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# Spontaneous decay of excited atomic states near a carbon nanotube

## Abstract

Spontaneous decay process of an excited atom placed inside or outside (near the surface) a carbon nanotube is analyzed. Calculations have been performed for various achiral nanotubes. The effect of the nanotube surface has been demonstrated to dramatically increase the atomic spontaneous decay rate – by 6 to 7 orders of magnitude compared with that of the same atom in vacuum. Such an increase is associated with the nonradiative decay via surface excitations in the nanotube.

Theoretical prediction of the Purcell effect in 1946 Purcell  has stimulated series of works, both theoretical and experimental, aimed at the detailed investigation of the phenomenon (see recent papers Dung ; Sonder ; Yang ; Ando ; Klimov  and references therein). The effect lies in the fact that the spontaneous decay rate of an excited atom essentially depends on whether or not the atom is located near optical inhomogeneities and interfaces of media with differing optical properties. Depending on the specific configuration of inhomogeneities (interfaces), the atomic spontaneous decay rate may both increase and decrease compared with that of the same atom in free space. The Purcell effect took on special significance recently in view of rapid progress in physics of low-dimensional nanostructures. It was shown to be of great importance for microcavities Dung , optical fibers Sonder , photonic crystals Yang , semiconductor quantum dots Sugawara .

In Ref. Klimov , it was first suggested on the basis of the model of an ideally conducting cylinder that spontaneous decay process of excited atomic states near a carbon nanotube (CN) might possess nontrivial peculiarities. However, the ideally conducting cylinder is not quite an adequate model to describe the optic properties of real CNs. It is our purpose in the present paper to give consistent consideration to spontaneous decay processes of the excited atom in the vicinity of CNs. We calculate atomic spontaneous decay rate variation for infinitely long achiral single-wall CNs of different radii and demonstrate that the decay rate may dramatically increase due to the nonradiative decay via CN surface excitations.

Quantum theory of the spontaneous decay of excited atomic states in the vicinity of CN requires the solution of two fundamental problems. They are (i) the problem of the macroscopic description of the optical properties of solitary CN and (ii) the quantization problem of an electromagnetic field in the presence of CN. We solve problem (i) based upon the model described in Refs. Slepyan ; Maks . According to that model, CN is changed by the infinitely thin anisotropically conducting cylinder with effective boundary conditions imposed in such a way that the field at a distance from the cylinder surface be identical to the actual electromagnetic field excited in the system. In so doing, only the axial conductivity of CN is taken into account and the transverse conductivity is neglected for the following reason. The axial conductivity forms by intraband and direct interband transitions of $`\pi `$-electrons in CN, while the transverse one only forms by indirect interband transitions Tasaki ; Saito . The intraband transitions dominate at lower frequencies and the interband ones start essentially contributing to the total CN conductivity at higher frequencies. However, the contribution of the indirect interband transitions, being strongly suppressed by depolarization fields, is always smaller compared with that of the direct interband transitions Tasaki ; Saito . We use the dispersion law for $`\pi `$-electrons in the tight-binding approximation with allowance made for the azimuthal momentum quantization. Energy dissipation is taken into account within the relaxation time approximation. The spatial dispersion of the CN conductivity is neglected (see Refs. Slepyan ; Maks  for its role in CNs).

The quantization procedure of the electromagnetic field, problem (ii), faces difficulties similar to those in quantum optics of 3D Kramers-Kronig media where the canonical quantization scheme commonly used does not work since, because of absorption, the respective operator Maxwell equations become non-Hermitian. A standard approach overcoming these difficulties involves a noise current term incorporated into the operator Maxwell equations Vogel . We use the analogous approach to quantize the electromagnetic field in the presence of CN. In this case, the noise current becomes the surface one and, therefore, may be incorporated into the boundary conditions for the Maxwell equations rather than into the Maxwell equations themselves. As this takes place, the effective boundary conditions for electric field and magnetic field operators in frequency-domain space take the form

$$𝐧\times \left(\widehat{𝐄}|_{r=R_{cn}+0}\widehat{𝐄}|_{r=R_{cn}0}\right)=0,$$

(1)
$$𝐧\times \left(\widehat{𝐇}|_{r=R_{cn}+0}\widehat{𝐇}|_{r=R_{cn}0}\right)+\frac{4\pi }{c}\widehat{J}_z^N𝐞_z=\frac{4\pi }{c}\sigma _{zz}(\omega )\widehat{E}_z𝐞_z,$$

where $`r`$ is the radial spatial coordinate, $`R_{cn}`$ the CN radius, $`𝐧`$ and $`𝐞_z`$ are the unit vectors along the external normal to the CN surface and along the CN axis, respectively, $`\sigma _{zz}(\omega )`$ is the axial dynamical conductivity of CN (see Eq.(36) in Ref. Slepyan ), $`\widehat{J}_z^N`$ is the axial noise current operator. The latter one is expressed in terms of 2D scalar bosonic field operator $`\widehat{f}(𝐑)`$ ($`𝐑`$ CN surface) as $`\widehat{J}_z^N=\sqrt{\mathrm{}\omega \text{Re}\sigma _{zz}(\omega )/\pi }\widehat{f}(𝐑)`$ and is responsible for correct commutation relations of $`\widehat{𝐄}`$ and $`\widehat{𝐇}`$ operators Vogel . Homogeneous Maxwell equations along with boundary conditions (1) describe quantum electrodynamics of CNs.

Let the excited atom with an electric dipole transition allowed be located in the vicinity of CN and let the atomic dipole moment be oriented along the CN axis. Following the quantization scheme above, one can by analogy with Ref. Dung  obtain the Volterra integral equation for atomic decay dynamics from the upper stationary state to the lower one

$$C_u(t)=1+_0^tK(tt{}_{}{}^{})C_u(t^{})dt^{}$$
(2)
with $`C_u`$ being the occupation probability amplitude of the upper state and the kernel given by

$$K(\tau )=\frac{4k_A^2|\mu _z|^2}{\mathrm{}}_0^{\mathrm{}}𝑑\omega \frac{\text{Im}G_{zz}(𝐫_A,𝐫_A,\omega )}{i(\omega \omega _A)}\left[e^{i\left(\omega \omega _A\right)\tau }1\right],$$
(3)
where $`\mu _z`$ and $`\omega _A`$ are the matrix element and the frequency of the atomic dipole transition, respectively, $`𝐫_A`$ is the radius-vector of the atomic position, $`k_A=\omega _A/c`$, and $`G_{zz}(𝐫,𝐫_A,\omega )`$ is the axial component of the classical electromagnetic field Green tensor in the presence of CN.

For further calculations we need Green tensor components $`G_{\alpha z}`$ ($`\alpha =r,\phi ,z`$ are the cylindrical coordinates associated with CN). We use the representation $`G_{\alpha z}=(k^2_\alpha _z+\delta _{\alpha z})g`$ with $`g(𝐫,𝐫_A,\omega )`$ being the scalar Green function of the electromagnetic field in the presence of CN. The latter one is expanded over cylindrical waves in terms of boundary conditions (1), so that at $`r,r_A>R_{cn}`$ one obtains

$$g=g_0\frac{R_{cn}}{(2\pi )^2}\underset{p=\mathrm{}}{\overset{\mathrm{}}{}}e^{ip\phi }_C\frac{\beta (\omega )v^2I_p^2(vR_{cn})K_p(vr_A)K_p(vr)}{1+\beta (\omega )v^2R_{cn}I_p(vR_{cn})K_p(vR_{cn})}e^{ihz}𝑑h,$$
(4)
where $`g_0=\mathrm{exp}(ik|𝐫𝐫_A|)/4\pi |𝐫𝐫_A|`$ is the free space Green function, $`\beta (\omega )=4\pi i\sigma _{zz}(\omega )/\omega `$, $`v=\sqrt{h^2k^2}`$, $`I_p(X)`$ and $`K_p(X)`$ are the modified cylindrical Bessel functions. Integration contour $`C`$ goes along the real axis of the complex plane and envelopes branch points $`\pm k`$ from below and from above, respectively. For $`r,r_A<R_{cn}`$, Eq.(4) is modified by the replacement $`I_pK_p`$ in the numerator of the integrand.

Consider decay process in the Markovian approximation. Then, factor $`[\mathrm{exp}(ix\tau )1]/ix`$ in Eq.(3) is changed by $`\pi \delta (x)+i𝒫(1/x)`$ ($`𝒫`$ denotes the principal value), and one arrives at the exponential decay model with $`K(\tau )=\mathrm{\Gamma }/2+i\delta \omega `$, where $`\mathrm{\Gamma }`$ and $`\delta \omega `$ are the decay rate and the Lamb shift of the upper atomic level, respectively. For the outward atomic position ($`r_A>R_{cn}`$), the decay rate is written in view of Eqs.(2)-(4) as

$$\frac{\mathrm{\Gamma }}{\mathrm{\Gamma }_0}=\xi (\omega _A)=1+\frac{3R_{cn}}{2\pi k_A^3}\underset{p=\mathrm{}}{\overset{\mathrm{}}{}}_C\frac{\beta _Av_A^4I_p^2(v_AR_{cn})K_p^2(v_Ar_A)}{1+R_{cn}\beta _Av_A^2I_p(v_AR_{cn})K_p(v_AR_{cn})}𝑑h,$$
(5)
with $`\beta _A=\beta (\omega _A)`$, $`v_A=\sqrt{h^2k_A^2}`$, $`\mathrm{\Gamma }_0=4k_A^{\mathrm{\hspace{0.17em}3}}|\mu _z|^2/3\mathrm{}`$ being the free space decay rate and $`\xi (\omega _A)`$ representing the influence of CN. For the inward position ($`r_A<R_{cn}`$), Eq.(5) is modified by the simple replacement $`r_AR_{cn}`$ in the numerator of the integrand. Note the divergence of the integral in Eq.(5) at $`r_A=R_{cn}`$, i. e. when the atom is located directly on the CN surface. This divergence originates from the averaging procedure over physically infinitely small volume when describing CN optical properties. Such an averaging does not assume any additional atoms on the CN surface, to take them into consideration the procedure must be modified. Thus, the applicability domain of our model is restricted by the condition $`r_AR_{cn}>a`$, where $`a=1.42`$ Å is the interatomic distance in CN.

The decay of the excited atom interacting with medium may proceed both via real photon emission (radiative decay) and via virtual photon emission with subsequent medium quasiparticle excitation (nonradiative decay). Both of these decay channels are present in atomic spontaneous decay rate $`\mathrm{\Gamma }`$ described by Eq.(5). The problem of the total $`\mathrm{\Gamma }`$ partition to radiative and nonradiative contributions is not trivial. Radiative contribution $`\mathrm{\Gamma }_r`$ was estimated by using a Poynting vector approach for the atom near a microsphere in Dung  and for the atom inside an optic fiber in Sonder . Following this approach, we estimate the spontaneous radiation intensity distribution $`I(𝐫,t)=𝐅(𝐫,𝐫_A,\omega _A)^2\mathrm{exp}(\mathrm{\Gamma }t)`$, where

$$F_\alpha (𝐫,𝐫_A,\omega _A)=4\pi ik_A^2\mu _z\left\{G_{\alpha z}(𝐫,𝐫_A,\omega _A)\frac{1}{\pi }𝒫_0^{\mathrm{}}\frac{\text{Im}G_{\alpha z}(𝐫,𝐫_A,\omega )}{\omega +\omega _A}𝑑\omega \right\},$$

at large distances $`|𝐫|\mathrm{}`$. In so doing, the second term does not contribute and the contribution of the first term is easily found by the stationary phase method Dingle  to give in the spherical coordinates ($`|𝐫|`$, $`\varphi `$, $`\theta `$) associated with the atom

$$\underset{|𝐫|\mathrm{}}{lim}𝐅(𝐫,𝐫_A,\omega _A)ik_A^2\mu _z\frac{e^{ik_A\left|𝐫\right|}}{|𝐫|}𝐞_\theta \mathrm{sin}\theta \underset{p=\mathrm{}}{\overset{\mathrm{}}{}}\mathrm{\Xi }_p(ik_A\mathrm{sin}\theta )e^{ip\varphi }$$

with $`𝐞_\theta `$ being the spherical ort and

$$\mathrm{\Xi }_p(X)=\{\begin{array}{cc}\frac{I_p\left(Xr_A\right)}{1+R_{cn}\beta _AX^2I_p\left(XR_{cn}\right)K_p\left(XR_{cn}\right)},& \text{if }r_A<R_{cn}\\ I_p(Xr__A)\frac{R_{cn}\beta _AX^2I_p^2\left(XR_{cn}\right)K_p\left(Xr_A\right)}{1+R_{cn}\beta _AX^2I_p\left(XR_{cn}\right)K_p\left(XR_{cn}\right)},& \text{if }r_A>R_{cn}.\end{array}$$

The relative contribution of the radiative decay is then given by

$$\frac{\mathrm{\Gamma }_r}{\mathrm{\Gamma }}=\frac{c}{2\pi \mathrm{}\omega _A}\underset{|𝐫|\mathrm{}}{lim}_0^{\mathrm{}}𝑑t_0^{2\pi }𝑑\varphi _0^\pi |𝐫|^2I(𝐫,t)\mathrm{sin}\vartheta d\vartheta $$

(6)
$$=\frac{3}{4\xi (\omega _A)}\underset{p=\mathrm{}}{\overset{\mathrm{}}{}}_0^\pi \mathrm{\Xi }_p(ik__A\mathrm{sin}\vartheta )^2\mathrm{sin}^3\vartheta d\vartheta .$$

Figure 1 shows the results of the numerical calculations of factor $`\xi (\omega _A)`$ according to Eq.(5) for metallic and semiconducting CNs of $`(m,0)`$ type (”zigzag”). The atom is located on the symmetry axis inside CN. The presence of CN is seen to drastically accelerate spontaneous decay process of an excited atomic state. Frequency range $`0.305<\mathrm{}\omega _A/2\gamma _0<0.574`$ ($`\gamma _0=2.7`$ eV is the carbon overlap integral) corresponds to visible light. Lower frequencies $`\mathrm{}\omega _A/2\gamma _0<0.305`$ correspond to infra-red waves emitted by highly excited Rydberg atomic states. At these frequencies, the large difference ($`34`$ orders of magnitude) is seen in the value of $`\xi (\omega _A)`$ for metallic ($`m=3q`$, $`q=1,2,\mathrm{}`$) and semiconducting ($`m3q`$) CNs. The difference is caused by the Drude-type conductivity (intraband electronic transitions) dominating in this region, whose relative contribution to the total CN conductivity is larger in metallic CNs than in semiconducting ones Slepyan ; Maks ; Tasaki ; Saito . As the frequency increases, interband electronic transitions start manifesting themselves and function $`\xi (\omega _A)`$ becomes irregular. At high frequencies, there is no significant difference between metallic and semiconducting CNs of close radii. Function $`\xi (\omega _A)`$ has dips when $`\omega _A`$ equals the interband transition frequencies; in particular, there is a dip at $`\mathrm{}\omega _A=2\gamma _0`$ for all CNs considered. It is essential that $`\xi (\omega _A)1`$ throughout the entire frequency range considered. This lets us formulate the central result of the present paper: the spontaneous decay probability of the atom in the vicinity of CN is larger by a few orders of magnitude than that of the same atom in free space. In other words, the Purcell effect is extraordinarily strong in CNs. This is physically explained by the photon vacuum renormalization: the density of photonic states (and, as a consequence, the atomic decay rate) near CN effectively increases ($`\rho ^{eff}(\omega )d\omega =\xi (\omega )\omega ^2d\omega /\pi c^3`$) since, along with ordinary free photons, there appear the photonic states coupled with CN electronic quasiparticle excitations.

In Refs. Slepyan ; Maks , the possibility was shown of the existence of slow surface electromagnetic waves in CNs. In Ref. Dung , such waves were shown to be responsible for the strong Purcell effect for the atom in the spherical microcavity. The results of the present paper agree qualitatively with those obtained in Ref. Dung . Quantitatively, $`\xi _{max}10^610^7`$ for CNs while $`\xi _{max}10^4`$ for the microcavity Dung , i. e. the Purcell effect is much stronger in CNs. It is worth noting that for the atoms with large enough $`\mathrm{\Gamma }_0`$, there is the risk of going beyond the applicability limits of the two-level model and Markovian approximation. Then, in the first case, the mutual overlap is possible of the levels due to their strong broadening and, in the second one, the atomic spontaneous decay may become nonexponential so that the problem may require the numerical solution of integral equation (2) with kernel (3).

Figure 2 shows $`\xi (\omega _A)`$ for the atom located outside CN at different distances from the CN surface. The qualitative behavior of $`\xi (\omega _A)`$ is similar to that represented in Figure 1 for the atom inside CN. Factor $`\xi (\omega _A)`$ is seen to rapidly decrease with raising the distance as it should be in view of the evident fact that photonic states coupled with CN electronic excitations (those increasing effective density $`\rho ^{eff}(\omega )`$) are spatially localized on the CN surface and their coupling strength with the excited atom decreases with raising the distance of the atom from CN.

Figure 3 shows the ratio $`\mathrm{\Gamma }_r/\mathrm{\Gamma }`$ calculated according to Eq.(6) for the atom in the centre of different CNs. (Note that $`\mathrm{\Gamma }_r/\mathrm{\Gamma }=W_s(\omega _A)/\mathrm{}\omega _A`$ with $`W_s(\omega _A)`$ being the total power of the atomic spontaneous radiation far from CN.) The ratio is very small indicating that the nonradiative decay dominates. However, the radiative decay is seen to essentially contribute in the vicinity of the interband transition frequencies so that the frequency dependence of $`W_s(\omega _A)`$ (which, in principle, can be measured experimentally) reproduces CN electronic structure peculiarities. The main conclusion one can draw from Figure 3 is the Purcell effect in CNs, along with the increase of the atomic spontaneous decay rate, manifests itself by decreasing the power of the spontaneous radiation.

Our model of the atomic spontaneous decay in the presence of CN includes, as a limiting case, the model of the ideally conducting cylinder considered in Ref. Klimov . In particular, our Eq.(5) reduces for the outward atomic position to Eqs.(15),(18) of Ref. Klimov  as $`\sigma _{zz}\mathrm{}`$. The inset in Figure 2 shows factor $`\xi (\omega _A)`$ at $`\omega _A=3\gamma _0/\mathrm{}`$ ($`k_AR_{cn}0.01`$) as a function of $`r_A/R_{cn}`$ for this case. The dependence is similar to that reported in Ref. Klimov  for z-oriented dipole at $`k_AR_{cn}=1`$. For the atom inside CN, Eq.(5) yields $`\xi (\omega _A)0`$ as $`\sigma _{zz}\mathrm{}`$ — the result is natural since in this case only one eigen electromagnetic mode can propagate in CN; this mode is essentially transverse and, consequently, is not coupled with the atomic dipole moment oriented longitudinally. However, the actual $`\xi (\omega _A)`$ behavior discussed above is quite different from that predicted by the ideally conducting cylinder model since the latter one does not account for CN electronic quasiparticle excitations responsible for the nonradiative atomic decay dominating the total spontaneous decay process.

Our theory may be generalized to cover the transverse atomic electric dipole orientation, electric quadrupole and magnetic dipole atomic transitions, properties of organic molecules inside/outside CNs Petrov  and of fullerene peapods Liu . The mechanism revealed of the photon vacuum renormalization is likely to manifest itself in other phenomena in CNs such as, for example, Casimir forces, electromagnetic fluctuations, etc. Bordag .

The results of the present work may be tested by methods of atomic fluorescent spectroscopy and may possess various physical consequences. In particular, the effect of the drastic increase of the atomic spontaneous decay rate may turn out to be of practical importance in problems of the laser control of atomic motion Scully , yielding the increase of the ponderomotive force acting on the atom moving in the vicinity of CN in a laser field. One might expect the Purcell effect peculiarities that we predict for CNs to manifest in macroscopic anisotropically conducting waveguides with strong wave deceleration (for example, in microwave spiral or collar waveguides with highly excited Rydberg atoms inside).

The work was financially supported by the Foundation for Basic Research of the National Academy of Sciences of the Republic of Belarus (Grants No F01-176 and No F02R-047).

Figure captions:

Figure 1: Factor $`\xi (\omega _A)`$ calculated from Eq.(5) for the atom in the center of different ”zigzag” CNs. Surface axial conductivities $`\sigma _{zz}`$ appearing in Eq.(5) were calculated in the $`\tau `$-approximation with $`\tau =3\times 10^{12}`$ s<sup>-1</sup>.

Figure 2: Factor $`\xi (\omega __A)`$ for the atom at different distances outside ”zigzag” (9,0) CN. Inset: $`\xi (\omega _A)`$ at $`\omega _A=3\gamma _0/\mathrm{}`$ as a function of $`r_A/R_{cn}`$ for the atom near (9,0) CN in the model of the ideally conducting cylinder.

Figure 3: Ratio $`\mathrm{\Gamma }_r/\mathrm{\Gamma }`$ calculated from Eq.(6) for the atom in the center of different ”zigzag” CNs.


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# Structural Relaxation and Mode Coupling in a Simple Liquid: Depolarized Light Scattering in Benzene

## 1 Motivation

On short time scales, all liquids show solid-like elasticity. This has been impressively illustrated by Brillouin scattering of X-rays : on a THz scale, sound propagates in water with almost the same speed as in ice, more than twice as fast as on the kHz or MHz scale of conventional ultrasonic measurements. Such a cross-over goes along with a decay of structural correlations; it is called relaxation, and more specifically $`\alpha `$ relaxation when it leads from solid-like to liquid-like response (correlations decaying to zero).

When a liquid can be supercooled far enough, $`\alpha `$ relaxation becomes critically slow, so that the material ultimately becomes a glass. The dynamics of glass-forming liquids has been studied in great detail. Stretching and time–temperature scaling have been identified as generic properties of $`\alpha `$ relaxation. Additional scaling laws have been uncovered by a mode-coupling theory (MCT). Originally proposed as a theory of the glass transition, MCT is now generally recognized to offer a unified description of microscopic and relaxational motion at comparatively high temperatures where $`\alpha `$ relaxation occurs on a GHz scale.

In experiments undertaken in both the supercooled and the normal liquid phase, $`\alpha `$ relaxation and mode-coupling dynamics are found to evolve continuously across the melting point of the concurrent crystalline phase: on a GHz to THz scale, the molecular dynamics seems to be insensitive to whether the liquid’s state is thermodynamically stable or not. This leads us to the hypothesis that the molecular dynamics in the normal liquid state will be insensitive to whether the liquid can be supercooled or not. A pioneering paper on water , studies of metallic melts , and our own experiments on several molecular liquids suggest that indeed $`\alpha `$ relaxation and mode-coupling effects also occur in liquids that cannot be supercooled into a glass.

For a more detailed test of our hypothesis, we now study one such liquid in depth. We choose benzene, which presents the following advantages: (i) the molecule is structurally very simple and highly symmetric; (ii) it is stiff on all relevant time or frequency scales ; (iii) many often studied glass formers are structurally related to benzene; (iv) benzene is an excellent light scatterer.

To investigate the dynamics of benzene over a wide dynamic range, we have used depolarized light scattering. A neutron scattering study is currently under way and will be published later; preliminary results support the conclusions we draw from light-scattering.

## 2 Context and Theory

### 2.1 $`𝜶`$ Relaxation

In zeroth approximation, relaxation may be modelled by an exponential decay of correlations. This ansatz goes back to Maxwell’s theory of viscoelasticity; it has been elaborated for dielectric response by Debye . The underlying physics is mean-field like: one considers thermal motion of an individual molecule upon which all the other molecules exert just a constant friction.

However, in glass-forming liquids $`\alpha `$ relaxation is found to be stretched: it is spread much more than an exponential decay in time or a Lorentz line (in our context: a Debye resonance) in frequency. Popular fit functions assume a fractional time or frequency dependence, as in Kohlrausch’s stretched exponential

$$\mathrm{\Phi }_\mathrm{K}(t)\mathrm{exp}[(t/\tau )^\beta ],$$
(1)
or in the Cole–Davidson susceptibility

$$\chi _{\mathrm{CD}}(\nu )[(1+i2\pi \nu \tau )]^\beta .$$
(2)
While the relaxation time $`\tau `$ depend strongly on the temperature $`T`$, the exponents $`\beta _\mathrm{K}`$ or $`\beta _{\mathrm{CD}}`$ vary only weakly. This can be seen as a consequence of time-temperature scaling: in a good first approximation, $`\alpha `$ relaxation has the form

$$\mathrm{\Phi }(t;T)\widehat{\mathrm{\Phi }}(t/\tau (T)).$$
(3)
Towards high temperatures, this scaling law has an obvious limitation: $`\alpha `$ relaxation can never become faster than the temperature-independent microscopic modes. Indeed, on heating glass-forming materials towards the boiling point the curves $`\mathrm{log}\tau `$ vs. $`T`$ become flatter and flatter, so that $`\tau `$ approaches, but never reaches the intrinsic time scale of microscopic motion . Depolarized light scattering in molecular liquids could clearly resolve an $`\alpha `$ peak and confirm its scaling up to temperatures far in the normal liquid phase .

### 2.2 Relaxation in Simple Liquids

Historically, relaxation in simple liquids (on a THz scale), and $`\alpha `$ relaxation in highly viscous liquids (originally measured mostly on Hz to MHz scales) have long been seen as two genuinely different processes . In the most simple monatomic liquids like argon or sodium, on which theory-oriented textbooks  concentrate, characteristic relaxation times are of the order of $`10^{13}`$ to $`10^{12}`$ s, which is not much longer than the mean time between collisions . Under such circumstances relaxation is closely mingled with microscopic motion, and it is impossible to obtain isolated experimental information on relaxation alone. On the other hand, results of scattering experiments and molecular dynamics simulations cannot be understood without taking into account relaxation. Therefore, experimental data are usually fitted by theoretical expressions that contain memory kernels built upon an ad-hoc model of relaxation.

Such fits, however, are rather insensitive to the functional form of the memory kernel, and therefore one seldom went beyond assuming simple exponential relaxation. In some cases, when fits were judged unsatisfactory, a sum of two exponentials was used ; this approach, though admittedly arbitrary, has recently been revived in the analysis of X–ray Brillouin scattering on liquid metals .

In the investigation of glass-forming liquids this double exponential approach has long been overcome by formulæ like (1) or (2). Today, after $`\alpha `$ relaxation has been observed across the melting point and up to a GHz to THz scale, it is no longer justified to consider relaxation in glass-forming materials and relaxation in simple liquids as two different physical processes. So we are led to suspect that the stretching and scaling properties of $`\alpha `$ relaxation hold in principle even in argon and sodium, although an experimental verification will be extremely difficult .

For the time being we prefer to investigate a molecular, non glass-forming liquid, benzene, which in a sense is intermediate between monatomics on the one side and molecular glass formers on the other side: the benzene molecule is small and highly symmetric, in contrast to glass-forming liquids which necessarily have a more complicated structure as to prevent crystallisation. Yet we will find structural relaxation in benzene to be slow enough  to allow for a direct, unambiguous observation of its stretching.

### 2.3 Mode-Coupling Theory

As mentioned in the beginning, mode-coupling theory (MCT)  provides a unified description of $`\alpha `$ relaxation and low-frequency vibrations. It is a microscopic theory, formulated as function of wavenumber $`q`$ and time $`t`$, and built upon the static structure factor $`S(q)`$ and the density correlation function $`\mathrm{\Phi }_q(t)=S(q,t)/S(q)`$. It starts with the formally exact equation of motion

$$0=\mathrm{\Omega }_q^2\ddot{\mathrm{\Phi }}_q(t)+\mathrm{\Phi }_q(t)+_0^tdt^{}M_q(tt^{})\dot{\mathrm{\Phi }}_q(t^{}).$$
(4)
The memory kernel $`M_q(t)`$ contains fast and slow fluctuations, $`M_q(t)M_q^{}(t)+m_q(t)`$. The fast component, approximated as $`M_q^{}(t)\gamma _q\delta (t)`$, can be shown to be irrelevant for the long-time behaviour.

The basic idea of MCT is now to expand the slow fluctuations $`m_q(t)`$ in polynomials of density fluctuations, and then to factorize all terms into pair correlations. In lowest order one obtains the bilinear functional

$$m_q\{\mathrm{\Phi }(t)\}=\underset{𝐩+𝐤=𝐪}{}V_{\mathrm{𝐪𝐩𝐤}}\mathrm{\Phi }_p(t)\mathrm{\Phi }_k(t).$$
(5)
The coupling coefficients $`V_{\mathrm{𝐪𝐩𝐤}}`$ can be derived from the static structure factor $`S(q)`$; as $`S(q)`$, they vary slowly with state variables like temperature $`T`$ or pressure $`P`$.

In this way the dynamics is completely determined by a closed set of integro-differential equations. Depending on the numeric values of $`V_{\mathrm{𝐪𝐩𝐤}}`$, the $`\mathrm{\Phi }_q(t)`$ either decay to zero or arrest at finite values. The border line $`T_\mathrm{c}(P)`$ which separates these two cases has been called the ideal glass transition.

For $`T<T_\mathrm{c}`$, the density correlations arrest at a finite Debye-Waller factor $`\mathrm{\Phi }_q(t\mathrm{})=f_q(T)`$, as expected for a glass. On the liquid side, with $`T>T_\mathrm{c}`$, the $`\mathrm{\Phi }_q(t)`$ slow down on approaching a plateau $`f_q(T)`$, but ultimately they decay to $`\mathrm{\Phi }_q(t\mathrm{})=0`$ in a process which is easily identified as $`\alpha `$ relaxation. Since the derivatives $`\ddot{\mathrm{\Phi }}_q(t)`$ become negligible at long times, Eq. (4) immediately reproduces the time-temperature scaling (3), with the corollary that the line shape of $`\widehat{\mathrm{\Phi }}_q`$ may vary with $`q`$. To first order, solutions of MCT equations are consistent with the Kohlrausch asymptote (1).

On cooling towards $`T_\mathrm{c}`$, $`\alpha `$ relaxation times are predicted to diverge with a fractional power law in $`TT_\mathrm{c}`$. A comparison with measured relaxation times and viscosities  shows that such a divergence does not correctly describe the glass transition . Instead, $`T_\mathrm{c}`$ is found to describe a cross-over that is typically located 15–20 % above the conventional glass transition temperature $`T_\mathrm{g}`$: while the density–density coupling of Eq. (5) becomes ineffective at $`T_\mathrm{c}`$, other transport mechanisms, not covered by the theory, remain active at lower temperatures. This interpretation of $`T_\mathrm{c}`$ is supported by various other experimental indications of a cross-over .

In liquids to which MCT has been applied in the past, the cross-over occurs at shear viscosities of the order of $`10^1`$ to $`10^3`$ Poise . We note that this is much closer to the viscosity of, say, water at room temperature (about $`10^2`$ Poise) than to the glass transition (which, according to wide-spread convention, occurs at $`10^{13}`$ Poise). We note also that the dynamic predictions of MCT are expected to work best not in the immediate vicinity of $`T_\mathrm{c}`$, but at somewhat higher temperatures where the concurrence of low-temperature transport processes can be neglected.

This suggests that MCT should be tested as a theory that describes the dynamics of glass-forming liquids at rather low viscosities, far above the glass transition, in a slightly supercooled or thermodynamically stable state. In the present work we want to show that the restriction to glass-forming liquids can be omitted altogether.

### 2.4 Applying Mode Coupling to Real-Life Liquids

Taken literally, Eqs. (4) and (5) assume a liquid composed of identical, spherical, and stiff particles: only in this case all interactions between the particles can be derived from $`S(q)`$. Extending the theory to mixtures is straightforward , but including orientational and innermolecular degrees of freedom poses extreme difficulties: the notational and calculational efforts required by models so simple as a liquid made of linear molecules , or a dilute solution of linear molecules in spheres  are intimidating. Thus, a MCT of molecular liquids is presently not available.

On the other hand, the time and temperature dependence of MCT solutions is insensitive to most of the structural information hidden in $`V_{\mathrm{𝐪𝐩𝐤}}`$. Taking into account orientational or innermolecular degrees of freedom may lead to new classes of solutions, but at least in some types of molecular liquids the fundamental mathematical structure of equations (4) and (5) will remain dominant.

In such cases, MCT solutions can be characterized by quite few parameters. Close to $`T_\mathrm{c}`$, the analytical expansions of $`\mathrm{\Phi }_q(t)f_q`$ depends in lowest order on just one nontrivial line shape parameter $`\lambda `$. Complete time correlation functions can be generated by numeric solutions of very simple MCT models:

In the minimal $`F_{12}`$ model , just one correlator $`\mathrm{\Phi }(t)`$ and two coupling coefficients in

$$m(t)=v_1\mathrm{\Phi }(t)+v_2[\mathrm{\Phi }(t)]^2$$
(6)
are sufficient to obtain relaxational stretching and the ideal glass transition. With just one more correlator, $`\mathrm{\Phi }_\mathrm{s}(t)`$, one can generate spectra with arbitrary $`\alpha `$ relaxation strengths $`f_q^\mathrm{s}`$: a bilinear memory kernel

$$m_\mathrm{s}(t)=v_\mathrm{s}\mathrm{\Phi }(t)\mathrm{\Phi }_\mathrm{s}(t)$$
(7)
couples $`\mathrm{\Phi }_\mathrm{s}(t)`$ to $`\mathrm{\Phi }(t)`$, whereas $`\mathrm{\Phi }(t)`$ does not depend on $`\mathrm{\Phi }_\mathrm{s}(t)`$.

The so defined two-correlator $`F_{12}`$ model is a physically meaningful tool for fitting experimental data. As such it has already been successfully employed in several studies of glass-forming liquids ; the theoretical background is explained especially in Ref. . A detailed numeric study has confirmed the stability of such fits .

## 3 Light Scattering Measurements

Benzene ($`T_\mathrm{m}=279`$ K, $`T_\mathrm{b}=353`$ K) was bought from Sigma Aldrich (99.9% puriss. p.a.), unpacked under inert gas and sealed into a Duran cuvette. To our surprise, the sample could be supercooled to 258 K where it remained liquid for several hours. Data were taken at seven temperatures between 258 and 352 K.

Light scattering experiments were performed using a grating double monochromator U 1000 and a six-pass Sandercock-Fabry-Perot tandem interferometer. In order to achieve stable operation at maximum resolution, both instruments are placed in insulating housings with active temperature control. The optics around the interferometer has been modified as described previously . Depending on the spectral range, the interferometer is used in series with an interference filter of either 150 or 1000 GHz bandwidth that suppresses higher-order transmission leaks of the tandem interferometer  below 3% or better. The filters are maintained at constant temperature. To account for any drift, the instrument function is redetermined periodically by automatic white-light scans.

In the present experiment, the slits of the monochromator are set to 30 – 60 – 60 – 30 $`\mu `$m, resulting in a resolution (fwhm) of 7.5 GHz; data are only used above 200 GHz. The interferometer is operated with mirror spacings of 0.4, 2.8, and 16.3 mm, corresponding to free spectral ranges of 375, 54, and 9.2 GHz; some additional data were taken with 7.5 mm (20 GHz).

On both spectrometers, a near-backscattering geometry ($`172^{}`$) is used to minimize scattering from transverse modes. In depolarized (HV) interferometer measurements, the usual leakage from the acoustic modes is seen; these lines are about a 100 times weaker than in polarized (VV) scattering, but still up to about 3 times stronger than the continuous HV spectrum. Subtracting separately measured VV spectra , we could completely remove the contamination from the HV data.

Intensity calibration is always a problem in light scattering. Best results were obtained by matching all data to the middle (54 GHz) spectral range of the interferometer. In this range intensities are reproduced after a full temperature cycle within about 3 %. The temperature-dependent intensity mismatch of other spectral ranges is higher and attains up to 20 %. Part of the problem may be due to distortions of the optical paths within the cryostat, which are particularly severe when the spectrometer is operated with small entrance opening. In the present study, intensities can also be estimated from a fit which is normalized by construction (see Figs. 3 below).

Finally, the spectra are multiplied with the detailed-balance factor,

$$\stackrel{~}{I}(\nu )=I(\nu )\mathrm{exp}(h\nu /2k_\mathrm{B}T),$$
(8)
averaged over energy-gain and energy-loss side, and converted from intensity to susceptibility

$$\chi _{\mathrm{ls}}^{\prime \prime }(\nu )=\stackrel{~}{I}(\nu )/\stackrel{~}{n}(\nu )$$
(9)
with the symmetrized Bose factor

$$\stackrel{~}{n}(\nu )=\frac{1}{\mathrm{exp}(h\nu /2k_\mathrm{B}T)\mathrm{exp}(h\nu /2k_\mathrm{B}T)}.$$
(10)
In other molecular liquids, comparison with neutron scattering  has shown that depolarized light scattering yields at least qualitatively a good representation of the dynamic susceptibility, and therefore we will interpret $`\chi _{\mathrm{ls}}^{\prime \prime }(\nu )`$ in very much the same way as a susceptibility from incoherent neutron scattering.

## 4 Data and Analysis

### 4.1 Susceptibilities on Logarithmic Scales

Fig. 1 shows susceptibilities from depolarized light scattering for seven temperatures between 258 and 352 K. In studies of glass-forming liquids, measuring susceptibilities over several decades and representing them on double logarithmic scales were decisive steps in detecting nontrivial, stretched relaxation . In the case of benzene, the same procedure, on the same absolute frequency scale, is less rewarding: too much of Fig. 1 is filled by an uninformative $`\nu ^1`$ white-noise wing.

Therefore we show the nontrivial part of our data in Fig. 2 on an enlarged scale: the strongly temperature-dependent dynamics between 15 GHz and 3 THz. With increasing frequency, the $`\chi ^{\prime \prime }(\nu )`$ begin to deviate from the white-noise limit $`\chi ^{\prime \prime }\nu ^1`$, reaching a maximum between 40 and 180 GHz which we will ascribe to structural $`\alpha `$ relaxation. A comparatively flat region leads over to a shoulder at about 2 THz, above which the susceptibilities strongly decrease. Above 5 THz we find an extended gap; innermolecular excitations are only expected above 12 THz .

The whole scenario is compatible with the high-temperature limit of what has been observed in many glass-forming systems. We note that the picture does not change up to the highest accessible temperatures: little below the boiling point, the $`\alpha `$ peak is still separated by almost a decade in frequency from the vibrational shoulder.

### 4.2 Absolute Intensities

The temperature dependence of the scattering intensity is surprising: the height of the $`\alpha `$ peak increases by about 15 on heating from 258 to 293 K; then it falls back and reaches at 352 K about the starting level. The apparent anharmonicity in the high-temperature, high-frequency limit is unexpectedly pronounced, though a similar trend has been observed in several other liquids.

To disentangle possible causes of these anomalies, we take advantage of mode-coupling fits. The physical meaning of these fits will be discussed later (Sect. 4.5); for the moment we take them just as a smooth parametrization of the measured data — with one specific advantage: Since the mode-coupling susceptibilities are obtained by Fourier transform of the derivative of a time correlation function, they obey the $`\chi ^{\prime \prime }(\nu )/\nu `$ sum rule by construction. Therefore we can take them as representing our light scattering data in absolute normalization.

Resulting curves are shown in 3: they are strictly identical to the mode-coupling fits included in Fig. 2 — except that the latter are multiplied by an amplitude $`A_{\mathrm{MC}}`$ to adjust them to the arbitrary experimental intensity. Thanks to the intrinsic normalization, Fig. 3 shows a highly regular temperature dependence. In particular, we see no longer indications for a softening of the microscopic excitation spectrum at high temperatures: in the high-frequency wing, up to the boiling point all susceptibilities coincide, as expected for harmonic motion. The $`\alpha `$ peak height increases steadily with $`T`$; only between 1 and 2 THz little experimental imperfections are visible.

The temperature dependence of $`A_{\mathrm{MC}}`$ is shown in the inset of Fig. 3. Up to 293 K the $`A_{\mathrm{MC}}(T)`$ scatter somehow, then they decrease systematically towards about 75 % of the low-temperature average. A similar decrease of depolarized scattering intensity has been observed in many other liquids. However, lacking a means of absolute normalization, it was never clear whether this decrease reflected a property of the sample or of the scattering process. Unstabilities of the experimental setup added to the difficulty. Fig. 3 it appears now that the decrease of scattering intensities at high temperatures is not due to the sample dynamics; it rather appears that $`A_{\mathrm{MC}}(T)`$ reveals a temperature variation of the Pockels coefficient that couples light scattering to the microscopic dynamics.

### 4.3 $`𝜶`$ Relaxation

For a quantitative analysis of $`\alpha `$ relaxation, we first test time-temperature superposition. Using the frequency-space representation of Eq. (3), and allowing for a temperature dependent amplitude, we rescale our data onto a master curve. Fig. 4 shows that the line shape is independent of temperature up to at least five times the peak frequency.

The $`\alpha `$ peak is obviously stretched, as can be seen by comparison to a Debye curve (dotted line). The data are far better described by one of the empirical expressions (1) or (2). The Fourier transform of the Kohlrausch stretched exponential \[Eq. (1)\] fits the master curve up to about twice the peak frequency (dashed line) with a stretching exponent $`\beta _\mathrm{K}0.73`$.

The Cole–Davidson function (2) with $`\beta _{\mathrm{CD}}0.33`$ describes the master curve to even higher frequencies (solid line). Consequently, we use Cole–Davidson fits to determine the mean relaxation time

$$\tau =dt\mathrm{\Phi }(t)/\mathrm{\Phi }(0)=\beta _{\mathrm{CD}}\tau ,$$
(11)
which in turn is used in the iterative construction of the master curve.

None of the empirical fit functions is able to fully describe the extremely flat high-frequency wing of the $`\alpha `$ peak. For about one decade, this wing roughly follows a power law $`\nu ^b`$ (dash–dotted line in Fig. 4). The exponent is about $`b0.13`$, the precise value depending on the choice of the frequency range. Such a power law is reminiscent of MCT, though it should not be taken literal as an MCT asymptote (see Sect. 4.5 below).

### 4.4 Relaxation Times

In a next step, we investigate the temperature dependence of the mean relaxation time $`\tau `$, as determined from the Cole–Davidson fits \[Eq. (11)\].

In Fig. 5 $`\tau `$ is plotted as function of temperature and compared to the shear viscosity $`\eta `$. In a good first approximation, $`\tau `$ and $`\eta `$ show the same temperature dependence. This completes the demonstration that the susceptibility peak under study is indeed due to $`\alpha `$ relaxation, in the same sense as in any glass-forming liquid. Furthermore, the approximate proportionality $`\tau \eta `$ can be used to extend available viscosity data  by more than 15 K into the supercooled phase, and by 9 K towards the boiling point.

Furthermore, Fig. 5 shows a Vogel–Fulcher fit

$$\tau \mathrm{exp}\left(\frac{E_0}{TT_0}\right)$$
(12)
to the mean relaxation times, with $`T_0=94.2`$ K and $`E_0=650.6`$ K. We abstain from any physical interpretation, since several decades in $`\tau `$ are needed for a meaningful verification of (12); we just employ the fit as a tool for a more detailed comparison of $`\tau `$ and $`\eta `$.

This comparison is performed in Figs. 6a and 6b where we divide either $`\eta `$ or $`\eta /T`$ by the Vogel-Fulcher estimate of $`\tau `$. A proportionality $`\tau \eta /T`$ is suggested by the Stokes-Einstein relation $`DT/\eta `$: when the diffusion constant $`D`$ is determined from a time correlation function,

$$\mathrm{\Phi }(t)\mathrm{exp}(Dq^2t),$$
(13)
one has $`\tau D^1`$ and thus $`\tau \eta /T`$. Of course the stretched $`\alpha `$ relaxation in benzene is not correctly described by Eq. (13). Therefore the theoretical grounds for assuming $`\tau \eta /T`$ are rather weak.

And indeed, Fig. 6 shows that $`\tau `$ is not proportional to $`\eta /T`$, nor to $`\eta `$, but something in between. Such a temperature dependence has been reported at least once before: in a neutron spin-echo experiment on the high-temperature dynamics of glycerol . We therefore conclude: the mean relaxation time observed by scattering shows the same temperature dependence as the shear viscosity — up to a prefactor of $`𝒪(𝒯)`$ which at present no theory is able to predict.

### 4.5 Mode-Coupling Fits

We now extend our analysis beyond the $`\alpha `$ peak, considering the full experimental frequency scale up to some THz. The theoretical reference is given by mode-coupling theory. MCT is perfectly compatible with the scaling properties of $`\alpha `$ relaxation obtained in the two preceeding subsections. Additionally, MCT predicts that $`\alpha `$ relaxation has a rather flat high-frequency wing which leads over to the microscopic molecular dynamics. This is just what we see in Figs. 24.

In glass-forming liquids, mode-coupling analysis usually concentrates on a scaling regime, designated as fast $`\beta `$ relaxation, which is located between $`\alpha `$ peak and microscopic frequencies. When the $`\alpha `$ relaxation becomes sufficiently slow, the dynamic susceptibility passes through a minimum, and for frequencies around this minimum simple asymptotic power laws are predicted. In benzene we find a susceptibility minimum at the two lowest temperatures. This once again supports qualitative accord with an MCT scenario, though the $`\beta `$ relaxation regime is not sufficiently developed to allow a scaling analysis.

The approximate power law $`\nu ^b`$ (Sect. 4.3, Fig. 4) in the high-frequency wing of the $`\alpha `$ peak is of the low-frequency asymptote of fast $`\beta `$ relaxation; however, the exponent $`b0.13`$ implies a line shape parameter $`\lambda 0.98`$ which, though formally allowed, is highly unlikely to represent the true asymptotic value, which whenever reliably determined has been found to fall into range of about 0.65–0.8. We therefore think that $`\nu ^b`$ represents not more than a transient: somehow related to the scaling properties of MCT, but not representing an analytical asymptote of the $`\beta `$ minimum.

Therefore, we use numerical instead of asymptotic solutions of MCT. Specifically, we use the two-correlator $`F_{12}`$ model, introduced in Sect. 2.3, which is defined by the equation of motion (4) \[with the set $`\{\mathrm{\Phi }_q\}`$ replaced by the pair $`\{\mathrm{\Phi },`$ $`\mathrm{\Phi }_\mathrm{s}\}`$\] and the memory kernels (6), (7). While $`\mathrm{\Phi }(t)`$ models the intrinsic dynamics of the system, $`\mathrm{\Phi }_\mathrm{s}(t)`$ shall be interpreted as the correlation function observed by depolarized light scattering.

The model contains seven parameters: two frequencies $`\mathrm{\Omega }`$$`\mathrm{\Omega }_\mathrm{s}`$ characterizing ballistic short-time motion, two damping coefficients $`\gamma `$$`\gamma _\mathrm{s}`$ representing fast contributions to the memory kernel in Eq. (4), and three coupling coefficients $`v_1`$, $`v_2`$ and $`v_\mathrm{s}`$. These parameters are all expected to vary smoothly and monotonously with temperature. An eighth parameter, the amplitude $`A_{\mathrm{MC}}`$ is not part of the model, but needed to adjust it to the arbitrary experimental intensity scale; these amplitudes have already been discussed above (Sect. 4.2, Fig. 3).

The inner loop of the fit routine calculates $`\mathrm{\Phi }(t)`$ and $`\mathrm{\Phi }_\mathrm{s}(t)`$ by iteratively solving Eq. (4) in the time domain . Then $`\mathrm{\Phi }_\mathrm{s}(t)`$ is converted into a susceptibility by blockwise Fourier transform, using the Filon method. The so obtained $`\chi _\mathrm{s}^{\prime \prime }(\nu )`$ are fitted to the experimental data.

This procedure is performed independently for each of the seven measured temperatures. In an attempt to reduce the number of free parameters we find that the microsopic frequency of the slave correlator can be kept at a constant value $`\mathrm{\Omega }_\mathrm{s}/2\pi =1000`$ GHz. All other parameters are found to show a weak, regular temperature dependence with only minor deviations from monotonicity, as can be seen in Figs. 7 and 8. Values are also numerically given in Table 1.

The time dependence of $`\alpha `$ relaxation is essentially given by the coupling coefficients $`v_1`$ and $`v_2`$. In Fig. 9 the values obtained from our fits are shown as points in a phase diagram. For large values of $`v_1`$ and $`v_2`$, the $`F_{12}`$ model becomes a glass. The phase boundary corresponding to the idealized liquid-glass transition is indicated in the figure.

In benzene, the coupling coefficients fall clearly in the liquid phase; with decreasing temperature the glass-transition singularity is only little approached. This correlates with the fact that the measured susceptibilities show only a very first onset of a fast $`\beta `$-relaxation minimum. For the same reason it would not be meaningful to use asymptotic scaling laws that are based on expansions in $`TT_\mathrm{c}`$. From the available $`v_1`$$`v_2`$, it is not even possible to extrapolate a hypothetical trajectory by which benzene would approach the glass transition if it could be further supercooled. Therefore it is impossible to indicate a meaningful value of the asymptotic line shape parameter $`\lambda `$.

## 5 Conclusion

We used depolarized light scattering to measure the dynamic susceptibility of liquid benzene. Four spectral ranges of two spectrometers were combined to cover frequencies from 0.5 GHz to several THz. White noise prevails up to 10 GHz (Fig. 1). Depending on temperature, a relaxational maximum is attained between 40 and 180 GHz. The high frequency wing of this maximum is extremly flat, and extends up to about 2 THz. In the supercooled state, the susceptibility passes through a slight minimum around 1 THz (Figs. 23).

Such a broad relaxation pattern cannot be described by exponential memory functions that underly conventional theories of simple liquids. Instead, our results look very similar to what has been observed in many glass-forming liquids. This confirms our starting hypothesis, and provides the basis for our quantitative data analysis.

As in glass-forming liquids, the relaxational $`\alpha `$ peak is stretched; it is even more stretched than the common fit formulæ are able to describe. Time-temperature scaling is obeyed with high precision and up to the boiling point, contradicting certain glass-transition theories which assume that $`\alpha `$ relaxation becomes Debye-like in the high temperature limit (Fig. 4).

Within the accessible temperature range, the mean relaxation time $`\tau `$ of benzene varies by more than a factor of 4, and it is roughly proportional to the shear viscosty $`\eta `$ (Fig. 5). This accord is *not* improved by applying the Stokes-Einstein formula according to which $`\tau `$ should go with $`\eta /\mathrm{T}`$ rather than $`\eta `$ (Fig. 6). Implications are discussed in Sect. 4.4.

Our observations are fully compatible with mode coupling theory. Originally, this theory attracted attention because of its ability to model a density-driven transition into a nonergodic state. Very soon, however, it became clear that this singularity does not describe glass formation. Instead, it is now generally recognized that MCT describes liquid dynamics at relatively low viscosities. In several studies of glass-forming liquids, fits were extended above the melting point of the concurrent crystalline phase, which was found to be irrelevant for the molecular dynamics under study. In our present work, we push this evolution one step further by applying MCT to a liquid that can hardly be supercooled (actually, benzene *can* be supercooled by nearly 20 K, which came out as quite a surprise). In our experiment, we cover the full range of existence, up to 1 K below the boiling point.

In this temperature range, we can no longer apply the asymptotic expansions that are used in most MCT studies of glass-forming materials. Instead, we use numeric solutions of the full mode-coupling equations of motion. An elementary model with two correlators and three coupling coefficients is sufficient for a satisfactory fit to our full experimental data set. All parameters show a smooth, physically reasonable temperature dependence (Figs. 78). Previous mode-coupling studies on glass-forming samples had mostly concentrated on the asymptotic predictions for fast $`\beta `$ relaxation. A phase diagram makes clear that this scaling regime is not accessible in benzene (Fig. 9). In such a situation numeric solutions of a minimal mode-coupling model provide the most adequate description of dynamic susceptibilities on the GHz to THz scale of structural relaxation and microscopic motion .

## Acknowledgments

We thank M. Goldammer, W. Götze, H. Schober, and W. Petry for invaluable support. M. Fuchs, M. R. Mayr, A. P. Singh and T. Voigtmann showed us how to solve the $`F_{12}`$ model. We acknowledge funding by the German DFG under project Me1958/3–1.

## References


text:
# Perturbative QCD analysis of 𝐵→ϕ𝐾^∗ decays

## A FACTORIZATION FORMULAS

In this appendix we present the explicit expressions of the factorizable and nonfactorizable amplitudes in Eq. (15). The effective Hamiltonian for the flavor-changing $`bs`$ transition is given by

$$H_{\mathrm{eff}}=\frac{G_F}{\sqrt{2}}\underset{q=u,c}{}V_q\left[C_1(\mu )O_1^{(q)}(\mu )+C_2(\mu )O_2^{(q)}(\mu )+\underset{i=3}{\overset{10}{}}C_i(\mu )O_i(\mu )\right],$$
(A1)
with the CKM matrix elements $`V_q=V_{qs}^{}V_{qb}`$ and the operators

$`O_1^{(q)}=(\overline{s}_iq_j)_{VA}(\overline{q}_jb_i)_{VA},O_2^{(q)}=(\overline{s}_iq_i)_{VA}(\overline{q}_jb_j)_{VA},`$ (A2)
$`O_3=(\overline{s}_ib_i)_{VA}{\displaystyle \underset{q}{}}(\overline{q}_jq_j)_{VA},O_4=(\overline{s}_ib_j)_{VA}{\displaystyle \underset{q}{}}(\overline{q}_jq_i)_{VA},`$ (A3)
$`O_5=(\overline{s}_ib_i)_{VA}{\displaystyle \underset{q}{}}(\overline{q}_jq_j)_{V+A},O_6=(\overline{s}_ib_j)_{VA}{\displaystyle \underset{q}{}}(\overline{q}_jq_i)_{V+A},`$ (A4)
$`O_7={\displaystyle \frac{3}{2}}(\overline{s}_ib_i)_{VA}{\displaystyle \underset{q}{}}e_q(\overline{q}_jq_j)_{V+A},O_8={\displaystyle \frac{3}{2}}(\overline{s}_ib_j)_{VA}{\displaystyle \underset{q}{}}e_q(\overline{q}_jq_i)_{V+A},`$ (A5)
$`O_9={\displaystyle \frac{3}{2}}(\overline{s}_ib_i)_{VA}{\displaystyle \underset{q}{}}e_q(\overline{q}_jq_j)_{VA},O_{10}={\displaystyle \frac{3}{2}}(\overline{s}_ib_j)_{VA}{\displaystyle \underset{q}{}}e_q(\overline{q}_jq_i)_{VA},`$ (A6)
$`i`$ and $`j`$ being the color indices. Using the unitarity condition, the CKM matrix elements for the penguin operators $`O_3`$-$`O_{10}`$ can also be expressed as $`V_u+V_c=V_t`$. The unitarity angle $`\varphi _3`$ is defined via

$$V_{ub}=|V_{ub}|\mathrm{exp}(i\varphi _3).$$
(A7)
Here we adopt the Wolfenstein parametrization for the CKM matrix upto $`O(\lambda ^3)`$,

$`\left(\begin{array}{ccc}V_{ud}& V_{us}& V_{ub}\\ V_{cd}& V_{cs}& V_{cb}\\ V_{td}& V_{ts}& V_{tb}\end{array}\right)=\left(\begin{array}{ccc}1\lambda ^2/2& \lambda & A\lambda ^3(\rho i\eta )\\ \lambda & 1\lambda ^2/2& A\lambda ^2\\ A\lambda ^3(1\rho i\eta )& A\lambda ^2& 1\end{array}\right).`$ (A8)
with the parameters ,

$`\lambda `$ $`=`$ $`0.2196\pm 0.0023,`$ (A9)
$`A`$ $`=`$ $`0.819\pm 0.035,`$ (A10)
$`R_b`$ $``$ $`\sqrt{\rho ^2+\eta ^2}=0.41\pm 0.07.`$ (A11)
The factorizable amplitudes $`F_{He}^{(q)}`$ and $`F_{Ha}^{(q)}=F_{Ha4}^{(q)}+F_{Ha6}^{(q)}`$ are written as

$`F_{Le}^{\left(q\right)}`$ $`=`$ $`8\pi C_FM_B^2{\displaystyle _0^1}𝑑x_1𝑑x_3{\displaystyle _0^{\mathrm{}}}b_1𝑑b_1b_3𝑑b_3\mathrm{\Phi }_B(x_1,b_1)`$ (A15)
$`\times \{[(1+x_3)\mathrm{\Phi }_K^{}(x_3)+r_K^{}(12x_3)(\mathrm{\Phi }_K^{}^t(x_3)+\mathrm{\Phi }_K^{}^s(x_3))]`$
$`\times E_e^{(q)}(t_e^{(1)})h_e(x_1,x_3,b_1,b_3)`$
$`+2r_K^{}\mathrm{\Phi }_K^{}^s(x_3)E_e^{(q)}(t_e^{(2)})h_e(x_3,x_1,b_3,b_1)\},`$
$`F_{Ne}^{(q)}`$ $`=`$ $`8\pi C_FM_B^2{\displaystyle _0^1}𝑑x_1𝑑x_3{\displaystyle _0^{\mathrm{}}}b_1𝑑b_1b_3𝑑b_3\mathrm{\Phi }_B(x_1,b_1)`$ (A19)
$`\times r_\varphi \{[\mathrm{\Phi }_K^{}^T(x_3)+2r_K^{}\mathrm{\Phi }_K^{}^v(x_3)+r_K^{}x_3(\mathrm{\Phi }_K^{}^v(x_3)\mathrm{\Phi }_K^{}^a(x_3))]`$
$`\times E_e^{(q)}(t_e^{(1)})h_e(x_1,x_3,b_1,b_3)`$
$`+r_K^{}[\mathrm{\Phi }_K^{}^v(x_3)+\mathrm{\Phi }_K^{}^a(x_3)]E_e^{(q)}(t_e^{(2)})h_e(x_3,x_1,b_3,b_1)\},`$
$`F_{Te}^{(q)}`$ $`=`$ $`16\pi C_FM_B^2{\displaystyle _0^1}𝑑x_1𝑑x_3{\displaystyle _0^{\mathrm{}}}b_1𝑑b_1b_3𝑑b_3\mathrm{\Phi }_B(x_1,b_1)`$ (A23)
$`\times r_\varphi \{[\mathrm{\Phi }_K^{}^T(x_3)+2r_K^{}\mathrm{\Phi }_K^{}^a(x_3)r_K^{}x_3(\mathrm{\Phi }_K^{}^v(x_3)\mathrm{\Phi }_K^{}^a(x_3))]`$
$`\times E_e^{(q)}(t_e^{(1)})h_e(x_1,x_3,b_1,b_3)`$
$`+r_K^{}[\mathrm{\Phi }_K^{}^v(x_3)+\mathrm{\Phi }_K^{}^a(x_3)]E_e^{(q)}(t_e^{(2)})h_e(x_3,x_1,b_3,b_1)\},`$
$`F_{La4}^{(q)}`$ $`=`$ $`8\pi C_FM_B^2{\displaystyle _0^1}𝑑x_2𝑑x_3{\displaystyle _0^{\mathrm{}}}b_2𝑑b_2b_3𝑑b_3`$ (A28)
$`\times \{[(1x_3)\mathrm{\Phi }_\varphi (x_2)\mathrm{\Phi }_K^{}(x_3)+2r_\varphi r_K^{}\mathrm{\Phi }_\varphi ^s(x_2)(x_3\mathrm{\Phi }_K^{}^t(x_3)+(2x_3)\mathrm{\Phi }_K^{}^s(x_3))]`$
$`\times E_{a4}^{(q)}(t_a^{(1)})h_a(x_2,1x_3,b_2,b_3)`$
$`+\left[x_2\mathrm{\Phi }_\varphi (x_2)\mathrm{\Phi }_K^{}(x_3)+2r_\varphi r_K^{}\mathrm{\Phi }_K^{}^s(x_3)((1x_2)\mathrm{\Phi }_\varphi ^t(x_2)(1+x_2)\mathrm{\Phi }_\varphi ^s(x_2))\right]`$
$`\times E_{a4}^{(q)}(t_a^{(2)})h_a(1x_3,x_2,b_3,b_2)\},`$
$`F_{Na4}^{\left(q\right)}`$ $`=`$ $`8\pi C_FM_B^2{\displaystyle _0^1}𝑑x_2𝑑x_3{\displaystyle _0^{\mathrm{}}}b_2𝑑b_2b_3𝑑b_3`$ (A33)
$`\times r_\varphi r_K^{}\{[(2x_3)(\mathrm{\Phi }_\varphi ^v(x_2)\mathrm{\Phi }_K^{}^v(x_3)+\mathrm{\Phi }_\varphi ^a(x_2)\mathrm{\Phi }_K^{}^a(x_3))`$
$`+x_3(\mathrm{\Phi }_\varphi ^v(x_2)\mathrm{\Phi }_K^{}^a(x_3)+\mathrm{\Phi }_\varphi ^a(x_2)\mathrm{\Phi }_K^{}^v(x_3))]E_{a4}^{(q)}(t_a^{(1)})h_a(x_2,1x_3,b_2,b_3)`$
$`[(1+x_2)(\mathrm{\Phi }_\varphi ^v(x_2)\mathrm{\Phi }_K^{}^v(x_3)+\mathrm{\Phi }_\varphi ^a(x_2)\mathrm{\Phi }_K^{}^a(x_3))`$
$`(1x_2)(\mathrm{\Phi }_\varphi ^v(x_2)\mathrm{\Phi }_K^{}^a(x_3)+\mathrm{\Phi }_\varphi ^a(x_2)\mathrm{\Phi }_K^{}^v(x_3))]E_{a4}^{(q)}(t_a^{(2)})h_a(1x_3,x_2,b_3,b_2)\},`$
$`F_{Ta4}^{\left(q\right)}`$ $`=`$ $`16\pi C_FM_B^2{\displaystyle _0^1}𝑑x_2𝑑x_3{\displaystyle _0^{\mathrm{}}}b_2𝑑b_2b_3𝑑b_3`$ (A38)
$`\times r_\varphi r_K^{}\{[x_3(\mathrm{\Phi }_\varphi ^v(x_2)\mathrm{\Phi }_K^{}^v(x_3)+\mathrm{\Phi }_\varphi ^a(x_2)\mathrm{\Phi }_K^{}^a(x_3))`$
$`+(2x_3)(\mathrm{\Phi }_\varphi ^v(x_2)\mathrm{\Phi }_K^{}^a(x_3)+\mathrm{\Phi }_\varphi ^a(x_2)\mathrm{\Phi }_K^{}^v(x_3))]E_{a4}^{(q)}(t_a^{(1)})h_a(x_2,1x_3,b_2,b_3)`$
$`+[(1x_2)(\mathrm{\Phi }_\varphi ^v(x_2)\mathrm{\Phi }_K^{}^v(x_3)+\mathrm{\Phi }_\varphi ^a(x_2)\mathrm{\Phi }_K^{}^a(x_3))`$
$`(1+x_2)(\mathrm{\Phi }_\varphi ^v(x_2)\mathrm{\Phi }_K^{}^a(x_3)+\mathrm{\Phi }_\varphi ^a(x_2)\mathrm{\Phi }_K^{}^v(x_3))]E_{a4}^{(q)}(t_a^{(2)})h_a(1x_3,x_2,b_3,b_2)\},`$
$`F_{La6}^{\left(q\right)}`$ $`=`$ $`16\pi C_FM_B^2{\displaystyle _0^1}𝑑x_2𝑑x_3{\displaystyle _0^{\mathrm{}}}b_2𝑑b_2b_3𝑑b_3`$ (A43)
$`\times \{[r_K^{}(1x_3)\mathrm{\Phi }_\varphi (x_2)(\mathrm{\Phi }_K^{}^t(x_3)+\mathrm{\Phi }_K^{}^s(x_3))2r_\varphi \mathrm{\Phi }_\varphi ^s(x_2)\mathrm{\Phi }_K^{}(x_3)]`$
$`\times E_{a6}^{(q)}(t_a^{(1)})h_a(x_2,1x_3,b_2,b_3)`$
$`+\left[r_\varphi x_2(\mathrm{\Phi }_\varphi ^t(x_2)\mathrm{\Phi }_\varphi ^s(x_2))\mathrm{\Phi }_K^{}(x_3)+2r_K^{}\mathrm{\Phi }_\varphi (x_2)\mathrm{\Phi }_K^{}^s(x_3)\right]`$
$`\times E_{a6}^{(q)}(t_a^{(2)})h_a(1x_3,x_2,b_3,b_2)\},`$
$`F_{Na6}^{\left(q\right)}`$ $`=`$ $`16\pi C_FM_B^2{\displaystyle _0^1}𝑑x_2𝑑x_3{\displaystyle _0^{\mathrm{}}}b_2𝑑b_2b_3𝑑b_3`$ (A46)
$`\times \{r_\varphi (\mathrm{\Phi }_\varphi ^v(x_2)+\mathrm{\Phi }_\varphi ^a(x_2))\mathrm{\Phi }_K^{}^T(x_3)E_{a6}^{(q)}(t_a^{(1)})h_a(x_2,1x_3,b_2,b_3)`$
$`+r_K^{}\mathrm{\Phi }_\varphi ^T(x_2)(\mathrm{\Phi }_K^{}^v(x_3)\mathrm{\Phi }_\varphi ^a(x_3))E_{a6}^{(q)}(t_a^{(1)})h_a(1x_3,x_2,b_3,b_2)\},`$
$`F_{Ta6}^{(q)}`$ $`=`$ $`32\pi C_FM_B^2{\displaystyle _0^1}𝑑x_2𝑑x_3{\displaystyle _0^{\mathrm{}}}b_2𝑑b_2b_3𝑑b_3`$ (A49)
$`\times \{r_\varphi (\mathrm{\Phi }_\varphi ^v(x_2)+\mathrm{\Phi }_\varphi ^a(x_2))\mathrm{\Phi }_K^{}^T(x_3)E_{a6}^{(q)}(t_a^{(1)})h_a(x_2,1x_3,b_2,b_3)`$
$`+r_K^{}\mathrm{\Phi }_\varphi ^T(x_2)(\mathrm{\Phi }_K^{}^v(x_3)\mathrm{\Phi }_K^{}^a(x_3))E_{a6}^{(q)}(t_a^{(2)})h_a(1x_3,x_2,b_3,b_2)\},`$
The expression of the factorizable amplitudes $`F_{Ha}`$ from the tree operators $`O_1`$ and $`O_2`$ are the same as $`F_{Ha4}^{(q)}`$ but with the evolution factor $`E_{a4}^{(q)}`$ replaced by $`E_{a1}^{(q)}`$.

The factors $`E(t)`$ contain the evolution from the $`W`$ boson mass to the hard scales $`t`$ in the Wilson coefficients $`a(t)`$, and from $`t`$ to the factorization scale $`1/b`$ in the Sudakov factors $`S(t)`$:

$`E_e^{(q)}\left(t\right)`$ $`=`$ $`\alpha _s\left(t\right)a_e^{(q)}(t)S_B\left(t\right)S_K^{}\left(t\right),`$ (A50)
$`E_{ai}^{(q)}\left(t\right)`$ $`=`$ $`\alpha _s\left(t\right)a_i^{(q)}(t)S_\varphi (t)S_K^{}(t).`$ (A51)
The Wilson coefficients $`a`$ in the above formulas are given by

$`a_1^{(q)}`$ $`=`$ $`C_2+{\displaystyle \frac{C_1}{N_c}},`$
$`a_3^{(q)}`$ $`=`$ $`\left(C_3+{\displaystyle \frac{C_4}{N_c}}\right)+{\displaystyle \frac{3}{2}}e_q\left(C_9+{\displaystyle \frac{C_{10}}{N_c}}\right),`$
$`a_4^{(q)}`$ $`=`$ $`\left(C_4+{\displaystyle \frac{C_3}{N_c}}\right)+{\displaystyle \frac{3}{2}}e_q\left(C_{10}+{\displaystyle \frac{C_9}{N_c}}\right),`$
$`a_5^{(q)}`$ $`=`$ $`\left(C_5+{\displaystyle \frac{C_6}{N_c}}\right)+{\displaystyle \frac{3}{2}}e_q\left(C_7+{\displaystyle \frac{C_8}{N_c}}\right),`$
$`a_6^{(q)}`$ $`=`$ $`\left(C_6+{\displaystyle \frac{C_5}{N_c}}\right)+{\displaystyle \frac{3}{2}}e_q\left(C_8+{\displaystyle \frac{C_7}{N_c}}\right),`$
$`a_e^{(q)}`$ $`=`$ $`a_3^{(q)}+a_4^{(q)}+a_5^{(q)}.`$
$`k_T`$ resummation of large logarithmic corrections to the $`B`$, $`\varphi `$ and $`K^{}`$ meson distribution amplitudes lead to the exponentials $`S_B`$, $`S_\varphi `$ and $`S_K^{}`$, respectively,

$`S_B(t)`$ $`=`$ $`\mathrm{exp}\left[s(x_1P_1^+,b_1)2{\displaystyle _{1/b_1}^t}{\displaystyle \frac{d\overline{\mu }}{\overline{\mu }}}\gamma (\alpha _s(\overline{\mu }^2))\right],`$ (A52)
$`S_\varphi (t)`$ $`=`$ $`\mathrm{exp}\left[s(x_2P_2^+,b_2)s((1x_2)P_2^+,b_2)2{\displaystyle _{1/b_2}^t}{\displaystyle \frac{d\overline{\mu }}{\overline{\mu }}}\gamma (\alpha _s(\overline{\mu }^2))\right],`$ (A53)
$`S_K^{}(t)`$ $`=`$ $`\mathrm{exp}\left[s(x_3P_3^{},b_3)s((1x_3)P_3^{},b_3)2{\displaystyle _{1/b_3}^t}{\displaystyle \frac{d\overline{\mu }}{\overline{\mu }}}\gamma (\alpha _s(\overline{\mu }^2))\right],`$ (A54)
with the quark anomalous dimension $`\gamma =\alpha _s/\pi `$. The variables $`b_1`$, $`b_2`$, and $`b_3`$, conjugate to the parton transverse momenta $`k_{1T}`$, $`k_{2T}`$, and $`k_{3T}`$, represent the transverse extents of the $`B`$, $`\varphi `$ and $`K^{}`$ mesons, respectively. The expression for the exponent $`s`$ is referred to . The above Sudakov exponentials decrease fast in the large $`b`$ region , such that the $`B\varphi K^{}`$ hard amplitudes remain sufficiently perturbative in the end-point region.

The hard functions $`h`$’s are

$`h_e(x_1,x_3,b_1,b_3)`$ $`=`$ $`K_0\left(\sqrt{x_1x_3}M_Bb_1\right)S_t(x_3)`$ (A57)
$`\times [\theta (b_1b_3)K_0\left(\sqrt{x_3}M_Bb_1\right)I_0\left(\sqrt{x_3}M_Bb_3\right)`$
$`+\theta (b_3b_1)K_0\left(\sqrt{x_3}M_Bb_3\right)I_0\left(\sqrt{x_3}M_Bb_1\right)],`$
$`h_a(x_2,x_3,b_2,b_3)`$ $`=`$ $`\left({\displaystyle \frac{i\pi }{2}}\right)^2H_0^{(1)}\left(\sqrt{x_2x_3}M_Bb_2\right)S_t(x_3)`$ (A60)
$`\times [\theta (b_2b_3)H_0^{(1)}\left(\sqrt{x_3}M_Bb_2\right)J_0\left(\sqrt{x_3}M_Bb_3\right)`$
$`+\theta (b_3b_2)H_0^{(1)}\left(\sqrt{x_3}M_Bb_3\right)J_0\left(\sqrt{x_3}M_Bb_2\right)].`$
We have proposed the parametrization for the evolution function $`S_t(x)`$ from threshold resummation ,

$`S_t(x)={\displaystyle \frac{2^{1+2c}\mathrm{\Gamma }(3/2+c)}{\sqrt{\pi }\mathrm{\Gamma }(1+c)}}[x(1x)]^c.`$ (A61)
where the parameter $`c`$ is chosen as $`c=0.4`$ for the $`B\varphi K^{}`$ decays. This factor modifies the end-point behavior of the meson distribution amplitudes, rendering them vanish faster at $`x0`$. Threshold resummation for nonfactorizable diagrams is weaker and negligible. $`K_0,I_0,H_0`$ and $`J_0`$ are the Bessel functions.

The hard scales $`t`$ are chosen as the maxima of the virtualities of the internal particles involved in the hard amplitudes, including $`1/b_i`$:

$`t_e^{(1)}`$ $`=`$ $`\mathrm{max}(\sqrt{x_3}M_B,1/b_1,1/b_3),`$ (A62)
$`t_e^{(2)}`$ $`=`$ $`\mathrm{max}(\sqrt{x_1}M_B,1/b_1,1/b_3),`$ (A63)
$`t_a^{(1)}`$ $`=`$ $`\mathrm{max}(\sqrt{1x_3}M_B,1/b_2,1/b_3),`$ (A64)
$`t_a^{(2)}`$ $`=`$ $`\mathrm{max}(\sqrt{x_2}M_B,1/b_2,1/b_3).`$ (A65)
When the PQCD formalism is extended to $`O(\alpha _s^2)`$, the hard scales can be determined more precisely and the scale independence of our predictions will be improved. Before this calculation is carried out, we consider the variation of, for example, $`t_e`$ in the following range,

$`\mathrm{max}(0.75\sqrt{x_3}M_B,1/b_1,1/b_3)<t_e^{(1)}<\mathrm{max}(1.25\sqrt{x_3}M_B,1/b_1,1/b_3),`$ (A66)
$`\mathrm{max}(0.75\sqrt{x_1}M_B,1/b_1,1/b_3)<t_e^{(2)}<\mathrm{max}(1.25\sqrt{x_1}M_B,1/b_1,1/b_3),`$ (A67)
in order to estimate the $`O(\alpha _s^2)`$ corrections. The range for $`t_a`$ is chosen in a similar way.

The nonfactorizable amplitudes $`_{He}^{(q)}=_{He3}^{\left(q\right)}+_{He4}^{\left(q\right)}+_{He5}^{\left(q\right)}+_{He6}^{\left(q\right)}`$ and $`_{Ha}^{(q)}=_{Ha3}^{\left(q\right)}+_{Ha5}^{\left(q\right)}`$, depending on kinematic variables of all the three mesons , are written as

$`_{Le3}^{(q)}`$ $`=`$ $`16\pi C_FM_B^2\sqrt{2N_c}{\displaystyle _0^1}d[x]{\displaystyle _0^{\mathrm{}}}b_1𝑑b_1b_2𝑑b_2\mathrm{\Phi }_B(x_1,b_1)`$ (A72)
$`\times \{\mathrm{\Phi }_\varphi (x_2)[(x_2+x_3)\mathrm{\Phi }_K^{}(x_3)+r_K^{}x_3(\mathrm{\Phi }_K^{}^t(x_3)+\mathrm{\Phi }_K^{}^s(x_3))]`$
$`\times E_{e3}^{(q)}(t_d^{(1)})h_d^{(1)}(x_1,x_2,x_3,b_1,b_2)`$
$`+\mathrm{\Phi }_\varphi (x_2)\left[(1x_2)\mathrm{\Phi }_K^{}(x_3)+r_K^{}x_3(\mathrm{\Phi }_K^{}^t(x_3)\mathrm{\Phi }_K^{}^s(x_3))\right]`$
$`\times E_{e3}^{(q)}(t_d^{(2)})h_d^{(2)}(x_1,x_2,x_3,b_1,b_2)\},`$
$`_{Ne3}^{(q)}`$ $`=`$ $`16\pi C_FM_B^2\sqrt{2N_c}{\displaystyle _0^1}d[x]{\displaystyle _0^{\mathrm{}}}b_1𝑑b_1b_2𝑑b_2\mathrm{\Phi }_B(x_1,b_1)`$ (A78)
$`\times r_\varphi \{[x_2(\mathrm{\Phi }_\varphi ^v(x_2)+\mathrm{\Phi }_\varphi ^a(x_2))\mathrm{\Phi }_K^{}^T(x_3)`$
$`2r_K^{}(x_2+x_3)(\mathrm{\Phi }_\varphi ^v(x_2)\mathrm{\Phi }_K^{}^v(x_3)+\mathrm{\Phi }_\varphi ^a(x_2)\mathrm{\Phi }_K^{}^a(x_3))]`$
$`\times E_{e3}^{(q)}(t_d^{(1)})h_d^{(1)}(x_1,x_2,x_3,b_1,b_2)`$
$`+(1x_2)(\mathrm{\Phi }_\varphi ^v(x_2)+\mathrm{\Phi }_\varphi ^a(x_2))\mathrm{\Phi }_K^{}^T(x_3)`$
$`\times E_{e3}^{(q)}(t_d^{(2)})h_d^{(2)}(x_1,x_2,x_3,b_1,b_2)\},`$
$`_{Te3}^{\left(q\right)}`$ $`=`$ $`32\pi C_FM_B^2\sqrt{2N_c}{\displaystyle _0^1}d[x]{\displaystyle _0^{\mathrm{}}}b_1𝑑b_1b_2𝑑b_2\mathrm{\Phi }_B(x_1,b_1)`$ (A84)
$`\times r_\varphi \{[x_2(\mathrm{\Phi }_\varphi ^v(x_2)+\mathrm{\Phi }_\varphi ^a(x_2))\mathrm{\Phi }_K^{}^T(x_3)`$
$`2r_K^{}(x_2+x_3)(\mathrm{\Phi }_\varphi ^v(x_2)\mathrm{\Phi }_K^{}^a(x_3)+\mathrm{\Phi }_\varphi ^a(x_2)\mathrm{\Phi }_K^{}^v(x_3))]`$
$`\times E_{e3}^{(q)}(t_d^{(1)})h_d^{(1)}(x_1,x_2,x_3,b_1,b_2)`$
$`+(1x_2)(\mathrm{\Phi }_\varphi ^v(x_2)+\mathrm{\Phi }_\varphi ^a(x_2))\mathrm{\Phi }_K^{}^T(x_3)`$
$`\times E_{e3}^{(q)}(t_d^{(2)})h_d^{(2)}(x_1,x_2,x_3,b_1,b_2)\},`$
$`_{Le5}^{(q)}`$ $`=`$ $`16\pi C_FM_B^2\sqrt{2N_c}{\displaystyle _0^1}d[x]{\displaystyle _0^{\mathrm{}}}b_1𝑑b_1b_2𝑑b_2\mathrm{\Phi }_B(x_1,b_1)`$ (A93)
$`\times r_\varphi \{[x_2(\mathrm{\Phi }_\varphi ^t(x_2)\mathrm{\Phi }_\varphi ^s(x_2))\mathrm{\Phi }_K^{}(x_3)`$
$`+r_K^{}x_2(\mathrm{\Phi }_\varphi ^t(x_2)\mathrm{\Phi }_\varphi ^s(x_2))(\mathrm{\Phi }_K^{}^t(x_3)\mathrm{\Phi }_K^{}^s(x_3))`$
$`+r_K^{}x_3(\mathrm{\Phi }_\varphi ^t(x_2)+\mathrm{\Phi }_\varphi ^s(x_2))(\mathrm{\Phi }_K^{}^t(x_3)+\mathrm{\Phi }_K^{}^s(x_3))]`$
$`\times E_{e5}^{(q)}(t_d^{(1)})h_d^{(1)}(x_1,x_2,x_3,b_1,b_2)`$
$`+[(1x_2)(\mathrm{\Phi }_\varphi ^t(x_2)+\mathrm{\Phi }_\varphi ^s(x_2))\mathrm{\Phi }_K^{}(x_3)`$
$`+r_K^{}(1x_2)(\mathrm{\Phi }_\varphi ^t(x_2)+\mathrm{\Phi }_\varphi ^s(x_2))(\mathrm{\Phi }_K^{}^t(x_3)\mathrm{\Phi }_K^{}^s(x_3))`$
$`+r_K^{}x_3(\mathrm{\Phi }_\varphi ^t(x_2)\mathrm{\Phi }_\varphi ^s(x_2))(\mathrm{\Phi }_K^{}^t(x_3)+\mathrm{\Phi }_K^{}^s(x_3))]`$
$`\times E_{e5}^{(q)}(t_d^{(2)})h_d^{(2)}(x_1,x_2,x_3,b_1,b_2)\},`$
$`_{Ne5}^{(q)}`$ $`=`$ $`16\pi C_FM_B^2\sqrt{2N_c}{\displaystyle _0^1}d[x]{\displaystyle _0^{\mathrm{}}}b_1𝑑b_1b_2𝑑b_2\mathrm{\Phi }_B(x_1,b_1)`$ (A96)
$`\times r_K^{}x_3\mathrm{\Phi }_\varphi ^T(x_2)(\mathrm{\Phi }_K^{}^v(x_3)\mathrm{\Phi }_K^{}^a(x_3))`$
$`\times \left\{E_{e5}^{(q)}(t_d^{(1)})h_d^{(1)}(x_1,x_2,x_3,b_1,b_2)+E_{e5}^{(q)}(t_d^{(2)})h_d^{(2)}(x_1,x_2,x_3,b_1,b_2)\right\},`$
$`_{Te5}^{\left(q\right)}=2_{Ne5}^{(q)},`$ (A97)
$`_{Le6}^{(q)}`$ $`=`$ $`16\pi C_FM_B^2\sqrt{2N_c}{\displaystyle _0^1}d[x]{\displaystyle _0^{\mathrm{}}}b_1𝑑b_1b_2𝑑b_2\mathrm{\Phi }_B(x_1,b_1)`$ (A102)
$`\times \mathrm{\Phi }_\varphi (x_2)\{[x_2\mathrm{\Phi }_K^{}(x_3)+r_K^{}x_3(\mathrm{\Phi }_K^{}^t(x_3)\mathrm{\Phi }_K^{}^s(x_3))]`$
$`\times E_{e5}^{(q)}(t_d^{(1)})h_d^{(1)}(x_1,x_2,x_3,b_1,b_2)`$
$`+\left[(1x_2+x_3)\mathrm{\Phi }_K^{}(x_3)+r_K^{}x_3(\mathrm{\Phi }_K^{}^t(x_3)+\mathrm{\Phi }_K^{}^s(x_3))\right]`$
$`\times E_{e5}^{(q)}(t_d^{(2)})h_d^{(2)}(x_1,x_2,x_3,b_1,b_2)\},`$
$`_{Ne6}^{(q)}`$ $`=`$ $`16\pi C_FM_B^2\sqrt{2N_c}{\displaystyle _0^1}d[x]{\displaystyle _0^{\mathrm{}}}b_1𝑑b_1b_2𝑑b_2\mathrm{\Phi }_B(x_1,b_1)`$ (A107)
$`\times r_\varphi \{x_2(\mathrm{\Phi }_\varphi ^v(x_2)\mathrm{\Phi }_\varphi ^a(x_2))\mathrm{\Phi }_K^{}^T(x_3)E_{e5}^{(q)}(t_d^{(1)})h_d^{(1)}(x_1,x_2,x_3,b_1,b_2)`$
$`+[(1x_2)(\mathrm{\Phi }_\varphi ^v(x_2)\mathrm{\Phi }_\varphi ^a(x_2))\mathrm{\Phi }_K^{}^T(x_3)`$
$`2r_K^{}(1x_2+x_3)(\mathrm{\Phi }_\varphi ^v(x_2)\mathrm{\Phi }_K^{}^v(x_3)\mathrm{\Phi }_\varphi ^a(x_2)\mathrm{\Phi }_K^{}^a(x_3))]`$
$`\times E_{e5}^{(q)}(t_d^{(2)})h_d^{(2)}(x_1,x_2,x_3,b_1,b_2)\},`$
$`_{Te6}^{(q)}`$ $`=`$ $`32\pi C_FM_B^2\sqrt{2N_c}{\displaystyle _0^1}d[x]{\displaystyle _0^{\mathrm{}}}b_1𝑑b_1b_2𝑑b_2\mathrm{\Phi }_B(x_1,b_1)`$ (A112)
$`\times r_\varphi \{x_2(\mathrm{\Phi }_\varphi ^v(x_2)\mathrm{\Phi }_\varphi ^a(x_2))\mathrm{\Phi }_K^{}^T(x_3)E_{e5}^{(q)}(t_d^{(1)})h_d^{(1)}(x_1,x_2,x_3,b_1,b_2)`$
$`+[(1x_2)(\mathrm{\Phi }_\varphi ^v(x_2)\mathrm{\Phi }_\varphi ^a(x_2))\mathrm{\Phi }_K^{}^T(x_3)`$
$`2r_K^{}(1x_2+x_3)(\mathrm{\Phi }_\varphi ^v(x_2)\mathrm{\Phi }_K^{}^a(x_3)\mathrm{\Phi }_\varphi ^a(x_2)\mathrm{\Phi }_K^{}^v(x_3))]`$
$`\times E_{e5}^{(q)}(t_d^{(2)})h_d^{(2)}(x_1,x_2,x_3,b_1,b_2)\},`$
$`_{La3}^{(q)}`$ $`=`$ $`16\pi C_FM_B^2\sqrt{2N_c}{\displaystyle _0^1}d[x]{\displaystyle _0^{\mathrm{}}}b_1𝑑b_1b_2𝑑b_2\mathrm{\Phi }_B(x_1,b_1)`$ (A120)
$`\times \{[(1x_3)\mathrm{\Phi }_\varphi (x_2)\mathrm{\Phi }_K^{}(x_3)+r_\varphi r_K^{}((1+x_2x_3)(\mathrm{\Phi }_\varphi ^t(x_2)\mathrm{\Phi }_K^{}^t(x_3)`$
$`\mathrm{\Phi }_\varphi ^s(x_2)\mathrm{\Phi }_K^{}^s(x_3))(1x_2x_3)(\mathrm{\Phi }_\varphi ^t(x_2)\mathrm{\Phi }_K^{}^s(x_3)\mathrm{\Phi }_\varphi ^s(x_2)\mathrm{\Phi }_K^{}^t(x_3)))]`$
$`\times E_{a3}^{(q)}(t_f^{(1)})h_f^{(1)}(x_1,x_2,x_3,b_1,b_2)`$
$`[x_2\mathrm{\Phi }_\varphi (x_2)\mathrm{\Phi }_K^{}(x_3)2r_\varphi r_K^{}(\mathrm{\Phi }_\varphi ^t(x_2)\mathrm{\Phi }_K^{}^t(x_3)+\mathrm{\Phi }_\varphi ^s(x_2)\mathrm{\Phi }_K^{}^s(x_3))`$
$`+r_\varphi r_K^{}(1+x_2x_3)(\mathrm{\Phi }_\varphi ^t(x_2)\mathrm{\Phi }_K^{}^t(x_3)\mathrm{\Phi }_\varphi ^s(x_2)\mathrm{\Phi }_K^{}^s(x_3))`$
$`+r_\varphi r_K^{}(1x_2x_3)(\mathrm{\Phi }_\varphi ^t(x_2)\mathrm{\Phi }_K^{}^s(x_3)\mathrm{\Phi }_\varphi ^s(x_2)\mathrm{\Phi }_K^{}^t(x_3))]`$
$`\times E_{a3}^{(q)}(t_d^{(2)})h_f^{(2)}(x_1,x_2,x_3,b_1,b_2)\},`$
$`_{Na3}^{(q)}`$ $`=`$ $`32\pi C_FM_B^2\sqrt{2N_c}{\displaystyle _0^1}d[x]{\displaystyle _0^{\mathrm{}}}b_1𝑑b_1b_2𝑑b_2\mathrm{\Phi }_B(x_1,b_1)`$ (A122)
$`\times r_\varphi r_K^{}\left[\mathrm{\Phi }_\varphi ^v(x_2)\mathrm{\Phi }_K^{}^v(x_3)+\mathrm{\Phi }_\varphi ^a(x_2)\mathrm{\Phi }_K^{}^a(x_3)\right]E_{a3}^{(q)}(t_f^{(2)})h_f^{(2)}(x_1,x_2,x_3,b_1,b_2),`$
$`_{Ta3}^{(q)}`$ $`=`$ $`64\pi C_FM_B^2\sqrt{2N_c}{\displaystyle _0^1}d[x]{\displaystyle _0^{\mathrm{}}}b_1𝑑b_1b_2𝑑b_2\mathrm{\Phi }_B(x_1,b_1)`$ (A124)
$`\times r_\varphi r_K^{}\left[\mathrm{\Phi }_\varphi ^v(x_2)\mathrm{\Phi }_K^{}^a(x_3)+\mathrm{\Phi }_\varphi ^a(x_2)\mathrm{\Phi }_K^{}^v(x_3)\right]E_{a3}^{(q)}(t_f^{(2)})h_f^{(2)}(x_1,x_2,x_3,b_1,b_2),`$
$`_{La5}^{(q)}`$ $`=`$ $`16\pi C_FM_B^2\sqrt{2N_c}{\displaystyle _0^1}d[x]{\displaystyle _0^{\mathrm{}}}b_1𝑑b_1b_2𝑑b_2\mathrm{\Phi }_B(x_1,b_1)`$ (A129)
$`\times \{[r_K^{}(1x_3)\mathrm{\Phi }_\varphi (x_2)(\mathrm{\Phi }_K^{}^t(x_3)\mathrm{\Phi }_K^{}^s(x_3))r_\varphi x_2(\mathrm{\Phi }_\varphi ^t(x_2)+\mathrm{\Phi }_\varphi ^s(x_2))\mathrm{\Phi }_K^{}(x_3)]`$
$`\times E_{a5}^{(q)}(t_f^{(1)})h_f^{(1)}(x_1,x_2,x_3,b_1,b_2)`$
$`+[r_\varphi (2x_2)(\mathrm{\Phi }_\varphi ^t(x_2)+\mathrm{\Phi }_\varphi ^s(x_2))\mathrm{\Phi }_K^{}(x_3)`$
$`+r_K^{}(1+x_3)\mathrm{\Phi }_\varphi (x_2)(\mathrm{\Phi }_K^{}^t(x_3)\mathrm{\Phi }_K^{}^s(x_3))]E_{a5}^{(q)}(t_f^{(2)})h_f^{(2)}(x_1,x_2,x_3,b_1,b_2)\},`$
$`_{Na5}^{(q)}`$ $`=`$ $`16\pi C_FM_B^2\sqrt{2N_c}{\displaystyle _0^1}d[x]{\displaystyle _0^{\mathrm{}}}b_1𝑑b_1b_2𝑑b_2\mathrm{\Phi }_B(x_1,b_1)`$ (A134)
$`\times \{[r_\varphi x_2(\mathrm{\Phi }_\varphi ^v(x_2)+\mathrm{\Phi }_\varphi ^a(x_2))\mathrm{\Phi }_K^{}^T(x_3)r_K^{}(1x_3)\mathrm{\Phi }_\varphi ^T(x_2)(\mathrm{\Phi }_K^{}^v(x_3)\mathrm{\Phi }_K^{}^a(x_3))]`$
$`\times E_{a5}^{(q)}(t_f^{(1)})h_d^{(1)}(x_1,x_2,x_3,b_1,b_2)`$
$`+\left[r_\varphi (2x_2)(\mathrm{\Phi }_\varphi ^v(x_2)+\mathrm{\Phi }_\varphi ^a(x_2))\mathrm{\Phi }_K^{}^T(x_3)r_K^{}(1+x_3)\mathrm{\Phi }_\varphi ^T(x_2)(\mathrm{\Phi }_K^{}^v(x_3)\mathrm{\Phi }_K^{}^a(x_3))\right]`$
$`\times E_{a5}^{(q)}(t_f^{(2)})h_f^{(2)}(x_1,x_2,x_3,b_1,b_2)\},`$
$`_{Ta5}^{(q)}=2_{Na5}^{(q)}.`$ (A135)
The expressions of the nonfactorizable amplitudes $`_{Ha}`$ and $`_{He4}`$ are the same as $`_{Ha3}^{(q)}`$ and $`_{He3}^{(q)}`$ but with the evolution factors $`E_{a3}^{(q)}`$ and $`E_{e3}^{(q)}`$ replaced by $`E_{a1}^{(q)}`$ and $`E_{e4}^{(q)}`$, respectively.

The evolution factors are given by

$`E_{ei}^{\left(q\right)}\left(t\right)`$ $`=`$ $`\alpha _s\left(t\right)a_i^{\left(q\right)}(t)S\left(t\right)|_{b_3=b_1},`$ (A136)
$`E_{ai}^{\left(q\right)}\left(t\right)`$ $`=`$ $`\alpha _s\left(t\right)a_i^{\left(q\right)}(t)S\left(t\right)|_{b_3=b_2},`$ (A137)
with the Sudakov factor $`S=S_BS_\varphi S_K^{}`$. The Wilson coefficients $`a`$ appearing in the above formulas are

$`a_1^{}`$ $`=`$ $`{\displaystyle \frac{C_1}{N_c}},`$
$`a_3^{(q)}`$ $`=`$ $`{\displaystyle \frac{1}{N_c}}\left(C_3+{\displaystyle \frac{3}{2}}e_qC_9\right),`$
$`a_4^{(q)}`$ $`=`$ $`{\displaystyle \frac{1}{N_c}}\left(C_4+{\displaystyle \frac{3}{2}}e_qC_{10}\right),`$
$`a_5^{(q)}`$ $`=`$ $`{\displaystyle \frac{1}{N_c}}\left(C_5+{\displaystyle \frac{3}{2}}e_qC_7\right),`$
$`a_6^{(q)}`$ $`=`$ $`{\displaystyle \frac{1}{N_c}}\left(C_6+{\displaystyle \frac{3}{2}}e_qC_8\right).`$
The hard functions $`h^{(j)}`$, $`j=1`$ and 2, are written as

$`h_d^{(j)}`$ $`=`$ $`[\theta (b_1b_2)K_0\left(DM_Bb_1\right)I_0\left(DM_Bb_2\right)`$ (A141)
$`+\theta (b_2b_1)K_0\left(DM_Bb_2\right)I_0\left(DM_Bb_1\right)]`$
$`\times K_0(D_jM_Bb_2),\text{for }D_j^20,`$
$`\times {\displaystyle \frac{i\pi }{2}}H_0^{(1)}\left(\sqrt{|D_j^2|}M_Bb_2\right),\text{for }D_j^20,`$
$`h_f^{(j)}`$ $`=`$ $`{\displaystyle \frac{i\pi }{2}}[\theta (b_1b_2)H_0^{(1)}\left(FM_Bb_1\right)J_0\left(FM_Bb_2\right)`$ (A145)
$`+\theta (b_2b_1)H_0^{(1)}\left(FM_Bb_2\right)J_0\left(FM_Bb_1\right)]`$
$`\times K_0(F_jM_Bb_1),\text{for }F_j^20,`$
$`\times {\displaystyle \frac{i\pi }{2}}H_0^{(1)}\left(\sqrt{|F_j^2|}M_Bb_1\right),\text{for }F_j^20,`$
with the variables,

$`D^2`$ $`=`$ $`x_1x_3,`$ (A146)
$`D_1^2`$ $`=`$ $`(x_1x_2)x_3,`$ (A147)
$`D_2^2`$ $`=`$ $`(1x_1x_2)x_3,`$ (A148)
$`F^2`$ $`=`$ $`x_2\left(1x_3\right),`$ (A149)
$`F_1^2`$ $`=`$ $`(x_1x_2)\left(1x_3\right),`$ (A150)
$`F_2^2`$ $`=`$ $`x_1+x_2+\left(1x_1x_2\right)\left(1x_3\right).`$ (A151)
The hard scales $`t^{(j)}`$ are chosen as

$`t_d^{(1)}`$ $`=`$ $`\mathrm{max}(DM_B,\sqrt{|D_1^2|}M_B,1/b_1,1/b_2),`$ (A152)
$`t_d^{(2)}`$ $`=`$ $`\mathrm{max}(DM_B,\sqrt{|D_2^2|}M_B,1/b_1,1/b_2),`$ (A153)
$`t_f^{(1)}`$ $`=`$ $`\mathrm{max}(FM_B,\sqrt{|F_1^2|}M_B,1/b_1,1/b_2),`$ (A154)
$`t_f^{(2)}`$ $`=`$ $`\mathrm{max}(FM_B,\sqrt{|F_2^2|}M_B,1/b_1,1/b_2).`$ (A155)


text:
# Finite size scaling in the solar wind magnetic field energy density as seen by WIND

## 1 Introduction

Statistical properties of the interplanetary magnetic field (IMF) fluctuations are a topic of considerable interest in space research. The subject is closely related to energy transport and acceleration processes in the solar wind \[????\]. An approach is to consider MHD turbulence as the process responsible for observed statistical features of the IMF fluctuations such as intermittency \[??\]. Single point measurements can not uniquely determine the existence of turbulence \[?\] and ideally one needs to construct a structure function from a range of spatial locations in the fluid. However, data taken over long intervals in the solar wind is routinely single point and can yield strongly suggestive, if not definitive results, and it is this type of data that we treat here.

A hallmark of statistical intermittency is the presence of large deviations from the average value on different scales. An increased probability of finding such large deviations is manifested in the departure of the PDF from Gaussian toward a leptokurtic distribution \[??\] (see also \[?\]). It is well established that such intermittency can be caused by the fluctuations in the rate of energy transfer of the turbulent cascade \[?\] as suggested in Kolmogorov’s 1962 theory \[?\]. Following Kolmogorov’s ideas Castaing proposed an empirical model for the PDF of velocity differences \[?\]. Given that: 1) for constant energy transfer rate $`ϵ`$, the fluctuating quantity has a Gaussian distribution and 2) the width of the Gaussian has a log-normal distribution it was shown that the resultant Castaing distribution gives a good fit to the velocity difference PDFs in laboratory fluid turbulence experiments. In the case of the solar wind, one can obtain a good fit to the PDF of velocity and magnetic field fluctuations by this method \[??\] or can consider the fluctuations about the mean value \[?\],but as we shall see this technique can not be applied over the entire dynamic range of the magnetic field. Fitting a curve to a real PDF over its full range is rather difficult due to the large statistical errors present for the less frequently occurring large fluctuations. In practice one has to discard significant amount of data in these tails of the PDFs and work only around the center of the distribution curves. For example, in ? all events larger then $`3`$ times the standard deviation of the original sample were neglected. The PDF rescaling method used in this paper is free of that limitation as we do not fit a specific distribution to the data. Instead, we extract the scaling properties of the fluctuations directly from the data. Importantly the scaling for the entire dynamic range of the investigated PDFs is obtained from the statistics of the smallest fluctuations. The scaling is thus derived using points in the center of the distribution (with very small statistical errors) and then applied to the PDFs as a whole.

We find that the PDF of fluctuations in magnetic energy density is mono scaling. The corresponding collapse of the rescaled PDF curves reveals the time scales over which similar physical processes occur and also confirms any correlations suggested by the inverse power-law form of the power spectra. Moreover, it quantifies the asymptotic behavior of the distribution of the fluctuations, which is essential for constraining turbulence models \[?\]. Given the scaling exponent we can then use a Fokker-Planck approach to model the statistical behavior of the time series.

The WIND solar wind magnetic field \[?\] dataset \[??\] comprises over $`1`$ million, $`46`$ second averaged samples from January 1995 to December 1998 inclusive, calculated from the WIND spacecraft key parameter database. The selection criteria for solar wind data was given by the component of the spacecraft position vector along the Earth-Sun line, $`X>0`$, and the vector magnitude, $`R>30`$ RE. The data set includes intervals of both slow and fast speed streams.

Similarly to other satellite measurements short gaps in WIND data file were present. To minimize the errors caused by such incomplete measurements we omitted any intervals where the gap was larger than $`15\%`$. The original data were not averaged nor detrended. The data is not evenly sampled but there are two dominant sampling frequencies: $`1/46`$ Hz and $`1/92`$ Hz. We use sampling frequency $`f_s`$ of $`1/46`$ as our base and treat other temporal resolutions as gaps when the accuracy requires it ($`\tau 92`$ seconds).

## 2 Scaling of the fluctuation PDF

Differencing techniques date back to the 1920s when Richardson conveyed the image of the turbulent cascade and proposed the velocity difference as an ideal field for statistical studies \[?\]. In MHD turbulence the differencing method can also be applied to magnetic field magnitude measurements. Here, however, we will first investigate the scaling properties of the magnetic energy density fluctuations given by $`B^2(t)`$. Let $`B(t)`$ represent the time series of the magnetic field magnitude and $`B^2(t)`$ its corresponding energy density. A set of time series $`\delta B^2(t,\tau )`$ is obtained for each value of time lag $`\tau `$:

$$\delta B^2(t,\tau )=B^2(t+\tau )B^2(t)$$
(1)
The PDF $`P(\delta B^2,\tau )`$ is then calculated for each time series $`\delta B^2(t,\tau )`$. Figure 2 shows the resultant unscaled PDFs of the magnetic field energy density fluctuations for different values of the time lag $`\tau =46\times 2^N`$ seconds where $`N=0,1,2,\mathrm{},17`$ giving a range of time scales between $`46`$ seconds and about $`70`$ days. We plot the PDF for all values of $`\delta B^2`$ for which there are at least $`150`$ samples per bin.

A generic one parameter rescaling method (the finite size scaling approach, see e.g. ???) is applied to these PDFs. We first assume that the distributions can be described by a stable, symmetric law (a Gaussian or Lévy \[?\]) within a finite scaling range. We use the peaks of the PDFs to obtain the scaling exponent $`s`$. This is important as the peaks are the most accurate parts of the distributions. Figure 4 shows these PDFs rescaled with respect to their $`\sigma (\tau )`$ (see e.g. \[??\]) and we see that these also do not collapse onto a single curve.

Figure 6 shows the peaks $`P(0,\tau )`$ of the unscaled PDFs (shown in Fig. 2) plotted versus $`\tau `$ on log-log axes. We see that there is a range of $`\tau `$ up to $`26`$ hours for which $`P(0,\tau )`$ is well described by a power law $`\tau ^s`$ with index $`s=0.42\pm 0.02`$. This break in the scaling at $`\tau 26`$ hours is consistent with that found previously (see e.g ???). Within this range we now attempt to collapse the entire unscaled PDF shown in Fig. 2 onto a single master curve using the following change of variables:

$$P(\delta B^2,\tau )=\tau ^sP_s(\delta B^2\tau ^s,\tau )$$
(2)
If the initial assumption of the stable and symmetric distributions was correct a single parameter rescaling, given by equation (2), for a mono-fractal process, would give a perfect collapse of PDFs on all scales. A self-similar Brownian walk is a good example of the process where such collapse can be observed (see e.g. ?). Figure 8 shows the result of the above one parameter rescaling applied to the unscaled PDF of IMF energy density fluctuations shown in Fig 2. We see that the rescaling procedure (2) using the value of the exponent $`s`$ of the peaks $`P(0,\tau )`$, as shown in Fig 6, gives good collapse of the curves onto a single common functional form for the entire range of the data.

The successful rescaling of the PDFs now reveals some key features of the processes governing the magnetic field energy density fluctuations. In particular, as we will show below, one can quantify an asymptotic behavior of the rescaled PDFs. A single parameter rescaling strongly suggests that the resultant distribution is stable and as such should converge to Gaussian or Lévy distribution for large fluctuations \[?\]. The leptokurtic character of the PDFs is still present after the rescaling indicating that the Lévy distribution is more appropriate to model the functional form of the curves. For a system where $`B^2`$ has an upper, physical or instrumental, limit such a distribution is truncated. Importantly, truncated Lévy distributions are still 1) stable and 2) go over to Gaussian for sufficiently large time lag $`\tau `$ \[?\]. Calculation of the Hurst exponent for the $`B^2`$ time series, by direct examination of the $`\sigma ^2\tau ^{2H}`$ relation as well as the “growth of range” algorithm, confirms such a limit does exist - we find a mean exponent $`H=0.28\pm 0.02`$ up to $`26`$ hours beyond which the variance of the signal saturates. We then fit a truncated Lévy distribution to the large $`\delta B^2`$ asymptotes of the rescaled PDFs. This Gamma distribution is of the form \[see ?\]:

$$P(\delta B^2)=C_\pm exp(\frac{|\delta B^2|}{\mathrm{\Delta }})|\delta B^2|^{(1+\frac{1}{\alpha })}$$
(3)
Two dashed lines on Fig. 8 show (displaced for clarity) the Gamma distribution of the large energy density fluctuations. This best fit of (3) to each of the tails of the rescaled PDFs is obtained for the power law index $`\alpha 0.66`$ and parameters $`C_{}=0.9`$, $`C_+=1`$ and $`\mathrm{\Delta }=100`$. The maximum time scale of about $`26`$ hours beyond which the scaling no longer holds is in good agreement with previous results \[??\], (see also ? and references therein).

It has been found previously \[?\] that the magnetic field magnitude fluctuations are not self-similar but rather multi-fractal. For such processes the scaling derived from $`P(0,\tau )`$ would not be expected to rescale the entire PDF as above. To verify this we repeated the rescaling procedure for magnetic field magnitude differences $`\delta B(t,\tau )=B(t+\tau )B(t)`$. Figure 10 shows the result of one parameter rescaling applied to the PDFs of the magnetic field magnitude fluctuations. The scaling procedure is satisfactory only up to $`3`$ standard deviations of the original sample. This confirms the results of ?? where a two parameter Castaing fit to values within $`3`$ standard deviations of the original sample yields scaling in one parameter and weak variation in the other. Attempts to improve the collapse by using information in the tails (values $`|\delta B|>3\sigma `$) would introduce a significant error in the estimation of the scaling exponent $`s`$.

However, the difference in scaling between the PDFs of $`\delta B^2`$ and $`\delta B`$ seen here may simply arise from the long range correlations present in the magnetic field magnitude measurements. This follows since:

$$(\delta B)^2=B^2(t+\tau )B^2(t)2(B(t)B(t+\tau )B^2(t))$$
(4)
The first two terms, $`B^2(t+\tau )B^2(t)`$ are the fluctuation of the magnetic energy density and as we have seen this quantity is mono-scaling. The last term, which includes $`B(t)B(t+\tau )`$, will however be significant when the autocorrelation function of the IMF magnitude time series is non negligible.

The Fokker-Planck equation provides an important link between statistical studies and the dynamical approach expressed by the Langevin equation \[?\]. The mono-scaling of the magnetic field energy density PDF, together with the finite value of the samples’ variance, indicates that a Fokker-Planck approach can be used to study the dynamics of the unscaled PDF $`P(\delta B^2,t)`$ in time and with respect to the coordinate $`\delta B^2`$ \[?\]. Recently a fractional Fokker-Planck equation has been obtained that can be used to treat Lévy walk PDF dynamics \[?\]. Alternatively, the anomalous diffusion of the PDF, consistent with truncated Lévy walk, can be obtained by introduction of a functional dependence of the diffusion coefficient on the “spatial” coordinate (in our case $`\delta B^2`$). One can then write a Fokker-Planck equation for the evolution of the PDF as:

$$\frac{P}{t}=_\beta (P\gamma (\delta B^2))+_\beta ^2DP$$
(5)
where $`PP(\delta B^2,t)`$ is a distribution function, $`\gamma `$ is called the friction coefficient and $`DD(\delta B^2)`$ is a diffusion coefficient which in this case depends on the magnetic energy density fluctuations. The differential operator $`_\beta =`$ should be understood as:

$$_\beta =\frac{}{(\delta B^2)}$$
(6)
Such a functional dependence of the diffusion coefficient on $`\delta B^2`$ leads to the anomalous diffusion resulting in the departure from the well known Einstein law relating variance of the signal and the time increments ?.

## 3 Summary

In this paper we have applied the generic finite size scaling method to study the scaling for the magnetic field energy density and magnitude fluctuations of the IMF using WIND MFI data. This yields the scaling properties of the solar wind magnetic field energy density fluctuations that do not assume a particular turbulent model. Instead, we use the smallest (and best represented statistically) fluctuations to obtain a single parameter that gives the scaling exponent sufficient to rescale the $`46`$ seconds averaged data over its entire dynamic range in $`\delta B^2`$. The simplest explanation suggested by these results is that the IMF energy density fluctuations are governed by a common physical process that is self-similar on the temporal scale up to $`\tau 26`$ hours. The rescaled PDF follows a non-Gaussian distribution with an asymptotic behavior well described by the Gamma distribution arising from a finite range Lévy walk. Such rescaling also indicates that a Fokker-Planck approach can be used to study the evolution (in $`\delta B^2`$ space) of the PDF. A similar rescaling procedure applied to magnetic field magnitude fluctuations confirms more complex, perhaps multi-fractal, character of the underlying dynamics in agreement with previous results.

## 4 Acknowledgment

S. C. Chapman and B. Hnat acknowledge support from the PPARC and G. Rowlands from the Leverhulme Trust. We thank M. P. Freeman and D. J. Riley for post processing the WIND data. We thank J. Greenhough for useful discussions and R.P Lepping for provision of data from the NASA WIND spacecraft.