text:
# The mean-squared displacement of a molecule moving in a glassy system

## I INTRODUCTION

The mean-squared displacement $`\delta r^2(t)`$ (MSD) is a very transparent concept for the discussion of liquid dynamics . For long times $`t`$, $`\delta r^2(t)`$ increases proportional to $`t`$ and to the diffusion constant of the fluid. In an ideal solid, on the other hand, the long-time limit of $`\delta r^2(t)`$ is a finite number characterizing the square of the particle’s localization length. Therefore, the long-time behavior of $`\delta r^2(t)`$ depends sensitively on control parameters like density or temperature if the system is close to a liquid-glass-transition point. The MSD is thus particularly well suited to study glass-transition precursors. It can be measured by incoherent inelastic-neutron-scattering experiments. However, $`\delta r^2(t)`$ has to be extracted as small-wave-number limit of the intermediate scattering function , and this makes it very difficult to produce accurate data for large time intervals. Dynamic light-scattering spectroscopy and sample-preparation techniques for colloidal suspensions made great progress in recent years. It was demonstrated that very informative data for the MSD of hard-sphere colloids near the glass transition can be obtained ; and promising results for this system have also been measured by direct-imaging techniques . Molecular-dynamics simulations are well suited to get accurate data for the MSD for liquids near the glass transition. This was demonstrated for a binary Lennard-Jones mixture , for a liquid of diatomic molecules , for models for the van-der-Waals liquid orthoterphenyl , for the SPC/E model for water , for a hard-sphere-colloid model , and for a model of silica . In this paper, general features and some quantitative results for the evolution of the glassy dynamics as exhibited by the MSD will be considered within the mode-coupling theory (MCT) for ideal liquid-glass transitions.

The basic version of MCT is built on approximately derived closed equations of motion for the auto-correlation functions of density fluctuations. The essential input informations are the equilibrium structure factors which are anticipated to vary smoothly with the system’s control parameters. At certain critical values for the latter, there occur bifurcations from solutions for an ergodic liquid to ones for an amorphous non-ergodic solid. Thus, MCT deals with a model for ideal liquid-glass transitions. The transition implies a novel dynamical scenario. Its features have been worked out by asymptotic solution of the equations. The leading-order asymptotic formulas establish universal results for the MCT transition like scaling laws, power-law divergencies for the time scales, and anomalous exponents for the spectra . Many tests of the relevance of the MCT results for the explanation of the dynamics of glass-forming liquids have been performed, which are reviewed to some extent in Ref. . Let us only mention here the recent analysis of data measured for propylene carbonate , studies by means of the optical Kerr effect , and the analysis of simulation data for a binary Lennard-Jones liquid  and for silica . The outcome of these tests qualifies MCT as a candidate for a theory of glassy dynamics and it seems justified to continue the preceding studies by unfolding some of its implications for the MSD.

The intention of this paper is to identify further MCT results for future tests of this theory. The previous work on the hard-sphere system (HSS)  shall be continued by analyzing in detail the MSD for a tagged particle. The work on the MCT for molecular systems  will be extended by evaluating the MSD for the interaction sites of a symmetric dumbbell consisting of two fused hard spheres as well as for the molecule’s center. The paper is structured as follows. In Sec. II, the equations to be solved are listed and the concepts to be used to discuss the results are described. Section III presents the results for the MSD and the analysis of its properties. In Sec. IV, the findings are summarized.

## II BASIC FORMULAS

### A Description of the system

In this section, the systems to be studied and the functions to be used for a description of their dynamics shall be defined. A system of $`N`$ atoms of mass $`m`$ distributed with density $`\rho `$ is considered as solvent. The points in configuration space are specified by the particle positions $`\stackrel{}{r}_\kappa `$, $`\kappa =1,2,\mathrm{},N`$. The basic variables for the description of the structure are the density fluctuations with wave vector $`\stackrel{}{q}`$, $`\rho _\stackrel{}{q}=_\kappa \mathrm{exp}(i\stackrel{}{q}\stackrel{}{r}_\kappa )`$. If $`\mathrm{}`$ denotes canonical averaging for temperature $`T`$, the structure factor is $`S_q=\rho _\stackrel{}{q}^2/N`$, where $`q=\stackrel{}{q}`$ is the wave number. As simplest example for a solute, a tagged atom of mass $`m_S`$ and position $`\stackrel{}{r}_S`$ shall be considered. The distribution of the atom is described by the density fluctuation $`\rho _\stackrel{}{q}^S=\mathrm{exp}(i\stackrel{}{q}\stackrel{}{r}_S)`$. The solute-solvent interaction shall be characterized by the direct correlation function $`c_q^S=\rho _\stackrel{}{q}^S\rho _\stackrel{}{q}/(\rho S_q)`$. As a more complicated solute, a symmetric rigid diatomic molecule shall be chosen. Its position is specified by two interaction sites $`(\stackrel{}{r}_A,\stackrel{}{r}_B)`$, which have the same mass $`m_A`$. The position of the molecule can also be described by its center $`\stackrel{}{r}_C=(\stackrel{}{r}_A+\stackrel{}{r}_B)/2`$ and the unit vector $`\stackrel{}{e}=(\stackrel{}{r}_A\stackrel{}{r}_B)/L`$, where $`L=\stackrel{}{r}_A\stackrel{}{r}_B`$. The configuration variables for the molecule can be built with the two density fluctuations $`\rho _\stackrel{}{q}^a=\mathrm{exp}(i\stackrel{}{q}\stackrel{}{r}_a)`$; $`a=A`$, $`B`$. Equivalently, one can use the number fluctuations $`\rho _\stackrel{}{q}^N=(\rho _\stackrel{}{q}^A+\rho _\stackrel{}{q}^B)/\sqrt{2}`$ and the “charge” fluctuations $`\rho _\stackrel{}{q}^Z=(\rho _\stackrel{}{q}^A\rho _\stackrel{}{q}^B)/\sqrt{2}`$. The solute-solvent interaction can be characterized by the direct interaction-site-solvent correlations $`c_q^A=c_q^B=\rho _\stackrel{}{q}^A\rho _\stackrel{}{q}/[\rho S_qw_q^N]`$ . Here $`w_q^{N,Z}=1\pm \mathrm{sin}(qL)/qL`$ denote the intra-molecular structure factors.

Three kinds of mean-squared displacement functions of time $`t`$ shall be discussed, $`\delta r_x^2(t)=[\stackrel{}{r}_x(t)\stackrel{}{r}_x(0)]^2`$. Here and in the following, the label $`x=S`$, $`C`$ and $`A`$ refers to the position of a tagged particle, of the center of the molecule, and of the atomic center in the molecule, respectively. It will be more convenient to use the following abbreviation

$$\mathrm{\Delta }_x(t)=\frac{1}{6}\delta r_x^2(t),x=S,C,A.$$
(1)
The MSD of the molecule’s constituents can be decomposed into one contribution due to translation of the center and one due to reorientation of the axis

$$\mathrm{\Delta }_A(t)=\mathrm{\Delta }_C(t)+\frac{1}{12}L^2[1C_1(t)],$$
(2)
where

$$C_1(t)=\stackrel{}{e}(t)\stackrel{}{e}$$
(3)
is the dipole correlator. The time derivatives of the MSD provide the velocity-auto-correlation function . Let us consider the one for the velocity $`\stackrel{}{v}_S(t)`$ of the tagged particle only, $`K_S(t)=\stackrel{}{v}_S(t)\stackrel{}{v}_S`$, where

$$_t^2\mathrm{\Delta }_S(t)=\frac{1}{3}K_S(t).$$
(4)
The non-trivial time dependence of $`\stackrel{}{r}_x(t)\stackrel{}{r}_x(0)`$ comes about since the forces on the solute fluctuate in time; and this is caused by the density fluctuations of the solvent and by the fluctuations of the probability density of the solute constituents. These quantities are described by the density correlator $`\varphi _q(t)=\rho _\stackrel{}{q}(t)^{}\rho _\stackrel{}{q}/\rho _\stackrel{}{q}^2`$ of the solvent, by the tagged-particle-density correlator $`\varphi _q^S(t)=\rho _\stackrel{}{q}^S(t)^{}\rho _\stackrel{}{q}^S`$, and by the molecule’s correlators $`\varphi _q^{N,Z}(t)=\rho _\stackrel{}{q}^{N,Z}(t)^{}\rho _\stackrel{}{q}^{N,Z}/w_q^{N,Z}`$. These correlators also determine the desired functions, since :

$`\varphi _q^S(t)`$ $`=`$ $`1q^2\mathrm{\Delta }_S(t)+O(q^4),`$ (6)
$`\varphi _q^N(t)`$ $`=`$ $`1q^2\mathrm{\Delta }_C(t)+O(q^4),`$ (7)
$`\varphi _q^Z(t)`$ $`=`$ $`C_1(t)+O(q^2).`$ (8)
### B MCT approximations

In this section, those equations shall be listed which have to be solved numerically. Within the Zwanzig-Mori theory, an exact equation of motion can be formulated for the density correlator: $`_t^2\varphi _q(t)+\mathrm{\Omega }_q^2\varphi _q(t)+_0^t𝑑t^{}M_q(tt^{})_t^{}\varphi _q(t^{})=0`$. Here $`\mathrm{\Omega }_q^2=v^2q^2/S_q`$ with $`v`$ denoting the thermal velocity specifies a characteristic frequency $`\mathrm{\Omega }_q`$, and $`M_q(t)`$ denotes a fluctuating-force correlator called the relaxation kernel . Within MCT, the kernel is split into a regular part $`M_q^{\mathrm{reg}}(t)`$ dealing with normal-liquid effects and a mode-coupling kernel $`\mathrm{\Omega }_q^2m_q(t)`$ describing the cage effect. If one introduces an operator $``$ for the regular dynamics by $`\varphi _q(t)=[_t^2\varphi _q(t)+_0^t𝑑t^{}M_q^{\mathrm{reg}}(tt^{})_t^{}\varphi _q(t^{})]/\mathrm{\Omega }_q^2`$, one can write

$$\varphi _q(t)+\varphi _q(t)+_0^t𝑑t^{}m_q(tt^{})_t^{}\varphi _q(t^{})=0.$$
(9)
The crucial step in the derivation is the application of Kawasaki’s factorization approximations to express the kernel $`m_q(t)`$ as mode-coupling functional $`_q`$ of the correlators

$`m_q(t)`$ $`=`$ $`_q[\varphi _k(t)],`$ (11)
$`_q[\stackrel{~}{f}_k]`$ $`=`$ $`{\displaystyle \frac{1}{2(2\pi )^3}}{\displaystyle 𝑑\stackrel{}{k}V(\stackrel{}{q};\stackrel{}{k},\stackrel{}{p})\stackrel{~}{f}_k\stackrel{~}{f}_p}.`$ (12)
Here $`\stackrel{}{p}`$ abbreviates $`\stackrel{}{q}\stackrel{}{k}`$. The coefficients $`V(\stackrel{}{q};\stackrel{}{k},\stackrel{}{p})`$ are given in terms of the structure factor .

None of the MCT results for structural relaxations, in particular none of the universal results to be cited in the following Sec. II C, depend on the model for $`M_q^{\mathrm{reg}}(t)`$. This holds up to the choice of some time scale to be denoted below as $`t_0`$. But, the kernel $`M_q^{\mathrm{reg}}(t)`$ shall be specified in order to have controllable quantitative results for all times. Specifically, a model with $`M_q^{\mathrm{reg}}(t)0`$ shall be chosen. The operator $``$ shall be complemented by an index $`\mathrm{H}`$ indicating that a Hamiltonian dynamics is considered for the short-time motion

$$^\mathrm{H}\varphi _q(t)=_t^2\varphi _q(t)/\mathrm{\Omega }_q^2.$$
(14)
This model overemphasizes oscillation features. A more realistic model would include at least some friction term as it is caused for low frequency phenomena by binary collision events. But, no detailed proposals for a treatment of such effects have been made so far within MCT. Some results also will be presented for a simplified colloid model. Here, the inertia term from Eq. (14) is neglected and the regular term is chosen as a $`q`$-independent white noise kernel. It is explained in more detail in Appendix A that this model corresponds to the conventional treatment of colloids by coarse-graining the time over intervals of the duration of collisions of the solvent molecules with the mesoscopic colloid particles. As a result, the short-time motion is treated by a Brownian dynamics

$$^\mathrm{B}\varphi _q(t)=\tau _q_t\varphi _q(t).$$
(15)
Here $`\tau _q=S_q/(D_0q^2)`$ with $`D_0`$ denoting the single-particle-diffusion constant.

Equations (9) and (II B) hold analogously for the solute correlators $`\varphi _q^x(t)`$, $`x=S`$, $`N`$ and $`Z`$. One gets $`\mathrm{\Omega }_q^{S\mathrm{\hspace{0.17em}2}}=v_S^2q^2`$ with $`v_S`$ denoting the tagged particle thermal velocity. The relaxation time for the Brownian motion is $`\tau _q^S=1/(D_0^Sq^2)`$ with $`D_0^S`$ denoting the tagged particle short-time diffusivity. The more involved expressions for the characteristic frequencies $`\mathrm{\Omega }_q^{N,Z}`$ can be found in Ref. . Brownian dynamics shall not be considered for the dumbbell molecule. The fluctuating-force kernels are functionals of the correlators $`\varphi _q^x(t)`$ and $`\varphi _q(t)`$:

$`m_q^x(t)`$ $`=`$ $`_q^x[\varphi _k^x(t),\varphi _p(t)],`$ (17)
$`_q^x[\stackrel{~}{f}_k^x,\stackrel{~}{f}_p]`$ $`=`$ $`{\displaystyle \frac{1}{(2\pi )^3}}{\displaystyle 𝑑\stackrel{}{k}V^x(\stackrel{}{q};\stackrel{}{k},\stackrel{}{p})\stackrel{~}{f}_k^x\stackrel{~}{f}_p},`$ (18)
for $`x=S,N,Z`$. Again, $`\stackrel{}{p}`$ abbreviates $`\stackrel{}{q}\stackrel{}{k}`$ and the coefficients $`V^x(\stackrel{}{q};\stackrel{}{k},\stackrel{}{p})`$ are given by $`S_q`$ and the direct correlation functions . It is cumbersome to calculate the required $`q0`$ limits in Eqs. (II A) numerically from numerical solutions for $`\varphi _q^x(t)`$. It is more adequate to carry out the limit analytically in the equations of motion for $`\varphi _q^x(t)`$ so that one gets equations of motion for the desired functions. The non-trivial parts of these equations are convolution integrals defined with the $`q0`$ limits of the kernels $`m_q^x(t)`$. One gets for the dipole correlator

$`_t^2C_1(t)+2v_\mathrm{R}^2C_1(t)`$ (19)
$`+\mathrm{\hspace{0.17em}2}v_\mathrm{R}^2{\displaystyle _0^t}𝑑t^{}m_Z(tt^{})_t^{}C_1(t^{})=0,`$ (20)
where $`v_\mathrm{R}`$ is the thermal angular velocity of the molecule . From the equation for $`\varphi _q^S(t)`$ one gets a Zwanzig-Mori equation for the velocity correlator

$$_tK_S(t)+v_S^2_0^t𝑑t^{}m_S(tt^{})K_S(t^{})=0.$$
(21)
Integrating twice over $`t`$ one gets with the aid of Eq. (4) and the initial conditions $`\mathrm{\Delta }_S(0)=0`$ and $`_t\mathrm{\Delta }_S(0)=0`$,

$$\text{H:}_t\mathrm{\Delta }_S(t)v_S^2t+v_S^2_0^t𝑑t^{}m_S(tt^{})\mathrm{\Delta }_S(t^{})=0.$$
(23)
The corresponding equation for Brownian short-time dynamics  is derived in Appendix A:

$$\text{B:}\mathrm{\Delta }_S(t)D_0^St+D_0^S_0^t𝑑t^{}m_S(tt^{})\mathrm{\Delta }_S(t^{})=0.$$
(24)
The same procedure leads to the equation of motion for the MSD of the center

$$\text{H:}_t\mathrm{\Delta }_C(t)v_\mathrm{T}^2t+v_\mathrm{T}^2_0^t𝑑t^{}m_N(tt^{})\mathrm{\Delta }_C(t^{})=0,$$
(25)
where the kernel is denoted by $`m_N(t)`$ and $`v_\mathrm{T}`$ is the thermal velocity for the molecule’s translation . The problem of the molecule’s dynamics reduces to that of a tagged atom with $`m_S=2m_A`$, if the limit $`L0`$ is considered.

The kernels in the preceding Eqs. (20)–(25) are given by mode-coupling functionals

$`m_x(t)`$ $`=`$ $`^x[\varphi _k^x(t),\varphi _p(t)],`$ (27)
$`^x[\stackrel{~}{f}_k^x,\stackrel{~}{f}_p]`$ $`=`$ $`{\displaystyle \frac{1}{6\pi ^2}}{\displaystyle _0^{\mathrm{}}}𝑑kk^4\rho S_kv^x(k)\stackrel{~}{f}_k^x\stackrel{~}{f}_k,`$ (28)
for $`x=S,N,Z`$. Here $`v^S(k)=c_k^{S\mathrm{\hspace{0.17em}2}}`$ , $`v^N(k)=2c_k^{A\mathrm{\hspace{0.17em}2}}w_k^N`$ and $`v^Z(k)=(L^2/6)c_k^{A\mathrm{\hspace{0.17em}2}}w_k^Z`$ . A fluctuating force with vanishing wave vector can couple to density fluctuations of the solvent for all wave vectors $`\stackrel{}{k}`$ provided the atom or molecule can absorb the recoil with wave vector $`\stackrel{}{k}`$. Therefore, one needs the superposition of density correlators $`\varphi _k(t)`$ and $`\varphi _k^x(t)`$ for all wave numbers $`k`$ for the calculation of the kernels $`m_x(t)`$.

### C Universal results

Universal properties of the MCT-glass-transition scenario are formulated by the leading-order asymptotic expressions for the long-time dynamics for states near the transition points. This paper focuses on features beyond the universal ones, but the universal formulas shall be used as reference. In this section, those formulas  shall be compiled which are needed in the following Sec. III for the description of the results.

The equilibrium structure of the system may depend on, say $`n`$, control parameters which can be combined to a control-parameter vector $`V`$. A separation parameter $`\sigma (V)`$, a smooth function of $`V`$, can be defined with the aid of the mode-coupling functional $`_q`$. For states with control parameters $`V`$ such that $`\sigma <0`$, correlation functions decay to zero: $`\varphi _q(t\mathrm{})=0`$. But for states with $`\sigma >0`$, density fluctuations exhibit spontaneous arrest: $`\varphi _q(t\mathrm{})=f_q>0`$. The Debye-Waller factor $`f_q`$ is to be evaluated from the mode-coupling functional $`_q`$ in Eqs. (9) via the equation $`f_q/(1f_q)=_q[f_k]`$ . The set of critical points $`V^c`$, defined by $`\sigma (V^c)=0`$, separates liquid states from glass states. This result holds for all correlators $`\varphi _A(t)=A(t)^{}A/|A|^2`$ of variables $`A`$ coupling to density fluctuations. While $`\varphi _A(t\mathrm{})`$ vanishes for the liquid, generically, the limit $`f_A=\varphi _A(t\mathrm{})`$ is positive for the glass. If $`A`$ refers to $`\rho _\stackrel{}{q}`$, $`\rho _\stackrel{}{q}^S`$ or $`\stackrel{}{e}`$, $`f_A`$ denotes the Debye-Waller factor $`f_q`$, the Lamb-Mössbauer factor $`f_q^S`$ or the Edwards-Anderson parameter $`f_1`$, respectively, of the glass. Crossing the transition points, the long-time limit changes discontinuously from zero to the critical value $`f_A^c`$. For the variation of $`f_A`$ upon approaching the transition from the glass side, one gets for small $`\sigma `$ in leading order

$$f_A=f_A^c+h_A\sqrt{|\sigma |}/\sqrt{1\lambda }.$$
(29)
Here $`h_A`$ is called the critical amplitude for variable $`A`$. Every point $`V^c`$ is characterized by a number $`\lambda `$, $`0<\lambda <1`$, which is called the exponent parameter. The significance of $`\lambda `$ is explained below in connection with Eqs. (30)–(II C). It is a matter of convention not to incorporate $`\sqrt{1\lambda }`$ in the amplitude $`h_A`$, in order to simplify some of the following formulas. The quantities $`f_A^c`$, $`h_A`$ and $`\lambda `$ are calculated from $`_q`$. They are equilibrium quantities which are the same for Hamiltonian and Brownian dynamics.

The parameter $`\lambda `$ determines an anomalous exponent $`a`$, $`0<a<1/2`$, which is called the critical exponent. There holds the equation $`\mathrm{\Gamma }(1a)^2/\mathrm{\Gamma }(12a)=\lambda `$, where $`\mathrm{\Gamma }`$ denotes the gamma function. The long-time decay at the critical point is given, up to corrections of order $`t^{2a}`$, by the power law

$$\varphi _A(t)=f_A^c+h_A(t_0/t)^a,\sigma =0,t/t_01.$$
(30)
The $`A`$-independent time $`t_0`$ is the relevant microscopic scale for the bifurcation dynamics. It depends on all details of the transient dynamics as well as on the mode-coupling functionals for parameters at the transition point.

The first scaling law of MCT deals with the dynamics for small $`\sigma `$ in a time interval where $`\eta =\varphi _A(t)f_A^c`$ is small. In a leading expansion for $`\sigma 0`$ and $`\eta 0`$, one gets

$`\varphi _A(t)`$ $`=`$ $`f_A+h_AG(t),`$ (32)
$`G(t)`$ $`=`$ $`\sqrt{|\sigma |}g_\pm (t/t_\sigma ),\sigma ><0,`$ (33)
$`t_\sigma `$ $`=`$ $`t_0/|\sigma |^\delta ,\delta =1/2a.`$ (34)
The functions $`g_\pm (\widehat{t})`$ are determined by $`\lambda `$. Thus, the control-parameter dependence of the dynamics is determined by the correlation scale $`\sqrt{|\sigma |}`$ and by the first critical time scale $`t_\sigma `$. One gets $`g_\pm (\widehat{t}0)=1/\widehat{t}^a`$, so that Eq. (30) is reproduced for fixed large $`t`$ if $`\sigma `$ tends to zero. Since $`g_+(\widehat{t}\mathrm{})=1/\sqrt{1\lambda }`$, also Eq. (29) is reproduced.

There holds $`g_{}(\widehat{t}\mathrm{})=B\widehat{t}^b+O(1/\widehat{t}^b)`$. The anomalous exponent $`b`$, $`0<b1`$, which is called the von Schweidler exponent, is to be calculated from the equation $`\mathrm{\Gamma }(1+b)^2/\mathrm{\Gamma }(1+2b)=\lambda `$. The constant $`B`$ is of order unity. Substituting this result into Eqs. (II C) one gets von Schweidler’s law for the decay of the liquid correlator below the plateau $`f_A^c`$

$$\varphi _A(t)=f_A^ch_A(t/t_\sigma ^{})^b,t_\sigma t,\sigma 0.$$
(36)
The control-parameter dependence is described by the second critical time scale

$$t_\sigma ^{}=t_0B^{1/b}/|\sigma |^\gamma ,\gamma =(1/2a)+(1/2b).$$
(37)
Following the terminology of the glass-transition literature, the decay of $`\varphi _A(t)`$ below the plateau $`f_A^c`$ is called the $`\alpha `$-process. For this process, there holds the second scaling law of MCT in leading order for $`\sigma 0`$:

$$\varphi _A(t)=\stackrel{~}{\varphi }_A(\stackrel{~}{t}),\stackrel{~}{t}=t/t_\sigma ^{},t_\sigma t.$$
(38)
The control-parameter-independent shape function $`\stackrel{~}{\varphi }_A(\stackrel{~}{t})`$ is to be evaluated from the mode-coupling functionals at the critical points $`V^c`$. The differences of the dynamics as they are caused by different models for the short-time dynamics merely enter via differences in the scale $`t_0`$. For short rescaled times $`\stackrel{~}{t}`$, one gets $`\stackrel{~}{\varphi }_A(\stackrel{~}{t})=f_A^ch_A\stackrel{~}{t}^b+h_A^{}\stackrel{~}{t}^{2b}+\mathrm{}`$, so that Eq. (36) is reproduced. The ranges of applicability of the first and the second scaling laws overlap; both scaling laws imply von Schweidler’s law for $`t_\sigma tt_\sigma ^{}`$.

Suppose, the system is driven through the transition point $`V^c`$ by smooth variation of some parameters $`\theta `$ like the temperature, the density or, for a colloid, the salt concentration of the solvent. Let $`\theta ^c`$ denote the value where $`V(\theta ^c)=V^c`$. Then one can write for $`\sigma `$, in leading order for small $`(\theta \theta ^c)`$, the expression $`\sigma =C_\theta (\theta \theta ^c)/\theta ^c`$. The constant $`C_\theta `$ depends on the choice of $`\theta `$ and connects the distance parameter $`ϵ=(\theta \theta ^c)/\theta ^c`$ with the relevant separation parameter $`\sigma `$.

### D The model

Hard spheres of diameter $`d`$ shall be used as model for the solvent atoms. For this case, all equilibrium quantities are specified by the packing fraction $`\phi =\pi \rho d^3/6`$. The MCT model for the hard-sphere system (HSS) shall be defined by two further technical assumptions. First, the structure factor $`S_q`$ and the direct correlation function $`c_q`$ are evaluated within the Percus-Yevick theory . Second, the wave numbers are discretized to 100 equally spaced values $`qd=0.2,0.6,1.0,\mathrm{},39.8`$. The details of the transformation of the functional in Eq. (12) to a polynomial in the 100 variables $`\varphi _q(t)`$ can be found in Ref. . Representative solutions are shown in Refs.  and  for the Hamiltonian dynamics and in Ref.  for the Brownian dynamics. There is a liquid-glass transition at the critical packing fraction $`\phi _c0.516`$ . For the exponent parameter one gets $`\lambda =0.735`$, and this implies

$$a=0.312,b=0.583,B=0.836,\delta =1.60,\gamma =2.46.$$
(40)
For the separation parameter $`\sigma `$ one gets in leading order

$$\sigma =1.54ϵ,ϵ=(\phi \phi _c)/\phi _c.$$
(41)
The microscopic time scales $`t_0`$ for Hamiltonian dynamics  and Brownian dynamics , respectively, are

$$t_0^\mathrm{H}=0.0236(d/v),t_0^\mathrm{B}=0.00265d^2/D_0.$$
(42)
As atomic solute, a tagged particle of the solvent shall be considered, i.e., $`m_S=m`$ and $`c_q^S`$ is identical with the direct correlation function $`c_q`$ of the HSS. As molecular solute, a symmetric dumbbell of two fused hard spheres of diameter $`d`$ and mass $`m_A=m`$ shall be chosen. The elongation $`\zeta =L/d`$ shall be used as control parameter of the solute. The wave numbers are chosen discrete as above. The direct correlation function $`c_q^A`$ is expressed as series of contributions $`c_{\mathrm{}}(q),\mathrm{}=0,1,\mathrm{}`$, obtained by expanding the molecule-solvent correlations in spherical harmonics . The sum over $`\mathrm{}`$ is truncated at $`\mathrm{}_{\mathrm{co}}=8`$. The $`c_{\mathrm{}}(q)`$ are evaluated with the Percus-Yevick theory . Representative results for molecule’s correlators $`\varphi _q^N(t)`$, $`\varphi _q^Z(t)`$ and $`C_1(t)`$ are shown in Ref. , and for $`\varphi _q^S(t)`$ for the Brownian dynamics in Ref. .

The figures to be discussed below and the numbers to be mentioned are evaluated for the above-specified model as follows. First, for a representative set of packing fractions, Eqs. (9) and (9) are solved for the density correlators $`\varphi _q(t)`$, and this for Hamiltonian as well as for Brownian dynamics. These correlators are used to define the kernels in Eqs. (II B), so that, as second step, the tagged particle correlators $`\varphi _q^S(t)`$ could be evaluated, also for both examples for the short-time dynamics. Furthermore, for every $`\phi `$, the equations for molecule’s correlators $`\varphi _q^{N,Z}(t)`$ are solved for 10 values for the elongation $`\zeta `$. These results are substituted into Eqs. (II B) for the kernels $`m_x(t)`$ so that, as last step, Eqs. (20)–(25) for the desired functions $`\mathrm{\Delta }_x(t)`$, $`C_1(t)`$ and $`K_S(t)`$ can be solved.

## III RESULTS

### A The diffusion-localization transition

If a tagged particle would experience a mere Newtonian friction force, the velocity correlations would decay exponentially, $`K_S(t)\mathrm{exp}[(t/\tau )]`$. The cage effect in dense liquids manifests itself by a qualitatively different behavior, namely by oscillatory variations with a decay of $`K_S(t)`$ to negative values . Figure 1(a) demonstrates this phenomenon. With increasing density, the crossover time to negative values shortens and the damping of the oscillations increases. A Green-Kubo formula relates the particle diffusivity $`D_S`$ to the zero-frequency velocity spectrum: $`D_S=(1/3)_0^{\mathrm{}}𝑑tK_S(t)`$ . Negative contributions to $`K_S(t)`$ reduce the diffusivity with increasing $`\phi `$. From Eq. (21), one gets $`D_S`$ as inverse of the zero-frequency spectrum of the relaxation kernel : $`D_S=1/_0^{\mathrm{}}𝑑tm_S(t)`$. From Eqs. (21), one obtains for the long-time asymptote of the MSD: $`lim_t\mathrm{}\mathrm{\Delta }_S(t)/t=D_S`$ .

For glass states, density fluctuations arrest for long times: $`\varphi _q^S(t\mathrm{})=f_q^S>0`$. The Lamb-Mössbauer factor $`f_q^S`$ is to be evaluated from the mode-coupling functional $`_q^S`$ in Eqs. (II B) via the equation $`f_q^S/(1f_q^S)=_q^S[f_k^S,f_p]`$ . It approaches unity for $`q`$ tending to zero. A localization length $`r_S`$ can be introduced to characterize the width of the $`f_q^S`$–versus–$`q`$ curve: $`f_q^S=1(qr_S)^2+O(q^4)`$. From Eq. (6), one gets for the MSD: $`lim_t\mathrm{}\mathrm{\Delta }_S(t)=r_S^2`$. Using Eqs. (21), one can express $`r_S^2`$ as inverse of the long-time limit of the relaxation kernel : $`r_S^2=1/m_S(t\mathrm{})=1/^S[f_k^S,f_p]`$. If the density increases, the localization length $`r_S`$ decreases. As a result, the frequency of the oscillations of the particles in their frozen cages increases, as is shown in Fig. 1(b). But, in contrast to what is found for liquid states, the damping of the oscillations decreases upon compression. This reflects the formation of anomalous oscillation peaks in the density-fluctuation spectra, which have properties of the so-called boson peaks of liquids and glasses .

The ideal liquid-glass transition implies a transition from a regime with particle diffusion for $`\phi <\phi _c`$ to one with particle localization for $`\phi \phi _c`$. The former is characterized by $`D_S>0`$ and $`1/r_S=0`$ and the latter by $`D_S=0`$ and $`1/r_S>0`$. The subtleties of the glass-transition dynamics occur outside the transient regime. They can be discussed best on logarithmic scales as in Fig. 2. For very short times, say $`tt_0`$, interaction effects are unimportant and $`lim_{t0}\mathrm{\Delta }_S(t)/t^2=v_S^2/2`$ reflects ballistic motion. For times larger than $`t_0`$, the cage effect leads to a suppression of $`\mathrm{\Delta }_S(t)`$ below the short-time asymptote. For such large times that $`\delta r_S^2(t)/d^2`$ reaches unity, the MSD approaches the diffusion asymptote, $`\mathrm{\Delta }_S(t)D_St`$, as is shown by the dotted straight lines drawn for the curves with labels $`n=1`$ and $`n=9`$. Upon increasing $`\phi `$ towards $`\phi _c`$, the diffusivity decreases towards zero. Figure 3 shows that there holds the power law $`D_S^{1/\gamma }ϵ`$ for $`ϵ<0.1`$.

The lowest line in Fig. 2 deals with the same glass state $`\phi =1.1\phi _c`$, which was considered in Fig. 1(b) for the label $`n=3`$. For this density, there is no obvious glassy dynamics. Rather, $`\mathrm{\Delta }_S(t)`$ has approached its long-time limit $`r_S^2`$ after the oscillations have disappeared for $`t1`$. Decreasing $`\phi `$ towards $`\phi _c`$, the softening of the glass manifests itself by an increase of the localization length $`r_S`$. At the transition point $`\phi =\phi _c`$, the critical value $`r_S^c=0.0746d`$ is reached. This upper limit for $`r_S`$ is consistent with Lindemann’s melting criterion . Using Eq. (29) for $`f_q`$ and $`f_q^S`$ and substituting these formulas into $`^S[f_k^S,f_p]`$, it follows that the glass instability at $`\phi _c`$ causes a $`\sqrt{\sigma }`$–anomaly for the localization length,

$$r_S^2=r_S^{c\mathrm{\hspace{0.17em}2}}h_S\sqrt{\sigma }/\sqrt{1\lambda }+O(\sigma ),$$
(43)
where $`r_S^{c\mathrm{\hspace{0.17em}2}}=0.00557d^2`$ and $`h_S=0.0116d^2`$. Figure 3 demonstrates that the leading asymptotic formula accounts for the $`r_S^2`$–versus–$`\phi `$ dependence for $`ϵ0.01`$. But the data for $`n4`$, i.e., for $`ϵ0.05`$, are not anymore described by the $`\sqrt{\sigma }`$–law. The range of applicability for the asymptotic description of $`r_S^2`$ is remarkably smaller than the one for the corresponding description of $`f_q`$ for intermediate wave numbers .

The glass curve for $`ϵ=0.01`$, shown in Fig. 2 with label $`n=6`$, exhibits a decay between the end of the transient oscillations and the arrest at $`r_S^2`$ which is stretched over a time interval of about two orders of magnitude. A similar two-decade interval is needed for the liquid curve with label $`n=6`$ to reach the critical value $`r_S^{c\mathrm{\hspace{0.17em}2}}`$. After crossing $`r_S^{c\mathrm{\hspace{0.17em}2}}`$, two further decades of an upward bent $`\mathrm{log}_{10}\mathrm{\Delta }_S(t)`$–versus–$`\mathrm{log}_{10}t`$ variation is exhibited before the diffusion asymptote is reached. The indicated slow and stretched time variation is referred to as glassy dynamics.

### B The structural-relaxation regime

For times outside the transient regime, say $`tC^{}t_0`$, the density correlators can be written in the form $`\varphi _q(t)=\varphi _q^{}(t/t_0)`$. Here $`t_0`$ is the scale introduced in Eq. (30). The functions $`\varphi _q^{}`$ are determined uniquely by the mode-coupling functional $`_q`$, i.e., they are given by the equilibrium structure. This holds for all choices of the regular kernels in Eq. (9), in particular for the two models defined by Eqs. (14) and (15. Corresponding results hold for the density correlators of the tagged atom  and of the molecule . The solutions of the specified MCT model for colloids are completely monotone . A function $`F(t)`$, defined for $`t>0`$, is called completely monotone if all derivatives exist and

$$(/t)^nF(t)0,n=\text{0, 1, }\mathrm{}.$$
(45)
According to Bernstein’s theorem , this property is equivalent to the existence of a distribution $`\rho (\gamma )0`$ so that

$$F(t)=_0^{\mathrm{}}e^{\gamma t}\rho (\gamma )𝑑\gamma .$$
(46)
Thus, one can write for $`tC^{}t_0`$: $`\varphi _q(t)=_0^{\mathrm{}}e^{\gamma (t/t_0)}\rho _q(\gamma )𝑑\gamma `$ with $`\rho _q(\gamma )0`$, i.e., the functions $`\varphi _q^{}`$ deal with relaxation. Corresponding formulas hold for the solute correlators $`\varphi _q^x(t)`$. Representative examples for $`\rho _q(\gamma )`$ are discussed in Ref. .

From Eqs. (II A), one gets $`C_1(t)=C_1^{}(t/t_0)`$ for $`tC^{}t_0`$, where $`C_1^{}`$ is completely monotone, and also

$$\mathrm{\Delta }_x(t)=\mathrm{\Delta }_x^{}(t/t_0),tC^{}t_0,x=S,C,A.$$
(47)
Here, the functions $`C_1^{}`$ and $`\mathrm{\Delta }_x^{}`$ are determined by the equilibrium structure. With Eq. (4) one can express the velocity correlator in terms of the structure function $`F(\tau )=_\tau ^2\mathrm{\Delta }_S^{}(\tau )`$:

$$K_S(t)=3F(t/t_0)/t_0^2,tC^{}t_0.$$
(48)
It can be shown that the function $`F`$ is completely monotone. The proof does not provide further insight and is delegated to Appendix A.

In Ref. , the curves for $`\varphi _q(t)`$ have been compared with the ones for $`\varphi _q^{}(t/t_0)`$. The interval for structural relaxation was larger for the colloid model than that for the model with the underlying Hamiltonian dynamics. Thus, the structural relaxation interval can be identified as the one, where the specified curves for the two models collapse. Figure 4 exhibits such comparison for the MSD. For $`ϵ0.01`$, the curves agree within the accuracy of the drawing. This holds, provided $`t20t_0`$, i.e., $`C^{}20`$. The result is nearly valid also for distance parameters as large as $`ϵ=0.1`$. But there is a small offset between the full and the dashed liquid curves for $`x=1`$. This means, that there is a smooth drift of $`t_0`$ with changes of $`\phi `$, which is different for the hard-sphere colloid and for the conventional HSS.

In Fig. 5, the rescaled velocity correlator $`t_0^2K_S(t)/3`$ for the critical packing fraction is shown as full line. This diagram is an extension and magnification of the dotted lines from Fig. 1 for $`t0.2`$. The dashed line is the analogous result $`t_0^{\mathrm{B}\mathrm{\hspace{0.17em}2}}_t^2\mathrm{\Delta }_S^{\mathrm{col}}(t)`$ calculated for the colloid model. The latter function is $`(t_0^\mathrm{B}D_0^S)^2F^{\mathrm{col}}(t)`$, where the completely monotone function $`F^{\mathrm{col}}(t)`$ was introduced in Appendix A in connection with Eqs. (A11) and (A14). According to Eq. (48), the two curves should collapse on the function $`F(t/t_0)`$. This is the case for $`t>20t_0`$ within small error margins. The curves demonstrate stretched relaxation to zero, which cannot be adequately represented on linear scales. It is shown also that oscillatory motion tends to mask glassy relaxation. From now on, the discussion will focus on the structural-relaxation regime $`t20t_0`$.

### C Scaling-law descriptions

In this section, it shall be examined how well the leading-order asymptotic results from Sec. II C can account quantitatively for the MSD. Let us start with $`\mathrm{\Delta }_S(t)`$ for $`\phi =\phi _c`$. This result for the critical dynamics, i.e. the dotted line in Fig. 2, is reproduced as full line in the semi-logarithmic presentation in Fig. 6. The transient dynamics for $`t20t_0`$ accounts for about 45% of the total increase of $`\mathrm{\Delta }_S(t)`$ from zero to the long-time asymptote $`r_S^{c\mathrm{\hspace{0.17em}2}}`$. The structural relaxation needed to approach $`r_S^{c\mathrm{\hspace{0.17em}2}}`$ up to 5%, i.e. 50% of the total increase, is stretched over a large interval of about four orders of magnitude time variation. The leading-order formula for the MSD at the transition point is in analogy to Eq. (30):

$$\mathrm{\Delta }_S(t)=r_S^{c\mathrm{\hspace{0.17em}2}}h_S(t_0/t)^a,\phi =\phi _c,tt_0.$$
(49)
The dashed line demonstrates that Eq. (49) describes – within a 5% error margin – about 25% of the total increase of $`\mathrm{\Delta }_S(t)`$. There remains the large part of the structural-relaxation interval between $`20t_0`$ and $`t^{}=792t_0`$ which is not adequately accounted for. About half of the structural-relaxation increase of $`\mathrm{\Delta }_S(t)`$ is outside the range of applicability of the leading-order asymptotic formula. Extending Eq. (49) by inclusion of the leading correction, one gets a description of the MSD up to errors of order $`(t_0/t)^{3a}`$: $`\mathrm{\Delta }_S(t)=r_S^{c\mathrm{\hspace{0.17em}2}}h_S(t_0/t)^a+k_S(t_0/t)^{2a}`$. From Ref.  one deduces $`k_S=0.0143d^2`$. The dashed-dotted line shows how inclusion of the correction term expands the range of the analytic description.

The first scaling law for the MCT-bifurcation dynamics, Eqs. (II C), implies with Eq. (6)

$`\mathrm{\Delta }_S(t)=r_S^{c\mathrm{\hspace{0.17em}2}}h_S\sqrt{\sigma }g_\pm (t/t_\sigma ),`$ (50)
$`\sigma ><\mathrm{\hspace{0.17em}0},\sigma 1,tt_0.`$ (51)
For the liquid states with $`\sigma <0`$, it describes how the $`\mathrm{\Delta }_S(t)`$–versus–$`t`$ curve crosses the plateau $`r_S^{c\mathrm{\hspace{0.17em}2}}`$. For the glass states with $`\sigma >0`$, it describes the approach towards the arrest at $`r_S^2=\mathrm{\Delta }_S(t\mathrm{})`$. The control-parameter independent functions $`g_\pm (\widehat{t})`$ for the HSS value of $`\lambda `$ are discussed in Fig. 10 of Ref. . The dashed lines in Fig. 7 exhibit Eq. (51) for three liquid states. They agree with the MCT solutions within a 5% error margin within the intervals marked by diamonds. Within these intervals, $`\mathrm{\Delta }_S(t)`$ increases from about $`0.0043d^2`$ to about $`0.0086d^2`$. Formulas like Eqs. (30) and (49) are the basis for the derivation of the MCT-scaling laws. Therefore, it follows from Fig. 6 that the part of the structural relaxation regime between $`20t_0`$ and $`t^{}`$ remains outside the range of validity of Eq. (51).

For small rescaled times $`\widehat{t}=t/t_\sigma `$, Eq. (51) reproduces Eq. (49) for $`\sigma 0`$. The r.h.s. of Eq. (51) becomes independent of $`\sigma `$ and agrees with Eq. (49). This explains, why the dashed lines in Fig. 7 for $`x=3`$ and 4 collapse for $`t10`$ and why the corresponding diamonds are located near $`t^{}`$. For $`x=2`$, the separation parameter $`\sigma `$ is already so large, that $`g_\pm (t^{}/t_\sigma )`$ differs remarkably from $`(t_\sigma /t^{})^a`$. Therefore, $`\mathrm{\Delta }_S(t)`$ does not reach the $`t^a`$ asymptote for $`tt^{}`$, and the corresponding diamond shifts away from $`t^{}`$. The $`x=3`$ curve follows the critical asymptote from Eq. (49) for a time interval of less than two decades. Such interval would not be large enough for a compelling experimental confirmation of the $`t^a`$ law. To identify the $`t^a`$ law in its pure form for the model under study, $`ϵ`$ must not exceed $`10^4`$.

For large rescaled times $`\widehat{t}`$, the master function for the glass approaches $`g_+(\widehat{t}\mathrm{})=1/\sqrt{1\lambda }`$, and Eq. (51) reproduces Eq. (43). According to the preceding paragraphs, this explains the solutions for the glass provided the long-time limit $`r_S^2`$ is located in the shaded interval of Fig. 7; and this is demonstrated in Fig. 3.

Function $`g_{}(\widehat{t})`$ for the liquid is zero for $`\widehat{t}_{}=0.704`$. Thus, $`\mathrm{\Delta }_S(\widehat{t}_{}t_\sigma )=r_S^{c\mathrm{\hspace{0.17em}2}}`$ and the interval for the increase of $`\mathrm{\Delta }_S(t)`$ to the plateau value $`r_S^{c\mathrm{\hspace{0.17em}2}}`$ expands proportional to $`t_\sigma `$ if $`\phi `$ increases towards $`\phi _c`$. For large $`\widehat{t}`$, one gets von-Schweidler’s law

$$\mathrm{\Delta }_S(t)=r_S^{c\mathrm{\hspace{0.17em}2}}+h_S(t/t_\sigma ^{})^b,\sigma 0,t_\sigma tt_\sigma ^{}.$$
(52)
Therefore, the long-time end of the range of applicability of Eq. (51) expands proportional to $`t_\sigma ^{}`$, as is indicated by the filled squares in Fig. 7. Formula (52) is exhibited by the crosses. These approach the plateau $`r_S^{c\mathrm{\hspace{0.17em}2}}`$ for $`tt_\sigma `$ and the dashed scaling-law lines for $`tt_\sigma `$. Since $`t_\sigma ^{}/t_\sigma \mathrm{}`$ for $`ϵ0`$, the time interval for the von-Schweidler-law description expands with decreasing $`ϵ`$.

Equation (32) formulates the factorization theorem for $`\delta \varphi _A(t)=\varphi _A(t)f_A^c`$: in a leading-order expansion for small $`\delta \varphi _A`$, the deviation $`\delta \varphi _A(t)`$ of the correlator from the plateau value $`f_A^c`$ factorizes in a control-parameter-independent amplitude $`h_A`$ and a function $`G(t)`$. The function $`G(t)`$ is the same for all variables $`A`$ and describes the time-and-control-parameter dependence of $`\varphi _A(t)`$ by a scaling law, Eq. (33). This theorem can be tested by identifying the time interval and the range of distance parameters $`ϵ`$ for which the diagrams for $`\widehat{\varphi }_A(t)=\delta \varphi _A(t)/h_A`$ collapse with $`G(t)`$. Figure 8 demonstrates such a test for the dipole correlators $`C_1(t)`$ for three values of the elongation parameter $`\zeta `$. The markers for $`20t_0,t^{},t_\sigma `$ and $`t_\sigma ^{}`$ have been added to ease a comparison with Fig. 7. Obviously, the scenario for the plateau crossing is the same for $`C_1(t)`$ as discussed above for $`\mathrm{\Delta }_S(t)`$. To corroborate this conclusion, the rescaled result for the MSD, $`\widehat{\mathrm{\Delta }}_S(t)=[r_S^{c\mathrm{\hspace{0.17em}2}}\mathrm{\Delta }_S(t)]/h_S`$ for $`ϵ=0.001`$, has been added to the figure. The $`x=2`$ results show that for negative $`\widehat{C}_1(t)`$ the full lines follow the sequence $`\zeta =`$ 0.6, 0.8 and 1.0 from top to bottom, where the latter two curves are very close to each other. The same behavior is observed for positive $`\widehat{C}_1(t)`$. This observation exemplifies a general implication of the leading corrections to the factorization theorem .

A possibility for the definition of a characteristic time scale $`\tau _A`$ for the $`\alpha `$-process of variable $`A`$ is given by the time needed to complete 95% of the total decay from the plateau $`f_A^c`$ to the equilibrium value zero, i.e., $`\varphi _A(\tau _A)=f_A^c/20`$. Within the range of validity of the second scaling law, Eq. (38), the $`A`$-dependent scales are coupled in the sense that $`\tau _A=\stackrel{~}{\tau }_At_\sigma ^{}`$. Here $`\stackrel{~}{\tau }_A`$ is an $`A`$-specific control-parameter-independent factor determined by $`\stackrel{~}{\varphi }_A(\stackrel{~}{\tau }_A)=f_A^c/20`$. Applying these results to the dipole correlator, one gets $`C_1(t)=\stackrel{~}{C}_1(\stackrel{~}{t})`$ for $`|\sigma |1`$ and $`t_\sigma t`$ where $`\stackrel{~}{t}=t/t_\sigma ^{}`$. For the $`\alpha `$-scale factors one finds $`\stackrel{~}{\tau }_1`$ = 18.8 (8.73, 2.66) for $`\zeta `$ = 1.0 (0.8, 0.6). The description of the $`\alpha `$-process for elongation parameter $`\zeta `$ = 0.8 is demonstrated in Fig. 8 of Ref. .

Using the second scaling law for the tagged-particle-density correlator, one gets from Eq. (6) the second scaling law for the $`\alpha `$-process of the MSD:

$$\mathrm{\Delta }_S(t)=\stackrel{~}{\mathrm{\Delta }}_S(\stackrel{~}{t}),\stackrel{~}{t}=t/t_\sigma ^{},\sigma 1,t_\sigma t.$$
(53)
An $`\alpha `$-relaxation time $`\tau _S`$ shall be defined by that time, where the diffusion asymptote $`D_St`$ is reached within 5%, i.e., $`\mathrm{\Delta }_S(\tau _S)=1.05D_S\tau _S`$. One gets $`D_S=\stackrel{~}{D}_S/t_\sigma ^{}`$ and $`\tau _S=\stackrel{~}{\tau }_St_\sigma ^{}`$, where $`\stackrel{~}{D}_S`$ and $`\stackrel{~}{\tau }_S`$ are to be determined from $`lim_{\stackrel{~}{t}\mathrm{}}\stackrel{~}{\mathrm{\Delta }}_S(\stackrel{~}{t})/\stackrel{~}{t}=\stackrel{~}{D}_S`$ and $`\stackrel{~}{\mathrm{\Delta }}_S(\stackrel{~}{\tau }_S)/\stackrel{~}{\tau }_S=1.05\stackrel{~}{D}_S`$. One finds $`\stackrel{~}{D}_S=0.0171`$ and $`\stackrel{~}{\tau }_S=11.6`$. One gets in particular $`D_S1/t_\sigma ^{}(\phi _c\phi )^\gamma `$, and Fig. 3 demonstrates how the diffusivity approaches this power-law asymptote for $`\phi `$ increasing to $`\phi _c`$. The asymptotic description of $`\mathrm{\Delta }_S(t)`$ by Eq. (53) is demonstrated in Fig. 9 of Ref. .

For times of order $`t_\sigma `$, the relative corrections to the first scaling law are of order $`\sqrt{\sigma }`$. For times of order $`t_\sigma ^{}`$, the corrections to the second scaling law are of order $`\sigma `$. Therefore, the second scaling law holds for larger separations $`\sigma `$ than the first one . For example, even for the large value $`ϵ=0.1`$, $`D_S^{1/\gamma }`$ differs from the linear asymptote by only 15%, as is demonstrated by the $`n=3`$ result in Fig. 3. The corrections to Eq. (53) increase if $`t`$ decreases towards $`t_\sigma `$. But for $`tt_\sigma `$, the description by the first scaling law becomes valid, which provides the leading corrections to Eq. (53). The descriptions by the two scaling laws overlap. Together, they provide a complete description of the dynamics for $`tt^{}`$. This holds provided $`ϵ`$ is small enough, as is demonstrated in Fig. 9 for $`ϵ=10^3`$ for $`\mathrm{\Delta }_S(t)`$ and $`\mathrm{\Delta }_C(t)`$ for $`\zeta =`$ 0.8, and for $`\mathrm{\Delta }_A(t)`$ for 4 values of $`\zeta `$. From the analogous figure for $`ϵ=10^2`$ one concludes that the scaling-law description accounts for the MSD quantitatively for $`tt^{}`$ and $`ϵ0.01`$. For larger distance parameters, corrections to scaling become visible.

### D Rotation-translation-coupling effects

It might be adequate to start the discussion of rotation-translation-coupling effects by two side remarks. Firstly, it was shown that the correlators for the dipole and the quadrupole dynamics for $`\zeta =0.8`$ are in semi-quantitative agreement with the experimental data for propylene carbonate . Thus, the results to be discussed for $`\zeta 0.6`$ can be considered as relevant for the interpretation of glass-forming van-der-Waals liquids. Secondly, the system under study exhibits two glass phases for $`\phi \phi _c`$. There is a critical elongation $`\zeta _c`$ so that for $`\zeta >\zeta _c`$ correlations of the molecule’s axis arrest for long times as do all other correlations of variables characterizing the structure. In particular $`C_1(t\mathrm{})=f_1>0`$. But for $`\zeta \zeta _c`$, dipole correlations exhibit ergodic behavior, i.e. $`C_1(t\mathrm{})=0`$. Precursor effects of this glass-glass transition at $`\zeta _c`$ disturb the standard transition scenario . This is the reason why $`\mathrm{\Delta }_A(t)`$ for $`\zeta =0.4`$ is remarkably different from $`\mathrm{\Delta }_A(t)`$ for the other $`\zeta `$ shown in Fig. 9; for $`\zeta =0.4`$, the elongation is too close to $`\zeta _c=0.380`$. For example, for $`\zeta =0.4`$, the corrections to von Schweidler’s law, which shift the dashed lines on to the full ones for $`t_\sigma <t<t_\sigma ^{}`$, are negative, while they are positive for the other cases.

The glass-transition of the HSS is driven by density fluctuations with wave numbers near the first-peak position of the structure factor $`S_q`$ close to $`q=7.0/d`$. For the scale factor for the $`\alpha `$-process of these fluctuations, defined by $`\stackrel{~}{\varphi }_q(\stackrel{~}{\tau }_q)=f_q^c/20`$, one gets $`\stackrel{~}{\tau }_{7.0}=6.0`$. For the $`\alpha `$-relaxation of the tagged-particle-density correlations for the same wave vector, one gets a similar number $`\stackrel{~}{\tau }_{7.0}^S=5.0`$. One concludes that the $`\alpha `$-scale factor $`\stackrel{~}{\tau }_S=\tau _S/t_\sigma ^{}=11.6`$ for the approach of $`\mathrm{\Delta }_S(t)`$ to the diffusion limit is in the range within which relevant density fluctuations decay to zero. The corresponding interval for the crossover from the end of the von-Schweidler decay to the beginning of diffusion is 2.2 decades. This is shown by the lowest curve in Fig. 9 and should be considered as the normal behavior for the density-fluctuation dynamics in simple systems. The MSD for the molecule’s center behaves quite similarly; $`\mathrm{\Delta }_C(t)`$ for $`\zeta =0.8`$ is nearly indistinguishable from $`\mathrm{\Delta }_S(t)`$. However, Fig. 9 demonstrates also that $`\mathrm{\Delta }_A(t)`$ behaves differently. For $`\zeta `$ = 1.0 (0.8, 0.6), the above specified crossover intervals are 3.3 (3.1, 2.8) decades wide. This means, the crossover intervals of $`\mathrm{\Delta }_A(t)`$ are larger than those of $`\mathrm{\Delta }_S(t)`$ or $`\mathrm{\Delta }_C(t)`$ by factors of about 13 (7, 4), and so are the $`\alpha `$-scales $`\tau _A`$ compared to $`\tau _S`$ or $`\tau _C`$. The reason is the reorientational contribution to the MSD of the constituent atom, i.e., the second term on the r.h.s. of Eq. (2). There are two effects. First, for $`t/t_\sigma ^{}\stackrel{~}{\tau }_1`$, the dipole correlations are decayed to zero, i.e., the molecule’s axis is distributed on the unit sphere with a constant probability density. Therefore, there is the positive offset $`X=(\zeta d)^2/12`$ between the two functions referring to the atom and the center. $`\mathrm{\Delta }_A(t)\mathrm{\Delta }_C(t)=X`$ for $`\stackrel{~}{t}=t/t_\sigma ^{}\stackrel{~}{\tau }_1`$ as is demonstrated in the linear representation of the $`\alpha `$-process master functions in Fig. 10. The slow decay of the relative offset $`X/D_Ct`$ explains that the ratio $`\stackrel{~}{\tau }_A/\stackrel{~}{\tau }_C`$ is larger than unity and this the more the larger $`\zeta `$ is. Second, steric hindrance for reorientations increases with $`\zeta `$. For $`\zeta >0.8`$, the $`\alpha `$-scale $`\stackrel{~}{\tau }_1`$ for dipole relaxations becomes comparable to or larger than $`\stackrel{~}{\tau }_C`$. Therefore, there appears a interval $`1<t/t_\sigma ^{}<\stackrel{~}{\tau }_1`$, after the end of the von-Schweidler-law regime and before the beginning of the diffusion regime, where the $`\mathrm{\Delta }_A(t)`$–versus–$`t`$ diagram, in contrast to the $`\mathrm{\Delta }_C(t)`$–versus–$`t`$ one, exhibits a curvature. This is shown for $`\zeta =0.8`$ and 1.0 in Fig. 10.

If a hard sphere gets expanded to a dumbbell with a small elongation, the molecule’s center gets restricted more tightly in its cage. Therefore, provided $`\zeta `$ is small, the localization length $`r_C^c`$ is smaller than $`r_S^c`$ and it decreases with increasing $`\zeta `$. For $`\zeta 1.0`$, the localization of one constituent atom of the molecule restricts the motion of its partner. Therefore, $`r_C^c`$ is smaller than $`r_S^c`$ also for large elongations. Counter intuitively, the theory does not lead to a monotonic interpolation between the specified limits. The $`r_C^{c\mathrm{\hspace{0.17em}2}}`$–versus–$`\zeta `$ diagram in Fig. 11 exhibits an oscillation and $`r_C^c`$ exceeds $`r_S^c`$ by about 10% for $`\zeta `$ near 0.6.

For $`\zeta \zeta _c`$, one gets $`C_1(t\mathrm{})=0`$. If one neglects the variation of the $`r_C^{c\mathrm{\hspace{0.17em}2}}`$–versus–$`\zeta `$ curve, Eq. (2) leads to $`r_A^{c\mathrm{\hspace{0.17em}2}}=r_S^{c\mathrm{\hspace{0.17em}2}}+(\zeta d)^2/12`$. The dotted line in Fig. 11 shows that this formula explains the increase of $`r_A^c`$ for $`\zeta `$ increasing up to $`\zeta _c`$. For $`\zeta `$ increasing above $`\zeta _c`$, the decrease of $`1f_1`$ and of $`r_C^c`$ explains the decrease of $`r_A^c`$.

It seems plausible that the number of paths for the molecule through the system’s configuration space decreases with increasing elongation. Therefore, one might expect that the diffusivity $`D_A=D_C`$ is smaller than $`D_S`$ and decreases with increasing $`\zeta `$. Figure 11 confirms this expectation for small and for large elongations. But, strangely, the calculated diffusivity is not a monotone function of $`\zeta `$; and for $`\zeta 0.6`$, $`D_C`$ exceeds $`D_S`$ by about 30%.

## IV CONCLUSIONS

MCT predicts that the long-time parts of the density-correlation functions $`\varphi _q(t)`$ of the solvent and $`\varphi _q^x(t)`$ of the solute deal with relaxation in the sense that they are superpositions of Debye-relaxation processes $`\mathrm{exp}[\gamma (t/t_0)]`$. They deal with structural dynamics in the sense that the weight functions $`\rho _q(\gamma )`$ and $`\rho _q^x(\gamma )`$ for these superpositions are uniquely determined by the equilibrium structure. The corresponding dynamics is therefore referred to as structural relaxation. Within the structural-relaxation regime, the subtleties of the normal-liquid dynamics merely enter via the value for an over-all time scale $`t_0`$, which is defined with the aid of the critical decay law, Eq. (30). The structural-relaxation interval was estimated for the hard-sphere system (HSS) under study as $`t>20t_0`$ (Sec. III B, Fig. 4). The specified properties of the MCT dynamics are asymptotic ones, valid for large times near the transition point. The estimation of the range of validity depends on the accuracy level required and also on the particular function under discussion Differentiation with respect to time, as is considered in Eq. (4) for the velocity correlator $`K_S(t)`$, enhances oscillation features, i.e. deviations from relaxation behavior. Figure 5 demonstrates indeed, that one would estimate the structural relaxation interval for $`K_S(t)`$ as $`t>40t_0`$, i.e. somewhat more restrictive than for the MSD.

For a normal liquid, the velocity correlator is positive for short times. It is also positive for times exceeding a cross-over time $`t_h`$, where it exhibits a hydrodynamic long-time tail proportional to $`t^{3/2}`$ . But, upon approaching the glass-transition point, the regime for hydrodynamics shrinks to lower frequencies. Therefore, the time $`t_h`$ diverges if the packing fraction $`\phi `$ approaches the critical value $`\phi _c`$. The cage effect causes $`K_S(t)`$ to be negative for $`t>20t_0`$. Even more, the correlation of the particle velocity at time $`t`$ with the opposite of its initial value, say $`\mathrm{\Psi }(t)=\stackrel{}{v}_S(t)[\stackrel{}{v}_S(t=0)]`$, is proportional to a completely monotone function $`F(t/t_0)`$, Eq. (48). The function $`\mathrm{\Psi }`$ represents a relaxation process in the sense of Eq. (46), where the weight function $`\rho (\gamma )`$ is given by the structural function. These results for the velocity correlator for $`t>20t_0`$ express concisely the essence of glassy dynamics, namely the relaxation caused by the cage effect and determined by the Boltzmann factors for the equilibrium structure.

The MSD increases with time according to the characteristic two-step pattern of the MCT-transition scenario. There is a stretched approach towards a plateau value $`r_S^{c\mathrm{\hspace{0.17em}2}}`$ followed by arrest at the square of the localization length $`r_S^2<r_S^{c\mathrm{\hspace{0.17em}2}}`$ within the glass or by the stretched start of the $`\alpha `$-process within the liquid, Fig. 2. The sensitive density dependence of the MSD near the plateau is described by the universal formulas for the first scaling law, as is demonstrated in Fig. 7. The same holds for the dipole correlator $`C_1(t)`$. This is shown in Fig. 8 by scaling $`C_1(t)`$ for three values of the molecule’s elongation on the same functions $`\sqrt{|\sigma |}g_{}(t/t_\sigma )`$. However, there is a large time interval at the beginning of the structural-relaxation regime, $`20t_0<t<t^{}800t_0`$, where the universal leading-order-asymptotic formulas do not describe the MSD, as is shown in Figs. 6 and 7. The theory predicts similar results for all systems with a structure similar to that of the HSS, i.e. for all van-der-Waals liquids. Obviously, it would be worthwhile to test by experiment or molecular-dynamics simulation whether the specified prediction is correct, in particular, whether MCT can reproduce properly the structural relaxation of the MSD outside the scaling-law regime.

The beginning of the $`\alpha `$-process of the MSD, i.e. the increase of $`\mathrm{\Delta }_x(t)`$ above the plateau $`r_x^{c\mathrm{\hspace{0.17em}2}}`$, is described by von Schweidler’s law, Eq. (52). It is exhibited in Fig. 9 for $`t>t_\sigma `$ by the dashed lines. The $`\alpha `$-process terminates in the diffusion law for long times, exhibited in Fig. 9 by the straight dashed-dotted lines. The $`\alpha `$-process follows well the second scaling law, Eq. (53), which is presented by the dotted lines. The cross-over interval from the end of the von-Schweidler-law description (indicated by the open diamonds) to the beginning of the diffusion process (indicated by the filled diamonds) for the MSD of an atom is about 2 decades wide, as shown by the lowest curve in Fig. 9. The same is true for the MSD of the molecule’s center. But, the cross-over interval for the MSD of the constituent atom of the molecule is much larger due to the rotation-translation coupling. The expansion is more than an order of magnitude for $`\zeta =1.0`$. It would be valuable for an assessment of the MCT for molecular systems if this prediction could be tested by molecular-dynamics simulation.

Bennemann et al.  have determined by molecular-dynamics simulation the MSD for the monomer and for the center of a polymer for a model of a glassy polymer melt. They identified for their data the $`\alpha `$-process in the sense of MCT and interpreted it consistently with the universal asymptotic formulas. They observed the expansion of the crossover interval for the monomer MSD relative to that for the center similar to what is shown in Fig. 9 for $`\zeta =1.0`$, and they attribute this expansion to the glassy dynamics of the Rouse modes. These modes for the polymer’s internal degrees of freedom are thus identified as part of the $`\alpha `$-process . Figures 9 and 10 corroborate their conclusions; albeit for the simplest polymer model only, namely a rigid hard-sphere dimer.

Let us consider a one-dimensional model, where two hard spheres are restricted to move in a finite interval. One calculates easily the localization length $`r_S`$ of one of the spheres, assuming the other sphere to move freely between the wall and its partner. Similarly, one can calculate the localization length $`r_C`$ of the center of a dumbbell built by the two spheres. One finds $`r_C>r_S`$, i.e., the freely moving partner provides a stronger hindrance for the motion in the cage than the bonded one. Possibly, the result $`r_C^c>r_S^c`$ shown in Fig. 11 for $`\zeta 0.6`$ is the analogue of this phenomenon for one-dimensional localization. To corroborate this reasoning, Fig. 12 exhibits as full lines the isotropic part $`g_0^S(r)`$ of the solute-solvent pair distribution function and the corresponding structure factor $`S_0^S(q)`$ for $`\phi =\phi _c`$ for a dumbbell with $`\zeta =0.6`$ . The dashed lines exhibit the results for a sphere with diameter $`d_{\mathrm{eff}}=1.215d`$ chosen such that its volume agrees with that of the dumbbell. The well-known excluded-volume effects for this effective spherical solute are larger than those for the tagged particle of the HSS. In particular, the structure factor peak is higher. Therefore, the localization length $`r_{\mathrm{eff}}^c=0.0588d`$ for the effective spherical solute is much shorter than the localization length $`r_S^c=0.0746d`$ for the tagged particle of the HSS. The ratio $`r_{\mathrm{eff}}^c/r_S^c`$ decreases with increasing $`\zeta `$. The pair distribution function of the effective sphere agrees reasonably well with $`g_0^S(r)`$ for the dumbbell for $`r>1.5d`$. Therefore, the two structure factors are close to each other on the wings of the $`S_0^S(q)`$-peaks and also for small $`q`$. However, packing cannot be done so efficiently around the dumbbell than around a sphere of the same volume. Therefore, the pair distribution function for the latter is much bigger for $`r`$ near $`d_{\mathrm{eff}}`$ than $`g_0^S(r)`$ for the dumbbell. This depletion effect leads to a reduction of $`S_0^S(q)`$ at the peak position and also for larger wave numbers. Hence, the depletion reduces the magnitude of the mode-coupling coefficients. As a result, the localization length $`r_0^c=0.0863d`$, calculated by using MCT equations for a simple system with only the isotropic part of the dumbbell structure factor, is not only larger than $`r_{\mathrm{eff}}^c`$, but it is even larger than $`r_S^c`$. The estimated $`r_0^c`$ is rather close to the true localization length $`r_C^c=0.0808d`$ for the dumbbell’s center. Only if $`\zeta `$ becomes even larger, mode-couplings to the non-isotropic parts of the density fluctuations take over and compensate for the depletion effects. This leads to the decrease of $`r_C^c`$ with increasing $`\zeta `$ for $`\zeta >0.6`$, as shown in Fig. 11.

The above discussed depletion effect means, that the dumbbell is surrounded by a liquid of lower averaged density than specified by the packing fraction. Hence, the dumbbell moves in a complex, which effectively has a larger distance from the glass-transition point than is specified by $`(\phi _c\phi )/\phi _c`$. Such lubrication phenomenon for the dumbbell in the complex might explain the increase of the diffusivity exhibited in Fig. 11 for $`\zeta 0.6`$. Diffusion in a dense liquid is a collective phenomenon. A particle can move over a distance comparable to its diameter only, if one of its neighbors moves. This neighbor can move only if its neighbor moves and so on. On the average, a flow pattern will be built like one knows it for the motion of a sphere in an incompressible ideal liquid. It was one of the original motivations for the formulation of the MCT-equation of motion to approximately treat the indicated back-flow phenomenon. Molecular-dynamics simulation has given evidence that a typical event underlying the mentioned averaged back-flow pattern might consist of quasi-one-dimensional motions of clusters of particles . It seems possible, that the bonding of two atoms to a molecule stabilizes the cluster, provided the elongation $`\zeta d`$ is smaller than the diameter of the ring formed by the moving cluster. If this was the case, the diffusivity for the molecule should be larger than that for a tagged atom. Hence, it is not obvious that the non-monotone variation of the diffusivity with changes of $`\zeta `$, which is shown in Fig. 11, is a mere artifact of the approximations underlying the presented theory.

###### Acknowledgements.

We thank M. Fuchs, W. Kob, M. Sperl, W. van Megen and Th. Voigtmann for helpful and stimulating discussions. S.-H. C. acknowledges financial support from JSPS Postdoctoral Fellowships for Research Abroad. This work was supported by Verbundprojekt BMBF 03-G05TUM.

## A MODE-COUPLING-THEORY MODELS FOR COLLOIDS

In this appendix, it will be shown how the MCT formulas for simple systems can be specialized to models for the dynamics of colloids. Within this frame, a representation of the velocity correlator in terms of a completely monotone function $`F^{\mathrm{col}}(t)`$ shall be derived. To begin, let us remember the definition of Laplace transforms of functions of time, say $`F(t)`$, to functions of the complex frequency $`s`$: $`F(s)=_0^{\mathrm{}}𝑑t\mathrm{exp}(st)F(t)`$. Applying this transformation to $`\varphi _q(t)`$, $`M_q^{\mathrm{reg}}(t)`$ and $`m_q(t)`$, one can rewrite Eq. (9) together with the initial conditions $`\varphi _q(t=0)=1`$ and $`_t\varphi _q(t=0)=0`$ as a double-fraction for $`\varphi _q(s)`$:

$$\varphi _q(s)=1/\{s+\mathrm{\Omega }_q^2/[s+M_q^{\mathrm{reg}}(s)+\mathrm{\Omega }_q^2m_q(s)]\}.$$
(A1)
The analogous result can be obtained for the tagged-particle correlator

$$\varphi _q^S(s)=1/\{s+(qv_S)^2/[s+M_q^{S,\mathrm{reg}}(s)+(qv_S)^2m_q^S(s)]\}.$$
(A2)
Equation (4) can be rewritten as a relation between the Laplace transforms $`\mathrm{\Delta }_S(s)`$ and $`K_S(s)`$ of $`\mathrm{\Delta }_S(t)`$ and $`K_S(t)`$, respectively:

$$K_S(s)=3s^2\mathrm{\Delta }_S(s).$$
(A3)
The small–$`q`$–expansion of Eq. (A2) leads to

$$K_S(s)=3v_S^2/[s+M_0^{S,\mathrm{reg}}(s)+v_S^2m_S(s)].$$
(A4)
Here $`M_0^{S,\mathrm{reg}}(s)=lim_{q0}M_q^{S,\mathrm{reg}}(s)`$, and $`m_S(s)=lim_{q0}q^2m_q^S(s)`$ is the transform of $`m_S(t)`$ from Eq. (27.

In a colloid, there is a contribution to the fluctuating force due to the interaction of the particles with the suspending liquid. This leads to contributions to the rates $`M_q^{\mathrm{reg}}(s)`$ and $`M_q^{S,\mathrm{reg}}(s)`$ which are large compared to the scale for the frequency $`s`$ one wants to consider. Therefore, it is the conventional first approximation step of a theory for colloid dynamics to coarse grain correlation functions on time scales of the order of $`1/M_q^{\mathrm{reg}}(s)`$ and $`1/M_q^{S,\mathrm{reg}}(s)`$. For the correlators considered here, this means that $`s+M_q^{\mathrm{reg}}(s)`$ in Eq. (A1), $`s+M_q^{S,\mathrm{reg}}(s)`$ in Eq. (A2), and $`s+M_0^{S,\mathrm{reg}}(s)`$ in Eq. (A4) are replaced by $`\nu _q=M_q^{\mathrm{reg}}(s=0)`$, $`\nu _q^S=M_q^{S,\mathrm{reg}}(s=0)`$, and $`\nu _0^S=M_0^{S,\mathrm{reg}}(s=0)=lim_{q0}\nu _q^S`$, respectively. Let us indicate the various functions, obtained by this specialization of MCT, by superscripts “col”. The equations of motion, obtained by the back transformation of the so modified Eqs. (A1) and (A2), are :

$`\tau _q_t\varphi _q^{\mathrm{col}}(t)+\varphi _q^{\mathrm{col}}(t)`$ (A5)
$`+{\displaystyle _0^t}𝑑t^{}m_q^{\mathrm{col}}(tt^{})_t^{}\varphi _q^{\mathrm{col}}(t^{})=0,`$ (A6)
$`\tau _q^S_t\varphi _q^{S,\mathrm{col}}(t)+\varphi _q^{S,\mathrm{col}}(t)`$ (A7)
$`+{\displaystyle _0^t}𝑑t^{}m_q^{S,\mathrm{col}}(tt^{})_t^{}\varphi _q^{S,\mathrm{col}}(t^{})=0.`$ (A8)
Here $`\tau _q=\nu _q/\mathrm{\Omega }_q^2`$ and $`\tau _q^S=\nu _q^S/(qv_S)^2`$ are times characterizing conventional colloid dynamics. The interaction potentials between the particles, which cause the cage effect, are not altered by the introduction of the solvent. Therefore, the expressions for the mode-coupling contributions to the kernels, Eqs. (9) and (II B), keep their functional form

$$m_q^{\mathrm{col}}(t)=_q[\varphi _k^{\mathrm{col}}(t)],m_q^{S,\mathrm{col}}(t)=_q^S[\varphi _k^{S,\mathrm{col}}(t),\varphi _p^{\mathrm{col}}(t)].$$
(A9)
Equations (A6)–(A9), together with the initial conditions $`\varphi _q^{\mathrm{col}}(t=0)=1`$ and $`\varphi _q^{S,\mathrm{col}}(t=0)=1`$ define a unique solution with all the general properties of correlation functions . Since the coarse graining has altered the $`s\mathrm{}`$ asymptote of the correlator transforms relative to that exhibited by Eqs. (A1) and (A2), the short-time behavior is altered, namely $`\varphi _q^{\mathrm{col}}(t0)=1|t|/\tau _q+\mathrm{}`$, $`\varphi _q^{S,\mathrm{col}}(t0)=1|t|/\tau _q^S+\mathrm{}`$. Since $`s`$ was dropped in the denominator of Eq. (A4), the velocity-correlator Laplace transform for the colloid dynamics does not tend to zero for large $`s`$; rather $`K_S^{\mathrm{col}}(s\mathrm{})=3D_0^S`$, with the abbreviation $`D_0^S=v_S^2/\nu _0^S`$. This suggests to rewrite the coarse-grained velocity correlator as

$`K_S^{\mathrm{col}}(s)/3=D_0^SD_0^{S\mathrm{\hspace{0.17em}2}}F^{\mathrm{col}}(s),`$ (A11)
$`F^{\mathrm{col}}(s)=m_S^{\mathrm{col}}(s)/[1+D_0^Sm_S^{\mathrm{col}}(s)],`$ (A12)
$`m_S^{\mathrm{col}}(t)=^S[\varphi _k^{S,\mathrm{col}}(t),\varphi _p^{\mathrm{col}}(t)].`$ (A13)
The solutions of Eqs. (A6)–(A9) are completely monotone . Kernel $`m_S^{\mathrm{col}}(t)`$ is a combination with positive coefficients of products of completely monotone functions because of Eqs. (A13) and (II B), and therefore it is completely monotone as well . Because of Bernstein’s theorem, one can write $`m_S^{\mathrm{col}}(s)=_0^{\mathrm{}}[s+\gamma ]^1\rho (\gamma )𝑑\gamma `$ with a non-negative distribution $`\rho (\gamma )`$. Therefore, there hold the following four properties  for $`m_S^{\mathrm{col}}(s)`$: (i) it is holomorphic for all complex $`s`$, except for negative real numbers, (ii) $`m_S^{\mathrm{col}}(s)^{}=m_S^{\mathrm{col}}(s^{})`$, (iii) $`m_S^{\mathrm{col}}(s)0`$ for $`\text{Re}s\mathrm{}`$, and (iv) $`\text{Im}m_S^{\mathrm{col}}(s)<0`$ for $`\text{Im}s>0`$. One concludes furthermore that $`1+D_0^Sm_S^{\mathrm{col}}(s)0`$ for all $`s`$ except, possibly, negative real values. From Eq. (A12) one concludes that also $`F^{\mathrm{col}}(s)`$ exhibits the properties (i)–(iv). Hence, $`F^{\mathrm{col}}(s)`$ is the Laplace transform of a completely monotone function $`F^{\mathrm{col}}(t)`$ (Ref. , chapter 5, theorem 2.6). The back transformation of Eq. (A11) leads to the desired representation

$$K_S^{\mathrm{col}}(t)/3=D_0^S\delta (t)D_0^{S\mathrm{\hspace{0.17em}2}}F^{\mathrm{col}}(t),$$
(A14)
where $`F^{\mathrm{col}}(t)`$ obeys Eqs. (III B).

Let us add, that the back transformation of Eq. (A12) leads to an equation of motion determining $`F^{\mathrm{col}}(t)`$ from the kernel $`m_S^{\mathrm{col}}(t)`$:

$$F^{\mathrm{col}}(t)=m_S^{\mathrm{col}}(t)D_0^S_0^t𝑑t^{}m_S^{\mathrm{col}}(tt^{})F^{\mathrm{col}}(t^{}).$$
(A15)
Integrating Eq. (A14) twice with respect to the time and using Eq. (A15), one gets an equation of motion for the MSD of the colloid

$$\mathrm{\Delta }_S^{\mathrm{col}}(t)=D_0^S\left[t_0^t𝑑t^{}m_S^{\mathrm{col}}(tt^{})\mathrm{\Delta }_S^{\mathrm{col}}(t^{})\right].$$
(A16)
This result was derived originally along a different route . It implies $`lim_{t0}\mathrm{\Delta }_S^{\mathrm{col}}(t)/t=D_0^S`$.


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# 1 Introduction

## 1 Introduction

The theoretical understanding of non-leptonic two body $`B`$ decays is a fundamental step for testing flavour physics and CP violation in the Standard Model and for detecting signals of new physics . The increasing accuracy of the experimental measurements at the $`B`$ factories  calls for a significant improvement of the theoretical predictions. In this respect, important progress has been recently achieved by systematic studies of factorization made by two independent groups . These studies, while confirming the physical idea  that factorization holds for hadrons containing heavy quarks, $`m_Q\mathrm{\Lambda }_{QCD}`$, give the explicit formulae necessary to compute quantitatively the relevant amplitudes at the leading order of the $`\mathrm{\Lambda }_{QCD}/m_Q`$ expansion. They also examine some of the contributions entering at higher order in $`\mathrm{\Lambda }_{QCD}/m_Q`$. The question which naturally arises is whether in practice the power-suppressed corrections, for which quantitative estimates are missing to date, may be phenomenologically important for $`B`$ decays. This problem was previously addressed in refs. . In particular, the main conclusion of refs.  was that non-perturbative penguin contractions of the leading operators of the effective weak Hamiltonian, $`Q_1`$ and $`Q_2`$, although formally of $`𝒪(\mathrm{\Lambda }_{QCD}/m_Q)`$, may be important in cases where the factorized amplitudes are either colour or Cabibbo suppressed. The most dramatic effect of these non-factorizable penguin contractions manifested itself in the very large enhancement of the $`BK\pi `$ branching ratios, as was also emerging from the first measurements by the CLEO Collaboration . In this case, the effect was triggered by Cabibbo-enhanced penguin contractions of the operators $`Q_1^c`$ and $`Q_2^c`$, usually referred to as charming penguins. Since the original publications, about three years ago, several other decay channels have been measured  and the precision of the measurements is constantly improving. With respect to previous analyses, it is now possible to attempt a more quantitative study of charming penguin effects and of the corrections expected to the factorized predictions. We now present the main conclusions of our new analysis.

### Factorization with $`|V_{ub}|`$ and $`\gamma `$ from other determinations

Using the available experimental information on $`|V_{ub}|`$ and on the CP angle $`\gamma `$ provided by the unitarity triangle analysis (UTA) , the branching ratios predicted with the factorized amplitudes, including the $`𝒪(\alpha _s)`$ corrections computed according to ref. , fail to reproduce the experimental $`BK\pi `$ branching ratios that are systematically larger than the theoretical predictions. In addition, $`BR(B_d\pi ^+\pi ^{})`$, which depends on the semileptonic form factor $`f_\pi (0)`$, is about a factor of 2 larger than its experimental value 111 Unless explicitly stated the $`BR`$s always refer to the average of particles and antiparticles, e.g. $`BR(B_dK^0\pi ^0)1/2(BR(\overline{B}_d^0\overline{K}^0\pi ^0)+BR(B_d^0K^0\pi ^0))`$.. We note that the value of $`BR(B_d\pi ^+\pi ^{})`$ within factorization is essentially fixed by the measured $`BR(B^+\pi ^+\pi ^0)`$ rate. Thus, contrary to the statement of ref. , the predicted value of $`BR(B_d\pi ^+\pi ^{})`$ is independent of the theoretical assumptions on the value of $`f_\pi (0)`$. This holds essentially true also for the $`BK\pi `$ $`BR`$s since the value of the “semileptonic” form factor at zero momentum transfer $`f_K(0)`$ is correlated to $`f_\pi (0)`$ by the approximate $`SU(3)`$ symmetry.

### Factorization fitting $`\gamma `$

Even if one ignores the value of $`\gamma `$ from UTA, which is only justified if there are contributions to $`\mathrm{\Delta }F=2`$ mixing due to physics beyond the Standard Model, there are serious difficulties in reproducing the experimental results. In particular, $`BR(B_dK^0\pi ^0)`$ and $`BR(B^+K^0\pi ^+)`$ are much smaller than their experimental values. Moreover, the value of $`\gamma `$ extracted from a fit to the data, $`\gamma =(163\pm 12)^o`$, is in total disagreement with that from the UTA, $`\gamma =(54.8\pm 6.2)^o`$ . In addition, in order to enhance the $`BK\pi `$ rates, the preferred values of $`f_K(0)=0.40\pm 0.02`$ and $`f_\pi (0)=0.34\pm 0.01`$ are incompatible with the latest theoretical estimates, $`f_\pi (0)=0.26\pm 0.05\pm 0.04`$, $`f_K(0)/f_\pi (0)=1.21\pm 0.09_{0.09}^{+0.00}`$  and $`f_\pi (0)=0.28\pm 0.05`$, $`f_K(0)/f_\pi (0)=1.28_{0.10}^{+0.18}`$ , whereas $`|V_{ub}|`$ must have a rather low value, $`|V_{ub}|=(2.79\pm 0.19)\times 10^3`$ instead of that extracted from inclusive  and exclusive  semileptonic $`B`$ decays, $`|V_{ub}|=(3.25\pm 0.29\pm 0.55)\times 10^3`$. We conclude that, even relaxing the constraint on $`\gamma `$, it is very difficult to reconcile the predictions from factorization with the experimental and theoretical findings. For this reason any attempt to extract, within factorization, the value of $`\gamma `$ from ratios of $`BR`$s, for which the discrepancies with the experiments can be accidentally hidden, is not very useful. We think that a preliminary step is to understand the missing dynamical effects.

### Factorization and charming penguins

The inclusion of charming penguin effects, which will be explained in detail in sec. 2, considerably improves the situation for the $`BK\pi `$ channels, with values of $`|V_{ub}|`$ and $`\gamma `$ well compatible with other determinations. In contrast to the $`BK\pi `$ case, charming penguins are not Cabibbo enhanced in $`B\pi \pi `$ decays and are thus expected a priori to play a minor role. For this reason they should be consistently neglected, together with all other $`\mathrm{\Lambda }_{QCD}/m_b`$ corrections. This would leave the problem of a too large predicted $`BR(B_d\pi ^+\pi ^{})`$ unsolved. A natural question is then whether the inclusion of $`\mathrm{\Lambda }_{QCD}/m_b`$ effects in $`B_d\pi ^+\pi ^{}`$ can improve the agreement of the predictions with the experimental data. In particular, besides the charming penguins, penguin contractions of $`Q_1^u`$ and $`Q_2^u`$ (GIM penguins in the notation of ref. ), which are Cabibbo suppressed in $`BK\pi `$, might play an important rôle. We show that, for numerical values of the charming and GIM penguin amplitudes of the expected size, $`\mathrm{\Lambda }_{QCD}/m_b0.1`$$`0.2`$, we can easily reproduce the experimental data for both $`BK\pi `$ and $`B\pi \pi `$ decays while respecting the constraints from the UTA. The sensitivity of $`B\pi ^+\pi ^{}`$ to $`\mathrm{\Lambda }/m_b`$ effects casts serious doubts on the possibility of extracting $`\mathrm{sin}2\alpha `$ from the coefficient of the $`\mathrm{sin}\mathrm{\Delta }m_{B_d}t`$ term obtained from CP asymmetry measurements. On the other hand, we find that the value of the rate asymmetry,

$$𝒜(B_d\pi ^+\pi ^{})=\frac{BR(\overline{B}_d^0\pi ^+\pi ^{})BR(B_d^0\pi ^+\pi ^{})}{BR(\overline{B}_d^0\pi ^+\pi ^{})+BR(B_d^0\pi ^+\pi ^{})},$$
(1)
could be unexpectedly large and call our experimental colleagues for separate measurements of the $`B`$ and $`\overline{B}`$ $`BR`$s. In particular, we find $`|𝒜(B^\pm K^\pm \pi ^0)|=0.18\pm 0.06`$, $`|𝒜(B_dK^\pm \pi ^{})|=0.17\pm 0.06`$. We also find $`|𝒜(B_d\pi ^+\pi ^{})|=0.30`$$`0.50`$. In the latter case, as discussed in the following, the results are subject to other effects on which we do not have control. For this reason we do not quote an error. We simply signal that there is room for a large asymmetry also in $`B_d\pi ^+\pi ^{}`$ decays.

## 2 Results

In this section we describe and discuss more in detail the different cases which have been considered in our analysis.

The physical amplitudes for $`BK\pi `$ and $`B\pi \pi `$ are more conveniently written in terms of RG invariant parameters built using the Wick contractions of the effective Hamiltonian . In the heavy quark limit, following the approach of ref. , it is possible to compute these RG invariant parameters using factorization. The formalism has been developed so that it is possible to include also the perturbative corrections to order $`\alpha _s`$, i.e. at the next-to-leading order in perturbation theory. We present results obtained with this formalism with the addition of the non-perturbative $`\mathrm{\Lambda }_{QCD}/m_b`$ corrections to factorization described below in this section. An alternative framework is provided by the approach of ref. . This method differs in the treatment of the $`𝒪(\alpha _s)`$ terms; unlike the method of ref. , the calculations are only valid at the leading logarithmic order and it is not clear how the independence of the final result from the renormalization scale of the operators of the effective Hamiltonian is recovered. Moreover the Sudakov suppression of the endpoint region, advocated in , is still rather controversial from both the theoretical and phenomenological point of view. For these reasons we prefer to postpone the analysis with the approach of ref.  until the theoretical situation will become clearer.

In the leading amplitudes, we have taken into account the SU(3) breaking terms by using the appropriate decay constants, $`f_K`$ and $`f_\pi `$, and form factors, $`f_K(0)`$ and $`f_\pi (0)`$. Strictly speaking, the form factors should be evaluated at the invariant mass of the emitted meson ($`f_K(m_\pi ^2)`$, $`f_\pi (m_K^2)`$ or $`f_\pi (m_\pi ^2)`$). The difference is however of higher order in $`\mathrm{\Lambda }_{QCD}/m_b`$ and not Cabibbo or colour enhanced and can safely be neglected (it is also numerically immaterial) . As for $`\mathrm{\Lambda }_{QCD}/m_b`$ corrections, we have assumed instead $`SU(3)`$ symmetry and neglected Zweig-suppressed contributions. In this approximation, by $`SU(3)`$ symmetry one can show that all the Cabibbo-enhanced $`\mathrm{\Lambda }_{QCD}/m_b`$ corrections to $`BK\pi `$ decays can be reabsorbed in a single parameter $`\stackrel{~}{P}_1`$. Several corrections are contained in $`\stackrel{~}{P}_1`$: this parameter includes not only the charming penguin contributions, but also annihilation and penguin contractions of penguin operators. It does not include leading emission amplitudes of penguin operators ($`Q_3`$$`Q_6`$) which have been explicitly evaluated using factorization. Had we included these terms, this contribution would exactly correspond to the parameter $`P_1`$ of ref. . The parameter $`\stackrel{~}{P}_1`$ ($`P_1`$) encodes automatically not only the effect of the annihilation diagrams considered in , but all the other contributions of $`𝒪(\mathrm{\Lambda }_{QCD}/m_b)`$ with the same quantum numbers of the charming penguins. In this respect it is the most general parameterization of all the perturbative and non-perturbative contributions of the operators $`Q_5`$ and $`Q_6`$ ($`Q_3`$ and $`Q_4`$), including the worrying higher-twist infrared divergent contribution to annihilation discussed in ref. . The parameter $`\stackrel{~}{P}_1`$ is of $`𝒪(\mathrm{\Lambda }_{QCD}/m_b)`$ and has the same quantum numbers and physical effects as the original charming penguins proposed in , although it has a more general meaning. In some of the previous analyses, see for example , penguin contractions of the operator $`Q_6`$, computed by using perturbation theory and factorization, are enhanced by taking a low effective scale for $`\alpha _s`$. This procedure produces a physical effect similar to that coming from the non-perturbative charming penguins that we are using here, since they have the same quantum numbers.

If one also includes $`B\pi \pi `$ decays we have several other parameters, for example $`P_1^{\mathrm{GIM}}`$ and $`P_3`$, in the formalism of ref. . A closer look to $`P_3`$ shows that this term is due either to Zweig suppressed annihilation diagrams (called CPA and DPA in ref. ) or to annihilation diagrams which are colour suppressed with respect to those entering $`\stackrel{~}{P}_1`$. For this reason we have put $`P_3`$ to zero. $`P_1^{\mathrm{GIM}}`$ will be discussed later on.

We give now the explicit expression of the $`B_dK^+\pi ^{}`$ amplitude as an illustrative example. In terms of the parameters defined in , this amplitude reads

$`𝒜(B_dK^+\pi ^{})=`$ $``$ $`V_{us}V_{ub}^{}\left(E_1(s,u,u;B_d,K^+,\pi ^{})P_1^{\mathrm{GIM}}(s,u;B_d,K^+,\pi ^{})\right)`$ (2)
$`+`$ $`V_{ts}V_{tb}^{}P_1(s,u;B_d,K^+,\pi ^{}).`$
Using the approach of , we have

$`E_1(s,u,u;B_d,K^+,\pi ^{})`$ $`=`$ $`a_1^u(K\pi )Q_1^u_{\mathrm{fact}}+a_2^u(K\pi )Q_2^u_{\mathrm{fact}}+\stackrel{~}{E}_1`$
$`P_1(s,u;B_d,K^+,\pi ^{})`$ $`=`$ $`{\displaystyle \underset{i=3}{\overset{6}{}}}a_i^c(K\pi )Q_i_{\mathrm{fact}}+\stackrel{~}{P}_1`$
$`P_1^{\mathrm{GIM}}(s,u;B_d,K^+,\pi ^{})`$ $`=`$ $`{\displaystyle \underset{i=3}{\overset{6}{}}}(a_i^c(K\pi )a_i^u(K\pi ))Q_i_{\mathrm{fact}}+\stackrel{~}{P}_1^{\mathrm{GIM}},`$ (3)
where $`Q_i_{\mathrm{fact}}`$ denotes the factorized matrix element, and the parameters $`a_i`$ are defined in . The tilded parameters represent $`\mathrm{\Lambda }_{QCD}/m_b`$ corrections; in $`BK\pi `$ channels the only Cabibbo-enhanced correction is given by $`\stackrel{~}{P}_1`$. This term has no arguments since we take it in the $`SU(3)`$ symmetry limit.

We use input parameters (like $`\overline{\rho }`$, $`\overline{\eta }`$, the form factors) with errors, and extract output quantities (like the $`BR`$s, the asymmetries, but also $`\gamma `$, or the form factors when they are not used as inputs) with their uncertainties. Let us explain how we used the input errors and extracted the output uncertainties. We proceed with the usual likelihood method, by generating the input quantities weighted by their probability density function (p.d.f.). In the case of theoretical quantities this is assumed to be flat, whereas the experimental quantities are extracted with Gaussian distributions. Probability density functions, averages and standard deviations are then obtained by weighting the output quantities by the likelihood factor

$$=e^{\frac{1}{2}_i(BR_iBR_i^{exp})^2/\sigma _i^2},$$
(4)
where $`\sigma _i`$ are the standard deviations of the experimental $`BR`$s, $`BR_i^{exp}`$, given in table 1. In cases where the experimental input has a systematic error dominated by theoretical uncertainties, we should extract the latter with a flat distribution . We have instead combined the errors in quadrature and extracted all the experimental quantities with gaussian distributions. Within the present accuracy, and taking into account the unknown non-perturbative parameters, this procedure is fully justified. We have also verified that by extracting the theoretical errors with a gaussian distribution, we obtain very similar results. For more details on the likelihood procedure, the reader is referred to , where all aspects are discussed at length.

### Results with factorization

We start by considering the case in which we use factorization and take the CKM parameters $`|V_{ub}|`$ and $`\gamma `$ from other experimental determinations. We discuss first $`BR(B^+\pi ^+\pi ^0)`$ since in this case, due to isospin symmetry, we do not have the complications due to penguin contractions. Thus, at fixed $`|V_{ub}|`$, the prediction for $`BR(B^+\pi ^+\pi ^0)`$ only depends on $`f_\pi (0)`$ (trivial dependences as from $`f_\pi `$ will be omitted in this discussion). By using the theoretical estimate and uncertainty of $`f_\pi (0)`$ from , and taking into account the uncertainties on $`|V_{ub}|`$, we predict in this case $`BR(B^+\pi ^+\pi ^0)=(5.0\pm 1.5)\times 10^6`$ in very good agreement with the experimental average given in table 1. A complementary exercise is to use as input $`|V_{ub}|`$ and the experimental value of $`BR(B^+\pi ^+\pi ^0)`$ in order to extract the value of $`f_\pi (0)`$. In this case we find $`f_\pi (0)=0.28\pm 0.06`$, in very good agreement with lattice and QCD sum rules estimates. This exercise shows that we do not need to rely on theoretical calculations for the form factors. Indeed also for $`f_K(0)`$ we only need $`f_K(0)/f_\pi (0)`$ which cannot differ too much from one. Moreover it is likely that a large part of the uncertainties of the theoretical predictions cancel in this ratio.

Here and in all the other cases where $`|V_{ub}|`$ and $`\gamma `$ are taken from other experimental determinations, we use as equivalent input parameters the values of $`\overline{\rho }`$ and $`\overline{\eta }`$ given in table 1 from the UTA analysis of ref. . These values correspond to

$$\gamma =(54.8\pm 6.2)^0.$$
(5)
By using $`f_\pi (0)`$ either from theory or from the fit to $`BR(B^+\pi ^+\pi ^0)`$ and assuming factorization, we then predict $`BR(B_d\pi ^+\pi ^{})`$ as a function of $`\gamma `$ only. Besides, in order to analyze all $`BK\pi `$ decays, we only need $`f_K(0)/f_\pi (0)`$ to which the previous considerations apply. Alternatively we may take only $`|V_{ub}|`$ from the experiments and fit the value of $`\gamma `$. In the first case, the results are given in table 2 labeled as “$`\gamma `$ UTA” and show a generalized disagreement between predictions and experimental data. In the second case, the value of $`\gamma `$ is fitted and the results are labeled as “$`\gamma `$ free”. In this case the disagreement is reduced for $`BR(B^+K^+\pi ^0)`$ and $`BR(B_dK^+\pi ^{})`$, and also for $`BR(B_d\pi ^+\pi ^{})`$, but it remains sizable for $`BR(B_dK^0\pi ^0)`$ and $`BR(B^+K^0\pi ^+)`$. The pattern $`BR(B^+K^0\pi ^+)`$:$`BR(B_dK^+\pi ^{})`$:$`BR(B_dK^0\pi ^0)`$:$`BR(B^+K^+\pi ^0)`$=2:2:1:1, which is suggested by the data, and is well reproduced when the contribution of the charming penguins is large, as discussed in the following, is lost in this case. Moreover the fitted value of $`\gamma =(163\pm 12)^0`$ is in striking disagreement with the results of the UTA. Although one may question on the quoted uncertainty of the UTA result, it is clearly impossible to reconcile the two numbers. Thus either there is new physics or $`\mathrm{\Lambda }_{QCD}/m_b`$ corrections are important. We now discuss the latter possibility.

### Factorization with Charming and GIM penguins

We now discuss the effects of charming penguins, parameterized by $`\stackrel{~}{P}_1`$. $`\stackrel{~}{P}_1`$ is a complex amplitude that we fit on the $`BK\pi `$ $`BR`$s. In order to have a reference scale for its size, we introduce a suitable “Bag” parameter, $`\stackrel{~}{B}_1`$, by writing

$$\stackrel{~}{P}_1=\frac{G_F}{\sqrt{2}}f_\pi f_\pi (0)g_1\stackrel{~}{B}_1,$$
(6)
where $`G_F`$ is the Fermi constant. We use $`f_\pi (0)`$ for both $`BK\pi `$ and $`B\pi \pi `$ channels since, as mentioned before, for charming penguins we work in the $`SU(3)`$ limit. $`g_1`$ is a Clebsh-Gordan parameter depending on the final $`K\pi `$ ($`\pi \pi `$) channel. In the case where $`|V_{ub}|`$ and $`\gamma `$ are taken from the UTA, by fitting the $`BK\pi `$ channels and $`B^+\pi ^+\pi ^0`$ only, we find

$$|\stackrel{~}{B}_1|=0.14\pm 0.05.$$
(7)
Note that the size of the charming penguin effects is of the expected magnitude. As for the phase $`\varphi =Arg(\stackrel{~}{B}_1)`$, it is very instructive to consider its distribution, which is displayed in fig. 1: the preferred value of $`\varphi `$ has a sign ambiguity since we are fitting the average of the $`B_d^0`$ and $`\overline{B}_d^0`$ $`BR`$s (or of the $`B^+`$ and $`B^{}`$ $`BR`$s). The ambiguity can be resolved by measuring separately particle and anti-particle $`BR`$s.

By using the distribution on the left of fig. 1, we compute the mean value of $`|\varphi |`$ with the result $`|\varphi |=(75\pm 44)^o`$ and leave the sign undetermined. This is a reasonable procedure, given the approximate symmetry of the distribution and the large uncertainty. In view of the discussion of the particle-antiparticle asymmetry which we present at the end of this paper, we note here that the value of $`\varphi `$ could be rather large. In table 3 we give the corresponding predicted values and uncertainties for the relevant branching ratios (label “Charming”). We observe a remarkable improvement for the $`K\pi `$ channels and a large shift in the value of $`BR(B_d\pi ^0\pi ^0)`$ 222 This effect was already noticed in ., in spite of the fact that in the latter case penguin effects are not Cabibbo enhanced (the $`\pi ^0\pi ^0`$ amplitude is however colour suppressed). The predicted value for $`BR(B_d\pi ^+\pi ^{})`$ remains however much larger than the experimental one.

If one fits the $`BK\pi `$ channels, $`B^+\pi ^+\pi ^0`$ and $`B_d\pi ^+\pi ^{}`$ simultaneously, one finds a better agreement for $`BR(B_d\pi ^+\pi ^{})`$ but a rather small value for $`BR(B^+\pi ^+\pi ^0)`$ (column “Charming with $`\pi ^+\pi ^{}`$” of table 3). This happens at the price of reducing the fitted value of the form factor, $`f_\pi (0)0.22`$, which is pushed down by $`BR(B_d\pi ^+\pi ^{})`$. In fact the latter has an experimental error much smaller than $`BR(B^+\pi ^+\pi ^0)`$, and therefore governs the fit. However, we do not think that this is the correct procedure: theoretically, $`BR(B^+\pi ^+\pi ^0)`$ is on much more solid grounds than $`BR(B_d\pi ^+\pi ^{})`$, since it is not affected by penguins or annihilations, and thus is much more suitable to constrain $`f_\pi (0)`$.

In order to reduce the predicted $`BR(B_d\pi ^+\pi ^{})`$ without affecting $`BR(B^+\pi ^+\pi ^0)`$, one may include other effects of the same order of the charming penguins, as for example the GIM penguins introduced in ref. . In this case we fit all the $`BR`$s given in table 1. With GIM and charming penguins included, we find

$`|\stackrel{~}{B}_1|`$ $`=`$ $`0.16\pm 0.03,|\varphi |=(56\pm 32)^o,`$
$`|\stackrel{~}{B}_1^{\mathrm{GIM}}|`$ $`=`$ $`0.23\pm 0.11,|\varphi ^{\mathrm{GIM}}|=(135\pm 37)^o,`$ (8)
where the notation is self-explaining. We have given the absolute value of $`\varphi `$ since, as in the previous case, the sign ambiguity persists when we include GIM penguins. The distribution is also shown in fig. 1. The results for the $`BR`$s can be found in table 3 with the label “Charming+GIM”. They show that the extra GIM parameter improves the agreement for the measured $`B\pi \pi `$ $`BR`$s. We do not claim, however, to be able to predict $`BR(B_d\pi ^+\pi ^{})`$: our results instead show that accurate predictions for $`B_d\pi \pi `$ decays can only be obtained by controlling quantitatively the $`𝒪(\mathrm{\Lambda }_{QCD}/m_b)`$ corrections, which is presently beyond the theoretical reach. Estimates for charming penguin effects can also be obtained by using some phenomenological model, as for example done in ref. . We observe that the sensitivity of the $`BR`$s to the value of $`\gamma `$ is lost, with the present experimental accuracy, once penguin effects are introduced. Indeed when one tries to fit $`B_1`$ ($`B_1^{\mathrm{GIM}}`$) and $`\gamma `$ simultaneously, one finds that the value of $`\gamma `$ is essentially undetermined. From the above discussion it clearly emerges that one of the important step for the improvement of this kind of analyses is a more precise measurement of $`BR(B^+\pi ^+\pi ^0)`$.

### Particle–Antiparticle asymmetries for the Branching Ratios

The large absolute values of $`\varphi `$, and the sizable effects that penguins have on the $`BR`$s, stimulated us to consider whether we could find observable particle-antiparticle asymmetries as the one defined in eq. (1). We find large effects in $`BR(B^+K^+\pi ^0)`$, $`BR(B_dK^+\pi ^{})`$ and $`BR(B_d\pi ^+\pi ^{})`$, as shown in fig. 2. As discussed before, for $`BR(B_d\pi ^+\pi ^{})`$ our predictions suffer from very large uncertainties due to contributions which cannot be fixed theoretically. For this reason, the values of the asymmetry reported in table 4 are only an indication that a large asymmetry could be observed also in this channel. The sign ambiguity of $`\varphi `$ is reflected in the asymmetry $`𝒜\mathrm{sin}\gamma \mathrm{sin}\varphi `$. This ambiguity can be solved only by an experimental measurement or, but this is extremely remote, by a theoretical calculation of the relevant amplitudes. For each channel, we give the absolute value of the asymmetry in table 4. Note that within factorization all asymmetries would be unobservably small, since the strong phase is a perturbative effect of $`𝒪(\alpha _s)`$ . The possibility of observing large asymmetries in these decays opens new perspectives. These points will be the subject of a future study.

## Conclusion

We have analyzed the predictions of factorization for $`B\pi \pi `$ and $`BK\pi `$ decays. We note that the normalization of all the other $`BR`$s is essentially fixed by the value of $`BR(B^+\pi ^+\pi ^0)`$ and $`SU(3)`$ symmetry. Even taking into account the uncertainties of the input parameters, we find that factorization is unable to reproduce the observed $`BR`$s. The introduction of charming and GIM penguins  allows to reconcile the theoretical predictions with the data. It also shows however that it is not possible, with the present theoretical and experimental accuracy, to determine the CP violation angle $`\gamma `$. Contrary to factorization, we predict large asymmetries for several of the particle–antiparticle $`BR`$s, in particular $`BR(B^+K^+\pi ^0)`$, $`BR(B_dK^+\pi ^{})`$ and $`BR(B_d\pi ^+\pi ^{})`$. This opens new perspectives for the study of CP violation in $`B`$ systems.

## Acknowledgments

We thank G. Buchalla and C. Sachrajda for useful discussions on our work. M.C. thanks the TH division at CERN where part of this work has been done. L.S. thanks Hsiang-nan Li for very informative discussions and J. Matias for pointing out a misprint.