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# PRECISION DETERMINATION OF V_ub AT AN 𝑒⁺𝑒⁻ B FACTORY

## I Current Methods

CLEO was the first experiment to measure the ratio $`|\mathrm{V}_{\mathrm{ub}}|/|\mathrm{V}_{\mathrm{cb}}|`$ by detection of inclusive leptons from semileptonic B meson decay beyond the kinematic endpoint for final states containing charm mesons cle (1993). Experimentally this is a clean measurement but only 5-20% of the leptons from $`bu\mathrm{}\nu `$, depending on the model, populate the endpoint region and so a large extrapolation, and hence a large theoretical uncertainty ($``$ 20%) severely limits the precision of the measurement. However this method is still useful as a reality check of more precise methods. More recently CLEO was able to reconstruct exclusive transitions using several analysis techniques that exploit the hermiticity of the CLEO detector to reconstruct the neutrino four vector cle (1996, 2000). Due to large backgrounds it has so far been found necessary to continue to work mostly in the lepton endpoint region. $`|\mathrm{V}_{\mathrm{ub}}|`$ is extracted from the measured branching fraction, and the rate which is computed using a variety of theoretical methods. The theoretical error is large ($``$20%) and dominates the experimental errors as the form factors governing the transitions are not derived from first principles, and the transitions are measured in only part of the phase space.

## II Future Methods

There are two main theoretical approaches to improve the determination of $`|\mathrm{V}_{\mathrm{ub}}|`$. The first of these is the operator product expansion (OPE) which is able to predict the inclusive $`bu\mathrm{}\nu `$ rate to $`510\%`$ within experimentally tractable regions of phase space (either the region of $`m_{\mathrm{had}}<m_\mathrm{D}`$ or the endpoint of the $`q^2`$ spectrum). The second theoretical approach is lattice QCD (LQCD). There has been a great deal of progress in LQCD in the last few years and within a few years unquenched calculations of the rate for exclusive semileptonic decays will be available. The LQCD calculations may have an error of a few % or better. Further discussion of the theoretical issues in the extraction of a precision value of $`|\mathrm{V}_{\mathrm{ub}}|`$ can be found in Falk (2001) Ligeti (2000) lat (2001).

The simulations reported here are for a symmetric $`e^+e^{}`$ B Factory. We use a fast (parametric) Monte Carlo of the CLEO III detector called TRKSIM with the CLEO $`\mathrm{{\rm Y}}(4S)B\overline{B}`$ event generator. Efficiencies and $`S/B`$ for asymmetric B factories will differ slightly but the general conclusions are likely to be unchanged. Powerful suppression of the $`bc\mathrm{}\nu `$ background can be achieved by full reconstruction of the companion $`B`$ decaying to $`BD^{()}(n\pi )`$. As $`B`$ tagging has a relatively low efficiency ($`2.85\times 10^3`$eff (1998), the technique was impractical for most analyses with pre B-factory samples, but will be used extensively in future. We assume 1% systematic error in lepton identification, and 2% systematic error in tracking in this paper.

### II.1 Inclusive hadronic mass spectrum

The companion $`B`$ is reconstructed and the remainder of the event is then required to have only one lepton, with momentum greater than 1.4 GeV, and missing mass consistent with a neutrino. We select $`bu\mathrm{}\nu `$ events with $`m_{\mathrm{had}}<m_\mathrm{D}`$. Figure 1(a) shows the simulated $`m_{\mathrm{had}}`$ distribution for an integrated luminosity of 1000 $`fb^1`$. Table 1 shows the estimate of the statistical and systematic error on $`\mathrm{V}_{\mathrm{ub}}`$ measured with this method.

### II.2 Inclusive $`q^2`$ spectrum

Using the inclusive $`q^2`$ endpoint results in a loss of statistics, but a gain in theoretical certainty compared to the low $`m_{\mathrm{had}}`$ region. The experimental advantage of this method compared to the $`m_{\mathrm{had}}`$ method is that $`S/B`$ is more favorable, therefore this method will be more attractive with very large data samples. $`B`$ tagging and event selection are the same as in the previous method. We select $`bu\mathrm{}\nu `$ events with $`q^2>11.6`$ GeV2. Figure 1(b) shows the simulated $`q^2`$ distribution for an integrated luminosity of 1000 $`fb^1`$. Table 1 also shows the estimate of the statistical and systematic experimental errors on $`\mathrm{V}_{\mathrm{ub}}`$ obtained with this method.

### II.3 Exclusive decays with Lattice prediction

LQCD aims to predict the decay rate of semileptonic decays such as $`D\pi \mathrm{}\nu `$ and $`B\pi \mathrm{}\nu `$ to $``$ few %, which corresponds to $`\delta \mathrm{V}_{\mathrm{ub}}^{\mathrm{stat}.}12\%`$ lat (2001). However many consistency checks will be required to demonstrate that the estimated lattice precision has been achieved. Here we outline one possible method.

From an unquenched LQCD calculation of $`f_D`$ and a measurement of $`D^+\mu ^+\nu `$ at a charm factory (for example CLEO-C cle (2001)) we obtain a precision direct measurement of $`\mathrm{V}_{\mathrm{cd}}`$. Using this value of $`\mathrm{V}_{\mathrm{cd}}`$, with an unquenched LQCD calculation of the rate and form factor shape of $`D\pi \mathrm{}\nu `$, we can make a direct test of the lattice with a measurement of $`d\mathrm{\Gamma }/dq^2(D\pi \mathrm{}\nu )`$. This measurement is also best done at a charm factory where the kinematics at threshold cleanly separates signal from background.

If the lattice passes the above test, the second step is to compare the lattice prediction of the shape of $`d\mathrm{\Gamma }/dq^2(B\pi \mathrm{}\nu )`$ to that of data at a B factory. If the shapes agree the third step is to measure $`\mathrm{\Gamma }(B\pi \mathrm{}\nu )`$ with data. To cleanly isolate the signal we fully reconstruct the companion $`B`$ meson, and select, for example, $`B\pi \mathrm{}\nu `$ events with the neutrino reconstruction or consistency methods. Combining the measurement with the lattice prediction of $`\mathrm{\Gamma }(B\pi \mathrm{}\nu )`$, we extract $`\mathrm{V}_{\mathrm{ub}}`$. The theoretical error on $`|\mathrm{V}_{\mathrm{ub}}|`$ may be as small as $`12`$%. Table 2 shows the results of our simulation. The numbers in the parentheses in Table 2 are obtained only using $`\pi `$’s in the range of $`0.4<p_\pi <0.8`$ GeV/$`c^2`$, where the systematic uncertainties involved in LQCD are well under control, therefore LQCD is most reliable lat (2001). To have a comparably small experimental error would require $`10,000fb^1`$. Such large data samples are beyond the reach of existing B factories where $`2000fb^1`$ are expected by the year 2010.

## III Conclusion

All possible theoretically clean measurements in the B sector are very important even if they are redundant within the standard model. It is essential to pursue both CP violating and CP conserving measurements (i.e., $`\mathrm{V}_{\mathrm{ub}}`$) to test the Standard Model and look for new physics. Inclusive methods will achieve $`\delta \mathrm{V}_{\mathrm{ub}}\mathrm{few}\%(\mathrm{experiment})510\%(\mathrm{theory})`$. The $`q^2`$ endpoint is the method of choice. The first test of CKM at the 10% level will come from inclusive methods of determining $`\mathrm{V}_{\mathrm{ub}}`$ and $`\mathrm{V}_{\mathrm{cb}}`$, and the measurements of sin$`2\beta `$, and $`\mathrm{V}_{\mathrm{td}}/\mathrm{V}_{\mathrm{ts}}`$. If the lattice can reach the predicted accuracy ($`12\%`$), it will become the method of choice for measurements of $`\mathrm{V}_{\mathrm{ub}}`$ (and $`\mathrm{V}_{\mathrm{cb}}`$) in the second decade of the 21st Century. However the lattice must first be calibrated. A charm factory can provide unique and crucial tests of lattice predictions. A $`10,00020,000fb^1`$ data sample is required to attain a total experimental error of $`12\%`$ on $`\mathrm{V}_{\mathrm{ub}}`$ commensurate with the lattice error.


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# Comment on “Detecting the Kondo Screening Cloud around a Quantum Dot”

## Abstract

We point out several mistakes in the recent work of I. Affleck and P. Simon (cond-mat/0012002).

Recently 1  it was claimed that the effect of the Kondo screening on persistent currents (PC) was studied in a mesoscopic ring coupled to a quantum dot. The system was considered in the framework of the Anderson impurity (AI) model for two situations — for large Kondo length scales $`\xi _KL`$ and small ones $`\xi _KL`$. Here $`\xi _K=\mathrm{}v_F/T_K`$, $`v_F`$ is the Fermi velocity of electrons in the ring and $`T_K`$ is the Kondo energy scale. We want to point out the following:
(i) Charge degrees of freedom (and, hence, PC) are totally decoupled from spin degrees of freedom in the “bare” Kondo problem 2 . Hence, the Kondo screening itself does not affect (except of initial phase shifts) charge PC (the Aharonov-Bohm effect), but rather spin PC (the Aharonov-Casher one) 3 . On the other hand, the AI (for which both spin and charge degrees of freedom are hybridized with the host) really influences charge PC 4 .
(ii) In the case $`\xi _KL`$ (i.e., $`T_K`$ being much less than energy spacings of electrons in the ring $`\mathrm{}v_F/L`$) one can neglect all other levels of electrons in the ring except of the lowest. (Sinusoidal oscillations of PC with the magnetic flux obviously results.) In this case the renormalization of the ground state energy of the localized electron due to the hybridization with ones from the ring (i.e., $`T_K`$ 2 ) is not determined by Eq. (1) of 1 . In the limit $`|ϵ_0|,Ut^{}`$ 1  it is rather proportional to $`2t^2/|(\mathrm{}v_F/L)+[(U+ϵ_0)ϵ_0/U]|`$, where $`t^{}`$ are hopping elements of dot-ring contacts, $`U`$ and $`ϵ_0`$ are the standard parameters of the AI Hamiltonian 1 ; 2 . Kondo logarithms (which appear if one takes into account thermodynamically large number of states in the Fermi sea of ring electrons) are absent in this case 2 . Here one can speak about the Kondo effect only in a “Pickwick sense” (the Abrikosov-Suhl resonance is too far from the Fermi energy and too wide). The other situation $`\xi _KL`$ ($`T_K\mathrm{}v_F/L`$) was studied exactly 6 years ago in 3 ; 4  (unlike the qualitative study of this case in 1 ). Here a thermodynamically large number of states of electrons of the ring produces exponential, generic for the correlated nature of the Kondo effect, dependence for $`T_K`$ 2 . Hence, in the ground state the oscillations of PC are “saw-tooth”-like (the sum of many harmonics) 3 ; 4 ; 5 . Their magnitude is proportional to $`ev_F/\mathrm{}L`$ 4 ; 5 . However the conclusion of 1  that PC in this case are those of ideal ring (i.e., without dot) is invalid. The intra-dot Coulomb repulsion manifests itself in the matrix of “dressed charges” (its components measure numbers of electrons which form low-lying charge and spin excitations of a system), being different from unity matrix (noninteracting case) 3 ; 4 . Only in the limit of zero magnetization the behavior of PC is reminiscent of the one for free electrons, while for any nonzero Zeeman splitting (which is the generic situation) it differs drastically. Moreover, the single velocity ($`v_F`$) present in the answer for PC is the consequence of the linearization of the dispersion law for electrons in the ring in the AI model. It is easy to show that the study of PC in a lattice Bethe ansatz-solvable model (e.g., 6  where the AI-like impurity was situated in the correlated electron ring) produces the answer for the PC similar to the ones for the AI model 4 , but with two different velocities for low-lying spin and charge excitations. The latters become equal to $`v_F`$ only if one linearizes the spectrum of the host.
(iii) PC for the multichannel Kondo impurity were exactly studied in 7  (notice that the results of 7  can be used for chiral fermions, too). Here multichannel Kondo screening also does not affect charge PC (as the consequence of the spin-charge separation) for any values of the local exchanges between the localized spin and channel electrons of the ring. However the correlation effects induced by the magnetic impurity introduce the interference of several Aharonov-Casher oscillation patterns for spin PC. There is also an interference between the Coulomb blockade-like (parity) effects and PC oscillations 7 .

This has been the text of my manuscript submitted to the Physical Review Letters on March 26, 2001. Several remarks are in order to clarify the brief above argumentation.

1. A number of recent publications considered persistent currents in quantum rings with magnetic impurities. There is a principal difference between persistent currents and usual transport currents. Recall, usual currents are transport, kinetic characteristics of any system. Their usual characteristics are the resistivity or conductivity and related to them transition amplitude. In the framework of the linear response theory the conductivity is the coefficient, which connects the value of the current with the value of an applied electric field. Hence, one can consider transport currents in a system only if it has the sourse and drain, cf. Fig. 1 (a), and the transport current is the consequence of the difference in potentials applied to the sourse and drain. One necessary needs this difference to study any transport current.

On the other hand, the persistent current is the thermodynamic characteristic of a ring. It is connected with the Aharonov-Bohm phase shift, which appears when charges move along a loop, pierced by a magnetic flux ABC . Then an external magnetic flux yields nonzero momentum of charges. In fact the persistent current is nothing else than the total orbital moment of all charges in the ring. Naturally, the persistent current can exist without any applied external electric field; it does not need any sourse and drain, cf. Fig. 1 (b). Persistent current is just the derivative of the energy of a system in equilibrium with respect to the applied magnetic flux. For noninteracting electron rings the charge persistent current is connected with the virtual movement of an electron around the magnetic flux. For interacting electron systems charge persistent currents pertain to the virtual movement(s) of charge-carrying excitations (in the ground state and at low temperatures — to the virtual movement of the low-lying charged excitations). Clearly, in the situation of Fig. 1 (b) (without any sourse and drain) it is inappropriate to speak about the conductance/conductivity or resistivity of a system — at least one should first properly define, what are the latters. The missunderstanding sometimes appears because several recent experiments on quantum rings studied namely the geometry of Fig. 1 (a), but not of Fig. 1 (b) (i.e., they measured transport currents between sourses and drains, but not the total orbital moment of the ring). Naturally, when the ring between the sourse and drain is pierced by an external magnetic flux in the geometry of Fig. 1 (a), the transport current is also affected by that flux. Hence, the conductance of the transport current also becomes flux-dependent. However this transport current is naturally not exactly equal to the persistent current. It turns out that the authors of Ref. 1  definitly wrote about persistent currents, not transport currents (cf., Fig. 1 and Fig. 1 of 1 ).

This difference in the basic features of transport and persistent currents produces the main difference in the answers, when one considers the effect of a magnetic (Kondo) impurity. The Kondo impurity introduces the interaction into the free electron problem 2 . It is well known that in the pure Kondo problem (a magnetic impurity, just a spin, coupled to the free electron host via a local exchange interaction) collective spin and charge degrees of freedom decouple from each other 2 . Notice that in the Anderson impurity model the hybridization impurity manifests both charge and spin degrees of freedom 2 . On the one hand, the resistivity of a transport current is strongly affected by the Kondo impurity 2 , because the resistivity is determined by the density of all states of the system, spin and charge. The Kondo (Abrikosov-Suhl) resonance (which is the characteristic feature of spin degrees of freedom, cf., 2 ; KO ) determines the magnetoresistivity of the transport current. Hence, the conductance of a quantum ring \[in the geometry of Fig. 1 (a)\] with embedded magnetic (Kondo) impurity is, obviously, affected by that impurity. On the other hand, the persistent current \[i.e., the total orbital moment of a quantum ring in the geometry of Fig. 1 (b)\] is determined by the virtual movement of only charge-carrying excitations around the magnetic flux. In the pure Kondo situation, in which a magnetic impurity (spin) is connected to the free electron host via a local spin exchange, the charge degrees of freedom are mostly not affected by the spin impurity 2  (the only possible effect is the possible presence of an initial phase shift, see 4. below). Hence, in this case the Kondo impurity does not influence the frequency and the magnitude of persistent currents in the geometry of Fig. 1 (b). Namely this property of metallic rings with embedded spin (Kondo) impurity was pointed out in our pioneering Letter of 1994 3 , which studied the effect of the Kondo impurity on persistent currents for the first time. The situation is very diffrent for the Anderson (hybridization) impurity. Here the impurity affects both spin and charge low-lying excitations 2 . In this case the Anderson impurity affects charge persistent currents of the geometry of Fig. 1 (b) 4 . For example, the Anderson impurity produces low-lying excitations, which carry charge $`2e`$ (spin-singlet bound states of electrons) and excitations, which carry spin $`1/2`$ and charge $`e`$ 2 . The virtual movement of excitations, which carry charge $`2e`$, naturally yields oscillations of charge persistent currents with the period $`\mathrm{\Phi }_0/2`$ (where $`\mathrm{\Phi }_0=hc/e`$), while unbound electron excitations, which carry charge $`e`$, produce oscillations of persistent currents with the period $`\mathrm{\Phi }_0`$ 4 . For the case with the dispersion law of host electrons being linearized about Fermi points the velocities of both types of low-lying excitations are equal to each other (and both are equal to the Fermi velocity) 2 . In the absence of the Zeeman effect of the external magnetic field the interference of those two type of oscillations of persistent currents produces oscillations with the period $`\mathrm{\Phi }_0`$, reminiscent of the ones in a free electron host. (Notice also the parity effect of persistent currents in a ring with the magnetic impuritry, i.e., different initial phases \[dia- or paramagnetic persistent currents\] and periodicities for different numbers of electrons in the ring, predicted in 3 ; 4 ; 5 ; 7 ). However the nonzero curvature of the spectrum of host electrons and the Zeeman effect of the applied magnetic field (it is small, naturally, for the case of GaAs-based quantum rings, where effective $`g`$-factors are small) must produce the real interfererence of two types of oscillations of charge persistent currents (with the periods $`\mathrm{\Phi }_0`$ and $`\mathrm{\Phi }_0/2`$), because their magnitudes become different from each other in that case. It turns out that we pointed out the difference between the characteristics of persistent currents and transport currents of a metallic ring with a Kondo impurity in Ref. 7 , where it is clearly shown that a magnetic Kondo impurity (spin) does not change the properties of charge persistent currents, but drastically affects the magnetoresistivity for charge transport currents, cf. subsections A and B of the Section IV of 7 .

2. To explain other inconsistencies of 1  let us start with the description of the low-energy behavior of the Anderson model. In this explanation we use different from 2 , variational approach to the Kondo problem var . This approach is well-known and later was reproduced in a number of books and textbooks, see e.g., Ful ; Mah . Naturally similar results can be obtained using the Bethe ansatz approach to the Kondo problem 2 , or using other approaches, like the non-crossing-like approximations BCW  or the slave-boson technique Col . For simplicity we consider the Anderson impurity Hamiltonian with $`U\mathrm{}`$ (similar results can be obtained for finite $`U`$). The variational wavefunction for the ground state can be taken as

$$|\psi =A(|0+\underset{ϵ}{}a(ϵ)|ϵ),$$
(1)
where $`|0`$ determines the state of host electrons, in which all states below the Fermi energy are occupied and the impurity level is empty, $`|ϵ`$ is the state with one electron at the impurity level and one hole below the Fermi energy, $`a(ϵ)`$ is the variational coefficient, and $`A`$ is the normalization constant. The minimization of the ground state energy with respect to $`a`$ yields the equation

$$\mathrm{\Delta }E=t^2\underset{ϵ}{}\frac{2}{(\mathrm{\Delta }Eϵ_0+ϵ)},$$
(2)
where we introduced $`\mathrm{\Delta }E`$, the renormalization of the ground state energy due to the Anderson impurity. If the number of states in the sum is thermodynamically large (namely it is the case for the small ratio $`\mathrm{}v_F/L`$), one can replace the sum by the integral, which for the constant density of states of conduction electrons $`N(0)`$ yields the famous Kondo logarithm and one obtains:

$$\mathrm{\Delta }E=De^{\frac{|ϵ_0|}{2N(0)t^2}}=De^{\frac{1}{N(0)J_{eff}}}T_K$$
(3)
($`D`$ pertains to the bandwidth of conduction electrons). It means that $`T_K`$ is namely the renormalization of the ground state energy due to the hybridization Anderson impurity. This, naturally, agrees with other definitions of the Kondo scale, see, e.g., Refs. 2 . This equation is equivalent, naturally, to Eq. (1) of 1 . In this case, obviously, the thermodynamically large number of harmonics produces the “saw-tooth”-like oscillations of persistent currents, which were obtained in Refs. 3 ; 4 ; 5 ; 7  and (partially) reproduced in 1 . However, it turns out that if the number of states in the sum is small (which is the case for the large ratio $`\mathrm{}v_F/L`$), one cannot replace the sum by the integral, and the Kondo logarithm does not appear in Eq. (2). One can, naturally, find the renormalization of the ground state energy (which also plays the role of the Kondo temperature in this case), however it will be not exponentially dependent on the effective exchange constant $`J_{eff}`$. For one electron level of the ring being involved it is namely the answer written above in the text of the Comment (in the limit $`U\mathrm{}`$; for finite $`U`$ one can follow for the variational approach GS ). This is actually the answer obtained in BS , to which the limiting case of the large ratio $`\mathrm{}v_F/L`$ of 1  pertains (1  actually introduces only the $`O(J^2)`$ corrections to the result BS ). Naturally, for only one level of conduction electrons being involved one clearly obtains only one harmonics (i.e., sinusoidal oscillations of the persistent current, cf. 1 ; BS ). This means that in the limiting case of large $`\mathrm{}v_F/L`$ one cannot use Eq. (1) of 1  for the determination of $`T_K`$. Actually this limit ($`\xi _KL`$) has no other, standard for the Kondo situation, features. For example, it is well known that the generic Kondo effect affects the Sommerfeld coefficient of the low temperature specific heat and magnetic susceptibility of the magnetic impurity: They become large (inverse proportional to the small Kondo temperature). However for the finite number of states of the case $`\xi _KL`$ the specific heat is exponentially small at low temperatures, and the magnetic susceptibility is determined by the (possible for systems with orbital degrees of freedom) van Vleck (zero temperature) terms, while temperature corrections are exponentially small, too Sch .

In Ref. 4  persistent currents were calculated for the ring with the Anderson impurity (which produces effective interactions for both spin and charge degrees of freedom). In this paper it is shown that persistent currents are determined by $`1/L^2`$ corrections to the energy ($`L`$ is the size of the ring), while the behavior of the impurity itself (its valence, magnetization, etc.) are determined by $`1/L`$ corrections, if the main contribution to the energy is of order of 1 (i.e., per site). \[This statement is true for any one-dimensional quantum ring with gapless low-lying excitations.\] The Kondo scale in the magnetic field behavior appears for the characteristics of the impurity, but not (in the main order in $`1/L`$) for persistent currents (it appears in higher-order corrections, too, but they are irrelevant for our discussion). The main quantities, which determine the values of persistent currents in ideal ballistic quantum mesoscopic rings are the (Fermi) velocities of low-lying excitations, which virtual movement defines the Aharonov-Bohm effect in interacting systems, and the matrix of “dressed charges” (this quantity measures the effective number of “initial” electrons which form each low-lying excitation). In principle both of those quantities depend on the magnetic field (in the Bethe ansatz scheme that dependence is obtained via solutions of integral equations for mentioned quantities). For the model of the Anderson impurity studied in Ref. 4  (with the linearized dispersion law of host electrons) the velocities of low-lying charge and spin excitations coincided with the initial Fermi velocity of electrons and do not depend on the external magnetic field (cf. 2 ). Notice that for hybridization impurity models on the lattice, cf. 6 , it is not true — there are two different from each other velocities of low-lying excitations and both of them depend on the magnetic field. However the matrix of “dressed charges” does depend on the magnetic field even for the linearized dispersion law of host electrons. This dependence does not reveal the Kondo scale (in the main order in $`1/L`$). For exactly zero magnetic field the answer for the charge persistent current is reminiscent of the one for a ring of noninteracting electrons (as it must be). However even a small deviation of the value of the field from zero produces very strong changes in the values of the components of the “dressed charge” matrix \[because of logarithmic corrections, present in the SU(2)-symmetric system; these corrections are well-known to one of the authors of 1 , who published many papers devoted to similar logarithmic corrections log \]. Hence the persistent current becomes to be different from the one of the ring with free electrons for small $`\mathrm{}v_F/L`$ (even if the value of the magnetic field is small compared to $`T_K`$, and the magnetization of the impurity is small). These corrections, being very small, are not very important for the magnetization of the impurity, however they are of great importance for persistent currents — e.g., the magnitudes of the oscillations of persistent currents with periods $`\mathrm{\Phi }_0`$ and $`\mathrm{\Phi }_0/2`$ will be different even for very small fields, i.e., an additional period of persistent currents can be observed. We emphasize that it is not rare that the effect of an (even small) magnetic field on the quantum dot embedded into the quantum ring is important (cf. field ).

By the way, in a recent preprint prepr  (which appeared after the authors of 1  became aware of my above written text of the Comment) one of the authors of 1  directly wrote (cf. P.7 of prepr ): “On the other hand, when $`\xi _KL`$ the Kondo effect doesn’t take place: the infrared divergence of the Kondo coupling, $`\lambda `$, is cut off by the finite size of the ring.” This is in obvious contradiction to the statements of 1 , where the authors proposed to study the influence of the Kondo effect on persistent currents in both cases — $`\xi _KL`$ and $`\xi _KL`$ — and obviously coincide with the above mentioned statement of our Comment.

3. The authors of Ref. 1  (and also some others, see, e.g., side ) claimed that the Bethe ansatz approaches of Refs. 3 ; 4 ; 5 ; 7 ; EJS  considered side-coupled quantum dots, see Fig. 2 (a).

These claims are absolutely wrong. The Bethe ansatz method can be used either for systems with periodic boundary conditions, or for systems with open boundary conditions (does not matter, whether one studies homogeneous systems or systems with impurities). The Bethe ansatz method is properly justified for discrete coordinates of particles KBI . Field theoretical models, solved by the Bethe ansatz, have to be continuous limits of their lattice counterparts (including the solution of the Kondo problem 2 ). (Notice that the continuous limit can be taken in different ways, which introduces some ambiguity.) Impurities can be included into the lattice Bethe ansatz scheme either as shown in Fig. 2 (b) and (c) for the impurity in the bulk of a ring or an open chain, i.e., the impurity is connected with two neighboring sites of the host, or connected with only one neigboring site only at the edge of an open chain, as shown in Fig. 2 (d). This is the direct consequence of the fact that impurities can be introduced into the Bethe ansatz monodromies either as special scattering matrices (this way implies no reflection in the problem at all) or as local boundary fields/potentials (reflectors), which can be applied only to the edges of an open chain. Please, pay attention that we distinguish the reflection and backward scattering (by the latter we mean the transfer from the one Fermi point to another — such processes are present in any lattice integrable theories, like the Heisenberg spin-$`\frac{1}{2}`$ chain or Hubbard chain KBI , but there is no reflection there for periodic boundary conditions). Scattering matrices of impurities have to satisfy Yang-Baxter (“triangular”, “star-triangle”) relations KBI  with scattering matrices of the host, to preserve the integrability of a problem in the framework of the Bethe’s ansatz. Hense, such impurities in periodic Bethe ansatz solvable systems have to be pure scatterers, but must not produce any reflection. On the other hand, local fields (reflectrors) can be used only for open chains in the lattice Bethe ansatz approach. They are described by reflection matrices, which satisfy reflection equations Skl . However for any system with open boundary conditions persistent currents are obviously zero. Hence, the only possibility to study persistent currents in Bethe ansatz-solvable models with impurities is to consider impurities, which produce only scattering phases, but not reflections, and which scattering matrices satisfy Yang-Baxter relations with scattering matrices of the host (and, naturally, mutually). In our papers 3 ; 4 ; 5 ; 7  (see also oth : It turns out that we studied the problem of the influence of magnetic impurities on charge and spin persistent currents in detail in a large number of refereed papers since 1994 and reported our results at international conferences), devoted to the influence of magnetic and hybridization impurities on persistent currents, we considered only integrable impurities of this class. The Bethe ansatz solution of the Kondo problem 2  also belongs to this class — impurities produces only scattering phases but not reflections. The side-coupled impurity \[cf. Fig. 2 (a)\] has, naturally, the properties of a reflector (which is correctly pointed out in 1 ) and, therefore, cannot be introduced into the Bethe ansatz solvable ring in principle, because it violates the Yang-Baxter relations. This is why, the claim that the side-coupled impurity could be introduced into the Bethe ansatz solvable ring is absolutely incorrect.

4. In the framework of the Bethe ansatz there are two independent very well known solutions to the Kondo problem (pure spin impurity in the free electron host, coupled to the host via the local exchange): the one by N. Andrei and the one by P. Wiegmann 2 . These solutions, being different in some details, produce the same correct answers for thermodynamic characteristics of the Kondo magnetic impurity. Those details are not important for the behavior of the thermodynamic characteristics of the host and the impurity. However, those details can produce the difference in the behavior of finite-size corrections (which namely determine persistent currents in metallic systems). One of those details is the phase factor for the Bethe ansatz equations, which govern the behavior of charge degrees of freedom in the solution of P. Wiegmann (cf., Wie ) and the absence of that phase in the approach of N. Andrei (cf., And ), see also 2 . The presence or absence of those phase factors are determined by the particular choosen schemes of taking the sclaling limit in those two approahes. The Bethe ansatz is developed for systems with discrete particles, because of its main property: Any multi-particle scattering process is considered as consequence of pair scattering processes between particles in the Bethe ansatz scheme KBI . Then, when studying continuous limit, one has to use some scaling approximation from the lattice counterpart. Therefore the consideration of the continuous scaling limit for the solution of the Kondo problem has some freedom in the determination of the phase shift. In 3  we used the scaling scheme intoduced by P. Wiegmann. This scheme determined the appearence of the initial phase shift for charge persistent currents, caused by the Kondo impurity. On the other hand, in Ref. 7  we studied persistent currents for a system with multichannel Kondo impurities, and used the scaling scheme introduced by N. Andrei. This is why there was no initial phase shift for charge persistent currents (even for the limiting case of the number of channels being equal to 1). However, as we pointed out above, the presence or absence of that initial phase shift is determined by the (non-controlable) scaling approximation. We do not know, which answer (with or without the phase shift) is generic in the real situation of a quantum dot in a ring. The only argument, which can be used, is that for the lattice exactly solvable problem of a magnetic impurity in a correlated electron ring (cf. 6 ) the Bethe ansatz equations for charge degrees of freedom have phase factors, which, naturally, produce initial phase shifts for charge persistent currents. These initial phase shifts are the consequences of the fact, that a magnetic impurity introduces the nonzero net chirality into the periodic lattice integrable problem.

5. It turns out that our previous results 3 ; 7  for spin and charge persistent currents in a metallic ring with a magnetic (spin) Kondo impurity coincide with the ones of Ref. EJS  and with the limiting case of $`\xi _KL`$ of 1  for zero magnetization of the system (up to the initial phase shift in 3 , see the discusssion in 4. above). In some of our studies we considered the behavior of chiral (only right- or left-moving) electrons. Refs. 1 ; EJS  consider both right- and left-movers together. However the fact that the answers of Refs. 3 ; 7  and 1 ; EJS  are similar implies that the chirality of host electrons does not play an important role in this problem. By the way, naturally, for the linearized dispersion law of host electrons one must consider for persistent currents only finite-size corrections, which depend on external fluxes. The constant term (of order of the size of the system) is the obvious artifact of the linearization of the spectra of host electrons and was, obviously, discarded in Refs. 3 ; 4 ; 5 ; 7 ; oth .


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# Persistent currents in Möbius strips

## I Introduction

An important theme in quantum mechanics is to find a relation between a global geometry of a sample (e.g., boundary conditions) and its physical properties. We address this issue by comparing flux periodicity of persistent currents in a cylinder and in a Möbius strip. The aim is to determine whether the geometrical (in some sense topological) difference is tangible and experimentally observable. At zero temperature, the persistent current $`I(\varphi )`$ in a ring can be expressed asImry

$$I(\varphi )=\frac{E(\varphi )}{\varphi }=\underset{n=1}{\overset{\mathrm{}}{}}I_n\mathrm{sin}(2\pi n\varphi ),$$
(1)
where $`\varphi `$ is the magnetic flux threading the ring in units of $`\mathrm{\Phi }_0=hc/e`$, $`E(\varphi )`$ is the ground state energy, and $`I_n`$ are the current harmonics.

The current $`I(\varphi )`$ is an anti-symmetric and periodic function of $`\varphi `$ with period 1. Possible occurrence of smaller flux periodicity in mesoscopic physics is one of the cornerstones of weak localization. For the cylinder geometry, conductance measurementsAASS  and magnetization of $`10^7`$ copper ringsLevy  indicate the emergence of periodicity $`1/2`$. It is shown to be intimately related to the procedure of averaging over disorder realizations and numbers of electrons in the ringsGefen ; Gilles ; AGI ; AASS . Very recently, a microscopic NbSe3 Möbius strip has been fabricatedTanda . Obviously, in this case, attention should be focused on a single sample measurementWebb  for which there is no self-averaging.

Let us first mention several intuitive points relevant to the flux periodicity in the Möbius strip, based on semi-classical arguments and geometryHayashi . First, recall that the periodicity is related to interference between trajectories (such as Aharonov-Bohm interference between different trajectories or weak-localization interference between time-reversed paths). In the cylinder (Möbius) geometry, an electron moving in the longitudinal direction along the ring encircles the system once (twice) before returning to its initial position. Therefore, we might expect different flux periodicities of the persistent current between the two cases. Second, unlike a cylinder which can be “pressed” into a one-dimensional ring, the Möbius strip cannot be pressed into a one-dimensional structure. This brings in another important factor, namely, the motion of electrons in the transverse direction. In a tight-binding model this motion is controlled by the transverse hopping. If it is very weak, the twice-encircling property of the Möbius strip implies the dominance of even harmonics $`I_{2n}`$. Contrary, for a strong transverse hopping, the current in the Möbius strip is expected to be effectively similar to that in the cylindrical stripMila . In the following we are mainly interested in a regime where the transverse hopping is slightly less than with the longitudinal one. Third, the role of disorder should be carefully examined. Weak disorder is not expected to significantly alter interference between semi-classical trajectories discussed above, while strong disorder should result in a reduced sensitivity to the pertinent geometry, due to localization effects. The most intriguing disorder effect might then be expected in a moderate strength of disorder which will be used below. The upshot of the present study is that the periodicity pattern in a Möbius strip is remarkably distinct from that of a cylinder, and that disorder plays a crucial role in making the statistical effect detectable.

## II Model

A Möbius strip is modelled by considering a non-interacting particle in a rectangle of length $`L_x`$ and width $`L_y`$, requiring its wave-function $`\psi (x,y)`$ to satisfy Dirichlet boundary conditions in the $`y`$ direction, and Möbius boundary conditions rmrk  in the $`x`$ direction:

$`\psi (x,L_y/2)=\psi (x,L_y/2)=0`$ $`\text{(Dirichlet B.C.)},`$ (2)
$`\psi (x+L_x,y)=\psi (x,y)`$ $`\text{(Möbius B.C.)}.`$ (3)
The quantized wave-numbers are $`k_y=(\pi /L_y)n_y`$ and $`k_x=(2\pi /L_x)([\frac{1}{2}]_{n_y}+n_x)`$, where $`n_y=1,2,\mathrm{}`$ and $`n_x=0,\pm 1,\pm 2,\mathrm{}`$. The notation $`[\alpha ]_n`$ represents $`\alpha `$ for $`n=\text{even}`$ and $`0`$ for $`n=\text{odd}`$. In the cylinder geometry, Eq. (3) should be replaced by $`\psi (x+L_x,y)=\psi (x,y)`$, and gives $`k_x=(2\pi /L_x)n_x`$. Thus, only the $`n_y=\text{even}`$ eigenstates are affected by the switch from the conventional cylinder (periodic) boundary conditions to the Möbius ones.

In the absence of disorder, the energies of the eigenstates both in the Möbius and cylinder strips are given by the formula

$$E_{n_xn_y}=ϵ_x\left(k_x\frac{2\pi \varphi }{L_x}\right)+ϵ_y(k_y),$$
(4)
where $`ϵ_x`$ and $`ϵ_y`$ provide the dispersion relation. Equation (4) is rather general for clean systems. To be more specific, let us model the Möbius strip by a tight-binding Hamiltonian. The Möbius strip is constructed from a rectangular lattice including $`N\times 2M`$ sites. The rectangle is twisted by $`180^{}`$, and its two sides are connected, such that longitudinal wire $`1`$ is attached to wire $`2M`$, wire $`2`$ is attached to wire $`2M1`$ and so on. The Möbius strip so constructed includes $`M`$ longitudinal wires with $`2N`$ sites on each one. The Hamiltonian is then

$`H_{\text{Möbius}}={\displaystyle \underset{n=1}{\overset{2N}{}}}{\displaystyle \underset{m=1}{\overset{M}{}}}\left[\epsilon _{nm}c_{nm}^{}c_{nm}t_1e^{2\pi i\varphi /N}c_{nm}^{}c_{n+1m}\right]`$
$`t_2{\displaystyle \underset{n=1}{\overset{2N}{}}}{\displaystyle \underset{m=1}{\overset{M1}{}}}c_{nm+1}^{}c_{nm}{\displaystyle \frac{t_2}{2}}{\displaystyle \underset{n=1}{\overset{2N}{}}}c_{nM}^{}c_{n+NM}+\text{h.c.}`$ (5)
where $`c_{nm}`$ is the fermion operator at the site $`(n,m)`$ ($`n=1,2,\mathrm{},2N`$, $`m=1,2,\mathrm{},M`$) and $`t_1`$ and $`t_2`$ are longitudinal and transverse hopping amplitudes respectively. The quantity $`\epsilon _{nm}`$ is the site energy. Connecting the two sides of the rectangle without twisting, we obtain a cylindrical strip which includes $`2M`$ longitudinal wires composed of $`N`$ sites. The Hamiltonian of the cylinder is

$`H_{\text{cylinder}}={\displaystyle \underset{n=1}{\overset{N}{}}}{\displaystyle \underset{m=1}{\overset{2M}{}}}\left[\epsilon _{nm}c_{nm}^{}c_{nm}t_1e^{2\pi i\varphi /N}c_{nm}^{}c_{n+1m}\right]`$
$`t_2{\displaystyle \underset{n=1}{\overset{N}{}}}{\displaystyle \underset{m=1}{\overset{2M1}{}}}c_{nm+1}^{}c_{nm}+\text{h.c.}`$ (6)
Locally the two Hamiltonians (5) and (6) look the same. But there is a couple of essential differences between them: a) The Möbius Hamiltonian (5) includes an extra term which describes long range hopping between distant parts of the $`M`$th wire rmrk . b) While the magnetic phase accumulated along the longitudinal direction on each link is the same (that is, $`2\pi \varphi /N`$), the corresponding number of links is different ($`2N`$ for the Möbius strip and $`N`$ for the cylinder).

## III The Spectrum

We first consider a system without disorder, namely, $`\epsilon _{nm}=0`$. The dispersion relation for an electron in the Möbius strip reads,

$`E_{n_xn_y}=`$ $``$ $`2t_1\mathrm{cos}\left[{\displaystyle \frac{2\pi }{N}}\left(\left[{\displaystyle \frac{1}{2}}\right]_{n_y}+n_x\varphi \right)\right]`$ (7)
$``$ $`2t_2\mathrm{cos}\left({\displaystyle \frac{\pi }{2M+1}}n_y\right),`$
where $`n_x=1,\mathrm{},N`$ and $`n_y=1,\mathrm{},2M`$. Defining new indexes $`k=[1]_{n_y}+2n_x`$ and $`q=[\frac{1}{2}]_k+n_y/2`$, one obtains a more suggestive form,

$`E_{kq}=`$ $``$ $`2t_1\mathrm{cos}\left[{\displaystyle \frac{\pi }{N}}(k2\varphi )\right]`$ (8)
$``$ $`2t_2\mathrm{cos}\left[{\displaystyle \frac{\pi }{2M+1}}\left(2q[1]_k\right)\right],`$
where $`k=1,\mathrm{},2N`$ and $`q=1,\mathrm{},M`$. It is instructive to compare it with the energy in the cylinder geometry, $`E_{kq}=2t_1\mathrm{cos}\left[\frac{2\pi }{N}(k\varphi )\right]2t_2\mathrm{cos}\left(\frac{\pi }{2M+1}q\right)`$, where $`k=1,\mathrm{},N`$ and $`q=1,\mathrm{},2M`$. Despite the apparent similarity between these two spectra, there are at least two important differences. First, the combination of flux and longitudinal momentum is distinct, namely, it is $`k\varphi `$ for the cylinder and $`k2\varphi `$ for the Möbius strip. For a small ratio $`t_2/t_1`$ this might affect the periodicity of the currentMila . Second, the mini-band structure is different.

We now turn to elucidate the current in disordered Möbius strips. The random numbers $`\epsilon _{nm}`$ are assumed to be uniformly distributed over the range $`W/2\epsilon _{nm}W/2`$, where $`W`$ represents the strength of disorder. The Hamiltonian Eq. (5) \[or Eq. (6)\] is treated numerically. As an example, the evolution of single-particle energies with flux in a disordered Möbius strip with $`N=20`$ and $`M=10`$ is shown in Fig. 1. The parameters are $`t_2/t_1=0.5`$ and $`W/t_1=0.5`$. The pattern of avoided crossing turns out to be remarkably different from that for a cylinder (see ref. 5 figure 1 therein). It must then be reflected in the behavior of persistent currents.

The first stage of the analysis is an inspection of the typical values of $`I_n`$, aiming in determination of their dependence on the ratio $`t_2/t_1`$. As expected, in the absence of averaging we find typical $`I_1`$ dominance in case of the cylinder geometry irrespective of the $`t_2/t_1`$ ratio. For the Möbius geometry the emerging picture is quite different. Figure 2 shows the Fourier components of the persistent current for a clean Möbius strip as a function of the ratio $`t_2/t_1`$ at and below the half-filling ($`N_e=200`$). For small ratios ($`t_2/t_1<0.1`$) we find, as can be naively expected, $`I_2`$ dominance. The expected effect of averaging in the cylinder case is to emphasize the $`I_2`$ contribution, while in the Möbius case the expected effect is to emphasize the $`I_4`$ contribution. For clean Möbius strip the $`I_n`$ with odd $`n`$, as a function of the number of electrons $`N_e`$, is anti-symmetric around half-filling. Therefore $`I_1`$ and $`I_3`$ completely vanish \[Fig. 2(a)\]. See further discussionin Sect. V. To avoid this particularity at the half-filling, we display in Fig. 2(b) also the case where the number of electrons ($`N_e=190`$) is below half-filling. For large ratios ($`t_2/t_1>0.8`$) we observe in Fig. 2(b) a cylinder-like regime where there is typically $`I_1`$ dominance. This is because the strong transverse hopping changes the periodicity of the Möbius strip to that of the conventional cylinder. The somewhat unexpected observation is that there is a distinct wide intermediate regime ($`0.1<t_2/t_1<0.8`$) where $`I_1`$, $`I_2`$, $`I_3`$ and $`I_4`$ are all comparable. This is the regime which is of experimental relevance. The expected effect of averaging in this regime is to emphasize both the $`I_2`$ and the $`I_4`$ contributions.

## IV Statistical Analysis

The problem arising in the analysis of persistent currents in disordered Möbius strips is how to characterize the statistics of the calculated data. It was already pointed out that essential properties of observables result from the averaging procedure and the nature of the underlying statistical ensemble Gefen ; Gilles ; AGI . On the other hand, fabrication of a Möbius strip requires an outstanding effortTanda , and hence, anticipated measurements of the persistent current would probably be performed on a single sample. Thus, somewhat unfortunately, the important results reported therein and the powerful calculation methods based on super-symmetry might be less useful for single-sample experiments since there is no averaging.

What is then the most efficient way to present our calculated results? The answer is provided by elementary statistics. An experimental result consists of a set of $`K`$ measurements $`I(\varphi _i)`$, $`i=1,2,\mathrm{},K`$ performed on a given sample. This sample is taken out of an ensemble of Möbius strips with different disorder realizations, electron numbers $`N_e`$, aspect ratios, etc. The set $`\{I(\varphi _i)|i=1,\mathrm{},K\}`$ can be regarded as an instance of a random vector in a $`K`$ dimensional space. Alternatively, this instance can be represented by the current harmonics $`(I_1,I_2,\mathrm{})`$ defined via Eq. (1). For our purpose it seems adequate to keep only the first 4 harmonics. The relevant statistical ensemble is then a set of “points” $`(I_1,I_2,I_3,I_4)`$ in four-dimensional probability space, each point corresponds to a possible experimental measurement of the current on the entire $`\varphi `$ interval. Let us denote the number of points within an infinitesimal four-dimensional volume element by $`P(I_1,I_2,I_3,I_4)dI_1dI_2dI_3dI_4`$. The distribution function $`P`$ is normalized to $`𝒩`$, the total number of members in the ensemble. The most probable (typical) experimental result is then determined by the quadruple $`I_1,I_2,I_3,I_4`$ at which $`P`$ is maximal. Another quantity, which seems more informative and easy to analyze, is the distribution

$$p_n(I_n)=_0^{\frac{1}{2}|I_n|}P(I_1,I_2,I_3,I_4)\underset{mn}{}d|I_m|.$$
(9)
This corresponds to the possibility of finding a sample whose current $`I(\varphi )`$ is approximately described by $`I(\varphi )I_n\mathrm{sin}(2\pi n\varphi )`$. (For a sample counted by $`p_n(I_n)`$, all the harmonics other than $`I_n`$ are at most half of $`I_n`$ in magnitude). The number of members in the ensemble that exhibit $`I_n`$ dominance is therefore $`𝒩_n=_0^{\mathrm{}}p_n(I_n)d|I_n|`$. If $`𝒩_n>𝒩_m`$ for any $`mn`$, the typical periodicity of $`I(\varphi )`$ is dominantly $`1/n`$.

In actual calculations, we assume that the lattice structure, the aspect ratio, and the strength of disorder are fixed, and that the temperature is very low. Then, two quantities are still fluctuating, namely, the filling factor (or the electron number $`N_e`$) and the specific realization of disorder. We generate an ensemble of $`𝒩=𝒩^a𝒩^b`$ members corresponding to $`𝒩^a`$ consecutive values of $`N_e`$, usually around half filling, and $`𝒩^b`$ realizations of disorder for each one of them. Actually, for our systems of size $`N=20`$, $`M=10`$ with $`t_1=1`$, $`t_2=0.5`$, and $`W=0.5`$, we take $`150N_e250`$, hence $`𝒩^a=101`$ and $`𝒩^b=250`$, so that $`𝒩=25250`$. The distributions $`p_n(I_n)`$ for the cylinder and Möbius ensembles are shown in Fig. 3.

## V Main Observations

The most striking result that can be deduced from Fig. 3 is the essential reduction of $`𝒩_1`$ for the Möbius ensemble compared with the cylinder one. For the present ratio $`N/2M=1`$, there is also a strong tendency towards $`\mathrm{\Phi }_0/4`$ periodicity, since $`𝒩_4>𝒩_{m4}`$ for the Möbius ensemble. This result is intriguing, because here we have no averaging procedure which is crucial to get the $`1/2`$ periodicity in cylindrical strips. However, this $`1/4`$ periodicity emerges only for the specific ratio $`N/2M=1`$. We have calculated the distributions $`p_n(I_n)`$ for Möbius strips with several aspect ratios. The value of $`𝒩_n`$ depends on the aspect ratio. No specific $`n`$ gives prominent $`𝒩_n`$ independently of the aspect ratio. On the other hand, the collapse of $`I_1`$ dominance in the Möbius ensemble is robust and persists in systems with different ratios $`N/2M`$ as well. We can safely say that $`𝒩_1`$, $`𝒩_2`$, $`𝒩_3`$, and $`𝒩_4`$ become all comparable in the Möbius ensemble.

The natural question that comes to mind is whether this result is a consequence of the Möbius geometry or, rather, it is due to the presence of disorder. In order to answer this question, we have performed the calculation of $`P^0(I_1,I_2,I_3,I_4)`$ for a “clean” Möbius ensemble (without disorder, only $`N_e`$ is being changed). We found out that the probability to find any $`I_n`$ dominance is extremely small. The immediate conclusion is that disorder is essential for the identification of Möbius strips via $`I_{n>1}`$ dominance. Does this mean that interference or weak-localization effects due to the presence of disorder is important? To clarify this point, we should understand how $`P^0(I_1,I_2,I_3,I_4)`$ is modified by disorder. The distribution $`P^0(I_1,I_2,I_3,I_4)`$ is, in fact, a function defined on a one dimensional curve $`[I_1(N_e),I_2(N_e),I_3(N_e),I_4(N_e)]`$ in $`(I_1,I_2,I_3,I_4)`$ space. For this reason, it is unlikely to find a sample where one of the $`I_n`$ is dominant. The effect of disorder is to give some “thickness” to this curve (see Fig. 4). Taking into account that the amplitudes of $`I_n(N_e)`$ for Möbius strips are all comparable, the thickness gives a finite probability to find samples where one of the $`I_n`$ is dominant. On the contrary, in the case of cylindrical strips, the amplitude of $`I_1(N_e)`$ is overwhelmingly larger than those of $`I_{n1}(N_e)`$, which makes it unlikely to find $`I_{n1}(N_e)`$ dominated samples even if we take the statistical effect of disorder into account. We should note here that the function $`I_n`$ with odd $`n`$ for the clean Möbius strip is an even function around the half-filling ($`N_e=200`$) and an odd function for odd $`n`$, while the function $`I_n`$ for arbitrary $`n`$ is an even function in the cylinder case.

Our findings regarding $`𝒩_n`$ for the Möbius ensemble are based on the fact that the amplitudes of $`I_n(N_e)`$ are all comparable for Möbius strips. As we have observed in Fig. 2, this is a robust statistical property in the intermediate regime $`0.1<t_2/t_1<0.8`$. The choice $`t_2/t_1=0.5`$ above, provides typical results for $`p_n(I_n)`$ and $`𝒩_n`$ in case that $`t_2/t_1`$ is within this distinct regime.

## VI Conclusions

We have studied the persistent currents of non-interacting electrons in Möbius strips. The spectral properties for a clean system were found analytically, and the effect of disorder on the currents was analyzed numerically. We have found that disorder is quite essential for the identification of Möbius strips. The issue of disorder averaging is not relevant for single sample experiments, and hence, special care is required for statistical analysis of the current harmonics. The fingerprint of the Möbius geometry is an enhanced probability to find samples in which $`I_n`$, with $`n>1`$ dominates. This should be contrasted with the case of cylinder geometry, where there is a clear $`I_1`$ dominance. The above assertion regarding the fingerprint of the Möbius geometry is correct provided the effect of disorder is properly taken into account.

We would like to thank T. Nakayama for very helpful discussions. One of the authors (Y.A.) was supported by the Invitation Fellowship for Research in Japan (Short Term) of the Japan Society for the Promotion of Science. Numerical calculations in this work have been mainly performed on the facilities of the Supercomputer Center, Institute for Solid State Physics, University of Tokyo.


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# Influence of adatom interactions on second layer nucleation

(March 6, 2002)

## Abstract

We develop a theory for the inclusion of adatom interactions in second layer nucleation occurring in epitaxial growth. The interactions considered are due to ring barriers between pairs of adatoms and binding energies of unstable clusters. The theory is based on a master equation, which describes the time development of microscopic states that are specified by cluster configurations on top of an island. The transition rates are derived by scaling arguments and tested against kinetic Monte-Carlo simulations. As an application we reanalyze experiments to determine the step edge barrier for Ag/Pt(111).

Whether thin films in epitaxy become rough or grow smoothly layer by layer depends on the onset of second layer nucleation on top of islands in the first layer: If the rate $`\mathrm{\Omega }`$ of this nucleation is large, it is likely that mounds are formed before layer completion, while small second layer nucleation rates favor layer by layer growth. Detailed theories have been developed in the past Tersoff/etal:1994 ; Rottler/Maass:1999 ; Heinrichs/etal:2000 ; Krug/etal:2000 ; Krug:2000  to predict $`\mathrm{\Omega }`$ in dependence on the island size $`R`$, the ratio $`\alpha _\mathrm{S}(\nu _\mathrm{S}/\nu _\mathrm{t})\mathrm{exp}(\mathrm{\Delta }E_\mathrm{S}/k_\mathrm{B}T)`$ of the hopping rates $`\nu _\mathrm{t}\mathrm{exp}(E_D/k_\mathrm{B}T)`$ and $`\nu _\mathrm{S}\mathrm{exp}(E_\mathrm{S}/k_\mathrm{B}T)`$ on top of the island and over the island edge, respectively, and the ratio $`D/Fa^4`$ of the adatom diffusivity $`D=(\nu _\mathrm{t}a^2/4)\mathrm{exp}(E_D/k_\mathrm{B}T)`$ and deposition flux $`F`$; $`a`$ is the lattice constant. Studies so far focused on adatoms that form stable nuclei once more than $`i`$ of them cluster together, but otherwise do not interact.

In this Letter we show how adatom interactions strongly influence the second layer nucleation. We consider two types of these interactions: (i) Clusters of size smaller than $`i+1`$ are metastable, i.e. the detachment of an adatom or the break up of clusters into two pieces requires a dissociation energy $`E_{\mathrm{dis}}k_BT`$, and (ii) the approach of two atoms by diffusion is hindered by additional barriers. As a generic model we consider a barrier $`E_{\mathrm{ring}}`$ in form of a ring with radius $`\xi `$ around each adatom. The occurrence of such barriers was explored by Fichthorn and Scheffler based on extensive density functional calculations Fichthorn/Scheffler:2000 . Similar interaction effects can be caused by Shockley surface states Hyldgaard/Persson:2000 .

The aim of this Letter is to develop a theory based on rate equations that allows us to take into account these interaction effects for nucleation processes in confined geometry as encountered on top of a growing island. As an application we quantify possible errors when determining the step edge barrier $`E_\mathrm{S}`$ Ehrlich/Hudda:1966+Schwoebel:1969  in second layer nucleation experiments under the assumption of non-interacting adatoms. For the Ag/Pt(111) system we compare the results at different levels of sophistication of the underlying theory for determining the step edge barrier.

In order to take into account the adatom interactions, we refer to our rate equation approach for second layer nucleation outlined in Heinrichs/etal:2000 . In this approach one considers one compact island with radius $`R`$ that evolves in time according to some growth law $`R=R(t)`$. To clearly separate the different types of interaction effects, we consider the presence of either metastable clusters or the ring barrier.

We denote by $`p_{n,\nu }(t)`$ the probability to find the island in a state where in total $`n`$ atoms are on top of the island in configuration $`\nu `$ at time $`t`$. The configuration label $`\nu `$ specifies the way the $`n`$ atoms are decomposed into clusters and which pairs of atoms have a distance smaller than $`\xi `$ and are thus “weakly bound” by their ring barriers.

In Fig. 1 the most important states are shown together with the rates $`W_{n,\nu n^{},\nu ^{}}`$ connecting them states-comm . The probabilities $`p_{n,\nu }(t)`$ obey the master equation

$$\frac{dp_{n,\nu }}{dt}=\underset{n^{},\nu ^{}}{}\left[W_{n^{},\nu ^{}n,\nu }p_{n^{},\nu ^{}}W_{n,\nu n^{},\nu ^{}}p_{n,\nu }\right],$$
(1)
where $`W_{n,\nu n^{},\nu ^{}}`$ is the rate from state $`(n,\nu )`$ to $`(n^{},\nu ^{})`$ and can depend on time through the growth law $`R=R(t)`$ (see below). Equations (1) are numerically solved subject to the initial condition $`p_{n,\nu }=\delta _{n,0}`$.

The rates $`W_{n,\nu n^{},\nu ^{}}`$ are expressed in terms of elementary rates $`W_F`$, $`W_l`$, $`\stackrel{~}{W}_{\mathrm{ring}}^{(n)}`$, $`\stackrel{~}{W}_F`$, $`\stackrel{~}{W}_b`$ and $`\stackrel{~}{W}_a`$ (cf. Fig. 1). The first two rates $`W_F`$ and $`W_l`$ refer to processes not involving the ring barrier: $`W_F=\pi FR^2`$ is the deposition rate of adatoms onto the island and $`W_l=(D/R^2)[\kappa _1a/(\alpha _\mathrm{s}R)+\kappa _2]^1`$ is the loss rate of adatoms that leave the island by surmounting the step edge barrier Heinrichs/etal:2000 . The coefficients $`\kappa _1,\kappa _2`$ are of order one Heinrichs/etal:2000 . In order to account for the reduced mobility of pairs of atoms bound via the ring barrier compared to individual atoms, the loss rate for such pairs is approximated to be equal to that of a single atom.

The latter four rates involve the ring barrier in form of the associated Boltzmann factor $`\alpha _{\mathrm{ring}}=\mathrm{exp}[\mathrm{\Delta }E_{\mathrm{ring}}/k_\mathrm{B}T]`$, $`\mathrm{\Delta }E_{\mathrm{ring}}=E_{\mathrm{ring}}E_D`$, and the ring radius $`\xi `$. $`\stackrel{~}{W}_F=\pi F\xi ^2`$ is the deposition (“flux”) rate into a ring. $`\stackrel{~}{W}_a=\stackrel{~}{\kappa }_a2D/(\pi \xi ^2)`$ is the attachment rate for two atoms in a circle which are confined to a separation distance smaller than $`\xi `$. It results from the time $`\xi ^2/2D`$ for the two atoms to encounter by diffusion on top of an island with radius $`\xi `$. For the relevant case $`a<\xi R`$ we can further derive the rates for formation and breakup of pairs weakly bound by their ring barriers. The breakup rate is given by

$$\stackrel{~}{W}_b=\stackrel{~}{\kappa }_b\frac{D\alpha _{\mathrm{ring}}}{a\xi }.$$
(2)
It results from the probability $`2\pi \xi /\pi \xi ^2`$ for two atoms to have distance $`\xi `$ times the rate $`\alpha _{\mathrm{ring}}D/a^2`$ to overcome the ring barrier. The rate for formation of an adatom pair weakly bound by their ring barriers is

$$\stackrel{~}{W}_{\mathrm{ring}}^{(n)}=\frac{n(n1)D}{R^2}\left(\stackrel{~}{\kappa }_1\frac{a}{\xi \alpha _{\mathrm{ring}}}+\stackrel{~}{\kappa }_2\right)^1,$$
(3)
if in total $`n`$ adatoms are on top of the island. The associated time $`(\stackrel{~}{W}_{\mathrm{ring}}^{(2)})^1`$ for two atoms results from two contributions: The time $`R^2/D`$ for first reaching the interaction distance $`\xi R`$ and the time for overcoming the barrier. The latter is given by $`[(2\pi \xi a/\pi R^2)\times (\alpha _{\mathrm{ring}}D/a^2)]^1`$, where the term $`2\pi \xi a/\pi R^2`$ is due to the probability for a pair to have a distance in the interval $`(\xi ,\xi +a)`$ and the term $`\alpha _{\mathrm{ring}}D/a^2`$ is the rate to overcome the ring barrier. The rate $`\stackrel{~}{W}_{\mathrm{ring}}^{(2)}`$ for a single pair has to be multiplied by the number $`n(n1)/2`$ of distinct pairs to obtain the total rate for $`n`$ adatoms.

The validity of all formulae for the elementary rates is tested against kinetic Monte-Carlo (KMC) simulations performed on a hexagonal lattice for the (111) surface. As an example we show in Fig. 2 scaling plots for the two rates $`\stackrel{~}{W}_{\mathrm{ring}}^{(n)}`$ and $`\stackrel{~}{W}_b`$ demonstrating the good agreement of the KMC data with the predictions of eqs. (2,3). All constants $`\stackrel{~}{\kappa }`$ in Eqs. (2,3) are of the order of one kappa-comm . The approach outlined above provides a general framework to treat the problem of second layer nucleation and may be applied and extended to a variety of situations. It furthermore allows one to gain detailed insight into the microscopic pathways followed during the nucleation process.

To apply our theory we consider the determination of step edge barriers in second layer nucleation experiments. In these experiments one measures the probability $`f[R(t)]`$ that a stable cluster has nucleated on top of the island until time $`t`$ (i.e. the fraction of “covered islands”). In systems with a substrate mediated ring barrier, second layer nucleation will be aggravated and nucleation sets in later. A repulsive ring barrier therefore has an effect similar to a reduced step edge barrier, and thus yields an apparent measurement value $`\mathrm{\Delta }E_\mathrm{S}^{(0)}`$ smaller than the “true” $`\mathrm{\Delta }E_\mathrm{S}`$. On the other hand, metastable dimers facilitate the formation of a stable nucleus, leading to values $`\mathrm{\Delta }E_\mathrm{S}^{(0)}`$ larger than $`\mathrm{\Delta }E_\mathrm{S}`$.

To estimate the significance of the interactions, we first present results for the relative error $`[\mathrm{\Delta }E_\mathrm{S}\mathrm{\Delta }E_\mathrm{S}^{(0)}]/\mathrm{\Delta }E_\mathrm{S}`$ as a function of the interaction parameters. By solving Eq. (1) we obtain the curves $`f[R(t);\mathrm{\Delta }E_\mathrm{S}]`$ that refer to processes including interactions. On the other hand, we can solve the rate equations neglecting the interaction ($`\mathrm{\Delta }E_{\mathrm{ring}}=0`$), thus obtaining $`f_0[R(t);\mathrm{\Delta }E_\mathrm{S}^{(0)}]`$. By fitting the curves $`f_0`$ to the “true ” curves $`f`$ we obtain the apparent $`\mathrm{\Delta }E_\mathrm{S}^{(0)}`$. For the ratio of attempt frequencies $`\nu _\mathrm{S}/\nu _\mathrm{t}`$ for adatom hopping over the step edge and on a terrace, we use the generic value of one (for a general discussion on attempt frequencies, see Ovesson/etal:2001 ). Using a generic growth law $`R(t)\sqrt{t}`$ (with the prefactor $`(D/Fa^4)^{i/2(i+2)}\sqrt{Fa^2}`$ from standard nucleation theory Venables/etal:1984 ) we show in the upper half of Fig. 3 results for the relative error as a function of $`\mathrm{\Delta }E_{\mathrm{ring}}`$. In the lower half of the figure we include the results of an analogous analysis for $`i=2`$ with metastable dimers (for a setup of the corresponding rate equations, see Heinrichs/etal:2000 ). Because the dependence on $`D/Fa^4`$ is only weak, this parameter is not varied in the plots. We see that for small $`\mathrm{\Delta }E_\mathrm{S}`$, even weak interactions $`\mathrm{\Delta }E_{\mathrm{int}}`$ lead to a large relative error. Closer inspection shows, that for fixed ratio $`\mathrm{\Delta }E_{\mathrm{int}}/\mathrm{\Delta }E_\mathrm{S}`$, the relative error decreases with increasing interaction energy (cf. the dashed line in Fig. 3). In the case of metastable dimers, the error reaches a plateau when the dissociation energy becomes so large that a dimer is stable on the time scale of the formation of a stable trimer. This signifies the transition to the $`i=1`$ case.

For Ag/Pt(111) detailed second layer nucleation measurements of the type discussed above were performed by Bromann et al. Bromann/etal:1995 . The system Ag/Pt(111) is particularly suited as a reference, since it has the advantage that many of the relevant parameters were determined both by experiment Brune/etal:1995 ; Bromann/etal:1995 ; Bott/etal:1996 ; Brune/etal:1999  and by first-principle calculations Feibelman:1994 ; Ratsch/etal:1997 ; Ratsch/Scheffler:1998 ; Fichthorn/Scheffler:2000 . Experimentally, the diffusion barrier $`E_D`$ for Ag adatom diffusion on strained Ag islands grown on Pt(111) is $`E_D60`$ meV Brune/etal:1995 . It has been shown by density functional calculations Fichthorn/Scheffler:2000  that silver adatoms diffusing on top of an already existing silver island on the platinum surface exhibit a strong barrier $`\mathrm{\Delta }E_{\mathrm{ring}}=E_{\mathrm{ring}}E_D50`$ meV at a distance $`\xi /a2.1`$.

The original analysis by Bromann et al. was based on a mean field-type theory for second layer nucleation (“TDT approach”, see Tersoff/etal:1994 ). However, it has been shown recently that even in the absence of interaction effects it is necessary to re-analyze the data with an extended theory Rottler/Maass:1999 ; Heinrichs/etal:2000  (see also Krug/etal:2000 ). In this theory fluctuation-dominated regimes occur for critical nuclei $`i2`$ Heinrichs/etal:2000 , and it yields, for the experimental conditions and a prefactor $`\nu _\mathrm{t}=10^9`$ Hz used in Bromann/etal:1995 , the second-layer nucleation rate $`\mathrm{\Omega }(R)=\pi ^2\kappa _1FR^5/(\mathrm{\Gamma }\alpha _\mathrm{s})`$ where $`\mathrm{\Gamma }=D/Fa^4`$. By contrast to the generic growth law $`R(t)\sqrt{t}`$ used for Fig. 3, in the analysis of Bromann et al. one has to deal with an exponential growth law $`R(t)`$ (for details see Bromann/etal:1995 ). Metastable states are not considered here, because $`i=1`$ in the temperature range of the experiment. In Fig. 4 we have fitted the measured fraction of covered islands $`f(R)`$ yielding $`\mathrm{\Delta }E_\mathrm{S}^{(0)}=65`$ meV, which is about twice the value obtained previously based on the TDT approach (see Table I). For the much less reliable prefactor ratio Roos/Tringides:2000  we find $`\nu _\mathrm{S}/\nu _\mathrm{t}=41`$. The rate equation theory without interactions yields essentially the same value $`\mathrm{\Delta }E_\mathrm{S}^{(0)}=68`$ meV thereby supporting the scaling approach Rottler/Maass:1999 ; Heinrichs/etal:2000 .

The next step in theoretical sophistication is the inclusion of the ring barrier. When using the value $`\mathrm{\Delta }E_{\mathrm{ring}}=50`$ meV Fichthorn/Scheffler:2000 , we find a significantly decreased value of $`\mathrm{\Delta }E_\mathrm{S}=52`$ meV. This decrease seems to be in contradiction to the reasoning above that $`\mathrm{\Delta }E_\mathrm{S}^{(0)}<\mathrm{\Delta }E_\mathrm{S}`$. However, the values were obtained by fitting both the prefactor $`\nu _\mathrm{S}/\nu _\mathrm{t}`$ and $`\mathrm{\Delta }E_\mathrm{S}`$ to the data and cannot be directly compared because the prefactors turn out to be very different (see table I). When fitting under the constraint $`\nu _\mathrm{S}/\nu _\mathrm{t}=1`$ Krug/etal:2000 , the value for $`\mathrm{\Delta }E_\mathrm{S}`$ increases from $`42`$ meV to $`48`$ meV in accordance with the general argument. Interestingly, the behavior of the standard error (see table I) indicates that the system is better described when including the interactions. However, this interpretation should not be driven too far, since the standard error is only an indication of the quality of the fit, but should not be interpreted as the measurement error.

It was recently argued that the often reported small prefactors for hopping on weakly corrugated surfaces are due to neglecting the interaction effects in the analysis of first layer nucleation experiments Ovesson/etal:2001 . We therefore also analyze the data using the theoretical prediction $`\nu _\mathrm{t}=10^{12}`$ Hz Ratsch/Scheffler:1998  in the rate equation approach. The three $`\alpha _\mathrm{S}`$ values obtained for each temperature shown in Fig. 4 lie very closely on a line in an Arrhenius plot (see the inset in Fig. 4). Both when using $`\nu _\mathrm{S}/\nu _\mathrm{t}`$ as fitting paramter and when setting $`\nu _\mathrm{S}/\nu _\mathrm{t}=1`$, we find comparatively large values $`\mathrm{\Delta }E_\mathrm{S}=74`$ meV and $`\mathrm{\Delta }E_\mathrm{S}=82`$ meV, respectively.

In summary we have developed a rate equation theory that allows us to quantify the influence of certain interaction effects on the nucleation on top of islands in epitaxial growth. The formalism is rather general and may be extended to other types of adatom interactions and other kinds of geometrical constraints. We applied the theory to second layer nucleation experiments designed to extract the additional step edge barrier. It was shown that the value of $`\mathrm{\Delta }E_\mathrm{S}`$ depends very sensitively on whether the interactions are carefully accounted for in the analysis.

We are indebted to W. Dieterich and F. Scheffler for very helpful discussions and thank the Deutsche Forschungsgemeinschaft for financial support through the SFB 513 and the Heisenberg program (P.M., Ma 1636/2-1).


text:
# Structure and mobility of cyclohexane as a solvent for Trans-Polyisoprene

## 1 Introduction

Polymeric solutions are important for the understanding of technologically important applications of polymers. Therefore they have been in the focus of molecular simulations over the recent decade. Many studies have been performed to investigate generic characteristics of polymer solutions by means of simple bead-spring models . However, to investigate the behavior of a system on the local scale, fully atomistic simulations will be required. Several authors have dealt with atomistically detailed descriptions of polymer solutions . But, there are only few studies how the polymer influences the solvent dynamics . Especially, the region of low weight fraction of polymer has not yet been studied. This contribution focuses on the liquid structure and dynamics of small solvent molecules in the neighborhood of oligomer chains in dilute solution. We use as an example trans-polyisoprene dissolved in cyclohexane. Cyclohexane is a rather spherical organic molecule and experimentally known to be a good solvent for polyisoprene . Polyisoprene by itself is one of the most commonly used polymers. Its natural form, cautschuk, is highly abundant in nature and for technological purposes, synthetic variations are easily industrially polymerised from isoprene. Still, the solutions of such important materials are not yet completely understood from a microscopic viewpoint.

## 2 Details of the System

Systems containing one or two 15-mers (C75H122) of trans-polyisoprene (PI) are simulated in a solution consisting of 250 or 500 molecules of cyclohexane (C6H12). An overview over all the systems is given in Table 1, also the resulting densities in the simulations are shown in that figure. Details of the self-developed forcefields are found in ref.  for trans-polyisoprene and refs.  for cyclohexane. The polyisoprene forcefield is in contrast to the original version enhanced with torsions for the methyl groups with a strength of 3.3 kJ/mol per atom (9.9 kJ/mol per methyl group). The cyclohexane forcefield is augmented with torsion potentials for all the C$``$C bonds. Each of them has a strength of 10 kJ/mol in order to prevent random flipping between configurations. The cyclohexane molecule can occur in the so-called chair or boat configuration. They are distinguished if the connection between C1 and C4 intersects the plane defined by the other carbons (chair) or not (boat). All simulations and analyses are performed using the YASP molecular dynamics package . No charges are used throughout the simulations.

Both forcefields have been proven useful in recent simulations. The polyisoprene forcefield was used to investigate the dynamics of oligomer melts  whereas the cyclohexane model was used in simulations of pure cyclohexane and its mixtures with cyclohexene at ambient conditions .

## 3 How to set up and equilibrate an atomistic simulation

In atomistic simulations, the way a system is initially set up and equilibrated is crucial. Thus, we describe the equilibration procedure for our systems in detail. For system 1 (one polymer chain solvated by 250 cyclohexanes) the 250 cyclohexane molecules were put onto a regular fcc lattice in a cubic box of 4 nm side-length corresponding to a density of $`\rho =545.8`$kg/m3. An $`NVE`$ simulation with a very short timestep of $`10^3`$ fs was started. The timestep was increased from $`10^3`$ fs to 1 fs in three steps; in each step it was multiplied by a factor of 10. Each simulation was run for 1000 steps at constant volume and energy. The velocities of the particles were reset from a Maxwell-Boltzmann distribution corresponding to 300 K before each run. The polyisoprene molecule was inserted at random, and the pre-equilibration procedure restarted. This time the initial timestep was set to $`10^6`$ fs and the steps were increased by factors of 100, only the last two increases were by factors of 10. The initial polyisoprene conformation was taken from the C75 chains of the melt system 3 of ref. . In the rare case that one of the short simulations failed because of a non-convergence of the SHAKE algorithm  an additional reset of the velocities was applied.

This method of pre-equilibration is very fast for a fully atomistic system. It avoids the use of unphysical soft-core simulations. By resetting the velocities to the desired temperature periodically, the system moves very efficiently away from its initial high energy. One can randomly insert the solute if the density is low and the timestep sufficiently short. The very short simulations at short timesteps have the additional advantage that not too much energy is transferred to internal degrees of freedom which would lead to longer simulations in later equilibration stages.

After the simulation was running stable under $`NVE`$ conditions at a timestep of 1 fs, the Weak-Coupling themostat  was switched on. 10 ps later the isotropic Weak-Coupling constant pressure routine was switched on to compress the system to the correct density. The compressibility was set to the experimental value of 1.12 GPa-1 of pure cyclohexane . Coupling times for pressure and temperature were $`\tau _T=0.2`$ ps and $`\tau _p=2.0`$ ps respectively. The first constant pressure run, however, started with $`\mathrm{\Delta }t=0.1`$ fs and $`\tau _p=200`$ ps. A stepwise increase of the timestep and decrease of the coupling times was performed until the simulations under production conditions were possible ($`\tau _T=0.2`$ ps, $`\tau _p=2.0`$ ps, $`\mathrm{\Delta }t=2`$fs).

A second system was produced the same way but independently with another 15-mer from the melt simulations. These two systems were merged to form the systems with two polymers. The system with only 250 cyclohexane molecules and 2 polymers was produced by taking out every second cyclohexane and letting the system relax to the correct density in an $`NpT`$ simulation.

After proper relaxation at the correct timestep using temperature and pressure coupling, the production runs were started. The relaxation lasted longer than the correlation time for the end-to-end length of the polymer to lose the memory of the melt structure. The production runs lasted up to 5 ns. The reorientation correlation time of the chains was around 2 ns. Configurations were saved every 1000 steps (i.e. 2 ps). The simulations were performed at ambient conditions ($`T=300\text{K}`$, $`p=101.3\text{kPa}`$) and at $`T=413\text{K}`$, $`p=101.3\text{kPa}`$. The higher temperature was chosen for consistency with simulations of solutions of polyisoprene in toluene  although cyclohexane and toluene are gases at that temperature in nature. This vaporization transition is not reproduced by the force-field. The cutoff for the Lennard-Jones interaction was set to $`0.9\text{nm}`$ and for the neighbor list  to $`1.0\text{nm}`$. The neighbor-list was updated every 10 timesteps and the total momentum of the box was reset to zero every 1000 timesteps. A pure cyclohexane system was simulated to investigate the influences of the newly added torsions in the forcefield in comparison to ref. .

## 4 Statics and Dynamics of Cyclohexane solvating Polyisoprene

In this section the carbons along the polymer chain are referred to in the following way: C1 is the non-methyl end of the monomer. C2 and C3 are connected by the double bond. C2 is connected to C1, C4 is the methyl carbon, and C5 is between C3 and C1 (cf. Fig. 1).

The first question we want to address is the way the cyclohexane molecules solvate polyisoprene. Therefore we investigate the number of cyclohexane carbons close to the five distinct carbons along the chain. We do not distinguish between different concentrations here. To avoid end effects, the end monomers are excluded from the calculation. The resulting radial distribution functions are shown in Figure 2.

The main difference between the two temperatures is that for $`\text{T}=300`$ K the neighbor peak is a double peak for some of the carbons. The two sub-peaks are about 0.07 nm apart. This structure does not persist at the elevated temperature. The overall height of the peaks is, however, unchanged. This indicates that the number of cyclohexanes solvating a monomer is not temperature dependent. The arrangement of the solvent molecules, however, is. C4 which is the side group, can come into closest contact with the solvent visible at the shoulder at $`r0.4`$ nm. It was also seen in the melt investigations that this carbon is most exposed . All carbons exhibit a peak at the first solvation shell at $`r0.550.6`$ nm. A second ($`r1.1`$ nm) and third ($`r1.55`$ nm) solvation shell are visible. The first peak is strongest for the two double bonded carbons. They are not very strongly shielded by hydrogens and are therefore rather easily accessible. This is in contrast to the melt simulations where the lacking mobility of these carbons prevented a close approach to neighboring chains . As the mobility of the solvent is much higher than that of the polymer, the differences in mobility of the polymer atoms is not important. At the higher temperature, the second and third solvation shell are slightly shifted to larger distances. The third solvation shell is rather broad.

The cyclohexane diffusion is found to be completely isotropic and the molecules have diffused several times their gyration radius. The diffusion coefficient is measured by fitting the mean-squared displacement of the center-of-mass of the cyclohexane molecules to $`\stackrel{}{r}^2=6Dt`$. The results are found in Table 2. The diffusion coefficient for pure cyclohexane in this model is found to be $`0.78\times 10^5\text{cm}^2/\text{s}`$ at $`T=300\text{K}`$. The value of $`0.89\times 10^5\text{cm}^2/\text{s}`$ reported in reference  is about $`15\%`$ higher. This is probably due to the missing internal torsions in that work which make it easier for the molecule to squeeze through small voids. The diffusivity of cyclohexane decreases with increasing polymer concentration. The polymer molecules can be viewed as obstacles for the solvent. This decrease is opposite to the pronounced increase of cyclohexane mobility in the presence of the smaller cyclohexene . We can thus conclude that the mobility of cyclohexane depends strongly on the size and concentration of the molecules with which it is mixed.

Pure cyclohexane reorients faster in the plane defined by the carbon ring than the plane flips. To investigate the reorientation behavior in the presence of the polymer, we measure the two principal reorientation times of an oblate molecule, i.e. $`\tau _{}`$ measures the reorientation of vectors connecting carbons across the ring, whereas $`\tau _{}`$ is the characteristic time for rotating the axis normal to the plane. This axis is defined in the simulations as cross-product of two C$``$C vectors across the ring. The former measures the reorientation of the molecule in its plane, whereas the latter measures the reorientation of the plane. In an earlier study, we found that pure cyclohexane, as well as cyclohexane in a mixture with cyclohexene, reorients faster in-plane than the plane reorients . This is expected for a dense liquid; in the gas-phase, one expects this order to be reversed due to the moments of inertia. The reorientation times presented in Table 2 were derived by an exponential fit to the first 25 ps of the correlation function at $`\text{T}=300\text{K}`$ (10 ps for $`\text{T}=413`$ K). These fits reproduced the curves very accurately. The reorientation times are measured as correlation times of the first Legendre polynomial $`P_1(t)=\stackrel{}{u}(t)\stackrel{}{u}(0)`$. The resolution and accuracy is better than for $`P_2(t)`$ as the corresponding times are longer. $`\stackrel{}{u}(t)`$ is the unit vector we are monitoring. We find signs for Debye rotation $`T_1=3T_2`$, however, as $`T_2`$ is very short this cannot be completely decided. The cyclohexane model used in this work is slightly more anisotropic than its predecessor without internal torsions. The in-plane reorientation is exactly the same as in the old model . The reorientation of the plane is about 10% slower as in the model lacking internal torsions.

The in-plane reorientation time is practically unaffected by the concentration of the polymer except for pure cyclohexane, whereas the reorientation of the plane becomes slower with increasing concentration. As the in-plane reorientation does not need any other molecule to make room for the transition to occur, the opposite is the case for the plane-flip. Therefore the polymers act as obstacles to the molecules in their neighborhood and make their dynamics more anisotropic as concentration increases. Pure cyclohexane appears to be a different case as it is rather strongly anisotropic; this manifests itself in a clearly faster in-plane reorientation than all the other cases. This suggests that the in-plane reorientation of the molecules close to the polymer is hindered by the chain. This effect is similar in strength for all concentrations.

At the elevated temperature, the reorientation times are clearly shorter. The anisotropy at this temperature becomes weaker, and in the range of concentrations here, it does not depend systematically on polymer content. Assuming an Arrhenius behavior, we can estimate activation energies for the different rotations and the diffusion; they are shown in Figure 3. Note that the activation energies for the diffusion are divided by a factor of two. These activation energies are on the order of $`E_{act}=10`$ kJ/mol for the rotations and on the order of 20 KJ/mol for the diffusion and are only weakly dependent on concentration. We see that the in-plane reorientation is stronger temperature dependent than the plane flip. At very high temperatures an inversion of the reorientation order may therefore be expected in line with the moments of inertia. This explains the seemingly contradictory finding that the plane-flip is found to be slower in the simulated range but has the smaller activation energy. This is due to the stronger temperature dependence of the in-plane reorientation.

The increasing anisotropy of reorientation with concentration has been reported for two other systems at higher concentrations. It has been found for water as solvent of polyvinylacohol  and benzene as solvent of polystyrene .

The diffusion is much stronger temperature dependent than both the rotations. This can be understood by the fact that for a molecule to diffuse the neighborhood has to give way in a much stronger fashion, i.e. the whole neighborhood has to rearrange whereas for rotation the particle can in principle stay in place.

## 5 Conclusion

Altogether, we showed that the increasing polymer concentration has a decelerating effect on the dynamics of the cyclohexane solvent molecules. The polymer chains are obstacles to the cyclohexane motion and make their reorientation more anisotropic. Additionally we see, in comparison with the model lacking internal torsions, that even for molecules as small and rigid as cyclohexane internal torsion potentials have an effect on the overall dynamics.

The simulations presented here were additionally used as starting points for coarse-graining simulations with investigations of the chain statics and dynamics .

## Acknowledgments

The author thanks Kevin van Workum for a critical reading of the manuscript. Financial support by the Emmy-Noether Program of the German Research Foundation (DFG) is gratefully acknowledged.