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# Theoretical description of phase coexistence in model C60

## I Introduction

A current model for C60 is based on a “smeared out” spherical representation of the fullerene molecules, early proposed by Girifalco Girifalco , where the carbon atoms give rise to a uniform interaction distributed over the molecular cage surface. A straightforward integration leads to an analytical central pair potential, characterized by a harsh repulsive core followed by a deep attractive well, which rapidly decays with the interparticle distance.

A detailed characterization of the thermodynamic properties of the Girifalco model is of relevant interest in several respects: for instance, first-principle studies of the C60 interaction give results very similar to those predicted through the Girifalco model Pacheco ; Silva1 ; the latter has been widely used to model Cn\>60 fullerenes with $`n=70`$, 76, and 84 (see Abramo ; Micali ; Silva ; Kahl  and references cited therein), as well as other hollow nanoparticles like carbon onions and metal dichalcogenides like GaAs and CdSe (also termed inorganic fullerenes) Safran . Umiguchi and coworkers Hasegawa0  proposed a semiempirical modification of the Girifalco interaction to account for the behavior of solid C60 at low temperature; such a generalization might prove useful for the analysis of the lattice properties under impurity doping.

As far as a more speculative analysis of the Girifalco model is concerned, several intriguing aspects are related to the overall appearance of its phase portrait, characterized by a narrow liquid pocket that extends only a few tens degrees over the triple point temperature Hasegawa ; noi . This borderline behavior, as for the existence of a stable liquid phase, basically depends on the interplay between entropic demands, imposed by excluded-volume effects at short distance, and energetic contributions, due to the attractive part of the interaction potential. We may recall, as an indication of the implied subtleties, the early controversy on the location of the liquid-vapor critical point Mooij ; Cheng , clarified in successive studies Hasegawa2 ; Fucile , and the discrepancies on the position of the freezing line and of the triple point, related to the procedure adopted for the calculation of the liquid-solid equilibrium Hasegawa ; Cheng ; CMHNC . Recently (and unexpectedly, on the basis of a previous study on the Lennard-Jones fluid Silva2 ), Fartaria and coworkers Silva1  have found that even the same simulation approach leads to distinct predictions on the freezing line of the Girifalco model, provided that different starting thermodynamic conditions are employed.

We have recently reconciled such disparate results in the context of extensive Monte Carlo calculations of the free energies of both the fluid and the solid phases of the model noi ; noi1 . We have concluded that the solid-fluid equilibrium is strongly affected by the deep, short-range attractive well in the interaction potential, at variance with systems whose freezing behavior is essentially dominated by steric effects. As a consequence, the freezing transition of the fluid is driven to lower densities (and the liquid pocket is reduced accordingly), mainly by energetic effects, in agreement with a common scenario recently proposed for fluids interacting through short-range forces Louis .

The unusual aspects of the phase behavior have occasioned several studies on the C60 model by means of refined theoretical tools, like for instance integral equation theories for the fluid phase Cheng ; CMHNC , various density functional approximations Hasegawa2 ; Mederos ; Hasegawa3 , and the hierarchical reference theory HRT . Preliminary studies have been recently carried out, based on the Modified Hypernetted Chain approach (MHNC, MHNC ), solved under a global thermodynamic consistency constraint Peppe , and on the Self-Consistent Ornstein-Zernike Approximation (SCOZA SCOZA ; Pin98 ; Sch02 Kahl1 . However, such investigations were often compared to simulation results later revised; for example, several authors Cheng ; CMHNC ; Kahl1  have estimated the freezing conditions on the basis of some well-known one-phase structural indicators, as the Hansen-Verlet Verlet , or the Giaquinta and Giunta pvg  criteria, whose limited applicability in the context of “energetic” fluids has been discussed in noi .

Hinging on the simulation study of Ref. noi , it is now worth reconsidering a detailed analysis of theoretical predictions for the phase diagram of the envisaged model. Following our preliminary investigations Peppe ; Kahl1  we shall adopt the MHNC and SCOZA theories to characterize the thermodynamic properties of the fluid phase. As far as the free energy of the solid phase is concerned, we use a Perturbation Theory (PT), discussing several degrees of refinement, as fully described in the text. Recent studies (see Amokrane ; Nava  and references) have demonstrated that the PT accurately describes the solid phase and the solid-fluid transition of models characterized by short-range interactions, as the depletion potentials resulting from the effective one-component representation of hard-sphere mixtures. A second-order expansion for the PT, also analyzed in this work, has been used in Ref. Foffi  to investigate the phase behavior of several simple models for globular protein solutions.

This paper is organized as follows: the theoretical approaches are described in section II. Results are reported and discussed in Section III. A short overview of our results and the conclusions are drawn in Section IV.

## II Model and theoretical approaches

### II.1 The Girifalco model potential

The Girifalco potential is well known in the fullerene literature, so we recall only its analytical expression Girifalco ,

$`v(r)`$ $`=`$ $`\alpha _1\left[{\displaystyle \frac{1}{s(s1)^3}}+{\displaystyle \frac{1}{s(s+1)^3}}{\displaystyle \frac{2}{s^4}}\right]`$ (1)
$`+\alpha _2\left[{\displaystyle \frac{1}{s(s1)^9}}+{\displaystyle \frac{1}{s(s+1)^9}}{\displaystyle \frac{2}{s^{10}}}\right],`$
where $`s=r/d`$, $`\alpha _1=N^2A/12d^6`$, and $`\alpha _2=N^2B/90d^{12}`$; $`N`$ and $`d`$ are the number of carbon atoms and the diameter, respectively, of the fullerene particles, $`A=32\times 10^{60}`$ erg cm6 and $`B=55.77\times 10^{105}`$ erg cm12 are constants entering the Lennard-Jones 12-6 potential through which two carbon sites on different spherical molecules are assumed to interact Girifalco . For C60, $`d=0.71`$ nm while the node of the potential (1), the minimum, and its position, are $`r_00.959`$ nm, $`\epsilon 0.444\times 10^{12}`$ erg and $`r_{\mathrm{min}}=1.005`$ nm, respectively.

### II.2 Perturbation theory of the solid phase

The perturbation approach is based on a separation of the potential (1) into a reference (purely repulsive) part, $`v_{\mathrm{ref}}(r)`$, and a residual, attractive part, $`v_{\mathrm{pert}}(r)`$. The reference system is then approximated by a solid of hard spheres with the same crystallographic structure, by means of a suitable definition of the hard-core diameter. Given these positions, the free energy of the system can be expanded around the free energy of the hard-sphere crystal, $`F_{\mathrm{hs}}`$, to obtain at first order HM :

$$\frac{\beta F}{N}=\frac{\beta F_{\mathrm{hs}}}{N}+\frac{\beta \rho }{2}v_{\mathrm{pert}}(r)\overline{g}_{\mathrm{hs}}(r)d𝐫,$$
(2)
where $`N`$ is the number of particles, $`\beta `$ the inverse of the temperature $`T`$ in units of the Boltzmann constant, and $`\rho `$ the number density; the second term is the thermal average of the perturbation energy over the reference system, where $`\overline{g}_{\mathrm{hs}}(r)`$ is the angular average of the pair distribution function of the hard-sphere solid, $`\rho ^{(2)}(𝐫_1,𝐫_2)`$ Weis ; Rascon .

We have followed the WCA prescription (after Weeks, Chandler, and Andersen WCA ) to split the potential (1), namely:

$`\begin{array}{cc}v_{\mathrm{ref}}(r)=& \{\begin{array}{cc}v(r)+\epsilon & \mathrm{if}rr_{\mathrm{min}}\\ 0& \mathrm{if}r>r_{\mathrm{min}}\end{array}\\ & \\ v_{\mathrm{pert}}(r)=& \{\begin{array}{cc}\epsilon & \mathrm{if}rr_{\mathrm{min}}\\ v(r)& \mathrm{if}r>r_{\mathrm{min}}\end{array}.\end{array}`$ (10)
The properties of the reference system have been connected to those of the hard-sphere solid through the “blip function” formalism WCA2 , i.e. the effective hard-sphere diameter $`\sigma _{\mathrm{𝚆𝙲𝙰}}`$ is determined by the implicit relation:

$$y_{\mathrm{hs}}(r)\{\mathrm{exp}[\beta v_{\mathrm{pert}}(r)]\mathrm{exp}[\beta v_{\mathrm{hs}}(r)]\}d𝐫=0,$$
(11)
where $`v_{\mathrm{hs}}(r)`$ is the hard-sphere potential (which depends on $`\sigma _{\mathrm{𝚆𝙲𝙰}}`$) and $`y_{\mathrm{hs}}(r)=g_{\mathrm{hs}}(r)\mathrm{exp}[\beta v_{\mathrm{hs}}(r)]`$ is the corresponding cavity function. Another definition of the hard-core diameter (BH, BH ), namely:

$$\sigma _{\mathrm{𝙱𝙷}}=_0^{\mathrm{}}\{1\mathrm{exp}[\beta v_{\mathrm{pert}}(r)]\}dr$$
(12)
has been tested in this work. The expression (12), which corresponds to a first-order approximation to Eq. (11HM , is appropriate to describe the rapidly rising repulsive interaction $`v_{\mathrm{pert}}(r)`$. Other prescriptions for the separation of the potential (1) (see Refs. BH  and Choi ) have been analyzed in this study; their predictions for the thermodynamic properties of the model at issue are, however, less accurate on the whole than those obtained through the WCA approach and will not be discussed further.

In the results’ section we also investigate a second-order correction to the free energy, early proposed by Barker and Henderson in Ref. BH2 , and recently applied to systems with short-range interactions by Foffi and coworkers Foffi , namely:

$`{\displaystyle \frac{\beta F}{N}}`$ $`=`$ $`{\displaystyle \frac{\beta F_{\mathrm{hs}}}{N}}+{\displaystyle \frac{\beta \rho }{2}}{\displaystyle v_{\mathrm{pert}}(r)\overline{g}_{\mathrm{hs}}(r)d𝐫}`$ (13)
$`{\displaystyle \frac{\beta \rho }{4}}\left({\displaystyle \frac{\rho }{P_{\mathrm{hs}}}}\right){\displaystyle v_{\mathrm{pert}}(r)^2\overline{g}_{\mathrm{hs}}(r)d𝐫},`$
where $`P_{\mathrm{hs}}`$ is the pressure of the solid of hard spheres. The correction in Eq. (13) was obtained by dividing the space into concentric spherical shells, and assuming that the volume of each shell has the compressibility properties of a macroscopic portion of the space (see Ref. BH2  for full details on the procedure and the approximations involved).

We have resorted to several well-established simulation results in order to obtain the properties of the hard-sphere crystal. Specifically, we have used the Hall analytical equation of state for the pressure Hall , which accurately fits the molecular dynamics data of Alder and coworkers Alder :

$$\frac{\beta P_{\mathrm{hs}}}{\rho }=\frac{3\eta }{\eta _{\mathrm{cp}}\eta }+\underset{\eta =0}{\overset{6}{}}a_n\gamma ^n$$
(14)
where $`\eta `$ is the packing fraction and $`\eta _{\mathrm{cp}}=\pi \sqrt{2}/6`$ is the close packing fraction; $`\gamma =4(1\eta /\eta _{\mathrm{cp}})`$ and $`a_0=\mathrm{2.557\hspace{0.17em}696}`$, $`a_1=\mathrm{0.125\hspace{0.17em}307\hspace{0.17em}7}`$, $`a_2=\mathrm{0.176\hspace{0.17em}239\hspace{0.17em}3}`$, $`a_3=\mathrm{1.053\hspace{0.17em}308}`$, $`a_4=\mathrm{2.818\hspace{0.17em}621}`$, $`a_5=\mathrm{2.921\hspace{0.17em}934}`$, $`a_6=\mathrm{1.118\hspace{0.17em}413}`$. The free energy is obtained by thermodynamic integration

$$\frac{\beta F_{\mathrm{hs}}(\rho )}{N}=\frac{\beta F_{\mathrm{hs}}(\overline{\rho })}{N}+_{\overline{\rho }}^\rho \frac{\beta P_{\mathrm{hs}}(\rho ^{})}{\rho ^{}}\frac{d\rho ^{}}{\rho ^{}},$$
(15)
where for the reference free energy, $`F_{\mathrm{hs}}(\overline{\rho })`$, we have used the Frenkel and Ladd Ladd  Monte Carlo result for the FCC crystal of hard spheres, namely: $`\beta F_{\mathrm{hs}}^{\mathrm{ex}}/N=\mathrm{6.537\hspace{0.17em}9}(09)`$ at $`\eta /\eta _{\mathrm{cp}}=0.7778`$ in the thermodymamic limit. Their determination followed the Einstein crystal method, based on the construction of a reversible path from the solid under consideration to an Einstein crystal with the same crystallographic structure. As for the radial distribution function, $`\overline{g}_{\mathrm{hs}}(r)`$, we have used the analytical form, proposed by Weis Weis  and Kincaid and Weis Kincaid , which expresses the distribution as a sum of gaussian peaks centered around the nearest-neighbour FCC lattice sites, with parameters calculated by Choi and coworkers Choi  to fit their simulation results. In Ref. Choi  an analytical form for the cavity function $`y_{\mathrm{hs}}(r)`$ inside the hard core entering Eq. (11) is also proposed, by directly extending to the solid the Henderson and Grundke scheme for the fluid phase HG .

### II.3 Liquid state theories

We have determined the thermodynamic and structural properties of the fluid region through the MHNC MHNC  and SCOZA SCOZA  theories. We recall that in the MHNC the Ornstein-Zernike equation,

$$h(r)=c(r)+\rho c(|𝐫𝐫^{}|)h(r^{})𝑑𝐫^{},$$
(16)
is coupled with the cluster expansion for the radial distribution function $`g(r)`$, namely:

$$g(r)=\mathrm{exp}[\beta v(r)+h(r)c(r)+B(r)],$$
(17)
where $`h(r)=[g(r)1]`$ and $`c(r)`$ are the pair and direct correlation functions respectively, and $`B(r)`$ is the bridge function HM . A closure to Eqs. (16) and (17) is obtained through the Percus-Yevick hard-sphere bridge function $`B^{\mathrm{PY}}(r,\sigma _{\mathrm{hs}}^{})`$, with the hard-core diameter $`\sigma _{\mathrm{hs}}^{}`$ fixed so to enforce the thermodynamic consistency of the theory (see e.g. report ). In particular we require the equality between the fluctuation pressure $`P_\mathrm{c}`$ and the virial pressure $`P_\mathrm{v}`$, namely,

$$P_\mathrm{c}\beta ^1_0^\rho \frac{\chi _0}{\chi _\mathrm{T}}d\rho ^{}=P_\mathrm{v}.$$
(18)
In Eq. (18) $`\chi _0`$ and $`\chi _\mathrm{T}`$ are the ideal gas and the isothermal compressibilities respectively; the latter is obtained as the $`q=0`$ limit of the Fourier transform of the direct correlation function, $`\chi _0/\chi _\mathrm{T}=[1\rho \stackrel{~}{c}(q=0)]`$, according to the fluctuation theory; the density integral is performed at a constant temperature.

The consistency between $`P_\mathrm{v}`$ and the pressure estimated via the energy route, $`P_\mathrm{e}`$, can be alternatively enforced along isochoric paths, namely:

$$P_\mathrm{e}\rho ^2\frac{F}{\rho }|_\mathrm{T}=P_\mathrm{v}.$$
(19)
In Eq. (19) the free energy is obtained by integrating the internal energy $`U`$ with respect to the (inverse) temperature at constant density, according to the relation:

$$\frac{\beta F(\rho ,T)}{N}=\frac{\beta F(\rho ,\overline{T})}{N}_{\overline{T}}^T\frac{U(T^{})}{Nk_BT^{}}\frac{dT^{}}{T^{}},$$
(20)
where $`(\rho ,\overline{T})`$ is a thermodynamic state whose absolute free energy $`\beta F(\rho ,\overline{T})/N`$ is known. In order to avoid to cross the liquid-vapor coexistence region, combinations of isothermal and isochoric paths are required to reach thermodynamic points located in the high-density, subcritical region of the phase diagram.

As shown in Ref. Peppe , the global consistency is in general more accurate than the local one; the latter procedure enforces the equality between the isothermal compressibility calculated via the fluctuation theory on the one hand, and via the virial route (i.e. by differentiating $`P_\mathrm{v}`$ with respect to the density) on the other hand. The improvement of the global over the local consistency approach becomes crucial when the range of the particle interaction is very short, and/or at high densities and low temperatures; the free energy and the chemical potential in particular turn out to be almost quantitatively predicted Peppe .

As far as the SCOZA theory is concerned, this represents an advanced liquid state theory that is based on a mean-spherical (MSA) type closure relation, replacing the prefactor $`\beta `$ in the closure for the direct correlation function by a yet undetermined, state dependent function $`K(\rho ,T)`$; this function is fixed by the consistency requirement between the energy and the compressibility route to thermodynamics Pin98 ; Sch02 . Thus for a hard-core potential of diameter $`\sigma _{\mathrm{hs}}`$ and with an attractive tail $`w(r)`$, the SCOZA closure relations to the OZ equation (16) read:

$$g(r)=0r<\sigma _{\mathrm{hs}}$$
(21)
$$c(r)=c_{\mathrm{hs}}(r)+K(\rho ,T)w(r)r\sigma _{\mathrm{hs}}.$$
(22)
In relation (22) $`c_{\mathrm{hs}}(r)`$ represents the direct correlation function for the hard-core system; we have used the Waisman parameterization Wai73 , i.e., $`c_{\mathrm{hs}}(r)=K_0/r\mathrm{exp}[z_0(r\sigma _{\mathrm{hs}})]`$ (with well-described density-dependent coefficients $`K_0`$ and $`z_0`$) which is known to give accurate results for the hard sphere system. The consistency requirement between the two thermodynamic routes mentioned above leads to the partial differential equation (PDE):

$$\frac{}{\beta }\left(\frac{1}{\chi _{\mathrm{red}}}\right)=\rho \frac{^2u}{\rho ^2},$$
(23)
where $`\chi _{\mathrm{red}}=\chi _\mathrm{T}/\chi _0`$ is the reduced (with respect to the ideal gas) dimensionless isothermal compressibility given by the compressiblity route and $`u`$ is the excess (over ideal gas) internal energy per volume provided by the energy route. Solution of the above PDE leads to $`K(\rho ,T)`$ and thus to the structure and thermodynamics of the system.

The SCOZA has proven to give reliable results for the location of the coexistence curve and stays — in contrast to most liquid state theories — reliable even in the critical region (see Sch02  for an overview). Many examples for continuum systems as well as for spin systems (in few cases including even binary mixtures Sch03 ) have demonstrated its validity. Limiting our considerations on continuum systems, the SCOZA suffers from two drawbacks (at least in its present version), despite its many merits: as the formalism of the SCOZA largely benefits from the availability of the semianalytic solution of the MSA for a hard-core Yukawa system (including an arbitrary number of Yukawa tails) Arr91 , its application is limited to systems where the attractive part of the interatomic potential, $`w(r)`$, can be approximated by a suitable number of Yukawa tails, while the repulsive core has to be replaced by a hard-core potential. In the present work this has been done at the node of the potential, $`r_0`$, as the SCOZA PDE becomes unstable for repulsive interactions. While in general the first problem does not represent a serious restriction, up to now no remedy has been found to include softness of the repulsive part of the interaction.

## III Results and discussion

In the first part of this section (Figs. 1-3) we compare the perturbation theory for the solid phase with the corresponding Monte Carlo results noi . Then, the PT free energies are combined with the simulation data for the fluid phase in order to determine the solid-fluid boundaries. In the second part (Figs. 4-6) we present a complementary approach where the MHNC and SCOZA theories are used to predict the liquid-vapor equilibrium, and — in combination with the simulation inputs for the solid phase noi  — the full phase diagram. Hinging on both comparisons, we have calculated in the last part (Fig. 7) the phase diagram on the basis of purely theoretical approaches.

As far as the PT is concerned, the expression (12) gives a hard-core equivalent diameter smoothly varying from $`\sigma _{\mathrm{𝙱𝙷}}=0.970`$ nm at $`T=2200`$ K to $`\sigma _{\mathrm{𝙱𝙷}}=0.972`$ nm at $`T=1800`$ K. Such a weak variation reflects clearly the stiff, rapidly varying nature of the repulsive part of the Girifalco potential. The more refined expression (11) for the hard-core diameter, $`\sigma _{\mathrm{𝚆𝙲𝙰}}`$, which adds a further dependence on the density, involves just a minor correction to $`\sigma _{\mathrm{𝙱𝙷}}`$ evaluated through Eq. (12).

We report in Figs. 1-2 the PT free energy, chemical potential and equation of state along several isotherms in the solid phase, as obtained by using either $`\sigma _{\mathrm{𝚆𝙲𝙰}}`$ or $`\sigma _{\mathrm{𝙱𝙷}}`$ as hard-sphere diameter, together with approximations (2) or (13) for the free energy. In the figures, the theoretical predictions are compared to the corresponding simulation results noi . As can be expected, the use of either $`\sigma _{\mathrm{𝚆𝙲𝙰}}`$ or $`\sigma _{\mathrm{𝙱𝙷}}`$ produces similar results. The PT predictions generally agree with simulation data all over the solid phase, especially in the chemical potential vs the pressure. The equation of state compares less favorably to Monte Carlo results (see Fig. 2), although wider discrepancies occur for $`\rho 1.27`$ nm-3, i.e. almost outside the coexistence region, since the melting line is located between $`\rho 1.25`$ and $`\rho 1.27`$ nm-3. Remarkably, the accuracy of the numerical estimates in the expression (2) results from the balance between two almost comparable — and relatively large with respect to their difference — contributions of opposite signs. The PT predictions slightly get worse if the second order correction to the free energy (however small, since it hardly exceeds 2% of the main contributions) is taken into account. As observed in the original paper BH , this can depend on the semimacroscopic derivation of the last term in Eq. (13), that is more appropriate for longer interaction ranges, in such a way that a reasonably large number of particles fits into the region of attractive potential. The derivative of the pressure involved in Eq. (13) can as well represent a source of numerical uncertanties.

We may anticipate that the fine reproduction of the chemical potential, as obtained through the first-order PT, eventually leads to the most accurate predictions for the phase behavior of the model. For such reason, we concentrate on the expansion (2) and show, in Fig. 3, the corresponding phase diagram; predictions corresponding both to $`\sigma _{\mathrm{𝚆𝙲𝙰}}`$ and to $`\sigma _{\mathrm{𝙱𝙷}}`$ are reported. The coexistence lines are determined by using the simulation results of Ref. noi  for the fluid phase. It appears that the PT gives accurate predictions for the coexisting temperatures and densities, with marginal effects related to distinct prescriptions for the hard-core diameter. By converse, a systematic overestimate characterizes the coexistence pressure above the triple point (see bottom panel of Fig. 3), especially if $`\sigma _{\mathrm{𝚆𝙲𝙰}}`$ is employed. We argue in this latter case that the definition of the cavity function inside the hard core Choi , directly borrowed from the theory of simple fluids HG , is to some extent unappropriate for the C60 model; moreover, numerical uncertainties can occur, due to the more cumbersome procedure needed to evaluate $`\sigma _{\mathrm{𝚆𝙲𝙰}}`$ through Eq. (11), which involves in particular the calculation of the slope of $`\overline{g}_{\mathrm{hs}}(r)`$ at close contact.

In summary, it turns out that a PT first-order expansion of the model’s free energy around a properly defined reference solid gives reliable predictions for the coexistence properties, and, more generally, for the solid phase behavior of the system at issue. This finding is noteworthy in that it implies that the hard-sphere behavior dominates, to a large extent, the structure of the solid phase; conversely, as discussed in noi , the properties of the fluid phase are markedly affected by energetic aspects related to the attractive part of the potential. Our results further support the use of the PT to characterize the solid phase of systems interacting through short-range forces, already documented in Refs. Amokrane ; Nava ; Foffi .

As far as the theoretical description of the fluid phase is concerned, we report in Fig. 4 the SCOZA and MHNC predictions for the free energy, the chemical potential, the pressure, and the internal energy, along with the corresponding Monte Carlo results of Ref. noi . It appears that the MHNC predicts to a high accuracy the chemical potential as a function of the pressure, a quantity directly related to the coexistence properties of the model. A satisfactory agreement with the simulation data also emerges for both the free and the internal energies, while a marked discrepancy affects the estimate of the pressure, especially in the high-density regime. On the other hand, as is visible in Fig. 4, the thermodynamic properties of the model are generally overestimated in the SCOZA framework.

The tendency of the MHNC to overestimate the pressure under the global consistency procedure, already observed in Ref. Peppe , appears somehow unexpected, especially considering the overall good performances of this theory. We can conjecture that it might depend on an overestimate of the effective hard-sphere diameter $`\sigma _{\mathrm{hs}}^{}`$ entering the bridge function as the adjustable parameter to enforce the thermodynamic consistency in Eq. (18) or (19). Indeed, the value of the virial pressure $`P_\mathrm{v}`$ depends on a delicate balance between contributions of opposite signs. The use of the Verlet-Weis bridge functions (which fit available simulation data), instead of the analytical Percus-Yevick ones, might as well improve the predictions for the pressure. As for the SCOZA, we argue that the discrepancies with simulation data must be related to the approximate treatment of the repulsive part of the potential. In particular, the substitution of the soft-core interaction with a purely hard-sphere potential for $`r<r_0`$ causes an enhanced repulsion (which reflects in the overestimate of the free energy and of the pressure), especially at high temperature, where shorter distances can be sampled by the system. We have indeed verified by few simulation runs along the isotherm $`T=2100`$ K (not reported here) that the agreement between SCOZA and Monte Carlo pressures considerably improves, provided that both approaches are compared on the same model, i.e. hard-spheres plus a Girifalco tail.

We report in Fig. 5 the SCOZA and MHNC predictions for the liquid-vapor coexistence properties of the model. The Gibbs Ensemble Monte Carlo (GEMC) binodal line obtained in Ref. Fucile  with a sample of 1500 particles is also shown for comparison. It comes out that both theories reproduce quite faithfully the binodal curve, especially as far as the vapor branch is concerned. The coexisting liquid densities are slightly underestimated, the SCOZA reverting this trend just below the critical point. The binodal curve obtained through the MHNC under the global consistency constraint definitely improves on the local one, as displayed in Fig. 5, thus confirming the preliminary evidence reported in Ref. Peppe . As for the SCOZA, an internal compensation between the overestimate of the chemical potential on one hand, and of the pressure on the other hand, could be at the origin of the fairly good agreement with the GEMC binodal curve.

The MHNC solution algorithm converges to a thermodynamic consistent solution up to $`T=1900`$ K (see Fig. 5). In view of early studies on HNC-type theories (see e.g. report ), the difficulties to explore the critical region may be intrinsic to such approaches, rather than an artifact of numerical procedures. Consequently, the available MHNC binodal points must be fitted to some expected behavior in order to determine the critical parameters; as a common practice, we have used the scaling law for the coexisting densities to calculate the critical temperature, $`T_{\mathrm{cr}}`$:

$$\rho _{\mathrm{liquid}}\rho _{\mathrm{vapor}}|TT_{\mathrm{cr}}|^\beta ,$$
(24)
where the exponent takes on the non-classical effective value $`\beta =0.32`$. Once the critical temperature is known, we have calculated the critical density, $`\rho _{\mathrm{cr}}`$, by fitting the MHNC binodal points with the law of rectilinear diameter: $`\rho _{\mathrm{liquid}}\rho _{\mathrm{vapor}}=\rho _{\mathrm{cr}}+A|TT_{\mathrm{cr}}|`$, with $`A`$ to be determined from the fit. At variance with the MHNC, within the SCOZA the critical region can be approached in principle with arbitrary precision and therefore neither a fitting procedure, nor a scaling behavior hypothesis must be invoked to calculate the critical point parameters. It emerges from Fig. 5 that the theoretical predictions closely bracket the GEMC critical point. The MHNC, SCOZA, and GEMC critical parameters are collected in Table 1.

In Fig. 6 we report the fluid-solid phase boundaries, as obtained by the combination of the MHNC and SCOZA predictions for the fluid phase and the simulation results of Ref. noi  for the solid phase; for a more comprehensive overview, we also show a sketch of the binodal curves just discussed, as well as the full simulated fluid-solid coexistence points. As it is apparent, the overall good quality of the MHNC thermodynamic predictions provides a faithful reproduction of the phase boundaries of the model. A small overestimate of the fluid-solid coexistence pressure only occurs above the triple point temperature. As for the SCOZA, the solid-vapor equilibrium and the melting line are satisfactorily predicted, while the observed shift of the chemical potential (see Fig. 4) gives rise to a marked discrepancy in the coexistence pressure above the triple point; on the other hand, the overestimate of the pressure of the fluid phase is reflected in the shift of the theoretical freezing line toward lower densities.

We have determined the MHNC and SCOZA triple points, also reported in Table 1, from the intersection between the corresponding binodal and freezing lines. It comes out that the MHNC predicts the existence of a stable liquid phase with a small shift of the triple and critical densities to lower values, with respect to the simulation results. The SCOZA also predicts a liquid pocket for the model, although restricted to a narrower temperature and density range.

It emerges that the MHNC theory for the fluid phase, and the first-order PT for the solid phase represent, among these envisaged here, the most accurate theoretical tools to enquire into the full phase portrait of the C60 model. The ensuing phase diagram is reported in Fig. 7. The MHNC binodal line is directly drawn from Fig. 5. As is visible, the agreement with simulation data is semiquantitative; the comparison of Figs. 36, and 7 demonstrates that the errors in the location of phase boundaries are essentially brought about by the MHNC, while the use of the PT for the solid phase does not introduce any appreciable discrepancy with simulation results. For such reason we do not expect a significant improvement of the overall appearance of the phase diagram if the SCOZA predictions for the fluid phase substitute the MHNC ones. In the bottom panel of Fig. 7, the overestimate of the fluid-solid coexistence pressure magnifies slightly the common trend already observed for the PT and MHNC approaches separately.

## IV Summary and concluding remarks

We have presented a theoretical investigation of the thermodynamic properties and the phase behavior of the Girifalco C60 model, in the framework provided by three refined theoretical tools, as the Modified Hypernetted Chain (MHNC) with a global thermodynamic consistency constraint and the Self-Consistent Ornstein-Zernike Approximation (SCOZA) for the fluid phase, and a Perturbation Theory (PT) with various degrees of refinement for the free energy of the solid phase.

The theoretical predictions are assessed against our recent simulation study noi . It turns out that the phase portrait of the model is predicted fairly well, in particular as for the solid-vapor coexistence and the melting line. By converse, the inaccuracies in the thermodynamic predictions sensitively affect the determination of the fluid-solid coexistence pressure above the triple point. The MHNC and SCOZA liquid-vapor binodals are sufficiently accurate; the critical point estimates closely bracket the Gibbs Ensemble Monte Carlo datum Fucile . In comparison with the simulation and the MHNC freezing lines (which turn to be practically superimposed), the SCOZA tends to underestimate the density of the liquid branch of the fluid-solid coexistence, with a corresponding shift of the triple point to lower densities and higher temperatures.

We have interpreted our results in view of the basic assumptions underlying each theory. It has emerged that the SCOZA mainly suffers from the substitution of the Girifalco soft-core repulsion at short distance with a purely hard-sphere interaction, which leads to a corresponding overestimate of the pressure and of the free energy in the fluid phase. We have also conjectured that the MHNC pressure might improve if the Verlet-Weis bridge functions were adopted instead of the Percus-Yevick ones, as currently adopted in this work. As for the PT, it turns out that both a second order expansion of the free energy, and a refined definition of the equivalent hard-core diameter, lead to a slight worsening of the theoretical predictions on the whole, which could be related to more cumbersome numerical procedures involved.

We have eventually succeeded in predicting to a satisfactory degree of accuracy the phase diagram of the Girifalco model, on the basis of purely theoretical approaches. We have selected for this purpose a sophisticated MHNC treatment of the fluid phase, and the first-order PT for the solid phase. We expect that our conclusions about the most suitable theoretical schemes to investigate the phase diagram of the Girifalco model, can be reasonably extended to other systems characterized by similar interparticle interaction laws. In particular, we plan to analyze the phase diagram of other higher-order Cn\>60 fullerenes, combining both simulations and theoretical schemes. We have already produced several Monte Carlo results for the Girifalco C84 fullerene, to be used for such purpose. The related calculations are currently in progress.

###### Acknowledgements.

ESP and GK acknowledge the financial support by the Österreichische Forschungsfonds (FWF) under Project Nos. P14371-TPH and P15758-TPH.


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# Thermal relaxation of field-induced irreversible ferromagnetic phase in Pr-doped manganites

## I Introduction

Over the last few years, a large amount of research has been undertaken towards understanding the physical properties of doped perovskite manganites, mainly because they exhibit a novel magneto transport property known as colossal magneto resistance (CMR). Among them, Pr-doped manganites Pr1-xAxMnO3 (A = Ca, Sr, Na) have been the subjects of several studies due to their diverse physical and structural properties with doping concentration at different temperatures. In the case of a 30% Ca doped sample, it undergoes a charge ordering (CO) transition near 220 K ($`T_{CO}`$), an AFM transition about 150 K ($`T_N`$), and a FM transition around 100 K ($`T_C`$). Below the AFM transition temperature, interestingly, application of a high magnetic field leads to the FM and metallic state. Although the nature of the induced FM and metallic phase has not been completely understood yet, it has been suggested that the induced state might be due to the development of FM clusters in the CO and AFM matrix after the application of a magnetic field. This implies that the field-induced state has its origin in a change of the electronic state of the Mn ions and is not directly related to the Pr moments. Neutron diffraction study on Pr0.7Ca0.3MnO3 by Cox et al, however, revealed the presence of ordered Pr 4f moments below 60 K. Very recently, Dho et al also reported evidence of long range ordering of the Pr spins in Pr0.8Ca0.2MnO3, implying that the field induced FM and metallic state might be associated with the development of the ordered Pr moments.

In this paper, we present various magnetization and relaxation data for two Pr-doped manganites Pr0.65Ca0.35MnO3 and Pr0.82Na0.18MnO3 with almost identical doping concentration. Our results clearly reveal that the field induced FM moment is present in both materials. Furthermore, this FM phase is remarkably sustained for 105 s even after the field is removed. It is the main purpose of this paper to show that the field induced irreversible FM state is different from the metamagnetic transition as well as the typical spontaneous FM moment. In addition, we discuss the origin of this irreversible FM state, which might be due to the ordered Pr moments that are able to control the direction of neighboring Mn spins.

## II Experimentals

Several single crystals of Pr0.65Ca0.35MnO3, corresponding to 35 % doping of holes onto the Mn sites, were grown by a floating zone method using an infrared image furnace. Many attempts to grow single crystal of Pr0.82Na0.18MnO3 with the same floating zone method were unsuccessful mainly because the sodium is rapidly evaporated upon melting. For the Na-doped compound, ploycrystalline samples synthesized by conventional solid state reaction were thus used. X-ray powder diffraction data of the crushed crystalline and polycrystalline samples at room temperature show them to be a single phase, in which both samples adopt an orthorhombic Pnma symmetry. The magnetization data were collected on a superconducting quantum interference device (SQUID) magnetometer, and the resistivity data were collected using four-point method.

## III Results

### A Irreversible field-induced phase transition in Pr0.65Ca0.35MnO3

The temperature-dependent dc magnetization and resistivity data of Pr0.65Ca0.35MnO3, taken under both zero-field-cooled (ZFC) and field-cooled (FC) conditions, are presented in Figure 1. The magnetization curves below 3 T did not reveal any discernible change indicative of a FM transition. Instead, two broad humps are seen at 160 and 230 K, which correspond to AFM and charge ordering transitions, respectively. Above 4 T, a clear field-induced transition is observed near 100 K, indicating that a metamagnetic transition from AFM to FM takes place by the application of a magnetic field. In addition, the M($`T`$) curves display a large splitting between the FC and ZFC curves below 25 K, indicating the existence of spin-glass-like state in the low temperature region. The temperature dependent resistivity data shown in the bottom panel are well correlated with the M($`T`$) curves discussed above. The resistivity curve exhibits a steep increase near $`T_{CO}`$ and an insulator-to-metal (I-M) transition occurs in the presence of a high magnetic field near the field-induced FM transition temperature. A clear splitting between the ZFC and FC resistivity data is observed below 25 K, which is consistent with the splitting in the M($`T`$) data.

To further understand the nature of the field-induced FM transition, we have explored the magnetization as a function of magnetic field at selected temperatures (Figure 2). Each panel includes an initial magnetization curve and a hysteresis loop between -5.5 T and +5.5 T. The M(H) curves measured at 50 K exhibit a distinctive metamagnetic transition from AFM to FM near 4 T. When the magnetic field is released, the field-induced FM state is returned to an initial AFM state near 2.5 T. As can be seen in the middle panel of Figure 2, however, the M(H) data at 20 K show that the initial field sweep curve yields an irreversible change. In particular, the induced FM moment partially remains even after field quenching. Furthermore, at 5 K the hysteresis loop exhibits little evidence of an AFM signature although the initial magnetization curve shows a metamagnetic transition. The hysteresis curve indicates a soft FM character without hysteretic energy loss. This FM state is thus apparent in the low temperature region, implying that the field-induced FM state becomes stable after the measurement of the initial magnetization curve. An important feature is that this irreversible field-induced phase transition is different from a reversible metamagnetic transition typically observed in the AFM material.

Figure 3 shows the resistivity curves for Pr0.65Ca0.35MnO3 as a function of magnetic field measured at 5 and 50 K. At 50 K, the resistivity suddenly drops near 4 T, indicating that the charge-ordered insulating phase is melted into the FM metallic state by the external field. Upon reducing the magnetic field, the metallic phase is gradually changed into the charge-ordered ground state. The resistivity data between -5.5 T and 5.5 T also show a hysteretic behavior as found in the magnetization data. However, the resistivity curve at 5 K shows a distinctive I-M transition about 4 T and the field-induced metallic state is sustained even after removing the magnetic field. All these transport behaviors are well consistent with the magnetization data discussed above.

The stability of the field-induced FM moments in the low temperature region was examined by measuring the long-time relaxation of the dc magnetization. The sample was cooled with a field of 5 T down to the measured temperature (5 T) and the time dependent magnetization data were then collected immediately after setting the magnetic field at 0.3 T. Figure 4 shows the M(t) curves as a function of time. An important feature is that the magnetization at 5 K was roughly constant for 105 s without any noticeable change. With increasing temperature, however, the magnetization gradually relaxes to the value of the AFM state. These results suggest that the field-induced FM moments are very stable at 5 K but are gradually destroyed at higher temperature.

The temperature dependence of the field-annealed FM moment was also investigated in order to compare with the ZFC magnetization curve shown in Figure 1. The sample was cooled down to 5 K in 5 T, followed by removing the magnetic field for 103 s. The magnetization data (filled symbol) were then collected immediately after setting a field of 0.3 T. As can be seen in the M($`T`$) curve given in Figure 5, a distinctive magnetic transition from FM to AFM is observed near 25 K. The ac susceptibility data obtained in zero field also exhibits almost identical temperature dependent behavior. On the other hand, the ZFC magnetization curve (open symbol) obtained at the same magnetic field (0.3 T) does not show any tangible FM transition over the entire temperature range. The magnetic transition from FM to AFM near 25 K is also accompanied by a metal-insulator transition. This clearly suggests that the FM transition below 25 K results from the field annealing.

### B Irreversible field-induced phase transition in Pr0.82Na0.18MnO3

In order to probe the role of the Pr concentration, we have also investigated the magnetization and transport properties of Pr0.82Na0.18MnO3. Since the Na-doped compound has almost the same doping level as well as the same average A-site ionic size by comparison with those of Pr0.65Ca0.35MnO3, its charge ordering and AFM transitions occur near the temperatures observed in Pr0.65Ca0.35MnO3. An important difference, however, is that the Pr concentration is much larger in Pr0.82Na0.18MnO3 than in Pr0.65Ca0.35MnO3. This would enable to see the pronounced Pr effect in the Na-doped sample that is crucial to elucidate the origin of the irreversible field induced ferromagnetism.

Figure 6 displays the magnetization curves of Pr0.82Na0.18MnO3 as a function of magnetic field at selected temperatures. The hysteresis loops between +5.5 T and -5.5 T (filled circle) were recorded just after the initial measurement from 0 T to +5.5 T (open circle). Above 100 K, the M(H) curves exhibit a metamagnetic transition from AFM to FM with increasing the magnetic field. The critical magnetic field decreases with decreasing the temperature. In addition, the field-induced FM state is returned to an initial AFM state upon removal of the magnetic field. At 80 K, however, the M(H) data show that the initial field sweep curve yields an irreversible change similar to that of Pr0.65Ca0.35MnO3 measured at 20 K. In particular, the induced FM moment is sustained even after field quenching. When the magnetic field is swept from 0 T to -5.5 T, the M(H) curve displays both FM and AFM signatures at low and high field regions, respectively. Below 60 K, the initial magnetization curve shows a metamagnetic transition but other M(H) data clearly exhibit a typical soft FM feature. It is worthwhile to note that the field-induced FM state is found in much broader region in Pr0.82Na0.18MnO3 compared with that of Pr0.65Ca0.35MnO3, which is due to the large Pr concentration in the Na-doped compound.

The temperature dependence of the field-annealed FM moment of Pr0.82Na0.18MnO3 was also investigated, which is given in Figure 7. The sample was cooled down to 5 K in the presence of a magnetic field of 5 T, followed by quenching the field for 103 s. The temperature dependent magnetization data (filled squares) were then collected immediately after setting a field of 0.3 T. As can be seen in the M(T) curve, a distinctive FM transition is observed near 90 K. On the other hand, the magnetization data without the field annealing (open squares) show little indication of a FM transition. These magnetic data also coincide with the resistivity curves. The field-annealed sample shows a distinctive I-M transition near the FM transition temperature while the sample without the field annealing is insulating. An interesting feature to be noted is that the irreversible field-induced FM phase is also discovered in other Pr-doped manganites such as Pr0.7Ca0.3MnO3, Pr0.67Ca0.33MnO3, and Pr0.65Ca0.35MnO3. The $`T_C`$ of the field-induced FM phase monotonously decreases from 60 K to 25 K with decreasing the Pr concentration. More interestingly, no irreversible field-induced FM transition behavior is found in Pr0.6Ca0.4MnO3 with the low Pr content, clearly suggesting that the field-induced FM exchange coupling is dependent on the Pr concentration.

## IV Discussions

It is worthwhile to address that the FM moment of Pr-doped manganites, produced by field annealing is different from a spontaneous magnetic moment found in a typical FM material as well as in the reversible metamagnetic transition. A distinctive feature in the field-annealed FM phase is that the ferromagnetism is induced by field annealing and survives even after field quenching. Now the question is how this irreversible field-induced FM phase in Pr0.65Ca0.35MnO3 and Pr0.82Na0.18MnO3 is stabilized in the CO and AFM matrix. To understand this unusual phenomenon, we employ a schematic energy diagram (Figure 8) that includes two local minima corresponding to the AFM and FM states. In zero magnetic field, the ground state of the two compounds is the pseudo CE-type CO and AFM state. As given in Figure 8(a), the FM state is not stable at this stage. In the presence of a high magnetic field, however, the FM phase is stabilized by means of the Zeemann energy term (-M$``$H), which is depicted in Figure 8(b). In the ordinary AFM material, the field-induced FM state immediately goes back to the AFM ground state when the field is removed. The field-induced FM phase in the Pr-doped manganites to be discussed is irreversible and stable even after quenching the field. This can be described by the introduction of pinning potential barrier (U), given in Figure 8(c). The only way to destabilize the FM state is the increase of the thermal fluctuation in the high temperature region. Above a critical temperature ($`T_0`$), the thermal fluctuation abruptly induces a transition from FM to AFM, as seen in Figure 5 and 7. Accordingly, we can simply estimate that the pinning potential barrier is $`k_BT_0`$, where $`k_B`$ is the Boltzmann constant, which is corresponding to about 2-8 meV in Pr-doped manganite samples. Our simple energy diagram well explains the reversible and irreversible FM states and also agrees with the M(H) curves given in Figure 2 and 6.

Another important issue to be addressed is that spin reorientation is the most likely cause of the irreversible field-induced FM state found in the Pr-doped manganites. In zero magnetic field, FM exchange coupling between the Pr 4f and Mn 3d spins is negligible because the Pr spins have no net moments in the AFM matrix. With an increase in the magnetic field, however, the Mn spins undergo a metamagnetic transition and simultaneously the localized Pr spins change to an ordered state. Consequently, the FM exchange coupling between the Pr and Mn spins is operative, making the field-induced FM state of Mn spins stable. The origin of this unique FM state thus appears to be associated with the coupled interaction between trivalent Pr ions and mixed valent Mn ions. Probably the ordered 4f Pr spin might pin the itinerant Mn spins. Namely they control the spin direction of Mn 3d electrons through the FM exchange coupling, which eventually leads to the development of the ferromagnetism. Accordingly, this field annealed FM state is pinned by the ordered 4f spins, which makes the FM phase stable. It is conceivable that the Pr 4f electrons may act as a pinning center for pinning itinerant charge carriers. This anomalous irreversible switching of the FM interaction is strongly dependent upon the order-disorder transition of the localized Pr spins.

Finally, it is worthy to mention that this field-induced irreversible FM phase is not easily observed in the Nd-doped samples Nd1-xCaxMnO3 although sizes and magnetic moments of the Pr and Nd ions are similar. One likely cause of this difference is ascribed to the different electronic states between the Pr and Nd ions. Unlike the Nd ion that has predominantly a 3+ state, the Pr ion can have a 4+ state as well as a 3+ state. This mixed valent nature appears to induce the strong FM exchange coupling in the Pr-doped manganite efficiently. Another plausible cause is due to subtle size difference between the Nd and Pr ions. The smaller Nd ion leads to slightly larger lattice distortion, which makes the FM exchange coupling between the Nd 4f and Mn 3d spins coupling difficult.

## V Conclusions

We have discovered a new type of ferromagnetism in Pr-doped manganites. The observed ferromagnetism is quite unusual in that the field annealing yields an irreversible field-induced FM state. This irreversible field-induced FM state is due to an irreversible switching of the FM interaction between the Pr and Mn spins by the magnetic field. If one calls a spontaneous magnetic moment typically observed in a FM material type I ferromagnetism, then this field-induced ferromagnetism might be dubbed type II ferromagnetism. We have adopted this terminology from type II superconductor. This is because although they are intrinsically different, they have some similar features, particularly in a mixed state. The FM moment induced by the ordered Pr spins that pin the itinerant charge carriers will play an important role in determining the physical properties of Pr0.65Ca0.35MnO3 and Pr0.82Na0.18MnO3. Indeed, we have found that the order-disorder transition of localized Pr spins is strongly correlated with a metal-insulator transition in the field-annealed sample of Pr0.65Ca0.35MnO3.

## VI Acknowledgement

The Creative Research Initiative Program supported this work.


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# Untitled Document

EFI-03-15 hep-th/0304108

Wess-Zumino Term in Tachyon Effective Action

Kazumi Okuyama

Enrico Fermi Institute, University of Chicago

5640 S. Ellis Ave., Chicago IL 60637, USA

kazumi@theory.uchicago.edu

We show that the source of RR field computed from the boundary state describing the decay of a non-BPS brane is reproduced by a particular form of the Wess-Zumino term in the tachyon effective action. We also obtain a simple expression of the S-charge associated with rolling tachyons.

April 2003

1. Introduction

Decay of an unstable brane is a very interesting process which might help us to understand some properties of string theory in time-dependent backgrounds \[115\]. The dynamics of tachyon field $`𝒯`$ on such a brane can be described by an effective field theory when the value of $`𝒯`$ and its derivatives satisfy some conditions . The proposed effective action of real tachyon $`𝒯`$ on non-BPS $`Dp`$-brane in Type II string theory is given by \[1620,,4\]

$$S_{DBI}=d^{p+1}x=M_pd^{p+1}xV(𝒯)\sqrt{1+_\mu 𝒯^\mu 𝒯}$$

where $`M_p`$ is the tension of the non-BPS brane. In this paper we use the unit $`\alpha ^{}=1`$. In (1.1), we suppressed the dependence on the gauge field and the scalar fields other than the tachyon. It was pointed out in  that if we take the potential $`V(𝒯)`$ to be

$$V(𝒯)=\frac{1}{\mathrm{cosh}\frac{𝒯}{\sqrt{2}}},$$

then the stress tensor of rolling tachyon computed from the boundary state is correctly reproduced by the effective action (1.1). This potential (1.1) was also discussed recently in \[21,,22\].

The tachyon effective action has another important term, i.e. the Wess-Zumino term (or the Chern-Simons term) describing the coupling of open string tachyon to the bulk RR field:

$$S_{WZ}=W(𝒯)𝑑𝒯C_{RR}$$

where $`W(𝒯)`$ is an even function of $`𝒯`$ which vanishes as $`𝒯\pm \mathrm{}`$. In order for a kink of $`𝒯`$ connecting the two vacua at $`𝒯=\pm \mathrm{}`$ to carry the correct RR charge and the tension of BPS $`D(p1)`$ brane, $`W(𝒯)`$ and $`V(𝒯)`$ should satisfy the condition 1 Our definition of $`W(𝒯)`$ is different from that in  by the factor of $`M_{p1}^{BPS}`$.

$$_{\mathrm{}}^{\mathrm{}}W(𝒯)𝑑𝒯=\frac{M_p}{M_{p1}^{BPS}}_{\mathrm{}}^{\mathrm{}}V(𝒯)𝑑𝒯=1.$$

Here $`M_{p1}^{BPS}`$ is the tension of BPS $`D(p1)`$-brane whose ratio to the tension $`M_p`$ of non-BPS $`Dp`$-brane is given by

$$\frac{M_p}{M_{p1}^{BPS}}=\frac{1}{\sqrt{2}\pi }.$$

Note that the last equality in (1.1) is satisfied for $`V(𝒯)=\frac{1}{\mathrm{cosh}(\frac{𝒯}{\sqrt{2}})}`$.

In this short note, we will show that the coupling of the open string tachyon to the RR field computed from the boundary state is reproduced by setting

$$W(𝒯)=\frac{1}{\sqrt{2}\pi }V(𝒯)=\frac{1}{\sqrt{2}\pi \mathrm{cosh}\left(\frac{𝒯}{\sqrt{2}}\right)}.$$

This $`W(𝒯)`$ obviously satisfies the condition (1.1).2 From the late time behavior of the source for the RR field in the boundary state, Sen showed that $`W(𝒯)`$ goes like $`e^{\frac{1}{\sqrt{2}}𝒯}`$ for large $`𝒯`$ . (1.1) has this property.

In section 2, we consider some properties of the equation of motion obtained from the action (1.1) with $`V(𝒯)`$ given by (1.1). In section 3, we show that the source of RR field computed from the boundary state is reproduced by (1.1). We also comment on the S-charge associated with the rolling tachyon. We conclude with a few comments in section 4.

2. Some Properties of $`S_{DBI}`$

To see the dynamics of tachyon field described by the action (1.1) with (1.1), it is convenient to perform a field redefinition from $`𝒯`$ to $`T`$ as

$$\mathrm{sinh}\frac{𝒯}{\sqrt{2}}=\frac{T}{\sqrt{2}}.$$

In terms of this variable $`T`$, the Lagrangian becomes

$$\frac{}{M_p}=\frac{1}{1+\frac{1}{2}T^2}\sqrt{1+\frac{1}{2}T^2+_\mu T^\mu T},$$

and the equation of motion derived from this Lagrangian is

$$\left(_\mu ^\mu T+\frac{1}{2}T\right)\left(1+\frac{1}{2}T^2\right)+_\mu T^\mu T_\nu ^\nu T_\mu T^\nu T_\nu ^\mu T=0.$$

When the tachyon $`T`$ depends only on time $`t`$, the second and the third terms in (2.1) cancel, and the equation of motion reduces to

$$_t^2T+\frac{1}{2}T=0.$$

Therefore, the general solution of homogeneous tachyon is given by3 The converse statement was proved in . They showed that the effective action is fixed to have the form (2.1) by requiring: (1) $`T=e^{\frac{1}{\sqrt{2}}t}`$ is a solution of the equation of motion at each order in the power series expansion in $`T`$, (2) The on-shell Lagrangian agrees with the disk partition function.

$$T=T_+e^{\frac{1}{\sqrt{2}}t}+T_{}e^{\frac{1}{\sqrt{2}}t}$$

with some constant coefficient $`T_\pm `$.

An interesting fact is that the form of stress tensor as a function of time is reproduced from this effective action . For instance, for the tachyon configuration describing the “full brane”

$$\frac{T}{\sqrt{2}}=\frac{\mathrm{cosh}\frac{t}{\sqrt{2}}}{\mathrm{sinh}\frac{t_0}{\sqrt{2}}},$$

the on-shell Lagrangian is evaluated as

$$\frac{}{M_p}=\frac{1}{1+e^{\sqrt{2}(tt_0)}}+\frac{1}{1+e^{\sqrt{2}(t+t_0)}}1.$$

This expression agrees with the disk partition function $`Z(x^0)`$ in the presence of boundary tachyon operator $`T_{WS}=\lambda \mathrm{cosh}(X^0/\sqrt{2})`$, if we identify the coupling $`\lambda `$ and the parameter $`t_0`$ in (2.1) as

$$\mathrm{sin}\pi \lambda =e^{\frac{1}{\sqrt{2}}t_0}.$$

In general, the worldsheet tachyon operator $`T_{WS}`$ in the $`(1)`$ picture is different from the tachyon field $`T`$ in the effective action (2.1). In particular, the periodicity of $`\lambda `$ cannot be reproduced by any first derivative effective actions . Moreover, the relative coefficient of $`T_{00}`$ and $`T_{ij}`$ computed from (1.1) does not agree with the boundary state result for the full brane. As pointed out in , if a tachyon configuration has a turning point $`_0T=0`$, the effective action (1.1) cannot reproduce the stress tensor computed from the boundary state.

However, after taking the “half S-brane” limit,

$$tt+a,t_0t_0+a,a\mathrm{}\mathrm{with}t,t_0\mathrm{fixed},$$

we can actually identify $`T_{WS}`$ with $`T`$. In this limit, the tachyon configuration and the on-shell Lagrangian become

$$\frac{T}{\sqrt{2}}=e^{\frac{1}{\sqrt{2}}(tt_0)},\frac{}{M_p}=\frac{1}{1+e^{\sqrt{2}(tt_0)}},$$

and the stress tensor agrees with the worldsheet computation for the half S-brane with $`T_{WS}=\lambda e^{\frac{1}{\sqrt{2}}X^0}`$ \[9,,10\]. It was argued in  that the action (1.1) is reliable only for the fluctuation of tachyon field around a single exponential $`e^{\pm t/\sqrt{2}}`$ (i.e. $`T_+=0`$ or $`T_{}=0`$ in (2.1)).

Next let us briefly discuss the inhomogeneous tachyon configuration. It is easy to see that the configuration with a single exponential

$$T=e^{ik_\mu X^\mu }$$

solves the equation of motion (2.1) provided $`k_\mu `$ is on-shell:

$$k_\mu k^\mu =\frac{1}{2}.$$

However, the sum of on-shell exponentials, e.g.

$$T=\frac{1}{2}e^{\frac{1}{2}(t+ix)}+\frac{1}{2}e^{\frac{1}{2}(tix)}=e^{\frac{1}{2}t}\mathrm{cos}\left(\frac{1}{2}x\right)$$

is not a solution of (2.1) because of the non-linearity of the equation of motion. It is interesting that this effective action (2.1) knows that the boundary interaction $`e^{X^0/2}\mathrm{cos}(X/2)`$ is not exactly marginal in the superstring case , although the single exponential $`e^{(X^0\pm iX)/2}`$ is exactly marginal. It seems difficult to find an exact inhomogeneous solution of (2.1). Instead, we can solve (2.1) numerically, or solve it perturbatively along the line of . It was observed that, during the inhomogeneous decay of an unstable brane, defect branes are formed at a finite time \[5,,9\] and the slope of the kink becomes infinitely steep . It would be interesting to see whether the tension of the defect brane calculated by this effective action agrees with the tension of the BPS brane.

3. Wess-Zumino Term and S-charge

In this section we will show that the source of RR field read off from the boundary state is reproduced by the Wess-Zumino term (1.1) with the choice $`W(𝒯)=\frac{1}{\sqrt{2}\pi }V(𝒯)`$.

The source of RR field generated by the rolling tachyon $`T_{WS}=\lambda \mathrm{cosh}X^0/\sqrt{2}`$ is

$$\begin{array}{cc}\hfill j(t)& =\frac{\mathrm{sin}\pi \lambda }{\sqrt{2}\pi }\left[\frac{e^{\frac{1}{\sqrt{2}}t}}{1+\mathrm{sin}^2\pi \lambda e^{\sqrt{2}t}}\frac{e^{\frac{1}{\sqrt{2}}t}}{1+\mathrm{sin}^2\pi \lambda e^{\sqrt{2}t}}\right].\hfill \end{array}$$

This source and the bulk RR $`p`$-form field couple via the Wess-Zumino term on the worldvolume of non-BPS $`Dp`$-brane

$$S_{WZ}=_{𝐑^{1,p}}JC_{RR}=𝑑td^p\xi j(t)C_{1,\mathrm{},p}$$

where $`J=j(t)dt`$.

Using the parameter $`t_0`$ (2.1), the source $`j(t)`$ is rewritten as

$$j(t)=\frac{1}{\sqrt{2}\pi }\left[\frac{e^{\frac{1}{\sqrt{2}}(tt_0)}}{1+e^{\sqrt{2}(tt_0)}}\frac{e^{\frac{1}{\sqrt{2}}(t+t_0)}}{1+e^{\sqrt{2}(t+t_0)}}\right]=\frac{1}{\sqrt{2}\pi }\frac{\mathrm{sinh}\frac{t}{\sqrt{2}}\mathrm{sinh}\frac{t_0}{\sqrt{2}}}{\mathrm{cosh}^2\frac{t}{\sqrt{2}}+\mathrm{sinh}^2\frac{t_0}{\sqrt{2}}}.$$

Note that the normalization of $`j(t)`$ was determined by requiring that the S-brane with $`T_{WS}=\lambda \mathrm{sinh}X^0/\sqrt{2}`$ should carry $`\pm 1`$ of unit RR charge . $`j(t)`$ has poles at $`t=\pm t_0+\pi i(2n+1)/\sqrt{2}`$ and the residues are

$$2\pi i\mathrm{Res}j(t)|_{t=\pm t_0+\frac{\pi i}{\sqrt{2}}(2n+1)}=\pm (1)^n(n𝐙).$$

The alternating sign of residues corresponds to the fact that, when $`t_0=0`$ (or $`\lambda =\frac{1}{2}`$), the Wick rotated configuration describes an array of branes and anti-branes.

From (3.1), (2.1) and (2.1), one can easily see that the RR source $`J`$ is written as

$$J=\frac{1}{\sqrt{2}\pi }\frac{dT}{1+\frac{1}{2}T^2}=\frac{1}{\sqrt{2}\pi }V(𝒯)d𝒯.$$

This relation holds also for the half S-brane. (The RR source of the half S-brane is obtained by taking the limit (2.1) in (3.1).) Therefore, we conclude that the function $`W(𝒯)`$ is given by $`\frac{1}{\sqrt{2}\pi }V(𝒯)`$, at least for the on-shell tachyon. Strictly speaking, the effective action $`S_{DBI}`$ (1.1) is reliable only for the half S-branes. However, as we saw above, the disk partition function $`Z=B|0_{NS}`$ and the RR source $`j=B|C_{RR}`$ are correctly reproduced by the effective action (1.1), (1.1) even for the full brane. It would be interesting to understand the physical meaning of this fact.

It is useful to rewrite $`J`$ as

$$J=\frac{1}{\pi }d\mathrm{tan}^1\left(\frac{T}{\sqrt{2}}\right).$$

From this expression, it is obvious that the integral of $`J`$ is $`1`$ when integrated over the kink configuration of $`T`$ connecting the two vacua $`T=\pm \mathrm{}`$. Therefore, $`J=W(𝒯)d𝒯`$ satisfies the condition (1.1).

The equation of motion of the bulk RR $`p`$-form field with the source term (3.1) is given by

$$(_t^2+_𝐱^2)C_{1,\mathrm{},p}=j(t)\delta ^{9p}(𝐱),$$

where $`𝐱`$ is the transverse coordinates of the non-BPS $`Dp`$-brane. The S-charge carried by the rolling tachyon is defined by

$$Q_s(t)=d^{9p}xF_{0,\mathrm{},p}=d^{9p}x_tC_{1,\mathrm{},p}.$$

From this definition of S-charge, one can show that $`Q_s(t)`$ is related to $`j(t)`$ in a simple way:

$$\frac{d}{dt}Q_s(t)=j(t).$$

Using (3.1), we can integrate the relation (3.1) to obtain

$$Q_s(t)=\frac{1}{\pi }\mathrm{tan}^1\left(\frac{T(t)}{\sqrt{2}}\right),$$

up to a constant shift.

We can check the general formula (3.1) by the explicit computation as follows. For the full brane, the RR $`p`$-form generated by the source (3.1) is

$$\begin{array}{cc}\hfill C_{1,\mathrm{},p}=\frac{1}{\sqrt{2}\pi 2^\nu \mathrm{\Gamma }(\nu +1)\mathrm{vol}(S^{8p})}\underset{n=0}{\overset{\mathrm{}}{}}& (1)^n\left[e^{\frac{2n+1}{\sqrt{2}}(tt_0)}e^{\frac{2n+1}{\sqrt{2}}(t+t_0)}\right]\hfill \\ & \times \left(\frac{2n+1}{\sqrt{2}r}\right)^\nu K_\nu \left(\frac{2n+1}{\sqrt{2}}r\right),\hfill \end{array}$$

where $`\nu =\frac{9p}{2}1`$, $`\mathrm{vol}(S^{d1})=\frac{2\pi ^{d/2}}{\mathrm{\Gamma }(d/2)}`$, and $`K_\nu (z)`$ is the modified Bessel function. $`r=\sqrt{𝐱^2}`$ is the radial coordinate of the transverse directions. Plugging this expression into the definition (3.1) of $`Q_s(t)`$, the S-charge of the full brane is obtained as

$$Q_{\mathrm{full}}(t)=Q_+(t)+Q_{}(t)$$

where $`Q_\pm (t)`$ are the S-charge of the half S-branes:

$$Q_+(t)=\frac{1}{\pi }\mathrm{tan}^1\left(e^{\frac{1}{\sqrt{2}}(tt_0)}\right),Q_{}(t)=\frac{1}{\pi }\mathrm{tan}^1\left(e^{\frac{1}{\sqrt{2}}(t+t_0)}\right).$$

It is easy to see that this expression satisfies (3.1). As a function of time, $`Q_{\mathrm{full}}(t)`$ has a kink at $`t=t_0`$ and an anti-kink at $`t=t_0`$, and approaches $`\frac{1}{2}`$ at large $`|t|`$. (More precisely, $`Q_{\mathrm{full}}(t)`$ has a “half” (anti)kink at $`t=\pm t_0`$. See the discussion below.) Note that the S-charge is independent of time when $`\lambda =\frac{1}{2}`$, or $`t_0=0`$

$$Q_{\mathrm{full}}(t)|_{t_0=0}=\frac{1}{2}.$$

This is consistent with the relation (3.1) since there is no source of RR field when $`\lambda =\frac{1}{2}`$.

The S-charge $`Q_s(t)`$ at fixed $`t`$ is not a gauge invariant quantity. The physical S-charge is the difference of $`Q_s(t)`$ in the far future and the far past:

$$\mathrm{\Delta }Q_s=Q_s(t=+\mathrm{})Q_s(t=\mathrm{}).$$

This is the definition of the integral of RR flux over the “transverse sphere” surrounding S-brane in Lorentzian space . For the half S-brane and the full brane, their physical S-charges are

$$\mathrm{\Delta }Q_\pm =\pm \frac{1}{2},\mathrm{\Delta }Q_{\mathrm{full}}=0.$$

The S-charge $`\mathrm{\Delta }Q_\pm =\pm \frac{1}{2}`$ of half S-brane reflects the fact that tachyon field describing the half S-brane runs from $`T=0`$ to $`T=\mathrm{}`$ which is the half way between the two vacua $`T=\pm \mathrm{}`$.

The tachyon configuration of the form $`\mathrm{sinh}t/\sqrt{2}`$, which connects the two vacua $`T=\pm \mathrm{}`$, can be obtained from the $`\mathrm{cosh}t/\sqrt{2}`$ configuration (2.1) by the shift $`tt+\pi i/\sqrt{2}`$, $`t_0t_0+\pi i/\sqrt{2}`$ . Under this shift of $`t`$ and $`t_0`$, $`T`$ in (2.1) becomes

$$\frac{T}{\sqrt{2}}=\frac{\mathrm{sinh}\frac{t}{\sqrt{2}}}{\mathrm{cosh}\frac{t_0}{\sqrt{2}}}.$$

The on-shell Lagrangian (or the disk partition function) of this configuration is the same as the cosh case (2.1), but the S-charge becomes

$$Q_{\mathrm{sinh}}(t)=Q_+(t)Q_{}(t),$$

and it satisfies $`\mathrm{\Delta }Q_{\mathrm{sinh}}=1`$ (we normalized $`j(t)`$ by requiring this relation ).

4. Discussion

In this paper, we showed that the source $`j(t)`$ of RR field computed from the boundary state is reproduced by the Wess-Zumino term of the form (1.1). We should comment on the relation between our $`W(𝒯)`$ and the Wess-Zumino term obtained in BSFT \[27,,28\]. The function $`W(𝒯)`$ in (1.1) is quite different from the BSFT result $`W(𝒯)e^{𝒯^2/4}`$. As emphasized in , the two actions have different regimes of validity, i.e. our $`W(𝒯)`$ is valid for nearly on-shell configurations while BSFT is valid far off mass shell. However, in view of the topological nature of WZ term in BSFT, namely the Chern character of superconnection, we expect our $`W(𝒯)`$ is related to that in BSFT by a nontrivial field definition.

We have two pictures suggesting there are some branes at $`t=\pm t_0`$ (or its shift in the imaginary direction):

(1) From the form of $`Q_{\mathrm{full}}(t)`$, when $`t_0`$ is large the full brane can be well approximated by the following configuration: The unstable $`Dp`$-brane exists only in the region $`|t|<t_0`$ and ends on the half $`Sp`$-branes at $`t=\pm t_0`$, and there is no brane before $`t_0`$ and after $`t_0`$. It was discussed in  that the non-BPS branes in Euclidean space can end on “half D-branes” which carry the half unit of RR charge. This is based on the fact that the unstable branes can be regarded as sphalerons in string theory .

(2) In \[15,,11\], it was observed that when $`t_0=0`$ the closed string state produced by the unstable $`Dp`$-brane is closely related to the array of BPS $`D(p1)`$-branes at $`t=\pi i(2n+1)/\sqrt{2}`$. This comes from the fact that the disk partition function $`Z(t)`$ has poles at $`t=\pi i(2n+1)/\sqrt{2}`$. When we turn on $`t_0`$, the poles of $`Z(t)`$ and $`j(t)`$ are shifted to $`t=\pm t_0+\pi i(2n+1)/\sqrt{2}`$. The closed string emission rate from the full brane is related to the cylinder amplitude between (anti)D-branes sitting at $`t=\pm t_0+\pi i(2n+1)/\sqrt{2}`$ .

It would be interesting to study the relation between these two pictures (see  for a discussion on the relation between S-branes and D-instantons).

Acknowledgement

I would like to thank Ben Craps and David Kutasov for useful comments and encouragement.

References

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text:
# Transition from tunneling to direct contact in tungsten nanojunctions

## I Introduction

The study of transition from tunneling to direct contact and electrical transport through atomic-sized metallic conductors has been the object of great attention during the last decade. Different types of phenomena, related to both the quantum character of transport and the atomic discreteness of the contact, were observed in 3D nanoconstrictions produced by scanning tunneling microscopes (STM) or mechanically controllable break junctions (MCBJ) agrait\_review . In particular, conductance measurements of breaking nanowires demonstrated a step-like structure of conductance versus electrode separation traces $`G(z)`$. For single-valence $`s`$-metals conductance plateaus are close to the integer multiples of the quantum conductance unit $`G_0=2e^2/h`$. However, simultaneous measurements of both the force and the conductance for breaking gold nanowires demonstrated that jumps between plateaus in the conductance staircase are always correlated with relaxations of the mechanical force and, therefore, with atomic rearrangements in the nanoconstriction rubio . Individual conductance curves $`G(z)`$ are inherently irreproducible due to the different dynamical evolution of the connective necks during the break. Therefore, analysis of experimental data includes construction of conductance histograms based on a large number of conductance traces. Peaks in the conductance histograms are related to the statistically more probable atomic configurations in the connective neck between the electrodes krans . For polyvalent metals the main (and sometimes the only) feature in the conductance histograms is a peak corresponding to one-atom point contact thesis . The conductance through such a contact is determined by a few conductance channels intimately related to atomic orbitals cuevas . Transition from tunneling to single-atom contact occurs in an avalanche-like way at an electrode separation of $`1.5`$ Å due to the metallic adhesion forces sutton . This sudden jump in conductance precluded measurements of $`G(z)`$ at sub-Ångstrom distances between the electrodes for all metals studied to date.

While measuring thermal expansion of MCBJ electrodes for different materials, we took notice of the unusually high stability of tungsten tunnel junctions at very close electrode separations thermo . In another study, transmission and scanning electron microscopy images showed no evidence of connective neck formation between tungsten wires correia . Moreover, measurements of adhesive forces between an atomically-defined W(111) trimer tip and a Au(111) sample revealed no spontaneous jump to contact cross . These unusual properties of tungsten nanocontacts motivated us to carry out further extensive investigations.

In this paper we present our experiments with tungsten MCBJ. Our aim was to examine the behavior of tungsten nanojunctions during the transition between tunneling and direct contact and to what extent this behavior is influenced by the unique mechanical and electronic properties of tungsten. We show that very often the adhesive jumps of conductance are absent and that the transition to single atom contact is smooth. This permitted us to investigate the junction at ultra-small electrode separations. By employing the conductance histogram technique we determined the preferential values of conductance during the fracture of the junction to be about $`1`$ $`G_0`$ and $`2`$ $`G_0`$. Also, we measured the conductance histograms of tantalum and molybdenum (as two nearest neighbors of tungsten in the periodic table of elements) to provide additional support for our interpretation.

## II Experimental setup

We employed the traditional MCBJ technique, described elsewhere agrait\_review , with a modified sample mounting (Fig. 1). This mounting includes two $`6\times 2.5\times 1`$ mm pieces of shear piezo-ceramic (which gives horizontal displacement of its surface when voltage is applied) glued at the center of a phosphor bronze bending beam. A polycrystalline tungsten wire with a diameter of 100 $`\mu `$m was attached to the top of the piezo’s with two small drops of hard epoxy (Stycast 850FT). The central section of the wire was then electrochemically etched in a 25% solution of KOH down to $`5`$$`10`$ $`\mu `$m at its thinnest part. The wire was broken at $`4.2`$ K in an ultra-high vacuum environment by bending the beam. The distance between the electrodes was fine tuned by changing the deflection of the bending beam or applying voltage to the left-hand side shear piezo. The relative displacement of the electrodes was calibrated using the exponential part of $`G(z)`$ traces in the tunneling regime (assuming a work function for tungsten $`\varphi 4.5`$ eV) as well as by measuring field emission resonance spectra rsi . The contact conductance was measured using a current-to-voltage converter with a gain of 0.1 V/$`\mu `$A. Conductance versus electrode separation traces $`G(z)`$ were measured in a slow mode ($`2`$$`30`$ points/s) using Keithley 2182 nanovoltmeters in order to cover over 7 orders of magnitude in the conductance during transition from tunneling to direct contact. Conductance traces for building conductance histograms were recorded with an AT-MIO-16XE-50 National Instruments data acquisition board (sampling rate of $`20000`$ points/s and resolution of $`16`$ bits). During this acquisition a ramp voltage with a frequency of $`5`$$`50`$ Hz was applied to the shear piezo to establish a repeated fracture of the junction.

The sample surfaces were characterized by scanning the electrodes with the two shear piezo’s in the constant current mode. We found atomically flat parts up to $`5`$$`10`$ nm in length alternating with irregularities of $`5`$$`15`$ Å in height. It should be noted that these STM-like measurements with two “blunt” electrodes are rather qualitative and the numbers presented are only rough estimates.

We analyzed thoroughly more than $`200`$ conductance histograms measured for $`12`$ different samples.

## III Results

We investigated the transition from the tunneling regime to direct contact for tungsten MCBJ by performing conductance measurements during slow, continuous approach or retraction of the electrodes. These measurements revealed a rich variety of $`G(z)`$ traces. All of them fall between two extreme cases shown in Fig. 2. Curve 1 demonstrates an avalanche-like transition from $`G0.01`$$`0.1`$ $`G_0`$ to $`100`$$`1000`$ $`G_0`$. This indicates the formation of a mesoscopic contact with a cross-section of $`10`$$`100`$ nm2 between two flat portions of the electrodes. Subsequent retraction of the electrodes produced only small changes in the contact conductance over a retreat distance of $`4`$ nm, which were followed by sudden disconnection (upper panel in Fig. 2). During $`5`$$`10`$ minutes after disconnection, the distance between the electrodes increased as deduced from the transient decrease of the measured tunnel current. After the full relaxation of the sample, the original curve could be reproduced accurately, indicating that no irreversible changes of the electrode relief occurred. The other extreme case – curve 2 in Fig. 2 – demonstrates a smooth transition from tunneling to direct contact with no sign of spontaneous formation of an adhesive neck. The majority of $`G(z)`$ curves exhibited combination of smooth changes of the conductance and sudden jumps with amplitudes ranging from $`0.1G_0`$ up to few $`G_0`$.

We also performed statistical analysis of conductance traces by employing the conductance histogram technique. We found that tungsten nanojunctions have a particular tendency to show reproducible, almost identical conductance traces when indentation of the electrodes is not sufficient. If proper care is taken and in every cycle contacts of $`G30`$$`40`$ $`G_0`$ are formed, the break occurs in a large variety of ways. In this latter case a statistical approach to data analysis is justified. In sharp contrast to other metals, the conductance histograms of tungsten do not necessarily exhibit the same pattern when the contact site is shifted by the right-hand side shear piezo or when the sample is replaced. A major part of histograms demonstrated no distinctive features \[Fig. 3(a)\]. However, on many occasions the histograms showed two peaks at respectively $`1`$$`1.2`$ and $`2`$$`2.2`$ $`G_0`$ \[Fig. 3(b)\], or only one of those two.

In Fig. 4 four characteristic conductance traces are presented. Curve 1 shows a smooth and completely featureless transition from direct contact to tunneling. For a tungsten junction this kind of transition is frequently present and gives rise to the featureless background in the conductance histograms. This background is suppressed when these featureless curves are rejected from the data set by employing a computer filtering algorithm note\_filter . Then, either peaks invisible in the original histogram appear \[inset in Fig. 3(a)\] or the contrast of peaks is significantly improved \[inset in Fig. 3(b)\]. Peaks in the histogram naturally arise from conductance traces with distinct features – plateaus – at about $`1G_0`$ and/or $`2G_0`$ as demonstrated by curves 2, 3a and 3b in Fig. 4. While curve 2 shows a smooth transition with no jumps, in the case of curves 3a and 3b clear jumps occur near $`1G_0`$ and $`2G_0`$, respectively. We note here that conductance traces like those represented by curve 2 are unique to tungsten and were not observed in other metallic contacts.

In our previous analysis we used an algorithm to select the traces with long plateaus note\_filter . However, it is also important to differentiate between the smooth curves and those with sudden jumps. For this reason every trace was characterized by the largest jump between neighboring data points in the conductance interval $`G/G_0[0.3,3.3]`$. By combining these two approaches the traces were classified into the three categories presented in Fig. 4. Using the data set for histogram in Fig 3(b) we found that $`30\%`$ of traces exhibited a smooth and featureless transition and roughly $`10`$% of curves show plateaus without sudden jumps. In the rest of the traces clear conductance jumps were found. In order to quantify at which conductance values conductance jumps with $`\mathrm{\Delta }G_{max}0.7G_0`$ are most likely to occur, we also built up histograms for the position of these sudden transitions. The peaks in the so-built histogram presented in Fig. 5 clearly demonstrate that large conductance jumps are most probable at $`G1G_0`$ and $`2G_0`$. We emphasize that the relative occurrence of the three different types of conductance traces is sample and site-dependent, and in certain data sets only traces with smooth transitions were present.

## IV discussion

Our experimental results for tungsten nanojunctions strikingly differ from those obtained for other metals studied so far, that exhibit conductance traces always falling into the same (material-specific) pattern. Especially, the adhesive jump to contact or the tensile overstretching followed by sudden disruption have respectively been found to be an unavoidable attendant of contact formation or breakage. This has precluded measurements of conductance at small electrode separations. The occasional absence of these processes is unique for tungsten junctions and we attribute it to the specific mechanical properties of this metal. In particular, this odd junction stability at ultra-small electrode separations permitted us to study the previously unaccessible regime of nanocontact conductance.

The adhesive jump is governed by the the competition between the adhesive and tensile forces taylor . The tensile forces are determined by the stiffness of the electrodes, which is composed from the stiffness of the nanoscale junction itself and the stiffness of the whole setup. The latter can have significant importance in an atomic force microscope with a soft cantilever, however it is not expected to play any role in an MCBJ due to the rigid sample mounting. The stiffness of the junction depends on the strength of the bonds in the material, but also the junction geometry and the crystallographic orientation of the electrodes have a crucial influence on it. Contacts with large opening angle have large stiffness, while in contacts with small opening angle a large amount of layers are involved in the elastic deformation and thus the stiffness is reduced. The stiffness is also reduced, if the contact surfaces are not perpendicular to the contact axis. Then, the electrodes can bend like a cantilever and the elastic behavior is defined by the smaller shear forces.

The elastic behavior of the material is basically determined by the strength of the bonds between the atoms, therefore it is similar at any length-scale and atomic scale systems are well described by bulk elastic constants rubio . The bulk elastic modulus of tungsten ($`E_\mathrm{W}=411`$ GPa) is outstandingly large among all metals. (As a comparison the Youngs modulus of Au, Pt, and Nb is $`E_{\mathrm{Au}}=78`$ GPa, $`E_{\mathrm{Pt}}=168`$ GPa, and $`E_{\mathrm{Nb}}=105`$ GPa, respectively.) On the other hand, the junction geometry is not controllable in MCBJ experiments. In previously studied metals the conductance traces imply that the junction breaks through the process of rupture. In this case the contact geometry is “self-organized” during the neck pulling, so the conditions for the adhesive jumps are similar during each disconnection. Our measurements imply that tungsten breaks in a more brittle way and a large variety of contact geometries are established during the fractures. This, together with the outstanding elastic modulus of tungsten can explain our observations. In “stiff” contact geometries the elastic forces can overcome the adhesion and thereby enable a smooth transition between tunneling and direct contact, while in softer contact geometries the adhesive jumps are still present.

Our interpretation can be tested by comparing the mechanical behavior during the break of further metals with different elastic modulus. For this reason we performed measurements on two neighbors of tungsten in the periodic system, molybdenum and tantalum. These metals have similar electronic properties to tungsten. The elastic modulus of molybdenum is relatively large ($`E_{\mathrm{Mo}}=329`$ GPa), while tantalum is much softer ($`E_{\mathrm{Ta}}=186`$ GPa). In agreement with that we found that tantalum always breaks in a jump-like way, while in molybdenum a part of the conductance traces showed a smooth transition.

To explain the avalanche-like motion of hundreds to thousands of atoms in the extreme case presented in Fig. 2 as curve 1, we consider the following three possibilities. The first one corresponds to the motion of a number of atomic layers in the direction normal to the electrode surfaces as assumed in the calculations by Taylor et al. taylor . This possibility would require an avalanche of a macroscopic amount of metal. Such a situation can take place only for contacts that act as a very soft spring and thus we do not consider it as the most likely explanation. The second possibility, that would result in the same behavior of the contact conductance, is the transition to direct contact due to bending of the electrodes. This arrangement is likely to occur when flat parts of the electrode surfaces are not perpendicular to the electrode axis. Then, the component of the adhesive force that is normal to the electrode axis causes bending. During our experiments, we observed anomalously high sensitivity of the tungsten MCBJ to acoustic vibrations, such as human voice, that suggests a transverse, spring-like motion of the electrodes. This observation is in favor of the “bending model.” As the last possibility, the contact between the electrodes may emerge as a result of dislocation glide or homogeneous shear motion of one of the electrodes agrait\_review . However, in this case it is not possible to explain the reversible behavior of contact conductance through many formation-breaking cycles.

The smooth conductance traces with plateaus at the first two conductance quanta (e.g., curve 2 in Fig. 4) are very close to those expected for conductance quantization in short constrictions torres . In spite of its attractiveness, we discarded this effect as the possible origin of the peaks in our histograms. Extremely small distances between the plateaus in conductance traces of tungsten, $`\mathrm{\Delta }z30`$ pm, suggest a constriction with an opening angle close to 90 degrees (an orifice). In this case the conductance quantization must be completely suppressed torres . The shape of these traces is better explained by the sequential closing of conduction channels due to different spatial distribution of the involved electronic states.

For transition $`d`$-metals five conductance channels are expected to contribute to the conductance of a single-atom contact according to the number of valence orbitals. The transmission values of these conductance channels were extensively studied for single-atom niobium junctions by tight binding calculations cuevas  and by measuring subgap structure in the superconducting state niobium . The calculations performed for a simplified one-atom contact geometry revealed a single dominant channel (as a result of the hybridization between the $`s`$ and $`d_{z^2}`$ orbitals), two medium-sized channels and two smaller channels that yield together a net conductance of $`G=2`$$`3`$ $`G_0`$. Both the conductance and the transmission coefficients showed a good agreement with the values determined from the experiment. Such a detailed investigation of the transmission eigenvalues is not available for the rest of the $`d`$-metals, and therefore the conduction properties of monoatomic contacts can only be deduced from the conductance histograms. For all non-magnetic transition metals studied so far (Nb, V, Rh, Pd, Ir, Pt) the histograms show a single well-defined peak centered in the region of $`G=1.5`$$`2.5G_0`$, that is attributed to the conductance through a single-atom contact agrait\_review ; thesis . To date, theoretical calculations have not been performed for the conductance of a single-atom tungsten contact, but its value is presumably in the same range of $`G1.5`$$`2.5G_0`$.

In tungsten the first peak in the histogram is situated at $`1`$ $`G_0`$, which is too low to be attributed to a single atom contact with all the channels open. Therefore, rather the second peak at $`2`$ $`G_0`$ is interpreted as the conductance of a monoatomic contact geometry, where the center atom is closely bound to both electrodes. The peak at $`1`$ $`G_0`$ is assumably connected to an arrangement where the electrodes are so much separated that only a part of the electronic states have noticeable overlap.

It is well known from STM studies that tungsten surfaces have long protruding surface modes, which have a crucial role in achieving atomic resolution. First principle calculations for the W(001) surface demonstrated that the tunnel current is primarily generated by the $`5d_{z^2}`$ dangling-bond surface states ohnishi ; chen . At distances $`>2`$ Å from the nuclei the charge density of the surface state is much higher than that of the atomic $`6s`$-state post  and so the surface states play a key role in the electron transport at small separations. The conductance through a single channel formed by such surface states can be a good candidate for explaining the conductance plateaus at $`1`$ $`G_0`$.

The occasional absence of adhesive jump enables us to monitor the transition between the two situations. However, the sequential closing of conductance channels – like curve 2 in Fig. 4 – may only occur for specific electrode configurations, which explains the relatively low percentage of this type of conductance traces.

The conductance histograms of tantalum and molybdenum were also studied. These two neighbors of tungsten in the periodic system have very similar electronic structure to W. Both for Ta and Mo the histograms show a single, well-defined peak situated around $`2`$ $`G_0`$ and $`2.5`$ $`G_0`$, respectively (see Fig. 6). This gives further support to the assumption that the conductance through a single atom contact is in the range of $`2`$ $`G_0`$ for tungsten as well. Though the electronic properties of Mo surfaces are similar to tungsten molybdenum  the histograms show no indication for a peak at $`1`$ $`G_0`$. In some occasions the computer filtering of the original data set reveals conductance traces with plateaus close to the conductance quantum, and accordingly a small peak around 1 $`G_0`$ is recovered in the histogram (see inset in Fig. 6(b)).

## V Conclusions

In conclusion, our measurements have shown that the evolution of conductance during the break of tungsten nanojunctions essentially differs from the ususal behavior of metallic contacts. Due to the large elastic modulus of W and the the non-ductile contact fracture, the adhesive jumps in the conductance traces are occasionally absent. Thank to these completely smooth transitions from direct contact to tunneling, the closing of conductance channels can be continuously monitored at ultra small electrode separations. The study of conductance histograms has shown, that the preferential values of conductance in tungsten junctions are $`1`$$`G_0`$ and $`2`$$`G_0`$. The smooth conductance traces with plateaus at these two values are explained by the sequential closing of conductance channels due to their different spatial distribution. The conduction through the long-protruding surface states of tungsten might be responsible for the plateaus at $`1`$$`G_0`$.

The limitations of MCBJ technique precluded us from drawing a more exact and persuasive conclusion. The current data can greatly be improved by simultaneous measurements of the conductance and the forces in the course of electrode approach for contacts with a well-defined tip/sample shape and orientation. To our opinion, the details of the process of avalanche-like transition to direct contact and subsequent break can be visualized with a high resolution transmission electron microscope operating in UHV.

## Acknowledgments

The authors are grateful to A.J. Toonen, J. Hermsen and J. Gerritsen for invaluable technical assistance. Part of this work was supported by the Stichting voor Fundamenteel Onderzoek der Materie (FOM) which is financially supported by the Nederlandse Organisatie voor Wetenschappelijk Onderzoek (NWO). The Hungarian Research Funds OTKA TO37451, TS040878, N31769 and a NWO grant for Dutch-Hungarian cooperation are also acknowledged. O.I.S. wishes to thank the NWO for a visitor’s grant.