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# Spin Glass Behavior in the Ru-1222 and Ru-1212 rutheno-cuprate families: a comparative study.

## I Introduction

A large number of reports have recently appeared focusing on the magnetic and superconducting properties of the rutheno-cuprates $`RSr_2Ln_{2x}Ce_xCu_2O_{10\delta }`$ (LnRu-1222)  and $`RuSr_2LnCu_2O_{8\delta }`$ (LnRu-1212) . However, despite the intensive research on these materials, some unanswered questions still remain. For instance, the oxygen non-stoichiometry, carrier concentration and valence state of Ru are not well understood yet . One of the most controversial questions is the exact type of magnetic ordering in the LnRu-1222 family. In contrast to the LnRu-1212 family, for which a consensus has been reached on the canted antiferromagnetic ordering for the Ru sublattice , the detailed magnetic ordering of the LnRu-1222 family is still lacking. Although the magnetic behavior of LnRu-1222 has been considered to be analogous to the magnetic response for LnRu-1212 samples, some recent results point towards various differences between them . In particular, strong evidences of spin glass behavior was found in GdRu-1222 . In the present work we extend this previous study to other LnRu-1222 compositions (Ln = Y, Dy, Ho). The verification of the spin glass behavior for these new samples and the differences between these results with those obtained for an YRu-1212 sample lead us to conclude that the spin-glass phase is characteristic of the Ru-1222 phase. We propose that the presence of oxygen vacancies in the RuO6 octahedra for Ru-1222 may cause the frustration of the magnetic ordering of the Ru ions, leading to a glassy behavior in this compounds, which does not usually occur for Ru-1212 samples. Studies comparing the oxygen non-stoichiometry for both families support such interpretation .

## II Experimental Details

Samples of composition $`RuSr_2Ln_{1.5}Ce_{0.5}Cu_2O_{10\delta }`$ (LnRu-1222) with Ln = Y, Ho, and Dy were synthesized through a high-pressure high-temperature (HPHT) solid-state reaction route . Briefly, a mixture of $`RuO_2+SrO_2+SrCuO_2+3/4CuO+1/4CuO_{0.011}+3/4Ln_2O_3+1/2CeO_2`$ was sealed in a gold capsule and submitted to a pressure of 6 GPa in a flat-belt-type-high-pressure apparatus, where it was allowed to react for 2 hours at 1200 $`{}_{}{}^{}C`$. It is expected that this procedure provides samples with oxygen content close to nominal , i. e. 10. All LnRu-1222 samples present a tetragonal structure within the I4/mmm space group as confirmed by X-ray powder diffraction (XRD) patterns obtained at room temperature (Philips-PW1800; CuKα radiation). The lattice parameters are $`a=b=3.824(1),\mathrm{\hspace{0.33em}3.819}(1),`$ and $`3.813(1)`$ Å and $`c=28.445(1),\mathrm{\hspace{0.33em}28.439}(1),`$ and$`\mathrm{\hspace{0.33em}28.419}(1)`$ Å for Ln = Dy, Y and Ho, respectively. The YRu-1212 was prepared using the same procedure, except that for this compound it was necessary to start from a slightly Ru poor composition in order to obtain a single phase sample of the desired stoichiometry . The lattice parameter obtained are $`a=b=3.818(1)`$ Å and $`c=11.5222(3)`$ Å. The details of the precise HPHT process are given in Ref. . All samples are single phase within the XRD resolution, except for YRu-1222 which presents a small amount of $`SrRuO_3`$ . All ac susceptibility measurements were performed in a commercial PPMS (Physical Properties Measurement System), while for the dc measurements a SQUID magnetometer MPMS-5 were employed, both equipments made by Quantum Design company.

## III Experimental Results

The ac susceptibility $`(\chi _{ac}=\chi ^{}+i\chi ^{\prime \prime })`$ technique is a very powerful method to provide evidence of a spin-glass behavior. In this case, both components $`\chi ^{}`$ and $`\chi ^{\prime \prime }`$ of $`\chi _{ac}`$ present a sharp, frequency dependent cusp. The position of the cusp in $`\chi ^{}`$ defines the freezing temperature $`T_f`$, which is coincident with the temperature of the inflection point in $`\chi ^{\prime \prime }`$. It is also well known that dc magnetic fields as low as a few hundreds of Oersted may suppress this cusp. In Fig. 1 we present the ac susceptibility for all four studied samples measured at a frequency $`\nu =1000`$ $`Hz`$ for three different dc fields $`H=50,`$ $`150`$ and $`500`$ Oe. All samples present a well defined peak at temperatures $`T_f=87.42,`$ $`103.3`$ and $`101.5`$ $`K`$ for Dy-, Ho- and YRu-1222, and $`T_N=140.6`$ $`K`$ for YRu-1212. All three LnRu-1222 samples present a strong suppression of the peak observed in $`\chi ^{}`$, which almost disappeared for $`H=500`$ $`Oe`$. Besides this suppression, the peak position is shifted to higher temperatures at higher fields. On the other hand, the peak for YRu-1212 present a much weaker dependence with the applied field and it is slightly shifted to lower temperatures with the increase of $`H`$. Another important difference between LnRu-1222 samples and the YRu-1212 one is the presence of an anomaly in the susceptibility at $`T_M=150`$ $`K`$ for LnRu-1222. Sample YRu-1212 does not present any anomaly in $`\chi ^{}`$ above $`T_p`$. This anomaly is more prominent for Y- and HoRu-1222 than for DyRu-1222, and is smeared out when the applied field is increased. It is striking that the anomaly observed in LnRu-1222 samples occurs at the same temperature, independently of Ln, and also that this temperature is close to the position of the peak observed for YRu-1212. These results are the first evidence that the peaks observed in $`\chi ^{}`$ have different origins for Ru-1222 and Ru-1212 families. In Fig. 2 we present the dc susceptibility as a function of temperature for different magnetic fields. The curves for all LnRu-1222 show a similar behavior. The field cooled (FC) measurements present a ferromagnetic-like shape, while the zero-field cooled (ZFC) curve present a well defined peak at temperatures, for $`H=50`$ $`Oe`$, $`T_p=83.7,`$ $`101.8`$ and $`140.8`$ K for Dy-, Ho- and YRu-1222 respectively. The two branch apart twice, one at $`T_M150`$ $`K`$ (for all LnRu-1222 samples), and again at $`T_{irr}T_f100`$ $`K`$ (Y- and HoRu-1222) or $`84`$ $`K`$ (DyRu-1222). At $`H=50`$ $`Oe`$ the ZFC and FC curves are not exactly reversible for any temperature below $`T_M`$, so $`T_{irr}`$ is not well determined. As the applied field is increased to 500 $`Oe`$, a significant reduction in the irreversibility is observed and both, ZFC and FC curves, tend to a ferromagnetic-like behavior. The irreversibility observed at temperatures above the peak in the ZFC curve is also greatly affected by the increase of the applied field, being hardly distinguishable at $`H=500`$ $`Oe`$. Comparing the results for dc magnetization with the ac susceptibility, we observe: (1) the anomaly in $`\chi ^{}`$ occurs at the same temperature of the deviation from the paramagnetic behavior in the magnetization data (at $`T_M`$); (2) the peak position in $`\chi ^{}`$ roughly coincides with $`T_{irr}`$. The coincidence of the peak temperature in $`\chi ^{}`$ with $`T_{irr}`$, the drastic reduction of the irreversibility and the ferromagnetic-like behavior of both ZFC and FC curves with quite small applied fields, are all consistent with the expected behavior of a spin-glass system. Now we turn our attention to the YRu-1212 sample again. The ZFC/FC irreversibility is also suppressed with the increase of $`H`$, but a significant irreversibility remains present even at $`H=500`$ $`Oe`$. Also, the peak in the ZFC curve is broadened at higher $`H`$, but it do not disappear (up to 500 Oe). Once more, the behavior of the YRu-1212 is quite different from the observed for LnRu-1222, which in turn is very similar with each other.

The most clear and conclusive way to experimentally separate an antiferromagnet from a spin-glass is to probe the frequency dependence of the peak in $`\chi ^{}.`$ As can be observed in Fig. 3, the peak shifts to lower temperatures and its intensity increases as the frequency of the excitation field is decreased, for all three LnRu-1222 samples. This frequency dependence of $`\chi ^{}`$ is a typical feature of the dynamics of spin-glass systems . On the other hand, no significant changes in the peak are observed for the YRu-1212 sample, which is the expected behavior expected for an antiferromagnet. A quantitative measure of the frequency shift is obtained from $`\mathrm{\Delta }T_f/[T_f\mathrm{log}(\omega )]`$. This quantity varies in the range of 0.004 - 0.018 for spin-glass systems , while for superparamagnets  it is of the order of 0.3. From the FC susceptibility measurements at different frequencies, presented in Fig. 3, we could estimate $`\mathrm{\Delta }T_f/[T_f\mathrm{log}(\omega )]0.0031,`$ 0.0021 and , 0.0018 respectively for $`Dy`$, $`Ho`$ and $`YRu1222`$, which is slightly low but yet consistent with expected behavior for spin-glasses.

There are basically two different possible interpretations of the spin-glass freezing: the first one assumes the existence of a true equilibrium phase transition at a finite temperature (canonical spin glasses ). The second interpretation assumes the existence of magnetic clusters and, in this case, the freezing is a nonequilibrium phenomenon . For isolated clusters (superparamagnets), the frequency dependence of their freezing temperature (in this context more correctly referred as blocking temperature) has been predicted to follow an Arrhenius law

$$\omega =\omega _0\mathrm{exp}[E_a/k_BT_f],$$
(1)
where $`E_a`$ is the potential barrier which separates two easy orientations of the cluster and $`\omega `$ is the driving frequency of the $`\chi _{ac}`$ measurement. However, for magnetically interacting clusters, a Vogel-Fulcher law has been proposed, which has the form:

$$\omega =\omega _0\mathrm{exp}[E_a/k_B(T_fT_0)],$$
(2)
where $`T_0`$ can be viewed as a phenomenological parameter which describes the intercluster interactions. Equation 2 implies a linear dependence of the freezing temperature with $`1/\mathrm{ln}[(\omega \tau _0)^1],`$ $`\tau _0=1/\nu _0=2\pi /\omega _0.`$ In Fig. 4 we present Vogel-Fulcher plots for the three LnRu-1222 samples, which shows that our data follows the expected linear behavior. From the best linear fit we obtained $`\nu _01\times 10^{12}`$ $`Hz`$, $`T_0=83.14,`$ 99.83, $`98.80`$ $`K`$ and $`E_a=90.25,`$ 74.35, 58.38 $`K`$ for $`Dy`$, $`Ho`$ and $`YRu1222`$, respectively.

Also, the existence of the spin-glass behavior has been checked through the measurement of its remanent magnetization. The remanent state can be achieved by two different procedures. The first one consists on cooling the sample in a certain magnetic field H from $`T>>T_f`$ down to the measurement temperature. After the temperature is stabilized the applied field is removed and the measurement is performed. This procedure gives us the thermoremanent magnetization (TRM). In the spin-glass case, the TRM quickly reaches its saturation value for low values of H. The second way to measure the remanence is to cool the sample in zero field down to the measurement temperature, and only after that a magnetic field H is turned on. After a short time the field is removed (the temperature remains constant) and the measurement is performed. This provides the isothermal remanent magnetization (IRM), which saturates at a higher H than the observed for the TRM. Both TRM and IRM coincide in the saturated region . Fig. 5 shows both TRM and IRM measurements for the three LnRu-1222 and the YRu-1212 samples. For the TRM experiments, all curves present an abrupt increase at lower fields, going through a small maximum just before reaching its saturation, while the IRM experiments, all curves present a much more gentle increase up to the saturation value. These results are in agreement with the expected behavior of a spin-glass, as exposed above. The TRM and IRM results for the YRu-1212 sample present a less pronounced dependence on the applied field, although it also increases with $`H`$.

## IV Discussion

The results presented in the previous section strongly support that all LnRu-1222 studied samples present a spin-glass transition at $`T_f`$, while the YRu-1212 sample is an antiferromagnet with spin canting. Once the magnetic behavior of the studied samples has been established, we have now to compare the different results obtained for each sample. This is done in two steps. First we compare the results for the LnRu-1222 to check for possible influences of the specific Ln ion on the spin-glass properties of the sample. A second and more important discussion is to find out why Ru-1222 and Ru-1212 present so distinct magnetic properties. In order to start these discussions, it is useful to review the crystallographic structure of both systems.

The structure of $`RuSr_2LnCu_2O_{8\delta }`$ (LnRu-1212) is derived from that of $`REBa_2Cu_3O_{7\delta }`$ (usually known as RE-123; in a more general categorization scheme , it is written as $`CuBa_2RECu_2O_{7\delta },Cu1212`$). To go from the former to the last structure, it is necessary to replace the $`Cu`$ in the charge reservoir by $`Ru,`$ thus transforming the $`CuO`$ chains in $`RuO_2`$ planes, and the $`Ba`$ ions are substituted by $`Sr`$. The structure of $`RuSr_2(Ln,Ce)_2Cu_2O_{10\delta }`$ (LnRu-1222), on the other hand, results from that of LnRu-1212 when a three-layer fluorite-type block $`(Ln,Ce)O_2(Ln,Ce)`$ substitutes the oxygen-free $`Ln`$ layer, between the two adjacent $`CuO_2`$ planes. It is believed that in rutheno-cuprates the $`RuO_6`$ octahedra in the charge reservoir are mainly responsible for both the magnetic ordering and the hole doping of the superconductive $`CuO_2`$ planes, while the $`Ln`$ ions do not order magnetically. The paramagnetic contribution of magnetic $`Ln`$ ions is usually associated to the increase of the magnetization observed at low temperatures in these systems. Then it is clear that the $`Ln`$ layer plays a less important role in determining the magnetic ordering in these ruthenates. In fact, it could be inferred from the data presented in Figs. 1 - 5 that the change of the $`Ln`$ ion did not change qualitatively the magnetic behavior of the LnRu-1222 samples. However, a few differences between them can be pointed, the more obvious of them being the variation of the freezing temperature as one goes from Ho to Dy or Gd . As shown in Fig. 6, this is related to the changes of the volume of the unit cell, due to the different ionic radii of the $`Ln`$ ions. In the same figure is also plotted $`T_M`$ which is almost constant for the samples studied in this work but, for the GdRu-1222 sample previously studied, the value of $`T_M`$ is much higher . Remembering that the GdRu-1222 sample was prepared by a different technique , it is more likely that this difference is a consequence of the synthesis process than an intrinsic effect of the different $`Ln`$ ions. Also, it is observed that the irreversibility observed in ZFC/FC magnetization curves at temperatures $`T_f<T<T_M`$ is quite small for GdRu-1222 and becomes more prominent as smaller $`Ln`$ ions are considered. Both, different ionic radii and synthesis process, seem to be important in the determination of this irreversibility.

A more intriguing question to be answered is why all Ru-1222 samples we have studied present a clear spin-glass behavior while the YRu-1212 sample is an antiferromagnet. This is intriguing because the differences between both structures are restricted just to the $`Ln`$ plane, which is isolated from the RuO2 planes which order magnetically, as already discussed. Therefore, it seems probable that the $`Ln`$ plane would affect the magnetic behavior of the compound by indirectly affecting the RuO2 planes. In order to produce a spin-glass state it is necessary to have a frustration of the magnetic order, which is accomplished by disorder. One could first try to find this randomness in the mixing of $`Ce`$ and $`Ln`$, which is only present in the Ru-1222 family. A random distribution of $`Ln`$ could cause small local perturbations in the crystalline structure in such a way that the RuO6 could be distorted, thus inducing the frustration of Ru magnetic moments. A more likely and simple explanation would come from oxygen non-stoichiometry, which could directly affect the RuO2 planes. The different magnetic behavior of the two families (Ru-1212 and Ru-1222) could only be explained if the Ru-1222 system are more susceptible to present oxygen vacancies than the Ru-1212 family. In fact, a work recently reported  concludes that GdRu-1212 can be obtained with a near stoichiometric oxygen content, while the GdRu-1222 phase is clearly oxygen-deficient even after 100-atm O2 annealing. Changes observed in the valence of Ru in GdRu-1222 as the oxygen content varies suggest that the vacancies occur in the RuO2 layers. The same work also shown that the oxygen content in GdRu-1212 is almost constant upon various annealings, while for GdRu-1222 a wider range in oxygen content is accessible. These results lead us to conclude that the most reasonable origin for the glassy behavior observed in our LnRu-1222 samples is the presence of oxygen vacancies. If this is true, our results show in a quite dramatic way the influence of the exact oxygen content of the sample. It is likely that some of the contradictory results reported on Ru-1222 in the literature are consequences of the difficulty to fully oxygenate samples of the Ru-1222 system. Although we do not observed any indication of a spin glass phase in the studied YRu-1212, we believe that degraded, oxygen-depleted Ru-1212 may also present a glassy behavior. It is important to notice that the samples we have studied in this work (as well as the GdRu-1222 sample, reported in Ref. ) were synthesized by routes which allow a higher oxygen content than more usual procedures.

## V Concluding Remarks

In summary, in this work we show that the frequency-dependent peak observed in the temperature dependence of the ac susceptibility $`\chi _{ac}`$, its suppression by a small magnetic field, combined with the remanent magnetization results, provide strong evidence of the existence of a spin glass phase over a significant temperature range in polycrystalline LnRu-1222. This is valid for samples with different $`Ln`$ and prepared by two different routes (considering also the GdRu-1222 sample, previously reported ), indicating that the glassy behavior is a characteristic feature of the Ru-1222 family. This is to be contrasted with the existence of long-range antiferromagnetic order with spin canting for the YRu-1212 sample. We believe that oxygen vacancies could frustrate the long-range order of the Ru spins, leading to a spin glass phase. Recent results pointing that the Ru-1222 phase is usually oxygen deficient, while the Ru-1212 family can be synthesized with near stoichiometric oxygen content, corroborate this idea and provide a possible explanation for the different behavior we found for these two families.

This work was supported by Brazilian agencies FAPESP and CNPq.

FIG. 1. Real part of the ac susceptibility as a function of temperature for different magnetic fields, for all four samples. Insets show the anomaly observed (in LnRu-1222 samples only) at $`T_f<T<T_M.`$

FIG. 2. dc magnetization as a function of temperature for different magnetic fields, for all four samples. Insets show the irreversibility observed (in LnRu-1222 samples only) at $`T_f<T<T_M.`$

FIG. 3. Real part of the ac susceptibility as a function of temperature for $`H=50`$ Oe and four different frequencies, for all four samples. The peak position defines the freezing temperature $`T_f`$ (for the $`LnRu1222`$ samples).

FIG. 4. Variation of the freezing temperature $`T_f`$ with the frequency of the ac field in a Vogel-Fulcher plot, for the three LnRu-1222 samples. The solid line is the best fit of Eq. 2.

FIG. 5. Thermoremanent magnetization (TRM, solid symbols) and isothermal remanent magnetization (IRM, open symbols) for all samples, measured as a function of the applied field, at $`T=30`$ K.

FIG. 6. Variation of the freezing temperature $`T_f`$ and of the magnetic transition $`T_M`$ as a function of the volume of the unit cells for LnRu-1222 compounds. The results for GdRu-1222 were extracted from Ref. .


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# Transition temperatures and contact angles in the sequential-wetting scenario of 𝑛-alkanes on (salt) water

## 1. Introduction

In recent experiments, $`n`$-alkanes of medium chain length (pentane, hexane, and heptane) have been observed to undergo two, instead of just one, changes of the wetting state when they are deposited on (salt) water and the temperature is raised subsequently . At sufficiently low temperature, the deposited liquid alkane, which is at coexistence with its vapor, forms discrete droplets on the surface of the substrate. These droplets make a non-zero contact angle with the substrate surface and, for volatile substances like alkanes of relatively low molecular weight, are interconnected only by a molecularly thin film. This state is referred to as partial wetting. At high enough temperatures, on the other hand, there will be a macroscopically (in principle, infinitely) thick film of liquid alkane covering the (salt) water surface completely. The contact angle in this so-called complete-wetting state is exactly zero. The transition between these two states can, in general, occur in two qualitatively different fashions: at a first-order transition, one observes an abrupt change of the film thickness from microscopic to macroscopic values; likewise, the contact angle $`\theta `$, which becomes smaller with increasing temperature, vanishes and, in doing so, its derivative with respect to temperature displays a square-root singularity of the form $`d\theta /dT\left(T_wT\right)^{1/2}`$, where $`T_w`$ denotes the wetting-transition temperature. In the second and much rarer case, the film thickness diverges continuously on approach of the wetting temperature . This type of wetting transition is, therefore, referred to as being continuous or ‘critical’. Although predicted earlier from theoretical considerations , it had escaped experimental observation until recently. For an $`n`$-nonane/methanol mixture, for which the wetting transition temperature is very close to the consolute point, so that bulk fluctuations become important, a logarithmic divergence of the film thickness on approaching $`T_w`$ has been observed , as well as a vanishing of the contact angle according to the power law $`1\mathrm{cos}\theta (T_wT)^{2\alpha _s}`$, with $`\alpha _s`$ being the surface specific heat exponent and having a numerical value of $`0.2\pm 0.3`$, which is compatible with short-range critical wetting ($`\alpha _s=0`$, implying $`\theta \left(T_wT\right)`$), but not with first-order wetting ($`\alpha _s=1`$). In the case of long-range critical wetting, in contrast, which was observed first for pentane on water, one finds a power-law divergence of the film thickness of the form $`l\left(T_wT\right)^1`$  (and the contact angle vanishes according to $`\theta \left(T_wT\right)^{3/2}`$, corresponding to a surface specific heat exponent of $`\alpha _s=1`$). This behavior follows from the leading terms of the tails of the long-range forces between substrate and adsorbate .

By now, it has become apparent that such a long-range critical wetting transition is a generic feature of all $`n`$-alkanes of medium chain length on water or brine, respectively . Salt was originally added to the aqueous substrate to decrease the wetting temperature in such a way that the transition occurs in the experimentally accessible range of $`080^{}`$C, i.e. for experimental convenience , but the cases in which brine, rather than pure water, is the substrate seem to be more relevant in industrial and environmental situations of practical interest, for example in secondary oil recovery .

The occurrence of long-range critical wetting in systems of alkane on (salt) water gives rise to another peculiar feature: the transition from partial to complete wetting takes place in two steps instead of just one!  As mentioned above, the true wetting transition to complete wetting is continuous and brought about by long-range forces between substrate and adsorbate, which change their nature from inhibiting complete wetting to supporting it at this temperature, $`T_{w,c}`$. This critical transition, however, is preceded by a first-order transition at a lower temperature, $`T_{w,1}`$, at which the film thickness shows an abrupt increase from being molecularly thin to a mesoscopic value (6–15 nm) . Accordingly, the temperature-derivative of the contact angle shows a finite discontinuity (while $`\theta `$ itself is a continuous function of $`T`$) at $`T_{w,1}`$ , which would be (very close to) the first-order wetting transition temperature if the long-range forces did not oppose complete wetting, i.e. the formation of a macroscopic wetting layer, at this lower temperature. The occurrence of such a transition, the first-order nature of which is corroborated by the experimentally observed hysteresis in the film thickness , is attributable to the short-range parts of the forces, as taken into account in Cahn’s original theory of wetting transitions .

For the intermediate state, in which a film of mesoscopic thickness is present, the term ‘frustrated-complete wetting’ has been coined . For a typical film thickness of 100 Å, the contact angle of the droplets that sit on top of this layer is very small ($`<1^{}`$), indicating that this state is energetically very close to complete wetting . In this state, the efficiency of oil recovery by drainage from a model reservoir is also similar to that from a system in the complete wetting state . On grounds of dynamic arguments, however, one expects considerable differences to the flow in a system with a truly macroscopic wetting layer . Therefore, accurate knowledge of both transition temperatures is highly desirable.

In the next section, we will outline the main features of a complete and consistent mean-field theory of the wetting behavior of $`n`$-alkanes of medium chain length (pentane and hexane) on pure water and on brine, respectively, for various concentrations of salt. In section 3, we will compare the results of our theory to experimental findings and predict the transition temperatures and contact angles for systems for which these properties have not been measured yet. Section 4 concludes the paper, assesses the current state of the theory and experiments on the sequential wetting of $`n`$-alkanes on aqueous substrates and briefly outlines plans for future investigations.

## 2. Methodology

The wetting state, in which a system consisting of three phases (the substrate ($`s`$), which may be solid or liquid, the liquid ($`l`$) phase of the adsorbate and vapor ($`v`$)) is present, is determined by the interfacial tensions between the three pairs of them, which we denote by $`\gamma _{sl}`$, $`\gamma _{sv}`$ and $`\gamma _{lv}`$. According to Young’s law, the contact angle is given by $`\gamma _{sv}\gamma _{sl}=\gamma _{lv}\mathrm{cos}\theta `$. In the partial-wetting state, $`\gamma _{sv}<\gamma _{sl}+\gamma _{lv}`$ and, therefore, $`\theta >0`$, while for complete wetting, the $`sv`$-interface is replaced an $`sl`$-interface and an $`lv`$-interface and, accordingly, Antonow’s rule $`\gamma _{sv}=\gamma _{sl}+\gamma _{lv}`$ holds. The contact angle is then zero. In the special case of sequential wetting, the ultimate transition to complete wetting, which occurs at $`T_{w,c}`$, is determined by the location at which the Hamaker constant changes sign, i.e. where the leading term of the algebraic tails of the long-range forces starts to favor having a thick wetting layer on top of the substrate, instead of opposing the formation of such a layer, which keeps the system in the frustrated complete wetting state for $`T_{w,1}TT_{w,c}`$. The first-order transition between a thin and a mesoscopically thick film, however, is not a true wetting transition. Its location is determined mainly by short-range forces , but the long-range tails, which are treated perturbatively in our approach, make a quantitative difference . $`T_{w,1}`$ is found by comparing the interfacial free energies of the situations corresponding to having only a molecularly thin film present in the density profile of an $`sv`$-interface and to having a mesoscopically thick film – only one of these two will be stable, the other just metastable, except for right at $`T_{w,1}`$, where both are equal in free energy per unit area (coexistence of thin and thick film).

To calculate the interfacial tensions, we employ a modified Cahn theory augmented for algebraically decaying long-range forces, which are treated in a perturbative fashion. The free-energy functional, which is to be minimized with respect to the density profile of the adsorbate, $`\rho (z)`$, reads :

$`\gamma [\rho ]`$ $`=`$ $`\gamma _0+\varphi (\rho _0)+{\displaystyle \underset{\mathrm{\Delta }z}{\overset{\mathrm{}}{}}}\left\{\mathrm{\Delta }f(\rho ,\rho _{bulk})+{\displaystyle \frac{c}{2}}\left({\displaystyle \frac{d\rho }{dz}}\right)^2\right\}𝑑z`$ (1)
$`+\left\{\mathrm{\Delta }f(\rho _0,\rho _{bulk})+{\displaystyle \frac{c}{2}}\left[(\rho _0\rho _1)/\mathrm{\Delta }z\right]^2\right\}\mathrm{\Delta }z`$
$`{\displaystyle \underset{z_c}{\overset{\mathrm{}}{}}}\left({\displaystyle \frac{a_3}{z^3}}+{\displaystyle \frac{a_4}{z^4}}\right)\rho (z)𝑑z{\displaystyle \underset{z_c}{\overset{\mathrm{}}{}}}\left({\displaystyle \frac{a_3^{}}{(z+\delta )^3}}+{\displaystyle \frac{a_4^{}}{(z+\delta )^4}}\right)\rho (z)𝑑z`$
$`{\displaystyle \frac{a_3^{}}{\delta ^3}}\rho _0\mathrm{\Delta }z.`$
The first three terms are the ingredients of standard Cahn theory (with $`\mathrm{\Delta }z=0`$) : the first one describes the surface tension of the substrate against vacuum; it is irrelevant to the wetting properties and no value for it needs to be specified. In the second term, $`\varphi `$ denotes the so-called contact energy, which describes the short-range interaction between the substrate and the adsorbate; therefore, it only depends on the density of the adsorbate right at the substrate surface, $`\rho (0)=\rho _0`$. The $`z`$-axis is chosen perpendicular to the substrate surface and only the half space $`z0`$, in which the adsorbate is present, is considered explicitly. $`\varphi \left(\rho _0\right)`$ is usually represented in a quadratic form: $`\varphi \left(\rho _0\right)=h_1\rho _0g\rho _0^2/2`$; the coefficients $`h_1`$ and $`g`$ can be deduced from measurements of the surface pressure . The third term concerns the cohesive properties of the adsorbate, like in the classical theory of the liquid–vapor interfacial tension of van der Waals : $`\mathrm{\Delta }f(\rho ,\rho _{bulk})`$, to be calculated from the Peng–Robinson equation of state in this case, measures the excess free energy of locally having a density $`\rho (z)`$ over having either of the bulk densities $`\rho _{bulk}`$; the second term in the integral is the square-gradient term, which penalizes inhomogeneities of the density. The coefficient $`c`$ is the influence parameter and is obtained by matching the computed liquid–vapor interfacial tensions to experimental results . In the modified Cahn theory, these two terms are to be integrated over from $`\mathrm{\Delta }z`$ to infinity, instead of integrating from zero to infinity as in standard Cahn theory . The first layer of adsorbed alkane molecules, which is of molecular thickness ($`\mathrm{\Delta }z=\sigma `$, the diameter of an adsorbate molecule) is treated in a lattice-gas approach, ensuring that states of low adsorption are properly accounted for . This discretized version of Cahn theory yields the next term in Eq. (1) – its ingredients are otherwise the same as in the continuum version. For brevity, the density at a distance of one molecular diameter from the substrate surface is denoted by $`\rho _1=\rho (\mathrm{\Delta }z)`$.

The last three terms on the right-hand side of Eq. (1) incorporate the long-range interaction into the free-energy functional. The underlying picture of the system in the computation of the long-range contribution is a five-layer structure : even if the substrate is brine, there is a thin layer of pure water (the so-called depletion layer) at the brine/alkane interface , so that it is always pure water that is in direct contact with the adsorbed alkane. A third (conceptual) medium is formed by the dense liquid layer of adsorbed alkane molecules which are in direct contact with the aqueous substrate . Moving away from the substrate surface, this layer is followed by the bulk liquid alkane and, ultimately, by the vapor phase. While the brine and the vapor phases are semi-infinite, the pure-water layer is of thickness $`\delta `$ (to be identified with the hydration radius of an ion ), the first layer of adsorbed dense liquid alkane has a spatial extent of one molecular diameter $`\sigma =\mathrm{\Delta }z`$, and the film thickness of liquid alkane is denoted by $`l`$.

For pure water as the substrate, the last two terms in Eq. (1) vanish. The first of the three terms of the long-range field decribes the interaction between the water layer and the adsorbate; the cutoff $`z_c`$ is numerically very close to $`1.5\sigma `$, the distance of closest approach of adsorbate particles that are not part of the first layer. The second integral concerns the long-range interactions between brine and the adsorbate across the intervening water layer of thickness $`\delta `$, which is reflected by having $`(z+\delta )`$ instead of just $`z`$ in the denominators of the first couple of leading terms taken into account here. The last term in Eq. (1) contains the remaining contribution which arises from the interaction of brine with the first layer of adsorbed alkane molecules – this interaction is not included in the preceding term since $`z_c>\sigma `$.

The amplitudes of the tails of the long-range field, $`a_3`$, $`a_4`$, $`a_3^{}`$ and $`a_4^{}`$ are calculated from a five-layer Dzyaloshinskii–Lifshitz–Pitaevskii theory that invokes Israelachvili’s simplifications to the dielectric spectrum , which allows one to obtain the long-range field from the static dielectric permittivities, $`\epsilon _j(0)`$, the indices of refraction, $`n_j`$, and a common characteristic UV absorption frequency of the different media. The explicit formulas for the amplitudes can be found in the more detailed article .

The current theory offers a complete and consistent description of the wetting behavior of $`n`$-alkanes on water or brine, as we will show in the next section.

## 3. Results and discussion

We employ the theory outlined in the preceding section to calculate the transition temperatures as a function of the salinity of the substrate and contact angles as a function of temperature in the sequential wetting of $`n`$-alkanes, namely pentane and hexane, on salt water. Figure 1 shows the calculated first-order and critical transition temperatures for pentane and hexane, respectively, on brine in the concentration range $`0c_{\mathrm{NaCl}}2.5`$ mol/L. The experimental points for the respective transition temperatures for hexane on brine  and for pentane on water  are indicated by open symbols. The overall agreement is very good, indicating that the theory incorporates the most important effects that lead to sequential wetting even quantitatively. Note that the first-order transition temperatures for pentane on brine are below the freezing point of the substrate for $`c_{\mathrm{NaCl}}>2.1`$ mol/L. Furthermore, it is seen that, within the theory, the line of first-order transition temperatures is almost parallel to the line of critical-transition temperatures for pentane on brine, too, just as it was observed experimentally for hexane on brine . An experimental check of this prediction is desirable.

To test the validity of the more or less arbitrary division of the forces acting between substrate and adsorbate into short-range and long-range parts, and of the perturbative treatment of the long-range parts, it might be useful to take a closer look at the contact angles, in particular in the frustrated-complete wetting state. In this latter state, the contact angle is very small ($`<1^{}`$), indicating that the relatively large film thickness of $`l60`$ Å is sufficient to decouple the two interfaces ($`sl`$ and $`lv`$) almost completely . In the context of the present theory, the contact angle can, asymptotically, be evaluated from the long-range part alone . To accomplish this, one uses the fact that the contact angle is related to the spreading coefficient through $`S=\gamma _{lv}(\mathrm{cos}\theta 1)`$. We consider the free-energy difference between the $`sv`$-interfaces in the complete wetting ($`cw`$) state and the frustrated-complete wetting ($`fcw`$) state, the origin of which lies completely in the range of distances between $`l`$ and infinity from the substrate. Using $`S_{cw}=0`$ and the fact that $`\rho (z)`$ is practically equal to $`\rho _l`$ for $`cw`$, while it is almost zero (the vapor phase is very dilute) in this range for $`fcw`$, we obtain for the spreading coefficient in the $`fcw`$ state:

$$S_{fcw}=\rho _l\underset{l}{\overset{\mathrm{}}{}}\left(\frac{a_3}{z^3}+\frac{a_4}{z^4}\right)𝑑z.$$
(2)
Noting that, asymptotically for large $`l`$, the film thickness will be given by $`la_4/a_3`$, we arrive at

$$1\mathrm{cos}\theta =\frac{\rho _l}{6\gamma _{lv}}\frac{a_3^3}{a_4^2}.$$
(3)
For partial wetting, we obtain $`\theta `$ from Young’s law, explicitly calculating $`\gamma _{sv}`$, $`\gamma _{sl}`$ and $`\gamma _{lv}`$ by numerical minimization, which causes the somewhat noisy results for the contact angle in this wetting state. Figure 2 shows $`\theta `$ as a function of temperature for pentane on pure water and for hexane on brine ($`c_{\mathrm{NaCl}}=2.5`$ mol/L) . It is seen that not only the transition temperatures for these two systems are very similar, but also the contact angles. The discontinuity of $`d\theta /dT`$ is clearly visible at $`T_{w,1}`$.

In Fig. 3, we focus on the behavior of the contact angle in the frustrated-complete wetting state; in this state, our data obtained from direct numerical minimization are too noisy and, therefore, useless because the energetical differences between the $`cw`$ and $`fcw`$ states are very small. The figure shows the analytical results obtained from relation (3), which is asymptotically valid in the case $`l\mathrm{}`$. From this equation, it can also be read off that $`\theta `$ is expected to vanish as $`\theta \left(T_{w,c}T\right)^{3/2}`$; this behavior of the contact angle is, however, only seen very close to $`T_{w,c}`$.

In the partial wetting state, upon approach to $`T_{w,1}`$, the contact angle (almost, but not quite) vanishes as $`\theta \left(T_{w,1}T\right)^{1/2}`$ as expected for a true first-order wetting transition. In this case, the (effective) exponent of $`1/2`$ is seen already far from $`T_{w,1}`$.

## 4. Conclusion

It has been shown that the modified Cahn theory, augmented for long-range interactions, which is summarized in Eq. (1), can reproduce the transition temperatures in the sequential wetting of $`n`$-alkanes on (salt) water . In the present work, we also predict the transition temperatures for pentane on brine as a function of salt concentration, which have not been measured yet. In principle, the theory allows us to calculate the contact angles as well. In practice, however, due to limitations of the precision in the numerical calculation, only the contact angles in the partial wetting state can be determined reasonably reliably. For the frustrated-complete wetting state, we may still estimate the asymptotic behavior of $`\theta `$ from the contributions of the long-range interactions between substrate and adsorbate alone.

Two of the remaining theoretical tasks are the a priori calculation of the thickness of the depletion layer $`\delta `$, which we find by matching to the experimentally observed transition temperatures , and the ‘ab initio’ calculation of the contact energy, which still has to be obtained from measurements of the surface pressure of the entire system and is, thus, not yet deduced from the properties of the isolated media.

From the experimental point of view, it remains of great interest to see a realization of a critical endpoint, a point at which the line of critical wetting transitions is intercepted by the line of first-order transitions, which will be first-order wetting transitions beyond this point. The discovery of such a system would also demonstrate that the parallelism of the two lines found in the system of hexane on brine is a coincidence rather than a necessity. Measurements of the contact angle in the partial and, particularly, in the frustrated-complete wetting state might be used to test the appropriateness of the present division of the substrate–adsorbate interactions into short-range and long-range forces. The vanishing of the contact angle in the frustrated-complete wetting state on approach of $`T_{w,c}`$ is of primary interested in this respect.

## Acknowledgements

We thank Emanuel Bertrand, Daniel Bonn, Harvey Dobbs, Yan Levin, Salima Rafaï and Ben Widom for fruitful discussions. Our research has been supported by the European Community TMR Research Network ‘Foam Stability and Wetting’ under contract no. FMRX-CT98-0171, by the ‘Fonds voor Wetenschappelijk Onderzoek (F.W.O.) – Vlaanderen’ and by the Research Council (‘Onderzoeksraad’) of the KU Leuven through junior fellowship F/01/028.


text:
# Multifractality of river runoff and precipitation: Comparison of fluctuation analysis and wavelet methods

(April 5, 2003)

## Abstract

We study the multifractal temporal scaling properties of river discharge and precipitation records. We compare the results for the multifractal detrended fluctuation analysis method with the results for the wavelet transform modulus maxima technique and obtain agreement within the error margins. In contrast to previous studies, we find non-universal behaviour: On long time scales, above a crossover time scale of several months, the runoff records are described by fluctuation exponents varying from river to river in a wide range. Similar variations are observed for the precipitation records which exhibit weaker, but still significant multifractality. For all runoff records the type of multifractality is consistent with a modified version of the binomial multifractal model, while several precipitation records seem to require different models.

, , , , , , , and

The analysis of river flows has a long history. Already more than half a century ago the engineer H. E. Hurst found that runoff records from various rivers exhibit ’long-range statistical dependencies’ . Later, such long-term correlated fluctuation behaviour has also been reported for many other geophysical records including precipitation data , see also . These original approaches exclusively focused on the absolute values or the variances of the full distribution of the fluctuations, which can be regarded as the first moment $`F_1(s)`$  and the second moment $`F_2(s)`$ , respectively. In the last decade it has been realized that a multifractal description is required for a full characterization of the runoff records . Accordingly, one has to consider all moments $`F_q(s)`$ to fully characterize the records. This multifractal description of the records can be regarded as a ’fingerprint’ for each station or river, which, among other things, can serve as an efficient non-trivial test bed for the state-of-the-art precipitation-runoff models.

Since a multifractal analysis is not an easy task, especially if the data are affected by trends or other non-stationarities, e.g. due to a modification of the river bed by construction work or due to changing climate, it is useful to compare the results for different methods. We have studied the multifractality by using the multifractal detrended fluctuation analysis (MF-DFA) method  (see also ) and the well established wavelet transform modulus maxima (WTMM) technique  and find that both methods yield equivalent results. Both approaches differ from the multifractal approach introduced into hydrology by Lovejoy and Schertzer .

We analyze long daily runoff records $`\{W_i\}`$ from six international hydrological stations and long daily precipitation records $`\{P_i\}`$ from six international meteorological stations. The stations are representative for different rivers and different climate zones, as we showed in larger separate studies . As a representative example, Fig. 1 shows three years of the runoff record of the river Danube (a) and of the precipitation recorded in Vienna (b). It can be seen that the precipitation record appears more random than the runoff record. To eliminate the periodic seasonal trend, we concentrate on the departures $`\varphi _i=W_i\overline{W}_i`$ (and $`\varphi _i=P_i\overline{P}_i`$) from the mean daily runoff $`\overline{W}_i`$. $`\overline{W}_i`$ is calculated for each calendar date $`i`$, e.g. 1st of April, by averaging over all years in the record.

In the MF-DFA procedure , the moments $`F_q(s)`$ are calculated by (i) integrating the series, (ii) splitting the series into segments of length $`s`$, (iii) calculating the mean-square deviations $`F^2(\nu ,s)`$ from polynomial fits in each segment, (iv) averaging $`[F^2(\nu ,s)]^{q/2}`$ over all segments, and (v) taking the $`q`$th root. In the paper, we have used third order polynomials in the fitting procedure of step (iii) (MF-DFA3), this way eliminating quadratic trends in the data. We consider both, positive and negative moments $`F_q(s)`$ ($`q`$ ranges from $`10`$ to $`+10`$) and determine them for time scales $`s`$ between $`s=5`$ and $`s=N/5`$, where $`N`$ is the length of the series. Figure 2 shows the results (filled symbols) for two representative hydrological stations. On large time scales, above a crossover occurring around 30-200 days, we observe a power-law scaling behaviour,

$$F_q(s)s^{h(q)},$$
(1)
where the scaling exponent $`h(q)`$ (the slope in Fig. 2) explicitly depends on the value of $`q`$. This behaviour represents the presence of multifractality.

In order to test the MF-DFA approach we have applied the well-established WTMM technique, which is also detrending but based on wavelet analysis instead of polynomial fitting procedures. For a full description of the method, we refer to . First, the wavelet-transform $`T(n,s^{})=\frac{1}{s^{}}_{i=1}^N\varphi _ig[(in)/s^{}]`$ of the departures $`\varphi _i`$ is calculated. For the wavelet $`g(x)`$ we choose the third derivative of a Gaussian here, $`g(x)=d^3(e^{x^2/2})/dx^3`$, which is orthogonal to quadratic trends. Now, for a given scale $`s^{}`$, one determines the positions $`n_i`$ of the local maxima of $`|T(n,s^{})|`$, so that $`|T(n_i1,s^{})|<|T(n_i,s^{})||T(n_i+1,s^{})|`$. Then, one obtains the WTMM partition sum $`Z_q(s^{})`$ by averaging $`|T(n_i,s^{})|^q`$ for all maxima $`n_i`$. An additional supremum procedure has to be used in the WTMM method in order to keep the dependence of $`Z(q,s^{})`$ on $`s^{}`$ monotonous . The expected scaling behaviour is $`Z(q,s^{})(s^{})^{\tau (q)}`$, where $`\tau (q)`$ are the Renyi exponents. Since $`\tau (q)`$ is related to the exponents $`h(q)`$ by $`h(q)=[\tau (q)+1]/q`$  we have plotted

$$[sZ(q,s/8)]^{1/q}s^{[\tau (q)+1]/q}s^{h(q)}.$$
(2)
We set $`s^{}=s/8`$ in the comparison with the MF-DFA results, since the wavelet we employ can be well approximated within a window of size $`8s^{}`$ (i.e. within 4 standard deviations on both sides), and this window size corresponds to the segment length $`s`$ in the MF-DFA. Figure 2 shows that both methods yield equivalent results for the $`q`$ values we considered.

Using the MF-DFA results, we have determined $`h(q)`$ from Eq. (1) for all runoff records and all precipitation records and for several values of $`q`$. Since a crossover occurs in $`F_q(s)`$ for time scales in the range of 30-200 days, we considered only sufficiently long time scales (above one year), where the results scale well. Figure 3 shows $`h(q)`$ for the runoff data, while Fig. 4 shows $`h(q)`$ for the precipitation data. Together with the results we show least-square fits according to the formula

$$h(q)=\frac{1}{q}\frac{\mathrm{ln}[a^q+b^q]}{q\mathrm{ln}2},$$
(3)
which corresponds to $`\tau (q)=\mathrm{ln}[a^q+b^q]/\mathrm{ln}2`$ and can be obtained from a generalized binomial multifractal model , see also . The values of the two parameters $`a`$ and $`b`$ are also reported in the figures. The results for all rivers can be fitted surprisingly well with only these two parameters (see Fig. 3). Instead of choosing $`a`$ and $`b`$, we could also choose the Hurst exponent $`h(1)`$ and the persistence exponent $`h(2)`$. From knowledge of two moments, all the other moments follow.

This surprising result does not hold for the precipitation records. As can be seen in Figs. 4(c) and 4(f) there are stations where Eq. (3) cannot describe the multifractal scaling behaviour reasonably well. According to Rybski et al., Eq. (3) is appropriate only for about 50 percent of the precipitation records .

In the generalized binomial multifractal model, the strength of multifractality is described by the difference of the asymptotical values of $`h(q)`$, $`\mathrm{\Delta }\alpha h(\mathrm{})h(\mathrm{})=(\mathrm{ln}b\mathrm{ln}a)/\mathrm{ln}2`$. We note that this parameter is identical to the width of the singularity spectrum $`f(\alpha )`$ at $`f=0`$. Studying 41 river runoff records , we have obtained an average $`\mathrm{\Delta }\alpha =0.49\pm 0.16`$, which indicates rather strong multifractality on the long time scales considered. For the precipitation records, on the other hand, the multifractality is weaker. The average is $`\mathrm{\Delta }\alpha =0.29\pm 0.14`$ for 83 records .

Our results for $`h(q)`$ may be compared with the different ansatz $`h(q)=1+H^{}C_1(q^{\alpha ^{}1}1)/(\alpha ^{}1)`$ with the three parameters $`H^{}`$, $`C_1`$, and $`\alpha ^{}`$ (LS ansatz), that has been used by Lovejoy, Schertzer, and coworkers  successfully to describe the multifractal behaviour of rainfall and runoff records for $`q>0`$. A quantitative comparison between both methods is inhibited, since here we considered only long time scales and used detrending methods. We like to note that formula (3) for $`h(q)`$ is not only valid for positive $`q`$ values, but also for negative $`q`$ values. We find it remarkable, that for the runoff records only two parameters were needed to fit the data. For the precipitation data, one needs either three parameters like in the LS ansatz or different schemes.

In summary, we have analyzed long river discharge records and long precipitation records using the multifractal detrended fluctuation analysis (MF-DFA) and the wavelet transform modulus maxima (WTMM) method. We obtained agreement within the error margins and found that the runoff records are characterized by stronger multifractality than the precipitation records. Surprisingly, the type of multifractality occurring in all runoff records is consistent with a modified version of the binomial multifractal model, which supports the idea of a ’universal’ multifractal behaviour of river runoffs suggested by Lovejoy and Schertzer. In contrast, according to , several precipitation records seem to require a different description or a three-parameter fit like the LS ansatz. The multifractal exponents can be regarded as ’fingerprints’ for each station. Furthermore, a multifractal generator based on the modified binomial multifractal model can be used to generate surrogate data with specific properties for each runoff record and for some of the precipitation records.

Acknowledgments: We would like to thank the German Science Foundation (DFG), the German Federal Ministry of Education and Research (BMBF), the Israel Science Foundation (ISF), and the Minerva Foundation for financial support. We also would like to thank H. Österle for providing some of the observational data.


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# Relative phase between strong and electromagnetic amplitudes in 𝜓(2𝑆)→0⁻0⁻ decays

## 1 Introduction

The relative phase between the strong and the electromagnetic amplitudes of the charmonium decays is a basic parameter in understanding the decay dynamics. Studies have been carried out for many $`J/\psi `$ two-body decay modes: $`1^{}0^{}`$ , $`0^{}0^{}`$ , $`1^{}1^{}`$  and $`N\overline{N}`$ . These analyses revealed that there exists a relative orthogonal phase between the strong and the electromagnetic amplitudes in $`J/\psi `$ decays .

As to $`\psi (2S)`$, it has been argued  that the only large energy scale involved in the three-gluon decay of charmonia is the charm quark mass, one expects that the corresponding phase should not be much different between $`J/\psi `$ and $`\psi (2S)`$ decays. There is also a theoretical argument which favors the $`\pm 90^{}`$ phase . This large phase follows from the orthogonality of the three-gluon and one-photon virtual processes. But an extensively quoted work  found that a fit to $`\psi (2S)1^{}0^{}`$ with a large phase $`\pm 90^{}`$ is virtually impossible and concluded that the relative phase between the strong and the electromagnetic amplitudes should be around 180 degree***In Ref. , the phase $`\delta =0^{}`$ between the strong amplitude and the $`negative`$ electromagnetic amplitude is corresponding to the phase $`\varphi =180^{}`$ between the strong amplitude and the $`positive`$ electromagnetic amplitude here..

However, it is pointed out in Ref.  that the contribution of the continuum process via virtual photon was neglected in almost all the data analyses in $`e^+e^{}`$ experiments. By including the contribution of the continuum process, $`\psi (2S)1^{}0^{}`$ decays have been reanalyzed and it is found  that the phase of $`90^{}`$ can not be ruled out. Unfortunately the current experimental information on $`\psi (2S)1^{}0^{}`$ decays are not precise enough to determine the phase.

For the time being the experimental information for $`\psi (2S)`$ decays is less abundant than that for $`J/\psi `$. Among the other modes used in $`J/\psi `$ decays to measure the relative phase, the only mode with experimental data in $`\psi (2S)`$ decays is the $`\psi (2S)0^{}0^{}`$ ($`i.e.`$ pseudoscalar meson pairs), including $`\psi (2S)\pi ^+\pi ^{}`$ and $`\psi (2S)K^+K^{}`$. But this is not enough to extract the phase between the strong and the electromagnetic amplitudes, since there are three free parameters, namely, the absolute values of the strong and the electromagnetic amplitudes, and the relative phase between them. Another $`0^{}0^{}`$ decay channel $`\psi (2S)K_S^0K_L^0`$ is thus needed to determine all these three parameters.

Although, as has been pointed out in Ref. , $`\psi (2S)0^{}0^{}`$ is allowed in leading-twist pQCD while $`\psi (2S)1^{}0^{}`$ is forbidden, the relative phases found in these two modes may not necessarily be the same, it is still interesting to test this since in $`J/\psi `$ decays, the phases in these two modes are found to be rather similar.

In this letter, the existing experimental data on $`\psi (2S)`$ decays to $`\pi ^+\pi ^{}`$ and $`K^+K^{}`$ are used as inputs to calculate the branching ratio of $`\psi (2S)K_S^0K_L^0`$ as a function of the relative phase. Once $`(\psi (2S)K_S^0K_L^0)`$ is known, the relative phase between the strong and the electromagnetic amplitudes in $`\psi (2S)0^{}0^{}`$ decays could be determined based on the calculations in this letter.

## 2 Theoretical framework

In $`\psi (2S)0^{}0^{}`$ decays, the G-parity violating channel $`\pi ^+\pi ^{}`$ is through electromagnetic process (the contribution from the isospin-violating part of QCD is expected to be small  and is neglected), $`K_S^0K_L^0`$ through SU(3) breaking strong process, and $`K^+K^{}`$ through both. As has been observed in $`J/\psi K_S^0K_L^0`$ , the SU(3) breaking strong decay amplitude is not small. Following the convention in Ref. , the $`\psi (2S)0^{}0^{}`$ decay amplitudes are parametrized as

$$\begin{array}{ccc}A_{\pi ^+\pi ^{}}\hfill & =& E,\hfill \\ A_{K^+K^{}}\hfill & =& E+\frac{\sqrt{3}}{2}M,\hfill \\ A_{K_S^0K_L^0}\hfill & =& \frac{\sqrt{3}}{2}M,\hfill \end{array}$$
(1)
where $`E`$ denotes the electromagnetic amplitude and $`\frac{\sqrt{3}}{2}M`$ the SU(3) breaking strong amplitude.

As has been discussed in Refs. , if $`\psi (2S)`$ is produced in $`e^+e^{}`$ experiment, the contribution of the continuum must be included in the total amplitude, that is

$$\begin{array}{ccc}A_{\pi ^+\pi ^{}}^{tot}\hfill & =& E_c+E,\hfill \\ A_{K^+K^{}}^{tot}\hfill & =& E_c+E+\frac{\sqrt{3}}{2}M,\hfill \\ A_{K_S^0K_L^0}^{tot}\hfill & =& \frac{\sqrt{3}}{2}M,\hfill \end{array}$$
(2)
where $`E_c`$ is the amplitude of the continuum contribution. Besides the common part, $`E_c`$, $`E`$ and $`\frac{\sqrt{3}}{2}M`$ can be expressed explicitly as

$$\begin{array}{ccc}E_c\hfill & & \frac{1}{s},\text{}\hfill \\ E\hfill & & \frac{1}{s}B(s),\hfill \\ \frac{\sqrt{3}}{2}M\hfill & & 𝒞e^{i\varphi }\frac{1}{s}B(s),\hfill \end{array}$$
(3)
where the real parameters $`\varphi `$ and $`𝒞`$ are the relative phase and the relative strength between the strong and the electromagnetic amplitudes, and $`B(s)`$ is defined as

$$B(s)=\frac{3\sqrt{s}\mathrm{\Gamma }_{ee}/\alpha }{sM_{\psi (2S)}^2+iM_{\psi (2S)}\mathrm{\Gamma }_t}.$$
(4)
Here $`\sqrt{s}`$ is the center of mass energy, $`\alpha `$ is the QED fine structure constant; $`M_{\psi (2S)}`$ and $`\mathrm{\Gamma }_t`$ are the mass and the total width of $`\psi (2S)`$; $`\mathrm{\Gamma }_{ee}`$ is the partial width to $`e^+e^{}`$.

The Born order cross sections for the three channels are thus

$`\sigma _{\pi ^+\pi ^{}}^{Born}(s)={\displaystyle \frac{4\pi \alpha ^2}{s^{3/2}}}[1+2\mathrm{}B(s)+|B(s)|^2]`$ (5)
$`\times |_\pi (s)|^2𝒫_{\pi ^+\pi ^{}}(s),`$
$`\sigma _{K^+K^{}}^{Born}(s)={\displaystyle \frac{4\pi \alpha ^2}{s^{3/2}}}[1+2\mathrm{}(𝒞_\varphi B(s))+|𝒞_\varphi B(s)|^2]`$ (6)
$`\times |_\pi (s)|^2𝒫_{K^+K^{}}(s),`$
$$\sigma _{K_S^0K_L^0}^{Born}(s)=\frac{4\pi \alpha ^2}{s^{3/2}}𝒞^2|B(s)|^2|_\pi (s)|^2𝒫_{K_S^0K_L^0}(s),$$
(7)
where $`_\pi (s)`$ is the pion form factor and the phase space factor $`𝒫_f(s)`$ ($`f=\pi ^+\pi ^{},K^+K^{},K_S^0K_L^0`$) is expressed as

$$𝒫_f(s)=\frac{2}{3s}q_f^3,$$

with $`q_f`$ the momentum of the final state particle in two-body decay. The symbol $`𝒞_\varphi 1+𝒞e^{i\varphi }`$ is introduced for briefness.

For the measurement of the narrow resonance like $`J/\psi `$ and $`\psi (2S)`$ in $`e^+e^{}`$ experiment, the radiative correction and the energy spread of the collider must be considered in the calculation of the observed cross sections. In fact, the observed cross sections and the proportions of the contributions from resonance and continuum depend sensitively on the experiment conditions . For $`\psi (2S)`$ decays to $`\pi ^+\pi ^{}`$ and $`K^+K^{}`$, the contributions of the continuum, as well as interference terms, must be subtracted from the total cross sections to obtain the correct branching ratios. For $`K_S^0K_L^0`$ mode, there is no continuum contribution. Although the observed $`K_S^0K_L^0`$ cross section depends on the energy spread, the branching ratio is simply the observed $`K_S^0K_L^0`$ cross section divided by the total resonance cross section. The formulae to calculate the experimentally observed cross section are presented in Ref. . In the following analysis, the energy spread of different $`e^+e^{}`$ colliders, as listed in Table 1, are adopted in the corresponding calculations. In addition, it is also assumed that experimental data are taken at the energy which yields the maximum inclusive hadronic cross section .

## 3 Experimental data and predictions of $`(\psi (2S)K_S^0K_L^0)`$

Presently the experimental data on $`\psi (2S)0^{}0^{}`$ are limited. The only results which have been published are from DASP :

$$(\psi (2S)\pi ^+\pi ^{})=(8\pm 5)\times 10^5,$$
(8)
$$(\psi (2S)K^+K^{})=(10\pm 7)\times 10^5,$$
(9)
which are based on about $`0.9\times 10^6`$ produced $`\psi (2S)`$ events. The uncertainties of the measurements are more than 60% because of the small data sample.

Another attempt to measure the branching ratios of $`\psi (2S)\pi ^+\pi ^{}`$ and $`K^+K^{}`$ is based on $`2.3\times 10^6`$ $`\psi (2S)`$ data collected by BESI, the results are :

$$(\psi (2S)\pi ^+\pi ^{})=(0.84\pm 0.55_{0.35}^{+0.16})\times 10^5,$$
(10)
$$(\psi (2S)K^+K^{})=(6.1\pm 1.4_{1.3}^{+1.5})\times 10^5.$$
(11)
Here the uncertainty for $`\pi ^+\pi ^{}`$ is also considerably large, around 70%; while for $`K^+K^{}`$, the uncertainty is about 30%.

It should be emphasized that the aforementioned values without subtracting the contributions from the continuum are not the real physical branching ratios. These values should be multiplied by the experimentally measured total resonance cross section of the corresponding experiment and the products are to be interpreted as the observed cross sections of these two modes under the particular experimental condition. More detailed discussion of this point is in Ref. .

Since in both of these two experiments, the $`\pi ^+\pi ^{}`$ branching ratios have large uncertainties, and the central values differ by almost an order of magnitude, an alternative way to do the analysis is to estimate $`(\psi (2S)\pi ^+\pi ^{})`$ in terms of pion form factor extrapolated from $`(J/\psi \pi ^+\pi ^{})`$ with better precision. For this purpose, $`(J/\psi \pi ^+\pi ^{})`$ = $`(1.58\pm 0.20\pm 0.15)\times 10^4`$ from MARKIII/SPEAR  is used. Although the contribution of the continuum is small for $`J/\psi `$ decays, it is taken into account in the calculation here which yields

$$|F_\pi (M_{J/\psi }^2)|=(9.3\pm 0.7)\times 10^2.$$
(12)
Extrapolate the result by $`1/s`$ dependence  the pion form factor becomes

$$|F_\pi (s)|=\frac{(0.89\pm 0.07)\text{ GeV}\text{2}}{s}.$$
(13)
With the pion form factor in Eq. (13), for example, BESI should observe a $`\pi ^+\pi ^{}`$ cross section of 11.6 pb at $`\psi (2S)`$ energy, of which 4.8 pb is from the resonance decays (the total $`\psi (2S)`$ cross section is 640 nb).

With the input of the branching ratios of $`\pi ^+\pi ^{}`$ and $`K^+K^{}`$, the branching ratio of $`K_S^0K_L^0`$ is calculated as a function of the phase between $`E`$ and $`\frac{\sqrt{3}}{2}M`$, as solved from Eqs. (5), (6) and (7) with radiative correction and energy spread of the $`e^+e^{}`$ collider considered. Three sets of inputs are used for the calculations :

* Input 1: DASP results in Eqs. (8) and (9);
* Input 2: BESI results in Eqs. (10) and (11);
* Input 3: pion form factor from Eq. (13) and $`(\psi (2S)K^+K^{})`$ from BESI measurement in Eq. (11).

Fig. 1 shows $`(\psi (2S)K_S^0K_L^0)`$ as a function of the phase for the three sets of inputs. It could be seen that $`(\psi (2S)K_S^0K_L^0)`$ is very sensitive to the relative phase. With all three sets of inputs, the variation shows the same trend. They reach the maxima and minima at roughly the same values of the phase. With the Input 1, $`(\psi (2S)K_S^0K_L^0)`$ varies in a larger range than the other two sets of inputs. This is because the $`\pi ^+\pi ^{}`$ branching ratio from DASP is large, so the electromagnetic amplitude $`E`$ and the continuum amplitude $`E_c`$ are relatively large compared with the strong decay amplitude $`\frac{\sqrt{3}}{2}M`$, so the interference is more important. On the contrary, with the Input 2, the $`\pi ^+\pi ^{}`$ branching ratio is small from BESI experiment, which means that $`E`$ and $`E_c`$ are relatively small, so the interference is less significant.

Table 2 lists the predictions of the $`\psi (2S)K_S^0K_L^0`$ branching ratios, as well as the relative strength $`𝒞`$, with some values of the phase which are most interesting from theoretical point of view. These phases are $`\varphi =90^{}`$, $`+90^{}`$, $`180^{}`$ and $`0^{}`$, for the three sets of inputs as discussed above. The first two phases are favored by the theory , and are the fitted results from $`J/\psi `$ data; while the third one is from an early fitting of $`\psi (2S)1^{}0^{}`$ mode . Here the uncertainties due to the experimental errors of $`\pi ^+\pi ^{}`$ and $`K^+K^{}`$ measurements are included in the table. With the third set of input, the theoretical uncertainty due to the extrapolation of the pion form factor from $`J/\psi `$ to $`\psi (2S)`$ according to $`1/s`$ dependence is not included.

In principle, the electromagnetic amplitudes of $`\psi (2S)\pi ^+\pi ^{}`$ ($`E_\pi `$) and $`\psi (2S)K^+K^{}`$ ($`E_K`$) are not necessarily the same as assumed in Eq. (1), a variation of $`E_K`$ by $`\pm (2030\%)`$ from $`E_\pi `$ is tested for various input. The changes of the predicted branching ratios of $`\psi (2S)K_S^0K_L^0`$ are well within the quoted errors since the uncertainties of the $`(\psi (2S)\pi ^+\pi ^{})`$ are large for Input 1 and Input 2; while for Input 3, the resulting branching ratio curve lies between the two curves from Input 1 and Input 2 in Fig. 1.

## 4 Discussions

From Fig. 1 and Table 2, it can be seen that with the Input 1, the central value of $`\psi (2S)K_S^0K_L^0`$ changes dramatically as the phase varies. Nevertheless, such predictions come with huge uncertainties due to the large experimental errors of the input $`(\psi (2S)\pi ^+\pi ^{})`$ and $`(\psi (2S)K^+K^{})`$. As a matter of fact, the results by DASP in Eqs. (8) and (9) can accommodate the assumption within one standard deviation that $`\frac{\sqrt{3}}{2}M=0`$ in Eq. (2), $`i.e.`$ the strong interaction is totally absent which means $`(\psi (2S)K_S^0K_L^0)=0`$. Such huge uncertainties make it virtually impossible to draw any useful conclusion about the phase even with $`(\psi (2S)K_S^0K_L^0)`$ measured.

However, with Input 2, because of the smaller error of $`(\psi (2S)K^+K^{})`$ and the relatively small $`\psi (2S)\pi ^+\pi ^{}`$ branching ratio, $`(\psi (2S)K_S^0K_L^0)`$ are calculated with much smaller uncertainty. The strong interaction amplitude $`\frac{\sqrt{3}}{2}M`$ is nonzero within two standard deviation, and $`(\psi (2S)K_S^0K_L^0)`$ is predicted at the order of $`10^5`$. The exact value depends on the phase and varies by a factor 2.7 from the minimum to maximum. The uncertainty of the prediction, depending on the phase, is between 33% to 50%. So with this result, once $`(\psi (2S)K_S^0K_L^0)`$ is measured, the phase between the strong and the electromagnetic amplitudes can be determined to be within one of the following regions: close to $`0^{}`$, around $`\pm 90^{}`$, or close to $`180^{}`$.

With Input 3, the usage of the better measured pion form factor at $`J/\psi `$ does not reduce the uncertainty of the predicted $`(\psi (2S)K_S^0K_L^0)`$ very much. This is due to the larger pion form factor and so larger contribution from the electromagnetic interactions ($`E`$ and $`E_c`$ in Eq. (2)) than with Input 2. But the predicted central values of $`(\psi (2S)K_S^0K_L^0)`$ vary in a larger range, with a factor of 4.9 from the minimum to maximum. This makes it more sensitive to determine the phase by $`(\psi (2S)K_S^0K_L^0)`$ than with Input 2.

By virtue of the calculations with Input 2 and Input 3, once $`(\psi (2S)K_S^0K_L^0)`$ is known, at least it can distinguish whether the strong and the electromagnetic amplitudes are roughly orthogonal (with phase around $`\pm 90^{}`$) or of the same or opposite phase ($`0^{}`$ or $`180^{}`$). This is highly desirable from the theoretical point of view.

To determine the relative phase between the strong and the electromagnetic interactions with small error, the branching ratios of $`\psi (2S)\pi ^+\pi ^{}`$ and $`\psi (2S)K^+K^{}`$ must also be measured to high precisions. These are expected from the forthcoming CLEOc and BESIII experiments .

## 5 Summary

$`\psi (2S)K_S^0K_L^0`$ branching ratio is calculated as a function of the relative phase between the strong and the electromagnetic amplitudes, based on the available experimental information of $`\psi (2S)\pi ^+\pi ^{}`$ and $`\psi (2S)K^+K^{}`$ decay branching ratios. With the results in this letter, a measurement of the $`\psi (2S)K_S^0K_L^0`$ branching ratio will shed light on answering the question that whether the phase between the strong and the electromagnetic amplitudes is large ($`\pm 90^{}`$) or small ($`0^{}`$ or $`180^{}`$) in the $`\psi (2S)0^{}0^{}`$ decays.


text:
# Introduction

## Introduction

The existence of Extra-Solar planets is well established. In the contemporary status of the searching program (e. g. DARWIN space infrared interferometer project) the following categories of extra-solar planets are described: Definite planets (20), possible planets (8), microlensed planets (5), borderline planets (2), dust clump planets (7) and pulsar planets (4), number in paranthesis denotes the number of planet.111Data taken from http://art.star.rl.ac.uk/darwin/planets It is well known that round the Sun the habitable zone – Ecosphere exists. Within the Sun Ecosphere are: Venus, Earth and Mars and Sun. It will be interesting to calculate the Ecosphere radius for “average” star with mass $`M_s=a_G^{3/2}m_p`$ ($`a_G`$ = the gravity fine structure constant and $`m_p`$ = proton mass).

To that aim in this paper we investigate the possibility of the calculations of the planet orbit radii as the function of the fine structure constant $`\alpha `$. We argue that the Ecosphere is defined as the part of space rounded the star which can be calculated assuming the present day value of the electromagnetic fine structure constant. Considering the existence of the ,,niche” for fine structure constant we calculate the niche for planet orbit radii and obtain $`R_{rel}=R(\alpha )/R(\alpha =1/137)=0.51.5`$ where $`R_{rel}`$ denotes the relative orbit radii. In the case of the Solar system in Ecosphere we find out the orbits of Venus, Earth and Mars. Considering the agreement of the calculation with the Ecosphere radius for Solar system we argue that our model for habitable zone can be applied to other planet systems also.

## Coincidence

In paper  the quantum heat transport on the atomic, nuclear and quark scale was discussed and the characteristic time scales were obtained. For atomic scale:

$$\tau _a=\frac{\mathrm{}}{m_e\alpha ^2c^2},$$
(1)
where $`m_e`$ is electron mass, $`\alpha `$ is the electromagnetic fine structure constant, $`c`$ is the light velocity. For nuclear scale:

$$\tau _n=\frac{\mathrm{}}{m_n(\alpha ^s)^2c^2},$$
(2)
where $`m_n`$ denotes nucleon mass, $`\alpha ^s0.15`$ is the coupling constant for strong interactions. In the case of free quark gas (if it exist!):

$$\tau _q=\frac{\mathrm{}}{m_q(\alpha _s^q)^2c^2}$$
(3)
and $`\alpha _s^q,m_q`$ are the fine structure constant for quark-quark interaction and quark mass respectively.

The atomic time scale, $`\tau _a`$, is proportional to the ,,atomic year”, $`T_a`$, viz.:

$$\tau _a=\frac{\mathrm{}}{m_e\alpha ^2c^2}\frac{a_B}{\alpha c}=T_a,$$
(4)
where $`a_B`$ is the Bohr radius.

It is quite interesting to observe that the ,,coincidence” holds:

$`AT_a`$ $``$ $`T_{\mathrm{Earth}},`$ (5)
$`Am_p`$ $`=`$ $`1g,`$
where $`A`$ is the Avogardo number, $`A=\mathrm{6.02\hspace{0.17em}10}^{23}`$, $`m_p=\mathrm{1.66\hspace{0.17em}10}^{27}`$ kg is the proton mass and $`T_{\mathrm{Earth}}`$ denotes the Earth year (in seconds).

From Kepler law the relation $`T_{\mathrm{Earth}}R_{\mathrm{Earth}}`$ can be concluded:

$$T_{\mathrm{Earth}}^2=\left(\frac{2m_{\mathrm{Earth}}\pi }{(m_{\mathrm{Earth}}K)^{1/2}}\right)^2R_{\mathrm{Earth}}^3.$$
(6)
In formula (6) we approximate Earth orbit as the circle with radius $`R_{\mathrm{Earth}}`$ and $`m_{\mathrm{Earth}}`$ is the Earth mass, $`K`$ is equal:

$$K=Gm_{\mathrm{Earth}}M,$$
(7)
where $`G`$ is gravity constant and $`M`$ denotes the mass of the central body (the Sun) which creates gravity forces. In the following we approximate the $`M`$ mass of the central body by the mass of the ,,average” star

$$Ma_G^{3/2}m_p=Nm_p,$$
(8)
where $`N=a_G^{3/2}`$ is the Landau-Chandrasekhar number, $`a_G`$ denotes the fine structure constant for gravity force. Comparing formulae (5) and (6) one obtains:

$$R^{3/2}=\frac{A\mathrm{}c}{2\pi \alpha ^2}\frac{1}{m_ec^2}\left(\frac{M_{pl}}{m_p}\right)^{1/2}\left(\frac{\mathrm{}c}{m_pc^2}\right)^{1/2}.$$
(9)
In formula (9) for planet radius we omit the subscript ,,Earth” because the radius does not depend on the planet mass. The $`R`$ denotes the planet orbit radius for average star with mass described by formula (8). The planet radius depends only on the three fundamental constant of the Nature: $`G,\mathrm{},c`$. The mass $`M_{pl}=(\frac{\mathrm{}c}{G})^{1/2}`$ is the Planck mass.

Considering formula (5), $`Am_p`$=1 g the planet radius (9) can be formulated in more ,,elegant” form:

$$R^{3/2}=\frac{\mathrm{}c}{m_p\alpha ^2}\frac{1}{m_ec^2}\left(\frac{M_{pl}}{m_p}\right)^{1/2}\left(\frac{\mathrm{}c}{m_pc^2}\right)^{1/2}.$$
(10)
The dependence of $`R`$ on $`\alpha `$ is quite interesting. For, it is well known that grand unified theories allow very sharp limits to be placed on the possible vales of the fine structure constant in a cognizable universe. The possibility of the doing physics on the background space-time at the unification energy and the existence of stars made of protons and neutrons endorse $`\alpha `$ in the niche :

$$\frac{1}{180}\alpha \frac{1}{85}$$
(11)
or

$$\frac{1}{195}\alpha \frac{1}{114}.$$
(12)
It is interesting to observe that one obtains the niche for planet radii — the Ecosphere which is the consequence of formulae (11) and (12). The Ecosphere spans from $`R_{rel}0.5`$ to $`R_{rel}1.5`$. In the case of the Solar system in this niche we find only the orbits of Venus Earth and on the border of the Ecosphere: Mars.

Considering the agreement of the calculations present in this paper with the habitable zone for Sun, we argue that our model for Ecosphere can be applied to other planet systems (other “worlds”) also.

## Results

In conclusion in the paper the Ecosphere radius as the function of $`\alpha `$ \- fine structure constant was calculated. Following the existence of the niche for $`\alpha `$ the niche for planet orbit radii was obtained. In the Sun Ecosphere only the orbit of Venus, Earth and Mars are placed. We argue that the formula (10) describes the Ecosphere radius for other planet systems (other “worlds”) also. Moreover with the new results concerning a time – varying fine structure constant  we speculate that for a distant planetary systems the Ecosphere can be quite different. The change of Ecosphere radius as the function of $`\alpha `$ can be calculated from formula (10).


text:
# About entanglement properties of kaons and tests of hidden variables models

Abstract

In this paper we discuss entanglement properties of neutral kaons systems and their use for testing local realism. In particular we analyze a Hardy-type scheme  recently suggested for performing a test of hidden variable theories against standard quantum mechanics. Our result is that this scheme could in principle led to a conclusive test of local realism, but only if higher identification efficiencies than in today experiments will be reached.

PACS: 13.20.Eb, 03.65.Bz

Keywords: neutral kaons, Bell inequalities, Pseudoscalar mixing, non-locality, hidden variable theories

Since 1935, the celebrated paper of Einstein-Podolsky-Rosen  suggested that Quantum Mechanics (QM) could be an incomplete theory, representing a statistical approximation of a complete deterministic theory in which observable values are fixed by some hidden variable.

In 1964 Bell  discovered that any realistic Local Hidden Variable (LHV) theory must satisfy certain inequalities which can be violated in QM leading to the possibility of an experimental test of the validity of QM as compared to LHV Bell theorem does not concern non-local hidden variables theories. For a recent progress toward an experimental verification of one of them see  and Ref.s therein..

Since then, many experiments (mainly based on entangled photon pairs) have been addressed to test Bell inequalities , leading to a substantial agreement with standard quantum mechanics (SQM) and strongly disfavouring LHV theories. However, so far, no experiment has yet been able to exclude definitively such theories. In fact, up to now one has always been forced to introduce a further additional hypothesis , due to the low total detection efficiency, stating that the observed sample of particle pairs is a faithful subsample of the whole. This problem is known as detection or efficiency loophole and it has been shown that it could be eliminated only by reaching a detection efficiency of $`0.81`$ when using maximally entangled states or $`0.67`$ for non-maximally entangled ones . Similarly the use of equalities  instead of Bell inequalities does not change the situation . Thus, searching for new experimental configurations able to overcome the detection loophole is of course of the greatest interest.

In the last years relevant progresses in this direction have been realised by using Parametric Down Conversion (a process where a UV photon decays in a pair of correlated photons of lower frequency inside a non-linear crystal) for generating entangled photon pairs with high angular correlation. The generation of entangled states by PDC has replaced other techniques, such as the radiative decay of excited atomic states, as it was in the celebrated experiment of A. Aspect et al. , for it overcomes some former limitations and in particular allows a much larger efficiency. Many interesting experiments have been realised using such a technique . However, even if an efficiency of $`30\%`$  was approached, the limit of a detection loophole free test of LHVT remains far.

A recent experiment  based on the use of Be ions has reached very high efficiencies (around 98 %), but in this case the two subsystems (the two ions) are not really separated systems during the measurement and the test cannot be considered a real implementation of a detection loophole free test of Bell inequalities, even if it represents a relevant progress in this sense.

Even if little doubts remain on the validity of the standard quantum mechanics, considering the fundamental importance of the question, the search for other experimental schemes for a definitive test of local realism is therefore of the utmost interest.

In the last years many papers  have been devoted to study the possibility of realising such a test by the use of pseudoscalar meson pairs as $`K\overline{K}`$ or $`B\overline{B}`$. If the pair is produced by the decay of a particle at rest in the laboratory frame (as the $`\varphi `$ at $`Da\varphi ne`$), the two particles can be easily separated to a relatively large distance allowing a space-like separation of the two subsystems and permitting an easy elimination of the space-like loophole, i.e. realising two completely space-like separated measurements on the two subsystems (where the space-like separation must include the setting of the experimental apparatuses too). A very low noise is expected as well.

The idea is to use entangled states (i.e. non factorizable in single particle states) of the form:

$`|\mathrm{\Psi }={\displaystyle \frac{|K^0(\stackrel{}{p})|\overline{K}^0(\stackrel{}{p})|\overline{K}^0(\stackrel{}{p})|K^0(\stackrel{}{p})}{\sqrt{2}}}=`$ (1)
$`={\displaystyle \frac{|K_L(\stackrel{}{p})|K_S(\stackrel{}{p})|K_S(\stackrel{}{p})|K_L(\stackrel{}{p})}{\sqrt{2}}}`$ (2)
(3)
where $`\stackrel{}{p}`$ is the momentum in the centre of mass frame.

Claims that these experiments could allow the elimination of the detection loophole in view of the high efficiency of particles detectors, have also been made. However, we have shown  that due to the necessity of identifying the state through some of its decays and since the decay channel can depend on the value of the hidden variables, the detection loophole appears in this case as well.

In a recent paper  a new scheme was proposed which seems to overcome the objections of Ref. . Considering the possible large relevance of this result for future experiments, in this paper, after having discussed some general properties of K entangled states, we consider critically this proposal. Our result is that this scheme represents an interesting alternative test of LHVT, however it could really overcome the detection loophole only if larger identification efficiencies of $`K^0`$ and $`\overline{K}^0`$ than the ones available in nowadays experiments will be reached.

The main idea of Ref.  is generating a non-maximally entangled state:

$$|\mathrm{\Phi }=\frac{|K_S|K_L|K_L|K_S+R|K_L|K_L+R^{}|K_S|K_S}{\sqrt{2+|R|^2+|R^{}|^2}}$$
(4)
where $`R=rexp[(i\mathrm{\Delta }m+(\mathrm{\Gamma }_S\mathrm{\Gamma }_L)/2)T]`$ and $`R^{}=r^2/R`$, $`\mathrm{\Delta }m`$ is the difference between $`K_L`$ and $`K_S`$ masses, whilst $`\mathrm{\Gamma }_S`$, $`\mathrm{\Gamma }_L`$ are their respective decay widths.

This can be obtained either by placing a regenerator slab on the path of kaons pairs produced in $`\varphi `$ decays, where r is the regeneration parameter, or by considering kaons produced in $`p\overline{p}`$ annihilation at rest, where r measures the relative strength of p to s wave channels.

Selecting the $`K_S`$ surviving after $`T=10\tau _S`$ one obtains the non-maximally entangled state (neglecting the small $`|R^{}|<710^3|r|`$)

$$|\mathrm{\Phi }=\frac{R|K^0|K^0+R|\overline{K}^0|\overline{K}^0+(2R)|\overline{K}^0|K^0(2+R)|K^0|\overline{K}^0}{2\sqrt{2+|R|^2}}$$
(5)
Varying $`R`$ this state ranges from a maximally entangled one (for R=0) to various degree of non-maximal entanglement. For a pure state, entanglement can be quantified by looking to the von Neumann entropy, $`S(\rho )=Tr[\rho log_2\rho ]`$, of the reduced density matrix $`\rho `$ of one of the two particles: a maximally entangled state corresponds to $`S=1`$ and a disentangled to $`S=0`$. The values of $`S`$ for the system of Eq. 5 are plotted in Fig.1 in function of the real and imaginary parts of $`R`$ For the state of Eq. 4 at $`T=0`$ one has $`S=0`$ if $`r`$ could reach $`\pm 1`$. . Incidentally, the possibility of realising different entangled states by manipulating the initial one is of large relevance for quantum information purposes (as studies on decoherence), since entanglement is the main resource for this field .

Then one selects, with an appropriate choice of parameters, the case $`R=1`$ (corresponding to $`S=0.59`$), for which QM predicts the probabilities of joint detection:

$`P_{QM}(K^0,\overline{K}^0)=\eta \eta ^{}/12`$ (6)
$`P_{QM}(K^0,K_L)=0`$ (7)
$`P_{QM}(K_L,\overline{K}^0)=0`$ (8)
$`P_{QM}(K_S,K_S)=0`$ (9)
(10)
where $`\eta `$ and $`\eta ^{}`$ are the detection efficiencies for identifying $`K^0`$ and $`\overline{K}^0`$ respectively.

In a hidden variable model with distribution $`\rho (a)`$ of the hidden variable (or variables set) $`a`$ the probability of observing a $`K^0`$ to the left and $`\overline{K}^0`$ to the right is:

$$P_{LR}(K^0,\overline{K}^0)=𝑑a\rho (a)p_l(K^0|a)p_r(\overline{K}^0|a)=\eta \eta ^{}/12_{A_{0,\overline{0}}}𝑑a\rho (a)$$
(11)
where $`p_l(K^0|a),p_r(\overline{K}^0|a)`$ are the single kaon probabilities of detecting a $`K^0`$ to the left and $`\overline{K}^0`$ to the right respectively and $`A_{0,\overline{0}}`$ is the set of hidden variables corresponding to a $`K^0`$ to the left and $`\overline{K}^0`$ to the right.

In a LHVT the necessity of reproducing Eq. 10 requires that if a $`K^0`$ ($`\overline{K}^0`$ ) is observed to the left (rigth) a $`K_S`$ propagates to the right (left). Thus one has $`p_l(K_S|a)=1,p_r(K_S|a)=1`$ if $`a`$ belongs to $`A_{0,\overline{0}}`$. This is at variance with QM predictions 10, since:

$$P_{LR}(K_S,K_S)=𝑑a\rho (a)p_l(K_S|a)p_r(K_S|a)_{A_{0,\overline{0}}}𝑑a\rho (a)$$
(12)
This result seems therefore to show that even if the detection efficiency of strangeness eigenstates is small, nevertheless LHVT can be tested without any additional hypothesis if the $`K_S`$, $`K_L`$ can be determined with perfect efficiency. Experimentally, this determination is realised by looking to the decay between time $`T_0=10\tau _S`$, where the state 5 is produced, and time $`T_1`$ such that a negligible $`K_L`$ contribution to decays used for tagging $`K_S`$ is still expected in the interval.

Of course, this result would be of the largest relevance because of the possibility of realising this test at $`\varphi `$ factories as $`Da\varphi ne`$.

However, this discussion does not consider that in a deterministic theory hidden variables could also fix the channel of decay and the precise time of decay.

Therefore, Eq. 12 becomes:

$$P_{LR}(K_S,K_S)=\underset{C}{}_{T_0}^{T_1}𝑑t\underset{C^{}}{}_{T_0}^{T_1}𝑑t^{}𝑑a\rho (a)p_l(K_S|a)p_r(K_S|a)p_{l,C}(t|a)p_{r,C^{}}(t^{}|a)$$
(13)
where $`C`$ and $`C^{}`$ run over the different decay channels (allowing an identification of $`K_S`$) and $`p_{i,C}(t|a)`$ gives the probability of the $`i=l,r`$ (left, right) meson to decay into the channel $`C`$ at time t.

Let us now consider how this modifies the discussion concerning Eq. 12. If the efficiencies $`\eta `$ and $`\eta ^{}`$ of $`K^0`$ and $`\overline{K}^0`$ detection were high, the situation would not substantially change . However, unluckily, they are very small. The method for this detection consists  in looking to distinct interaction of $`K^0`$ and $`\overline{K}^0`$ with matter (interaction and therefore identification that in principle could depend on the hidden variables value): this led in Ref.  to the identification of 70 unlike-strangeness events and 19 like-strangeness events over $`810^7`$ analyzed events! Thus, the few $`K^0`$-$`\overline{K}^0`$ identified events could easily correspond to $`K_S`$ which would not have decayed in the temporal window that allows their identification and thus could not contribute to the integral 13 (on the other hand if $`\eta `$ and $`\eta ^{}`$ were sufficiently large this would not be possible). Furthermore, it must also be considered that $`|K_S`$ and $`|K_L`$ are not perfectly orthogonal, for $`K_S|K_L=3.310^3`$ . This means that a fraction of $`K_S`$ in the LHVT belongs to a hidden variable set corresponding to decays characteristic of $`K_L`$ (and vice versa), giving a further fraction of states not contributing to $`P_{LR}(K_S,K_S)`$ as defined in Eq. 13. Albeit very small this contribution cannot be neglected due to the small value of $`P_{LR}(K^0,\overline{K}^0)=\eta \eta ^{}/12`$.

In summary, the small fraction of simultaneously identified left $`K^0`$ and right $`\overline{K}^0`$ could be easily accounted for, in a LHVT, by a fraction of $`K_S`$ that does not decay in an identifiable form, since they decay outside of the temporal window $`T_0<T<T_1`$ or in an allowed channel for $`K_L`$, as three pions or pion, lepton, neutrino.

From a numerical point of view, let us consider the optimistic case where all kaons decayed before the time $`T=10\tau _s`$ are identified and therefore the surviving $`K`$ of a pair where one of members decayed does not represent a background: the background contribution from CP violating decays of $`K_L`$ to specific $`K_S`$ decays (used to tag them) becomes a $`50\%`$ of the one due to true $`K_S`$ contribution in the interval $`21\tau _S<t<22\tau _S`$ and it is 1.35 times larger than $`K_S`$ contribution in the interval $`22\tau _S<t<23\tau _S`$. This means that $`T_1`$ must be kept smaller than $`21\tau _S`$. At $`T=T_1=21\tau _S`$ a fraction $`1.510^5`$ of the $`K_S`$ present at $`T_0`$ is still undecayed and a fraction $`7.210^4`$ is decayed in channels such that they could not be identified as $`K_S`$. This gives the possibility of including in this set all the $`K_S`$ pairs that would correspond to identified left $`K^0`$ and right $`\overline{K}^0`$, if the identification efficiency of $`K^0`$, $`\overline{K}^0`$ is smaller of this amount, as for the experiment . Namely, since not all the $`K_S`$ are identified and since hidden variables can be related also to decay channel and time (and therefore to the possibility of identifying the $`K_S`$), an experimental falsification of LHVT would require that

$$P^{Measured}(K^0,\overline{K}^0)=\eta \eta ^{}/12>7.310^4.$$
(14)
On the other hand, if inequality 14 is not verified, the hidden variable set corresponding to the observed $`(K^0,\overline{K}^0)`$ could correspond to $`K_S`$ pairs which would not be observed as such and then do not contribute to an experimentally detectable difference between SQM and a LHVT.

The experimental realization of inequality 14 (i.e. $`\eta \eta ^{}>9\%`$) seems very difficult to be obtained.

A similar result can also be obtained, with a somehow different argument, rewriting the Equations 10 in the Clauser-Horne like inequality:

$$P(K^0,\overline{K}^0)>P(K^0,K_L)+P(K_L,\overline{K}^0)+P(K_S,K_S)$$
(15)
and considering the possibility of a misidentification of a $`K_S`$ or $`K_L`$

The experimental measured probabilities become:

$`P_{Measured}(K^0,\overline{K}^0)=\eta \eta ^{}/12`$ (16)
$`P_{Measured}(K^0,K_L)=(\eta m_S)/6`$ (17)
$`P_{Measured}(K_L,\overline{K}^0)=(\eta ^{}m_S)/6`$ (18)
$`P_{Measured}(K_S,K_S)={\displaystyle \frac{2}{3}}m_L+{\displaystyle \frac{1}{3}}m_L^2`$ (19)
(20)
where $`m_S`$ ($`7.310^4`$ from the previous discussion) and $`m_L`$ ($`5.710^5`$ due to two pions decays in the time interval $`T_0<t<T_1`$) correspond to the probability of misidentification of a $`K_S`$ or a $`K_L`$ respectively.

Inserting Eq. 20 in 15 and assuming $`\eta =\eta ^{}`$ it follows that an experimental violation of the inequality 15 requires $`\eta =\eta ^{}>2.310^2`$ (where the effect due to $`m_L`$ dominates).

From the previous discussion follows that the observation of $`P_{LR}(K_S,K_S)=0`$ in presence of a small $`P_{LR}(K^0,\overline{K}^0)0`$ is not sufficient for rejecting in general every conceivable LHVT if the identification efficiency of $`K^0`$ and $`\overline{K}^0`$ is not sufficiently high. On the other hand, in the proposed scheme, one cannot hope to increase the $`K^0`$,$`\overline{K}^0`$ detection efficiency by simply increasing strongly the width of the interposed materials since the $`K^0`$,$`\overline{K}^0`$ measurement must be performed in a small time interval around $`T_0`$ before the coefficient $`R`$ of the state 5 changes substantially. Therefore, an eventual experiment addressed to use this scheme for a conclusive test of local realism should be very carefully planed in order to satisfy all the discussed requests and in particular a high $`K^0`$,$`\overline{K}^0`$ detection efficiency.

In conclusions we have shown that entangled neutral kaons states represent a very interesting physical system for studying entanglement and for stating severe limits to hidden variable models. However, because of the results of Ref. , most of the previous proposals  are not suitable for a conclusive loophole free test of Local Hidden Variable Theories against Standard Quantum Mechanics. Furthermore, the results of this paper show that, considering the possible dependence of channel and time of decay on hidden variables, the recent scheme of Ref.  could in principle led to a conclusive test, but only if higher identification efficiencies of $`K^0`$ and $`\overline{K}^0`$ will be reached.

Acknowledgements

We would like to acknowledge support by MURST contract 2001023718-002. We thank the anonymous referees for useful suggestions.

Figures Captions

Fig.1 Three dimensional plot of the von Neumann entropy of the reduced density matrix in function of the real and imaginary parts of the parameter $`R`$ of Eq. 5.

Fig.2 Histogram of the ratio of the CP-violating contribution from $`K_L`$ decays over the contribution of $`K_S`$ decays for pairs surviving at $`T=10\tau _s`$ and for bins of $`1\tau _s`$ from $`T=18\tau _s`$ to $`T=23\tau _s`$.


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# Comment on “𝑐-axis Josephson tunneling in 𝑑_{𝑥²-𝑦²}-wave superconductors”

Recently, Maki and Haas (MH) presented an expression, Eq. (3), for the critical current $`I_c`$ for coherent $`c`$-axis tunneling across the interface between identical $`d_{x^2y^2}`$-wave superconductors twisted a relative angle $`\alpha `$ about the $`c`$-axis. They implied that Eq. (3) was valid to all orders in the $`c`$-axis tunneling probability $`t_{}`$, accounting for “the effects of Andreev reflections at the grain boundary”. However, they made many qualitative and quantitative errors, which invalidate their conclusions.

The errors are present in their Eq. (3). MH state that this result is obtained “by applying the Ambegaokar-Baratoff formalism”, but a derivation is neither given nor cited. The result of Ambegaokar and Baratoff (AB) is based on the tunneling Hamiltonian approximation, valid to lowest order in $`t_{}`$, while the MH result clearly involves higher orders in $`t_{}`$. Therefore, we first take this equation at face value and examine its consequences.

MH assumed a cylindrical, two-dimensional Fermi surface in each superconductor adjacent to the interface, in contrast to the experimental tight-binding Fermi surface of Bi2Sr2CaCu2O8+δ (Bi2212). In the s-wave limit, the MH Eq. (3) for $`I_c`$ is independent of $`t_{}`$, which is clearly unphysical. Even if Eq. (3) were to apply for $`I_cR/e`$, it is wrong, because exact calculations for s-wave superconductors have shown that $`I_cR/e`$ for an $`SIS`$ junction depends upon $`t_{}`$. At low temperature $`T`$, $`I_cR/e`$ increases from the AB value to twice that value as $`t_{}`$ increases from 0 to unity. Only as $`TT_c`$ does $`I_cR/e`$ become independent of $`t_{}`$.

In addition, the MH result disagrees with an exact calculation of $`I_c`$ for tunneling between $`SIS`$ layered superconductors obtained by Arnold and Klemm (AK), given in their Eq. (18). Comparing the MH Eq. (3) with the AK Eq. (18), we identify many significant differences. The exact AK Eq. (18) contains the phase difference $`\delta \varphi `$ across the tunnel barrier in the coefficient of each order in $`t_{}`$, and $`I_c`$ is optimized for each $`\alpha `$ by setting $`\delta \varphi =\delta \varphi ^{}<\pi /2`$. Each Andreev reflection should also involve $`\delta \varphi `$, but the MH Eq. (3) evidently set $`\delta \varphi ^{}=\pi /2`$. The MH gap $`\mathrm{\Delta }_0`$ is evidently independent of $`T`$. This disagrees with the AB limit. In the d-wave case, as $`t_{}0`$, the MH result also disagrees with the d-wave AB limit.

Andreev reflections at the interface could only arise if it were an $`SNS`$ junction. It would then be much stronger than the intrinsic interplanar couplings in the single crystals, which are generally agreed to be of the $`SIS`$ type. However, MH neglected altogether the intrinsic tunneling between the junctions in the layered superconducting half-spaces adjacent to the interface. Furthermore, the $`t_{}(𝐤)`$ employed by MH in their Eq. (6) is inappropriate for the cylindrical Fermi surface they employed.  As shown previously,  tight-binding Fermi surfaces of layered superconductors such as Bi2212 misoriented relative to each other also introduce a strong $`\alpha `$ dependence of $`I_c`$ for coherent tunneling, even in the s-wave case, especially with a $`t_{}(𝐤)`$ analogous to that used in Eq. (6) of MH.

The $`I_c`$s observed by Li et al. are equal to those observed in single crystals, which are not “small”, as claimed by MH. Li et al. fed the c-axis current into the top of the crystal. We have studied this case theoretically,  and find that within a few layers from the current leads, the current becomes uniform over the crystal surface on the scale of the c-axis penetration depth, $`\lambda _c>100\mu `$m. However, in the whisker experiment of Takano et al., the current was fed in from the edge, producing current inhomogeneities on the scale of the Josephson penetration depth, $`23\mu `$m.

Finally, we note that the $`\alpha `$ dependence of $`I_c`$ observed in the experiments of Takano et al. may have an extrinsic origin, due to systematic variations with $`\alpha `$ of the Bi2212-Bi2Sr2Ca2Cu3O10+δ mixture and additional insulating barrier thicknesses near the cross-whisker interface.