not universal (see e.g. the case of GRB010921), and other interpretations such as dust echoes (Esin & Blandford 2000), late shell collisions (Kumar & Piran 2000) or ion-proton shell interactions (Beloborodov 2003) should be explored.

What is the lesson we should learn from all this? In my opinion, it can be listed in six points (some of them, admittedly, a bit tautologic): 1) we need fast high-energy arcsec localization to pinpoint the GRB position and start very deep serches as soon as the alert is distributed. This can also help to quickly find ‘dim’ and/or rapidly decaying OTs. The Swift satellite will be able to fulfill this task; 2) as HETE-2 and INTEGRAL can already provide real-time GRB alerts, we need very fast-response robotic telescopes. The REM telescope (Zerbi et al., these proceedings), starting on March 2003, will secure observational coverage beginning within 10 seconds after the GRB trigger; 3) sometimes, error boxes with sizes of several arcmin of radius are provided. In this case, the use of telescopes with large-field imagers should be encouraged; 4) as some afterglows can be optically faint due to local dust obscuration or high-$`z`$ effects, wider use of near-infrared imaging should be made. This also will be addressed by REM; 5) the use of new techniques for OT searches (such as color-color diagram, image subtraction, along with the development of pipelines for fast reduction of wide-field images) should also be encouraged; 6) finally, and when applicable, co-operation among groups (and possibly from GRBs also…) would be desirable to expand our understanding of these still enigmatic and therefore fascinating phenomena.

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text:
# The Smallest Molecular Switch

## Abstract

Ab-initio total energy calculations reveal benzene-dithiolate (BDT) molecules on a gold surface, contacted by a monoatomic gold STM tip to have two classes of low energy conformations with differing symmetries. Lateral motion of the tip or excitation of the molecule cause it to change from one conformation class to the other and to switch between a strongly and a weakly conducting state. Thus, surprisingly, despite their apparent simplicity these Au/BDT/Au nanowires are shown to be electrically bi-stable switches, the smallest two-terminal molecular switches to date. Experiments with a conventional or novel self-assembled STM are proposed to test these predictions.

Electronic devices that switch between high and low resistance states are at the heart of the modern information technology. As miniaturization of this technology continues to progress the long-standing fundamental problem of identifying and understanding the smallest physical systems that are capable of switching behavior is attracting growing interest . Recently it has been discovered experimentally that some molecular wires (i.e., single molecules carrying an electric current between a pair of metal nano-electrodes) can exhibit electrical bistability and switch between strongly and weakly conducting states, either spontaneously or in response to a change in the applied bias voltage. It has been suggested that this intriguing behavior may be due to charging of the molecule and/or changes of the molecular geometry (conformation), however the complexity of the experimental systems has so far prevented the development of a quantitative explanation. On the theoretical side, the possibility of making molecular wire switches by introducing a third (gate) electrode into the system has been explored, as has the possibility of designing two-terminal molecular wires that switch due to electric field-induced conformational changes. In this Letter we demonstrate theoretically that a much smaller and simpler two-terminal molecular wire can exhibit bi-stability and switching than has been thought possible until now, and present a realistic theory of its behavior. We consider a 1,4 benzene-dithiolate (BDT) molecular wire with one sulfur end group bonded to a gold substrate and the other to a monoatomic gold scanning tunneling microscope (STM) tip as depicted in Fig.1. Our ab-initio total energy calculations demonstrate that this system has low-energy conformations of two distinct types that have different symmetries. Flipping between these conformations is predicted to occur in response to lateral motion of the STM tip, and also, for some positions of the STM tip, in response to excitation of the wire by a current pulse or spontaneously at finite temperatures. The symmetry change when the molecular wire flips results in a large change in its current-voltage characteristic. Thus its electrical conductance exhibits bi-stability and switching. Theoretical work stimulated by a pioneering molecular wire experiment has elucidated various aspects of electron transport through Au/BDT/Au wires. However the possibility that wires of this type may be bi-stable or capable of switching is far from obvious a priori and has not been investigated until now . Thus as well as identifying the smallest two-terminal molecular switch to date and shedding new light on the mechanisms of molecular bistability and switching, the present work reveals an unexpected new dimension of the physics of Au/BDT/Au molecular wires, one of the most important paradigms of molecular electronics. The molecular switch that we describe should be amenable to experimental study with presently available techniques. Thus our findings also raise the prospect of bridging the gap that has persisted in this field between theory and experiment since molecular switching was first observed.

In our ab-initio calculations of the energetics of Au/BDT/Au wires the STM tip was represented by a tetrahedron of Au atoms and the Au (111) substrate by a cluster of three Au atoms as shown in Fig.1. We searched for low-energy molecular wire conformations holding the positions of the Au atoms fixed and keeping one of the S atoms of the BDT over the hollow site between the three Au substrate atoms since it is believed that organic thiol molecules bond to Au (111) surfaces via a sulfur atom at this location. All other coordinates of the atoms of the wire were allowed to vary freely. The lowest energy conformation of the molecular wire when the Au tip atom is directly over the hollow bonding site of the substrate and 9.9Å from the substrate is depicted in Fig.1(a). The molecule orients itself so that the Au tip atom is approximately coplanar with the benzene ring. We will refer to this as an edge conformation of the wire since the Au tip atom faces the edge of the benzene ring. If the Au tip is moved further from the substrate, so that it becomes geometrically possible for the molecule to stand perpendicularly to the substrate with the terminal Au atom of the STM tip directly over the upper S atom, we find this upright geometry to be unstable energetically: As long the tip atom is close enough to the molecule for a chemical bond to form between the Au and S atoms, the molecule relaxes to a tilted position. We note that such non-linear bonding geometries of Au, S and C atoms have also been found in recent ab-initio simulations of monoatomic Au wires bonded to other organic thiolate molecules .

When the Au tip is moved laterally away from the position over the hollow substrate bonding site, we find the molecular wire’s ground state conformation to change dramatically. This is illustrated in Fig.1(b) where the tip has been displaced laterally by $`3`$Åin the $`x`$ direction from its ($`x=0`$) position in Fig.1(a). Interestingly, the molecule adopts an orientation in which it tilts as far from the normal to the substrate as it can while maintaining the chemical bond between the Au tip atom and the upper S atom of the molecule. Most importantly, however, as the lateral tip displacement increases from $`x2`$Å to $`3`$Å the molecule rotates about its S-S axis from its edge conformation through an angle of $`\pi /2`$ to an orientation in which the Au tip atom is over the flat face of the benzene ring, as in Fig.1(b). We shall refer to this as a face conformation. Thus the ground state conformation of the molecular wire switches from edge to face as the STM tip moves laterally away from the location where the molecule bonds to the substrate. If the tip is moved instead in the opposite (negative $`x`$) direction from its position in Fig.1(a) the ground state conformation of the molecular wire again switches from edge to a strongly tilted face geometry although the substrate and tip both have a pronounced left-right asymmetry. For the $`x=3`$Å position of the tip in Fig.1(b) we find the molecular wire to also have a metastable conformation that corresponds to a local energy minimum. This is the upright edge conformation in Fig.1(c) whose energy is 0.11eV above the ground state face geometry of Fig.1(b).

We now examine the implications of the conformational switching and bi-stability described above for electrical conduction through the molecular wire. In recent years much progress has been made developing theories of electron transport through molecules . An important conclusion has been that the current at low bias is carried by molecular $`\pi `$ orbitals. The overlap between the $`\pi `$ orbitals and the states of the contacts is sensitive to the orientation of the molecule relative to the contacts, which implies a strong orientation-dependence of the molecular wire’s conductance. Such overlap effects have been found in semi-empirical and density functional  transport calculations. Thus it is reasonable to expect them to result in a significant change in conductance when an Au/BDT/Au wire switches between an edge and a face conformation, and our calculations show this to be the case. Since semi-empirical calculations have been successful in explaining the experimental current-voltage characteristics of a variety molecular wires consisting of organic thiol molecules bonded to gold electrodes we adopted this approach here. In Fig. 2 we show the calculated differential conductance of the molecular wire in its ground state conformation for a sequence of positions of the STM tip along a linear trajectory over the molecule that passes through the locations that the tip occupies in Fig.1. (Fig.1(a) and (b) correspond to $`x=0`$Å and $`3`$Å on the trajectory, respectively.) When the tip is furthest from the center where the molecule bonds to the substrate (i.e. for $`x=4`$Å and $`4`$Å in Fig. 2) the molecule in its ground state is in the face conformation and is highly conducting at a source-drain bias around $`1.5`$ Volts. When the tip moves towards the center ($`x=2,0,2`$Å in Fig. 2), the molecule’s ground state switches to the edge configuration which is seen to be much less conducting in the same range of bias. Our calculations of the $`dI/dV`$ characteristics of the molecular wire in a variety of face and edge conformations that have energies higher than the ground state (including the metastable edge conformation in Fig.1(c)) yielded very similar results to those in Fig. 2. I.e., All face conformations of the molecular wire were found to be highly conducting at the first conductance peak near $`1.5`$ V while all edge conformations are weakly conducting there. Thus whenever the molecule is made to flip from a face conformation to an edge conformation, either by displacing the STM tip laterally or by exciting the molecule thermally or by a current pulse, the molecule is predicted to switch from a highly conducting to a weakly conducting state, and vice versa.

This large difference in conductance between the edge and face conformations can be understood within Landauer theory  by considering the transmission probabilities $`T`$ for electrons to scatter through the molecular wire, taking account of $`\pi `$ orientational effects. Representative results are shown in Fig. 3 for several face ( Fig. 3(a)) and edge (Fig. 3(b)) conformations. The Fermi energy of gold in our semi-empirical model is near $`10`$ eV . The transmission peaks immediately below the Fermi energy can be attributed to the highest occupied molecular orbitals (HOMO)s of the BDT and those above to the lowest unoccupied molecular orbital (LUMO). The Fermi energy lies nearest the HOMO, so the onset of conductance is due to electron transmission through the HOMO. In the face conformations there is a strong overlap between the first HOMO molecular $`\pi `$ orbital and the atomic orbitals on the Au tip atom. This results in the strong transmission due to the first HOMO below the Fermi energy (beginning near $`10.5`$ eV) in Fig. 3(a) and in the strong conductance peak seen for the face conformations in Fig. 2. However, in the edge conformations the molecular $`\pi `$ orbitals are oriented differently and their overlap with the orbitals on the Au tip atom is weaker. This results in the weaker transmission through the first HOMO below the Fermi energy in Fig. 3(b) and the lower conductance of the edge conformations in Fig. 2.

Thus we arrive at the unexpected prediction that a molecule as simple as BDT can be made to switch through its interaction with a suitable STM tip. The ON state corresponds to the molecule oriented in such a way that its ring faces the tip, whereas in the OFF state the edge of the ring faces the tip. The switching can be induced by passing the tip over the molecule (the transition between Fig.1(a) and Fig.1(b)) or by exciting the molecule to a different conformation for a fixed tip position (the transition between Fig.1(b) and Fig.1(c)).

We predict an unusual and striking experimental signature of switching induced by the motion of the tip: The conductance should be low at the center of the STM image of the molecule where the edge conformation is stable and high when the tip moves away from the center of the image and the face conformation becomes stable. Experimental observation of switching induced by passing the tip over the molecule may be facilitated at low temperatures where thermal excitation of the higher energy conformations is minimal. \[For example, we find the highly conducting excited face conformation obtained by rotating the molecule from the (weakly conducting) ground state edge conformation in Fig.1(a) through $`\pi /2`$ about the S-S axis corresponds to an energy saddle point $`kT_{room}`$ above the ground state; thus this excited state will be populated significantly at room temperature.\] Hysteresis may occur in the STM image of the molecule at low temperatures, as is evident from the greater similarity of the $`x=0`$Å ground state in Fig.1(a) to the $`x=3`$Å excited state in Fig.1(c) than to the ground state in Fig.1(b). This also suggests interesting experiments that may combine scanning by the tip and activation of switching by current pulses.

Experimental studies may employ a conventional STM to contact a molecule adsorbed on a metal substrate. An alternative may be to self-assemble a monoatomic STM tip for the top probe. Realizing such a system would rely on growing the top electrode epitaxially on a heterogeneous self-assembled monolayer (SAM) of insulating and conducting organic molecules, choosing a conducting molecule that is shorter than the insulating one. Such a SAM would have a “divot” at the site of each conducting molecule. It has been suggested that when the top layer is grown, a metal atom that bonds chemically to the conducting molecule should occupy the divot forming a tip. Our calculations indicate that the top electrode may sit quite high over the insulating part of the SAM (we considered gold contacts with pentanethiol as the insulator and BDT as the conductor). Thus there is room for the formation of a monoatomic tip contacting the conducting molecule. In such systems the switching rate between the ON (face) and OFF (edge) state for a fixed tip position would depend on steric constraints imposed by the local environment of the molecule; analogous effects have been observed recently in STM experiments on more complicated (three-ring) switching molecules in an insulating host matrix. For an insulating host SAM such as an alkanethiol that does not bond chemically to the upper metal contact, one may also consider the possibility of sliding the top metal electrode laterally a few Angstroms (and the self-assembled tip with it) relative to the substrate and SAM by applying suitable mechanical or electrostatic forces to the metal contacts, thus realizing a mobile self-assembled STM tip that could probe switching of the molecule induced by motion of the tip.

In conclusion, we have shown that one of the simplest and most studied molecular wires, surprisingly, becomes a bistable molecular switch if one of its two metal contacts is a monoatomic scanning tunneling microscope tip. This is the smallest two-terminal molecular switch to date. The switching mechanism that we have introduced here relies on the coupling between the molecule and contacts and thus should be broadly applicable. We have proposed experiments with a conventional or novel self-assembled STM to test our predictions, and hope that the ideas put forward here will facilitate bridging the gap between theory and molecular switching experiments.

This work was supported by NSERC and the Canadian Institute for Advanced Research.


text:
# Addition Energies of Fullerenes and Nanotubes as Quantum Dots: The Role of Symmetry

## Abstract

Using density-functional theory calculations, we investigate the addition energy (AE) of quantum dots formed of fullerenes or closed single-wall carbon nanotubes. We focus on the connection between symmetry and oscillations in the AE spectrum. In the highly symmetric fullerenes the oscillation period is large because of the large level degeneracy and Hund’s rule. For long nanotubes, the AE oscillation is fourfold. Adding defects destroys the spatial symmetry of the tubes, leaving only spin degeneracy; correspondingly, the fourfold behavior is destroyed, leaving an even/odd behavior which is quite robust. We use our symmetry results to explain recent experiments. \[Phys. Rev. Lett. 91, 116803 (2003).\]

Quantum dots (QDs) have been one of the most active research areas in condensed matter physics because of their fundamental interest as controllable electronic systems and their importance to potential applications such as quantum computing. Two-dimensional (2D) QDs formed in semiconductor heterostructures have been studied intensively for a decade 2d . Recently, new systems, such as nanotubes (1D) and nanoparticles or fullerenes (0D), became available experimentally and have been attracting more and more attention 01d . An important difference between the molecule-based and heterostructure-based QDs is that the molecules have a known atomic structure with definite symmetry. Here we show that this symmetry plays an important role in transport through the dots.

Our tool for probing symmetry in molecular QDs is the Coulomb blockade of transport in the tunneling regime 2d ; 01d : the electrostatic energy of an additional electron on a dot blocks the flow of current through the dot. As a result, the conductance through the dot depends strongly on gate voltage, forming a series of sharp peaks. The spacing between these Coulomb blockade peaks is proportional to the addition energy (AE) – the second difference of the ground state energy with respect to electron number. The shape of 2D semiconductor QDs is generally irregular. Their levels and wavefunctions can either be treated statistically by random matrix theory Alhassid00  or be calculated by density functional theory (DFT) with a model irregular effective potential dft2d . In this way, most of the experiments on Coulomb blockade peak spacings in these dots can be understood statistically baranger1 ; baranger2 .

In contrast, the regular atomic structure of the new 0D and 1D QDs has high spatial symmetry, implying orbital degeneracies and so quite different behavior. For example, for a long closed single-wall carbon nanotube (SWCNT), each orbital should be fourfold degenerate because of the combination of $`K`$-$`K^{}`$ valley degeneracy and spin. Therefore, a fourfold shell filling is expected, in contrast to the twofold even/odd effects observed in the AE of semiconductor quantum dots. Recently, some non-tunneling experiments indeed observed four-electron shells fourfold1 ; fourfold2 . A later tunneling experiment found only twofold spin shells twofold ; in fact, a remarkably strong even/odd oscillation in the AE spectra was observed. Other experiments, however, did not observe even this twofold even/odd oscillation no\_even/odd .

So far it is not clear how to reconcile these different experiments. Indeed, for the new types of QDs many basic questions need to be addressed: What are the differences between the 0D and 1D systems? What is the effect of native defects? What is the environmental influence under real experimental conditions? To answer these questions unambiguously and to explain the different experiments, calculations free from empirical parameters are needed.

Here we report the first first-principles investigation of the AE spectra of fullerenes and closed SWCNTs. Our main findings are: (1) For fullerenes there is no even/odd oscillation in the AE spectra because of the highly degenerate energy levels and Hund’s rule – the shell filling is multifold. (2) For closed SWCNTs, the observability of periodic behavior depends on the energy window. Around the neutrality point, there is a strong even/odd oscillation, and it is fourfold for long clean tubes. Far from the neutrality point, the regular oscillation tends to vanish. (3) We investigate the effect of both native defects and disturbance by an electrostatic potential. Defects destroy the fourfold oscillation, reducing it to twofold, while the effect of a potential disturbance is only minor. The overall even/odd behavior around the neutrality point is surprisingly robust.

All our findings can be explained by the electronic structure symmetry and its robustness: By causing degenerate levels, the underlying symmetry provides the necessary condition for an oscillation in AE. Whether this symmetry is observed depends on its robustness, both upon addition of electrons and upon other pertubations such as native defects. In this way we show that symmetry provides a reasonable explanation of the various experimental results.

Our calculations are carried out using the SIESTA package, a first-principles code of full DFT with a flexible and finite-range numerical LCAO basis set siesta . In our calculation, the PBE version of the generalized gradient approximation pbe  is adopted for the electron exchange and correlation, and optimized Troullier-Martins pseudopotentials tmpp  are used for the atomic cores.

Two main technical difficulties have to be overcome. First, the self-consistency convergence is difficult because of the degenerate or nearly degenerate levels (even when using advanced charge mixing pulay ). We overcome this by introducing an electronic temperature: the result of an initial calculation at high temperature is used as input to a lower temperature calculation (and the process may be repeated)add . In this way self-consistency can be achieved on the one hand, and the results are kept reliable on the other. Second, for an AE calculation using periodic boundary conditions, we have to treat the added charge properly. A uniform charge background is introduced to compensate the net charge, a Madelung correction term is added to the total energy, and a simple cubic supercell is adopted so that the quadrupole contribution vanishes by symmetry. This treatment turns out to be successful for AE calculations dmol . In our calculation different ground-state spin configurations are fully considered for each charge state.

An important parameter for interpreting the AE spectra is the ratio between the exchange shift and mean level spacing, $`J/\mathrm{\Delta }`$. There is a recent model calculation of this ratio for SWCNTs ratio , but first-principles results are not, to our knowledge, available. Here we propose a method to calculate this parameter motivated by a simplified two-level system:

Consider a closed-shell (charged) system and add to it an electron. Because of the exchange interaction, the top spin-degenerate level ($`ϵ_0`$) splits into two nondegenerate levels ($`ϵ_1`$ and $`ϵ_2`$). The splitting is determined by the exchange interaction ($`J`$) and Coulomb interaction ($`C`$) between electrons 1 or 2 and 3: $`ϵ_1=ϵ_0+C_{1,3}`$, $`ϵ_2=ϵ_0+C_{2,3}J_{2,3}`$. Because the Coulomb energies $`C_{1,3}`$ and $`C_{2,3}`$ are approximately equal, the splitting is approximately the exchange shift $`J`$. The mean level spacing $`\mathrm{\Delta }`$ is determined by averaging the level spacings within the energy range of interest. Obviously, when $`J/\mathrm{\Delta }`$ is larger than $``$ 0.5, the ordering of the spin shells will be destroyed by the exchange interaction.

Fullerenes – The balls we have calculated include C60, C76, C240, and C540; the results are summarized in Fig. 1. Because of similar spatial symmetry ($`I_h`$), the level structures of C60, C240, and C540 near the neutrality point are similar: 5-fold degeneracy for the highest occupied molecular orbital and 3-fold for the lowest unoccupied molecular orbital (Fig. 1 inset). As a result, the AE spectra of these three balls is similar. Hund’s rule is fully obeyed as electrons are added or removed: high spin configurations (up to $`S=5/2`$) are always preferred because of the large level degeneracy in each shell (up to 10). There is a weak peak (thin arrow in Fig. 1) at the middle of each shell where electrons with opposite spin begin to fill – a result of the slightly larger on-site Coulomb energy – and a strong peak (solid arrow in Fig. 1) between two adjacent shells because of the large inter-shell level spacing. Consequently, there is no regular even/odd oscillation in the AE spectra.

Among the five fullerene balls, C76 has a lower spatial symmetry ($`D_2`$), leading to a more distributed level structure (see inset to Fig. 1). However, because of the clustering of many nearly degenerate levels (around $`7.8`$ eV, for instance), there is no regular even/odd oscillation. This clustering leads to even higher spin configurations (up to $`S=7/2`$) and a very large value of $`J/\mathrm{\Delta }`$ ($``$1.2). Under these conditions, an unusual “anti-even/odd” oscillation in the AE spectra – peaks for odd numbers of electrons and valleys for even – sometimes occurs, for instance around electron number $`12`$.

We have carefully studied how the results in Fig. 1 are influenced by three computational factors: (1) electronic temperature, (2) size and type of basis set, and (3) charge-induced structure change. We find that the effects of these factors are small add .

Experimentally, it is now possible to measure tunneling transport through a single fullerene molecule: recently Coulomb blockade effects were observed in a single C60 “molecular transistor” c60\_trans . Although no experimental AE spectra of fullerenes are available to date, our theoretical results shed light on possible future experiments.

Perfect carbon nanotubes – We have calculated AE spectra for the following closed SWCNTs: the (5,5) tubes C250, C510, and C1010 (capped by C60); the (9,0) tube C294 (capped by C78); and the (10,10) tube C640 (capped by C240). Fig. 2 shows the main features: (1) near the neutrality point there are strong even/odd oscillations, (2) for short tubes (C250 and C294) the oscillation is twofold while for longer tubes (C510 and C1010) it is fourfold, and (3) far from the neutrality point the even/odd oscillation tends to vanish.

Further analysis reveals that the strong even/odd oscillation near the neutrality point is due to the large mean level spacing $`\mathrm{\Delta }`$ – much larger than the exchange-induced level shift $`J`$ (see Fig. 2 for values of $`J/\mathrm{\Delta }`$). This large $`\mathrm{\Delta }`$ originates from the low density of states in infinitely-long metallic nanotubes (see Fig. 3). For very long tubes, the $`K`$ and $`K^{}`$ valleys are degenerate – a result of the equivalence of the two atoms in the primitive cell of graphene – so each level should be fourfold degenerate (including spin). For the short tubes (C250 and C294) this fourfold degeneracy is destroyed by the symmetry breaking caused by the caps \[Fig. 2 (a)\]. As the tube gets longer (from C250 to C510 and finally to C1010), the effect of the caps becomes weaker. Consequently, we see nearly fourfold oscillations in Fig. 2 (b) for C510 and C1010.

Our finding is consistent with a recent experiment showing four-electron periodicity in the conductance as a function of gate voltage fourfold1 . However, the nanotube in that experiment was an “open” device in that the contacts were transparent. For closed nanotube dots, only twofold spin-shell filling has been found twofold , which has not been understood so far. We show below that the effect of native defects can explain this observation.

Even the longest tube considered here (C1010, 12.4 nm long) is still much shorter than those in experiments (tens to hundreds of nanometers) fourfold1 ; fourfold2 ; twofold . As the tube becomes longer, $`\mathrm{\Delta }`$ becomes smaller, and one should question whether the strong even/odd oscillation near the neutrality energy survives. Because the real tubes are impossible to handle computationally, we calculate $`J/\mathrm{\Delta }`$ near the neutrality energy for the C250, C510, and C1010 tubes, and extrapolate the trend. The result is $`J/\mathrm{\Delta }=`$ 0.09, 0.10, and 0.10, respectively. Because the ratio does not vary with length, a strong even/odd effect near the neutrality energy should still be present in the very long tubes in real experiments.

Far from the neutrality energy, Fig. 3 shows that the density of states increases rapidly, causing a rapid increase in $`J/\mathrm{\Delta }`$ to $`0.5`$ (see Fig. 2). Consequently, the regular even/odd behavior tends to vanish, similar to the case of the fullerenes. Of course, for the nanotubes in current experiments this regime corresponds to adding a very large amount of charge.

We have carefully checked the above results for the influence of computational factors, as for the fullerenes; for details see Ref. add, .

Imperfect carbon nanotubes – Up to now, we have discussed ideal closed tubes. In real experiments, however, nanotubes always have some defects. In addition, in most transport experiments a nanotube QD is in an environment of external charges (trapped in the insulating substrate, for instance); therefore, there may be effects due to an external electrostatic potential point\_charge .

To investigate the defect effect, we consider the native (5-7-7-5) defect 5775\_1 ; 5775\_2  which is formed under tension by rotating one C-C bond by 90. Experimentally, the concentration of this (5-7-7-5) defect varies depending on the preparation process; as a rough estimate, 1/(hundreds of atoms) seems reasonable liu . We introduced three (5-7-7-5) defects into the C510 tube at widely separated locations and with random orientations. All the structures were relaxed to equilibrium.

Four calculated AE spectra are shown in Fig. 4. Different defect configurations have, of course, different effects, resulting in wide distributions of both the baseline energy (charging energy) and the amplitude of even/odd oscillation. Two interesting facts are (1) the even/odd oscillation is quite robust – it survives for most defect configurations – and (2) the defects destroy the fourfold shell filling in the longer tubes and reduces it to twofold. The second result explains why only twofold shell filling was observed in the tunneling transport experiment twofold .

To see the influence of an external electrostatic potential, we attached 9 Na atoms randomly onto the surface of one side of the C510 tube. Because of the large difference in electron affinity between C and Na (the $`2p`$ electrons are included as valence electrons), almost one full ($`3s`$) electron is transferred from each Na atom to the tube. The Na atoms, then, will act as point charges near the tube. In this way, we created an electrostatic potential disturbance for the tube. The calculated AE spectra are shown in Fig. 2 (b) (dashed line). As can be seen, the effect is almost negligible. Because the concentration of external charges is experimentally unknown, this small effect only shows that it is much weaker than the defect effect for comparable concentrations.

This work was supported in part by the NSF (DMR-0103003).


text:
# Gamma-Ray Burst Luminosity Functions Based on Luminosity Criteria

## 1. Introduction

Since there are no large systematically selected samples of gamma-ray bursts (GRB) with redshifts available yet, the derivation of their luminosity function requires a luminosity criterion to estimate the redshifts. In this paper, we use the results of five recent studies using one or more luminosity criteria to compare the resulting luminosity functions and to derive from each the expected source counts and the Euclidean value of $`<V/V_{\mathrm{max}}>`$.

These studies are presented in detail in Fenimore and Ramirez-Ruiz (2000) (FR), Schmidt (2001) (S), Schaefer, Deng and Band (2001) (SDB), LLoyd-Ronning, Fryer, and Ramirez-Ruiz (2002) (LFR), and Norris (2002) (N). The luminosity criteria used in these studies are variability (FR, SDB, LFR), spectral lag (SDB, N) and spectral hardness (S). References to original work on these luminosity criteria are given in the individual papers.

Our use of the spectral hardness was based on its correlation with $`<V/V_{\mathrm{max}}>`$ (Schmidt 2001), which we interpreted in terms of a correlation between the peak luminosity of GRBs and the observed photon spectral index $`\alpha _{23}`$ (based on BATSE channels 2 and 3). This appears to be supported by the correlation of the isotropic-equivalent energy $`E_{\mathrm{rad}}`$ and $`\alpha _{23}`$ shown in Figure 1. The data used are based on BeppoSAX observations of 12 GRBs with redshifts (Amati et al. 2002). We derived the values of $`\alpha _{23}`$ from those given for the Band $`\alpha `$ and $`\beta `$ parameters and the redshift. It is curious, however, that no correlation is seen between $`E_{\mathrm{rad}}`$ and either the Band $`\alpha `$ or $`\beta `$ parameter.

## 2. Luminosity Functions

Generally, the authors used one or two luminosity criteria to assign peak luminosities to each GRB in a sample complete above a stated flux limit. The luminosity function $`\mathrm{\Phi }(L,z)`$ was then derived, see the references. Since ’LFR’ and ’N’ gave only the luminosity distribution of their samples, we derived the luminosity function using the spectral properties and cosmological parameters adopted by the authors.

The redshift dependence or cosmological evolution of $`\mathrm{\Phi }(L,z)`$ derived or adopted in four of the studies was a density evolution $`(1+z)^3`$ up to redshifts $`z=210`$. ’LFR’ concluded that in addition there was luminosity evolution $`(1+z)^3`$. ’N’ did not consider any evolution. Details about the application of the luminosity criteria, and the evolution of the luminosity function can be found in the individual papers. Finally, since not all luminosity functions were given in terms of numbers per unit volume per unit time, we applied a normalization factor such that, following the procedure discussed in the next section, each produces a rate of 53 GRBs per year above a photon flux of 5 ph cm-2 s-1.

Figure 2 shows the luminosity functions $`\mathrm{\Phi }(L,z)`$ at $`z=0`$, where $`L`$ refers to the peak luminosity $`L_{peak}`$ at a time resolution of 1024 ms. The cosmological parameters used are $`\mathrm{\Omega }_M=0.3`$, $`\mathrm{\Omega }_\mathrm{\Lambda }=0.7`$, and $`H_0=65`$ km s-1 Mpc-1. The ’N’ luminosity function extends to $`\mathrm{log}L_{\mathrm{peak}}46`$ where its ordinate is $`+2.3`$. The five luminosity functions show considerable divergence, partly caused by differences in the cosmological evolution.

## 3. Source Counts and $`<V/V_{\mathrm{max}}>`$

For a given luminosity function $`\mathrm{\Phi }(L,z)`$, the source counts $`N(>P)`$ as a function of photon flux $`P`$ can be derived (see Schmidt 2001). We show in Figure 3 the resulting expected source counts for the five luminosity functions. Also shown are the observed counts based on the BD2 sample of GRBs described in Schmidt (1999). Even though we had normalized the five luminosity functions (see section 2), the expected source counts show considerable divergence. The counts for ’N’ are very flat, probably a consequence of not including any cosmological evolution. At low values of $`P`$ the other four predicted counts are high, only partially caused by the incompleteness of the counts setting in for $`P<0.5`$ ph cm-2 s-1. Obviously, most of the curves have no predictive value in estimating the number of GRBs that may be detected by future deep missions.

The Euclidean value of $`<V/V_{\mathrm{max}}>`$, which to first order characterizes the steepness of the source counts $`N(>P)`$, has the advantage that it accounts for the variation of sensitivity over a survey. We have derived $`<V/V_{\mathrm{max}}>`$ for each of the luminosity functions, where for the individual sources $`V/V_{\mathrm{max}}=(P/P_{lim})^{3/2}`$. We use for the limiting photon flux $`P_{lim}=0.25`$ ph cm-2 s-1, which characterizes both the BD2 sample and the BATSE catalog. The results are given in Figure 3. Conservatively assuming that the observed value $`<V/V_{\mathrm{max}}>=0.34`$ has an r.m.s. error of $`\pm 0.01`$ (Schmidt 2001), we see that four of the predicted values deviate by $`624`$ sigmas. The agreement for ’S’ reflects the fact that $`<V/V_{\mathrm{max}}>`$ for each spectral class was used directly to set its contribution to the luminosity function.

## 4. Discussion

The key to understanding the systematics of Figure 3 is twofold. First, the Euclidean value of $`<V/V_{\mathrm{max}}>`$ is a distance indicator for uniformly distributed cosmological objects (Schmidt 2001). Second, $`<V/V_{\mathrm{max}}>`$ is larger for objects with stronger positive cosmological evolution. Hence, if the expected value of $`<V/V_{\mathrm{max}}>`$ is larger than the observed one, the model luminosities $`L`$ are too low and/or the cosmological evolution is too strong (see Schmidt 1999, Table 1). Since the observed value of $`<V/V_{\mathrm{max}}>`$ is known quite accurately, important information about $`\mathrm{\Phi }(L,z)`$ is missed if it is not used. We recommend that any study of $`\mathrm{\Phi }(L,z)`$ take into account the Euclidean value of $`<V/V_{\mathrm{max}}>`$.

I thank N. Lloyd-Ronning, J. Norris, and B. Schaefer for useful information and discussions.

## References

Amati, L. et al. 2002, A&A, 390, 81

Fenimore, E. E., and Ramirez-Ruiz, E. 2000, astro-ph/0004176

LLoyd-Ronnig, N. M., Fryer, C. L., and Ramirez-Ruiz, E. 2002, ApJ, 574, 554

Norris, J. P. 2002, astro-ph/0201503

Schaefer, B. E., Deng, M., and Band, D. L. 2001, ApJ, 563, L123

Schmidt, M. 1999, ApJ, 523, L117

Schmidt, M. 2001, ApJ, 552, 36


text:
# JAMMING DURING THE DISCHARGE OF GRAINS FROM A SILO DESCRIBED AS A PERCOLATING TRANSITION

## Abstract

We have looked into an experiment that has been termed the “canonical example” of jamming: granular material, clogging the outlet of a container as it is discharged by gravity. We present quantitative data of such an experiment. The experimental control parameter is the ratio between the radius of the orifice and the radius of the beads. As this parameter is increased, the jamming probability decreases. However, in the range of parameters explored, no evidence of criticality —in the sense of a jamming probability that becomes infinitely small for a finite radius— has been found. We draw instead a comparison with a simple model that captures the main features of the phenomenon, namely, percolation in one dimension. The model gives indeed a phase transition, albeit a special one.

The suggestive idea that jamming is at the origin of a new state of matter, amenable to be described in a thermodynamic formalism, has been recently proposed Liu . Our experiment is akin to the familiar experience of shaking a saltcellar; salt grains plug the outlet of the container due to the formation of arches. Shaking or tapping is needed to break up the arch and restore the flow after each jam. A similar situation is found in many industrial applications, such as dosage hoppers, and in various transport phenomena. Ad hoc laws have been put forward based on experience and observation drescher , but the physics of arching is still poorly understood. A new vision of jamming has recently been put forward, relying on the concept of fragile matter, which encompasses not only granular materials but foams, unstructured glasses and other systems cates . The common feature they share is that they support certain stresses, called compatible, developed as a response to the external forces, but are unstable against incompatible stresses.

We have devised a simple arrangement to conduct a quantitative study of the jamming that halts a granular flow. Our assembly consists of a scaled cylindrical silo with a circular opening at the base. The bin is filled with monodisperse glass spheres (radius standard deviation is about 1%). Beads of different sizes were used in separate trials, but always with a diameter larger than 1 mm in order to reduce the relative importance of disturbances – such as humidity or electrostatic interactions – against gravity. The diameter of the bin is larger than 30 bead diameters; in this way, the finite size of the system can be neglected, as reported in the literature hirshfeld  and checked specifically for our set-up size . The silo is always filled with the same procedure (a distributed filling zhong , pouring the grains rapidly in the silo) in order to obtain a repeatable compaction of the material (a volume fraction of about 0.59) from run to run. Besides, the pressure at the base of a silo is known to be almost constant as long as the height of the material above it exceeds a certain level duran . Indeed, the results of our experiment are repeatable –irrespective of the amount of material in the silo– provided that the height reached by the beads is larger than twice the diameter of the silo. We refill the silo from time to time so that this condition is met. We have used a transparent glass silo in order to check that a mass flow develops inside it zhong ; a funnel was therefore not formed during the experiments.

When the experiment begins, beads pour freely from the outlet due to gravity. Soon thereafter, however, if the diameter of the orifice does not exceed a few bead diameters, an arch is formed arresting the flow. An electronic balance beneath the silo measures the number of grains $`s`$ which fall between two successive jams. The size of the avalanche is stored in a computer and then the arch at the outlet is destroyed so as to trigger another avalanche. This is accomplished by means of a jet of compressed air aimed at the orifice from beneath the silo. In this way, the compaction of the granular material remains approximately constant during an experimental run – shaking would instead pack the grains together more densely nowak . Further information on the set-up will be provided elsewhere. We made sure that variables such as the pressure of compressed air or the material from which the bin is made have a negligible effect in the data that we are presenting pres . The parameter that we control is the ratio between the diameter of the outlet orifice and the diameter of the beads, called $`R`$ in the following. Both the size of the orifice and the size of the beads may be changed; only the ratio $`R`$ is relevant.

For a fixed value of $`R`$, the data collected after a large number of avalanches – several thousands typically – are best viewed in the form of a histogram. In Fig. 1, $`n_R(s)`$, which is the number of avalanches consisting of $`s`$ grains for a given $`R`$, is presented for $`R=3`$ in a semi-logarithmic plot. From the histograms of all the orifice sizes studied ($`1<R<4.5`$) it is possible to define the jamming probability $`J(R,N)`$ as the probability of finding an avalanche of size less than or equal to $`N`$ grains for a given $`R`$. That is to say, $`J(R,N)`$ is the probability that an orifice of relative size $`R`$ gets obstructed at least once before more than $`N`$ grains fall through it. Then $`J`$ can be evaluated as

$$J(R,N)=\frac{\underset{s=0}{\overset{N}{}}n_R(s)}{\underset{s=0}{\overset{\mathrm{}}{}}n_R(s)}$$
(1)
We have obtained $`J`$ for different values of $`R`$ from the experiment; the results are shown in Fig. 2. The curves in the graph show that the bigger the size of the orifice, the smaller the probability that it gets blocked before an avalanche larger than $`N`$ grains falls. Also, $`J`$ grows with $`N`$ for fixed $`R`$. These data are consistent with those found in a two dimensional hopper to , obtained with a fixed number of grains, much smaller than in our experiment.

One could conceivably speculate from Fig. 2 that $`J`$ would perhaps tend to a step function as $`N\mathrm{}`$. The question is whether for that limit the jamming probability is one below a certain size $`R_c`$, while it is zero above $`R_c`$. In other words, whether there is a finite value of $`R`$ beyond which the orifice would not jam at all for an infinitely large silo. We can assess this by evaluating the size of the orifice for which the jamming probability is one half –let us call it $`R_0(N)`$. This can be easily obtained from the fit of $`J(R,N)`$ (see Fig. 2). The particular fitting function for $`J`$ chosen to obtain $`R_0(N)`$ is almost irrelevant because the slope of $`J`$ is quite large at $`R=R_0`$. In Fig. 3a we plot $`R_0`$ versus $`N`$ in semi-logarithmic scale. It is unclear whether $`R_0`$ saturates. Several functions can be fit reasonably well to $`R_0(N)`$ (see Fig. 3a), some of which saturate for $`N\mathrm{}`$, while others do not. Values of $`N`$ much bigger than $`10^5`$ are experimentally inaccessible in our laboratory. Therefore we cannot conclude whether there is or not a critical value for $`R_0`$. The family of curves used to fit $`J`$ also depends on $`\alpha `$, which is related to the slope of $`J`$ at $`R_0`$. The inverse of $`\alpha `$ is the width of the transition region from $`J=1`$ to $`J=0`$. The values for $`1/\alpha `$ are plotted in Fig. 3b. It decreases with $`N`$ but it is not possible to ascertain if it cancels out for a finite value of $`N`$, as would be the case for a step function. Both parameters, $`R_0`$ and $`\alpha `$, are not related in a simple way.

These results can be understood in the framework of a one-dimensional percolation model. Let us call $`p_R`$ the probability that one grain gets past the outlet of size $`R`$ without blocking it. Assuming that these events are independent, an avalanche of size $`s`$ would consist of one jamming event, $`s`$ non-jamming events and another jamming event. The probability of this sequence is

$$n_R(s)=(1p_R)^2p_R^s$$
(2)
This also holds if one considers the grains falling in clusters, or groups, rather than one at a time. In this case, $`p_R`$ is the probability that a group of grains passes the outlet without jamming, *i.e.* without forming an arch. If outgoing groups have $`k`$ grains in average, the probability of finding an avalanche of $`s`$ grains would be $`n_R(s)=(1p_R)^2p_R^{s/k}`$. From Eq. 2 one obtains $`log(n_R)=2log(1p_R)+slog(p_R)`$, so $`log(n_R)`$ has a linear dependence on $`s`$, exactly as observed experimentally. The value of $`p_R`$ can be determined from the histogram. The exponential dependence of $`n_R(s)`$ on $`s`$ precludes the interpretation of these data in the framework of self-organized criticality (SOC) bak , because there exists a characteristic avalanche size manifested in the exponential distribution of events. Conversely, experiments with rough grains in different experimental conditions frette  and numerical simulations in a two dimensional silo manna  yield a power law distribution – a signature of SOC.

Incidentally, the exponential distribution is a compelling evidence that arch formation is an uncorrelated process. From the temporal point of view, this is also revealed by the autocorrelation function of the series of avalanches and by the first return map (see Fig. 1, inset), which show no sign of memory between consecutive avalanches.

From the avalanche size distribution given by Eq. 2, the mean size avalanche $`S`$ can be explicitly calculated, yielding:

$$S=\frac{\underset{s=0}{\overset{\mathrm{}}{}}s^2n_R(s)}{\underset{s=0}{\overset{\mathrm{}}{}}sn_R(s)}=\frac{1+p_R}{1p_R}$$
(3)
The mean avalanche sizes obtained from our data are shown along with the above expression in Fig. 4. Indeed the histogram given by Eq. (2) and the mean avalanche size (3) are those of a one-dimensional percolation model stauffer , which leads to a second order phase transition, but only at $`p_R=1`$. This is marked by a divergence to infinity in the mean avalanche size $`S`$, which is a measure of the susceptibility of the system. Let us remark that the limit $`p_R=1`$ is unattainable, so such a phase transition would never be observed. In practice, however, $`p_R`$ could be made high enough (if the radius of the outlet orifice is big enough), so that jamming would seldom be observed.

We can put forward the idea that the jamming transition bears an analogy with the glass transition. By increasing $`R`$ one selects larger bridges only, so $`1/R`$ could be thought of as the “temperature”. In the glass transition, the characteristic viscous time is certainly infinite for zero temperature; for a finite temperature, it can be extremely large but a power law divergence is not found mezard . In the same sense, the mean avalanche size (or the susceptibility, for that matter) is infinite for $`1/R0`$, and could be very large for finite values, but there would not exist a critical exponent for $`S`$.

In this paper, we have shown that jamming events during the discharge of a silo of glass beads are uncorrelated and show no evidence of self-organized criticality, in contrast with other avalanche studies frette ; manna  which were performed in different geometries. Moreover, we showed evidence that suggest that the classical claim of the existence of a critical outlet size beyond which no jamming occurs –*i.e.* $`J`$ becomes a step function– could be invalid in a thermodynamic sense. Comparison between experiment and recent numerical simulations pugnaloni  could help to gather more understanding. Finally, other interesting aspects that have not been considered, such as the influence of the roughness of the beads and their packing fraction, also merit further investigation.

The Spanish Ministry of Science and Technology (Project BFM2002-00414), the Government of Navarre and the University of Navarre have supported this work. L. A. P. acknowledges a fellowship from Fundación Antorchas (Argentina) and the British Council. We thank Dr. G. C. Barker for his helpful comments, and Dr. O. Dauchot for discussing his ideas with us.