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# Finite temperature results on the 2𝑑 Ising model with mixed perturbation

## 1 Introduction

Quantum field theories (QFT) in two space-time dimensions at finite temperature are an appealing and complex subject which has attracted much attention from both theoretical and experimental point of view. It could be useful to recall, that a finite temperature QFT can be obtained by considering the model on a cylinder with the radius of compactification proportional to the inverse of the physical temperature.

Since the 2$`d`$ Ising model fuses together the simplicity and the full features of more complex models, we considered the most general, relevant perturbation of such model (both thermal and magnetic) in order to cope with the problem of finite temperature corrections to thermodynamic observables (in particular, as it will be clear later, such corrections are nothing but the finite size scaling behaviour of the model as a function of the radius of compactification).

In this respect we recall that, taking advantage of integrability, the finite temperature study of the pure magnetic perturbation of the model was performed in  where an expression for the one point functions was proposed in the framework of Form Factors. Such results were found to be in agreement with the high precision numerical analysis of .

In this paper, we investigate the finite temperature features of the model in the region of the coupling constants ($`h`$ representing the coupling to the spin operator, and $`t=|\beta \beta _c|/\beta `$ the deviation from the critical temperature) where the thermal perturbation is small with respect to magnetic one, $`t/h^{8/15}0`$.

The main idea underlying our approach is to evaluate the Finite Size Scaling (FSS) on the cylindric geometry of the main thermodynamic observables (magnetization, free energy, magnetic susceptibility) by means of high precision numerical data coming from numerical diagonalization of the Transfer Matrix. Consequently, the finite temperature corrections to such observables, i.e. the FSS behaviour, are given by standard Thermodynamic Bethe Ansatz (TBA) prescriptions.

Such an approach is known to work when the perturbations are separately switched on, giving rise to Integrable QFTs (see ). The contemporary presence of both of them destroys the integrability, however since we are in the region of the phase diagram where $`t/h^{8/15}0`$, we postulate that the functional forms coming from TBA still hold.

We showed that this expectation is indeed correct (at least within the precision of our data), and as a side result we were able to evaluate the infinite volume quantities with higher precision than before . It is important to point out that such functional form can be rigorously derived only when integrable theories are concerned, however we expect that when integrability is lost, they still hold under pair creation threshold which is just the regime explored in our simulations.

The work is organized as follows: in sect. 2 we briefly present the model and the numerical transfer matrix technique; sect. 3 is devoted to the study of the FSS of some observables of the Ising model in magnetic field; in sect. 4 we present our numerical results; finally, in sect. 5 we give our conclusion.

## 2 The model and the technique

The Ising model in a magnetic field at an arbitrary temperature is defined by the partition function

$`Z(\beta ,h_{\mathrm{}})={\displaystyle \underset{\sigma _i=\pm 1}{}}e^{\beta _{n,m}\sigma _n\sigma _m+h_{\mathrm{}}_n\sigma _n},`$ (1)
where the spin variable $`\sigma _n`$ takes the values $`\pm 1`$; the notation $`n,m`$ represents nearest neighbor sites on the lattice; the sites are labeled by $`n=(n_o,n_1)`$ and the two sizes of the square lattice are $`L`$ and $`R`$ (they are taken to be different because our transfer matrix calculations will treat the two directions asymmetrically); the total number of sites of the lattice will be denoted as $`N=LR`$.
The coupling $`\beta `$ is the inverse of the temperature, while the magnetic perturbation is introduced by the coupling $`h_{\mathrm{}}H\beta `$, where $`H`$ is the magnetic coupling. This model undergoes a second order phase transition when $`h_{\mathrm{}}=0`$ and $`\beta `$ reaches its critical value $`\beta _c`$

$`\beta _c{\displaystyle \frac{1}{2}}\mathrm{log}(\sqrt{2}+1)=0.4406868\mathrm{}.`$ (2)
The observables which we shall consider are the following:
the Magnetization

$`M(\beta ,h_{\mathrm{}})={\displaystyle \frac{1}{N}}{\displaystyle \frac{}{h_{\mathrm{}}}}(\mathrm{log}Z(\beta ,h_{\mathrm{}}))={\displaystyle \frac{1}{N}}{\displaystyle \underset{i}{}}\sigma _i.`$ (3)
the Magnetic Susceptibility

$`\chi (\beta ,h_{\mathrm{}})={\displaystyle \frac{M(\beta ,h_{\mathrm{}})}{h_{\mathrm{}}}}.`$ (4)
the Free Energy

$`f(\beta ,h_{\mathrm{}})={\displaystyle \frac{1}{N}}\mathrm{log}Z(\beta ,h_{\mathrm{}})f_b.`$ (5)
where the bulk constant $`f_b=0.9296953982\mathrm{}`$ can be found in . Since we will often refer to exact results coming from the QFT which describes the Ising model in the scaling limit, we recall that its action is given by

$`𝒜_{\text{IM}}=𝒜_{\text{CFT}}+\tau {\displaystyle d^2xϵ(x)}+h{\displaystyle d^2x\sigma (x)}`$ (6)
where the first term is the action of the Minimal Unitary CFT describing the critical point of the model , $`h`$ is the coupling constant associated to the magnetic field and $`\tau `$ gives the deviation from the critical temperature (for a review on this subject see ). Such a theory is integrable either when $`h=0`$, $`\tau 0`$ and one can prove that it describes a massive Majorana fermion, or in the case $`h0`$, $`\tau =0`$ which turns out to be a non-trivial theory of eight self-conjugated particles whose spectrum follows the numerology of the exceptional group $`E_8`$ as proved by Al. B. Zamolodchikov in . Simple arguments from CFTs are sufficient to conclude that in the general case $`h0`$, $`\tau 0`$ integrability111We would like to stress that we will always refer to the integrability of the continuum theory because we will use exact results coming from the latter. We are not at all interested in the integrability of the lattice model since our approach is numeric and hence it is not related to the lattice integrability of (1). is lost .

In order to analyze the finite temperature behaviour of the model our choice was to employ the numerical transfer matrix technique. The basic idea is to rewrite the Boltzmann weight by means of the so-called transfer matrix $`T`$, which turns out to be a a positive symmetric $`2^R\times 2^R`$ matrix such that

$`Z(\beta ,h_{\mathrm{}})={\displaystyle \underset{\sigma _i=\pm 1}{}}e^{\beta _{n,m}\sigma _n\sigma _m+h_{\mathrm{}}}=\text{tr}T^L={\displaystyle \underset{i}{}}\lambda _i^L`$ (7)
where the $`\lambda _i`$ are the (real) eigenvalues of $`T`$ (details can be found in ). The numerical computation of eigenvalues and eigenvectors of the transfer matrix enables us to compute all the observables we need, provided that we specify the values of $`h_{\mathrm{}}`$, $`\beta `$ and $`R`$. As an example, the free energy

$`f(\beta ,h_{\mathrm{}})`$ $`=`$ $`{\displaystyle \frac{1}{RL}}\mathrm{log}Z(\beta ,h_{\mathrm{}})`$ (8)
can be written, in the limit $`L\mathrm{}`$, as

$`f(\beta ,h_{\mathrm{}})`$ $``$ $`{\displaystyle \frac{1}{R}}\mathrm{log}\lambda _{max}`$ (9)
which is exactly what we need for the numerical study of the thermodynamic observable as functions of the length of the cylinder $`R`$.

## 3 Finite temperature results, the integrable case

Taking advantage of the integrability of the model (6) when ($`\tau =0,h0`$), Delfino  applied Form Factor method to propose a compact expression for the finite size (i.e. finite temperature) corrections of the one point functions of the Ising model with pure magnetic perturbation (see also  for a discussion on the finite temperature analysis of 2$`d`$ integrable Quantum Field Theory).
Using these results, a given one point function $`\mathrm{\Phi }_R`$ calculated on a cylinder of radius $`R`$ is related to its infinite plane value $`\mathrm{\Phi }_{\mathrm{}}`$ by

$`{\displaystyle \frac{\mathrm{\Phi }_R}{\mathrm{\Phi }_{\mathrm{}}}}=1+{\displaystyle \frac{1}{\pi }}{\displaystyle \underset{i=1}{\overset{3}{}}}𝒜_i^\mathrm{\Phi }K_0(r_i)+𝒪(e^{2r_1})`$ (10)
where $`r_i=m_iR`$ and $`m_i`$, with $`i=1,2,3`$, are the first three masses of Zamoldchikov’s mass spectrum .
The main result of  is to compute exactly the universal constants $`A_i^\mathrm{\Phi }`$. A numerical check of (10) has been performed by Caselle et al.  using Transfer Matrix technique to study the Ising model perturbed with a magnetic field. As already pointed out in , the one point function of the perturbing operator $`\sigma `$ can be obtained by TBA calculations. In fact, following TBA prediction for the FSS behavior of the free energy, it is possible to write down

$`f(R)=f(\mathrm{})+{\displaystyle \underset{i=1}{\overset{3}{}}}{\displaystyle \frac{E(r_i)}{R}}+𝒪(e^{2r_1})`$ (11)
where $`E(r_i)`$ is given by

$`E(r_i)={\displaystyle \frac{m_i}{\pi }}K_1(r_i).`$ (12)
and $`K_1(r)`$ is the modified Bessel function of the second kind.
Hence, for the free energy we have

$`{\displaystyle \frac{f(R)}{f(\mathrm{})}}=1{\displaystyle \underset{i=1}{\overset{3}{}}}{\displaystyle \frac{𝒜_i^f}{\pi }}{\displaystyle \frac{K_1(r_i)}{r_i}}+𝒪(e^{2r_1});𝒜_i^f={\displaystyle \frac{𝒞_i^2}{A_f}}`$ (13)
which gives us the first few orders (under the lowest particle pair creation threshold) of the finite size corrections; the constants $`𝒞_i`$ are given by Zamolodchikov’s mass spectrum (see ref. ). A first derivative with respect to the magnetic field gives us just expression (10) for the magnetization 222The constants $`𝒜_i^\sigma `$ coincide with the coefficients $`A_i^\sigma `$ found by Delfino with the Form Factor approach in .

$`{\displaystyle \frac{\sigma _R}{\sigma _{\mathrm{}}}}=1+{\displaystyle \underset{i=1}{\overset{3}{}}}{\displaystyle \frac{𝒜_i^\sigma }{\pi }}K_0(r_i)+𝒪(e^{2r_1});𝒜_i^\sigma ={\displaystyle \frac{𝒞_i^2}{2A_f}}`$ (14)
then a further derivative gives us the functional form of the finite size corrections for the magnetic susceptibility

$$\frac{\chi (R)}{\chi (\mathrm{})}=1\underset{i=1}{\overset{3}{}}\frac{𝒜_i^\chi }{\pi }[K_0(r_i)8r_iK_1(r_i)]+𝒪(e^{2r_1});𝒜_i^\chi =\frac{𝒞_i^2}{2A_f}.$$
(15)
The exact values of the constants are given in table 1.

The aim of the next section is twofold: on the one hand, we perform a numerical check for the finite size formulas for free energy and magnetic susceptibility in the case of the integrable model (for internal energy and magnetization this was proved in ); on the other hand we check that all the functional forms also hold in the case of the mixed perturbation considered in . The latter case implies that the constants acquire a non-trivial dependence with respect to both $`h_{\mathrm{}}`$ and $`t`$. Their functional form can be derived by the same scaling arguments employed in .

## 4 Numerical analysis

In order to check the behaviour of our data coming from the numerical diagonalization of the transfer matrix, we use the effective procedure presented in our previous work  and in .

First, for each value of $`h_{\mathrm{}}`$ we fit the value of $`\mathrm{\Phi }_R`$ according to the functional form of the finite size corrections found in the previous section. As an example we can consider the susceptibility, hence the fitting function is given by (see previous section)

$$\frac{\chi (R)}{\chi (\mathrm{})}=1\underset{i=1}{\overset{3}{}}\frac{𝒜_i^\chi }{\pi }[K_0(r_i)8r_iK_1(r_i)]+𝒪(e^{2r_1});$$
(16)
where we keep the quantities $`𝒜_i^\chi `$ and $`\chi (\mathrm{})`$ as free parameters. Our fitting procedure follows a very stringent list of acceptance criteria as presented in . The first non trivial result is that the fits are acceptable (for all the observable considered here) even if the temperature is not set to its critical value. In this case the behaviour of the observables as function of $`R`$ cannot be proved to hold rigorously because the corresponding QFT is not integrable. Notwithstanding this, in the regime $`t/h^{8/15}0`$ considered here and within our numerical precision, such functional forms continue to hold.

To the best of our knowledge the present is the first evidence about the validity of formulas like that of previous section for non-integrable theories. It could suggest that, when small perturbations of integrable QFTs are considered, then the finite temperature behaviour of the thermodynamic observables remains the same and the only price to pay is a change in the constants $`𝒜_i^\varphi `$ which acquire a non-trivial dependence with respect to the couplings $`t`$ and $`h_{\mathrm{}}`$. The following quantitative results were found:

1. The numerical results for the infinite $`R`$ observables $`f(\mathrm{})`$, $`\sigma _{\mathrm{}}`$, $`\chi (\mathrm{})`$ are not only in complete agreement with respect to the estimates of , but they show an improvement in their precision of about one order of magnitude. As an example of this we quote the following results for the susceptibility $`\beta =\beta _c`$, $`h=0.07`$

$`\chi (\beta _c,0.07)=0.7574405(3)`$ (17)
compared with the value obtained in

$`\chi (\beta _c,0.07)=0.757441(1);`$ (18)
$`\beta =0.4349\mathrm{}`$, $`h=0.07`$

$`\chi (0.07,0.4349\mathrm{})=0.8465333(3)`$ (19)
compared with the value obtained in

$`\chi (0.07,0.4349\mathrm{})=0.846533(1).`$ (20)
We stress that it is remarkable that such an improvement comes independently of the fact that $`\beta `$ is fixed at its critical value or not. Moreover such an improvement in precision could be expected since in this latter case we used the functional form of the finite temperature corrections instead of fitting with a set of generic exponentially decaying functions.
2. As anticipated, we supposed that the constants $`𝒜_i^\varphi `$ are functions of $`t`$ and $`h_{\mathrm{}}`$. In order to test such a conjecture, we first define the following subtracted quantities in order to discard all the corrections which depends only on the magnetic field $`h_{\mathrm{}}`$,

$$𝒜_i^\varphi (t)|_h_{\mathrm{}}𝒜_i^\varphi (0)|_h_{\mathrm{}}=𝒥_{1,i}^\varphi (h_{\mathrm{}})t+𝒥_{2,i}^\varphi (h_{\mathrm{}})t^2+𝒥_{3,i}^\varphi (h_{\mathrm{}})t^3+\mathrm{}$$
(21)
As pointed out in , it is a crucial step in order to compute the leading corrections due to the thermal perturbation. In this way we are able to fit our data with (21). The precision of our data enable us to compute only the linear term of such an expansion.

By means of the expansion for the scaling functions we are in the position to fit the amplitude $`𝒥_1^𝒪(h_{\mathrm{}})`$ as a function of the magnetic field alone. We recall that, in principle, the functional form of the $`𝒥_{1,i}^\varphi (h_{\mathrm{}})`$ is non-trivial to be obtained, however, they can be determined by the same Renormalization Group and CFT arguments given in  in order to construct the scaling functions of the thermodynamic observables. The results are

* Free Energy: The fit with the scaling function

    $`𝒥_{1,1}^f(h_{\mathrm{}})={\displaystyle \frac{𝒲_1}{h_{\mathrm{}}^{\frac{8}{15}}}}+𝒲_2h_{\mathrm{}}^{\frac{2}{15}}+𝒲_3h_{\mathrm{}}^{\frac{8}{15}}+\mathrm{}`$ (22)
    and we can give a reliable estimate only of the leading term of the expansion

    $`𝒲_1=90(8).`$ (23)
    * Magnetization: The fit with the scaling function

    $`𝒥_{1,1}^\sigma (h_{\mathrm{}})={\displaystyle \frac{_1}{h_{\mathrm{}}^{\frac{8}{15}}}}+_2h_{\mathrm{}}^{\frac{2}{15}}+_3h_{\mathrm{}}^{\frac{8}{15}}+\mathrm{}`$ (24)
    gives us

    $`2.09<_1<2.15.`$ (25)

The other observables were outside our numerical precision.
3. Finally, a further check about the validity is given by the analysis of the data at the critical temperature $`\beta _c`$. In this case the scaling function for the coefficients $`𝒜_1^\varphi `$ depend only on the magnetic field $`h_{\mathrm{}}`$ and is given by

$`\widehat{𝒜}_1^\mathrm{\Phi }(h_{\mathrm{}})=𝒜_1^\mathrm{\Phi }(1+b_{1,\mathrm{\Phi }}|h_{\mathrm{}}|^{\frac{16}{15}}+b_{2,\mathrm{\Phi }}|h_{\mathrm{}}|^{\frac{22}{15}})+\mathrm{}.`$ (26)
Employing them as fitting functions, we find

$`8.07<`$ $`𝒜_1^\chi `$ $`<8.20`$ (27)
$`16.12<`$ $`𝒜_1^f`$ $`<16.28`$ (28)
where the numerical values of the amplitudes perfectly agree with their theoretical counterparts: $`𝒜_1^\chi =8.09997\mathrm{}`$ and $`𝒜_1^f=16.1999\mathrm{}`$ computed according to the formulæ given in the previous section. Such results can be considered as further checks (beside the results of ref.  where magnetization and internal energy were considered) of the results coming from form factors.

The complete list of the numerical values of the parameters we used for the numerical diagonalization of the Transfer Matrix is given in table 2. A significant sample of the data employed in the computation of finite temperature corrections is given in table 3.

## 5 Conclusions

Let us recall our main results. Our numerical study confirms the conjecture that the functional forms of the finite temperature corrections derived by means of Thermodynamic Bethe Ansatz for the Ising model with magnetic perturbation at $`t=0`$ ($`T=T_c`$) still holds when $`t0`$ supposing that $`t/h^{8/15}0`$. We stress that, the functional form of finite temperature corrections works well even if integrability is lost because we explored a region of the phase space where anelastic effect can be neglected. As explained in  the thermal perturbation results only in a correction to the mass spectrum of the integrable Ising field theory in magnetic field; no other effects due to the loss of integrability are expected.

Finally, it could be worth to notice that, the high precision of our data allowed us to achieve the following numerical results: first we obtained the infinite volume estimates of the observables with typically one order of magnitude of precision more than the method previously employed in ; second we get information about the first subleading correction due to the reduced temperature.


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# Intermittency in aging

## 1  Introduction

Many systems in nature, such as glasses, spin-glasses, colloids and granular materials, present an extremely slow relaxation towards equilibrium and, when external conditions are modified, the physical properties of these materials evolve as a function of time: they are aging. For example, when a glassy material is quenched from above its glass transition temperature $`T_g`$ to a temperature lower than $`T_g`$, any response function of the material depends on the time $`t_w`$ elapsed from the quench . Another example of aging is given by colloidal-glasses, whose properties evolve during the sol-gel transition which may last several days . An important feature of aging materials is the dependence of their physical properties on the thermal history of the sample. Indeed experimental procedures, based on multiple cycles of cooling, heating and waiting times, have shown the existence of two spectacular effects: memory and rejuvenation. Specifically, aging materials present a rejuvenation for any negative temperature perturbation and at the same time during heating they remind the stops at fixed temperature done during cooling (see for example  and references therein). Several models have been proposed to explain such a beahvior but from an experimental point of view it is not easy to distinguish between them. The above mentioned experimental procedures have been, indeed, extremely useful to fix several constrains for the phenomenological models, but these procedures are mainly based on the study of the response of the system to an external perturbation. Therefore they are unable to give new insight on the system dynamics. Let us consider for example the trap model which is based on a phase space description. Its basic ingredient is an activation process and aging is associated to the fact that deeper and deeper valleys are reached as the system evolves . The dynamics in this model has to be intermittent because either nothing moves or there is a jump between two traps. This contrasts, for example, with mean field dynamics which is continuous in time. Therefore, from an experimental point of view, it is extremely important to study not only the response of the system but also its thermal fluctuations. This analysis is also related to another important aspect of aging dynamics, that is the definition of the temperature. Indeed recent theories  based on the description of spin glasses by a mean field approach proposed to extend the concept of temperature using a Fluctuation Dissipation Relation (FDR) which generalizes the Fluctuation Dissipation Theorem (FDT) for a weakly out of equilibrium system (for a review see ref. ). In order to understand this generalization, we recall the main consequences of FDT in a system which is in thermodynamic equilibrium. We consider an observable $`V`$ of such a system and its conjugate variable $`q`$ . The response function $`\chi _{Vq}(\omega )`$, at frequency $`f=\omega /2\pi `$, describes the variation $`\delta V(\omega )`$ of $`V`$ induced by a perturbation $`\delta q(\omega )`$ of $`q`$, that is $`\chi _{Vq}(\omega )=\delta V(\omega )/\delta q(\omega )`$. FDT relates the fluctuation spectral density of $`V`$ to the response function $`\chi _{Vq}`$ and the temperature T of the system:

$$S(\omega )=\frac{2k_BT}{\pi \omega }\mathrm{𝐼𝑚}\left[\chi _{Vq}(\omega )\right]$$
(1)
where $`S(\omega )=<|V(\omega )|^2>`$ is the fluctuation spectral density of $`V`$, $`k_B`$ is the Boltzmann constant, $`\mathrm{𝐼𝑚}\left[\chi _{Vq}(\omega )\right]`$ is the imaginary part of $`\chi _{Vq}(\omega )`$. Textbook examples of FDT are Nyquist’s formula relating the voltage noise to the electrical resistance and the Einstein’s relation for Brownian motion relating the particle diffusion coefficient to the fluid viscosity .

When the system is not in equilibrium FDT, that is eq.1, may fail. Indeed theoretical works  predict a violation of eq.1 which has been observed  in many numerical simulations (,-) and in a few experiments -.

Because of the slow dependence on $`t_w`$ of the response functions, it has been proposed to use a FDR which generalizes eq.1 and which can be used to define an effective temperature $`T_{eff}(\omega ,t_w)`$ of the system :

$$T_{eff}(\omega ,t_w)=\frac{S(\omega ,t_w)\pi \omega }{\mathrm{𝐼𝑚}\left[\chi _{Vq}(\omega ,t_w)\right]2k_B}$$
(2)
It is clear that if eq.1 is satisfied $`T_{eff}=T`$, otherwise $`T_{eff}`$ turns out to be a decreasing function of $`t_w`$ and $`\omega `$. The physical meaning of eq.2 is that there is a time scale (for example $`t_w`$) which allows to separate the fast processes from the slow ones. In other words the low frequency modes, such that $`\omega t_w<1`$, relax towards the equilibrium value much slower than the high frequency ones which rapidly relax to the temperature of the thermal bath. Therefore it is conceivable that the slow frequency modes keep memory of higher temperatures for a long time and for this reason their temperature should be higher than that of the high frequency ones. This striking behavior has been observed in several numerical models of aging ,-. Further analytical and numerical studies of simple models show that eq.2 is a good definition of temperature in the thermodynamic sense . In spite of the large amount of theoretical studies there are only a few experiments where FDR is studied in aging materials. The experimental analysis of the dependence of $`T_{eff}(\omega ,t_w)`$ on $`\omega `$ and $`t_w`$ is very useful to distinguish among different models of aging because the FDT violations are model dependent ,-. Furthermore the direct analysis of the noise signal allows one to understand if the dynamics is either intermittent or continuous in time.

Recently, a few experiments have analyzed this problems in real materials , , , . The violation of FDT measured in an experiment on a spin glass  seems to be in agreement with theoretical predictions, which were originally based on mean field approach of spin glasses. In contrast, experiments done on dielectric measurements on glycerol , colloidal glasses and polymers  present only a qualitative agreement with theory.

The previous analysis of Laponite  and of polycarbonate was mainly based on the study of the time evolution of the noise spectra which is surprisingly similar in these two very different materials. In both cases the effective temperature defined using eq.2 is huge and the persistent time of the violation is extremely long. We have therefore analyzed directly the time evolution of the noise signal in both experiments and we find a strongly intermittent beahvior in both materials. In this paper we describe the results of this analysis and we want also to point out the common features observed in the slow relaxation dynamics of these two materials.

The paper is organized as follows. In section 2 and 3 we recall the main results of the experiment on Laponite and polycarbonate respectively. We also describe the analysis performed on the time evolution of the noise signal. In section 4 we compare the results of the two experiments and we discuss their relevance for recent aging models. Conclusions are done at the end of the section.

## 2  Laponite electric properties

### 2.1 The experimental apparatus

The Laponite  solution is used as a conductive liquid between the two golden coated electrodes of a cell (see fig.1). It is prepared in a clean $`\mathrm{N}_2`$ atmosphere to avoid $`\mathrm{CO}_2`$ and $`\mathrm{O}_2`$ contamination, which perturbs the electrical measurements. Laponite particles are dissolved at a concentration of $`2.5\%`$ mass fraction in pure water under vigorous stirring during $`300s`$. To avoid the existence of any initial structure in the sol, we pass the solution through a $`1\mu m`$ filter when filling our cell. This instant defines the origin of the aging time $`t_w`$ (the filling of the cell takes roughly two minutes, which can be considered the maximum inaccuracy of $`t_w`$). The sample is then sealed so that no pollution or evaporation of the solvent can occur. At this concentration, the light scattering experiments show that Laponite  structure functions are still evolving $`500h`$ after the preparation . We only study the beginning of this glass formation process.

The two electrodes of the cell are connected to our measurement system, where we alternately record the cell electrical impedance $`Z(t_w,\omega )`$ and the voltage noise density $`S_Z(t_w,\omega )`$ (see fig.1). Taking into account that in this configuration $`\mathrm{𝐼𝑚}\left[\chi _{Vq}(t_w,\omega )\right]=\omega \mathrm{𝑅𝑒}\left[Z(t_w,\omega )\right]`$, one obtains from eq.2 that the effective temperature of the Laponite solution as a function of the aging time and frequency is:

$$T_{eff}(t_w,\omega )=\pi S_Z(t_w,\omega )/2k_B\mathrm{𝑅𝑒}\left[Z(t_w,\omega )\right]$$
(3)
which is an extension of the Nyquist formula.

The electrical impedance of the sample is the sum of 2 effects: the bulk is purely conductive, the ions of the solution follow the forcing field, whereas the interfaces between the solution and the electrodes give mainly a capacitive effect due to the presence of the Debye layer. This beahvior has been validated using a four-electrode potentiostatic technique  to make sure that the capacitive effect is only due to the surface. In order to test only bulk properties, the geometry of the cell is tuned to push the surface contribution to low frequencies. Specifically the cell is composed by two large reservoirs in contact with the electrodes which have an area of $`25cm^2`$. The reservoirs are connected by a rigid tube (see fig.1) whose section and length give the main contribution to the bulk electrical resistance. Thus by changing the sizes of the tube the bulk resistance can be changed from $`300\mathrm{\Omega }`$ to $`100K\mathrm{\Omega }`$. We checked that the dynamics of the system does not depend on the value of the bulk resistance. For a bulk resistance of about $`10^5\mathrm{\Omega }`$ the cut-off frequency of the equivalent R-C circuit (composed by the series of the Debye layers plus the bulk resistance) is about $`0.02Hz`$. In other words above this frequency the imaginary part of the cell impedance is about zero.

### 2.2  FDR measurements

In fig.2(a), we plot the real part of the impedance as a function of the frequency $`f`$, for a typical experiment and two different times. The time evolution of the resistance of one of our sample is plotted in fig.2(b): it is still decaying in a non trivial way after $`24h`$, showing that the sample has not reached any equilibrium yet. This aging is consistent with that observed in light scattering experiments .

As the dissipative part of the impedance $`Re(Z)`$ is weakly time and frequency dependent, one would expect from the Nyquist formula that so does the voltage noise density $`S_Z`$. But as shown in fig.3, FDR must be strongly violated for the lowest frequencies and earliest times of our experiment: $`S_Z`$ changes by several orders of magnitude between highest values and the high frequency tail 111This low frequency noise cannot be confused with the standard $`1/f`$ noise observed in many electronic devices. We recall that the $`1/f`$ appears only when an external current produced by an external potential goes through the device. In our cell no external potential is applied. This violation is clearly illustrated by the behavior of the effective temperature in fig.4222The usual representation of the effective temperature in simulations is the slope of the response versus correlation plot, but it is not suited for our experimental data: the system being almost only dissipative, the response function is close to a delta distribution, thus FDR is only one point in this representation.. For long times and high frequencies, the FDR holds and the measured temperature is the room one ($`300K`$); whereas for early times $`T_{eff}`$ climbs up to $`3.10^3K`$ at $`1Hz`$. Moreover, $`T_{eff}`$ could be even larger for lower frequencies and lower aging times: indeed, we found in all the tested samples no evidence of a saturation of this effective temperature in our measurement range. In order to be sure that the observed violation is not due to an artifact of the experimental procedure, we filled the cell with an electrolyte solution with pH close to that of the Laponite sol such that the electrical impedance of the cell was the same. Specifically we filled the cell with $`NaOH`$ solution in water at a concentration of $`10^3mol.l^1`$. The results of the measurements of $`T_{eff}`$ are shown in fig.5 at two different times after the sample preparation. In this case we did not observe any violation of FDR at any time.

### 2.3  Statistical analysis of the noise

In order to understand such a beahvior we have directly analyzed the noise voltage across the Laponite cell. This test can be safely done in our experimental apparatus because the amplifier noise is negligible with respect to the thermal noise of the Laponite cell even when FDT is satisfied. In fig.6(a) we plot a typical signal measured $`2h`$ after the gel preparation when the FDT is strongly violated. The signal plotted in fig.6(b) has been measured when the system is relaxed and FDT is satisfied in all the frequency range. By comparing the two signals we immediately realize that there are very important differences. The signal in fig.6(a) is interrupted by bursts of very large amplitude which are responsible for the increasing of the noise in the low frequency spectra (see fig.3). The relaxation time of the bursts has no particular meaning, because it corresponds just to the characteristic time of the filter used to eliminate the very low frequency trends. As time goes on, the amplitude of the bursts reduces and the time between two consecutive bursts becomes longer and longer. Finally they disappear as can be seen in the signal of fig.6(b) recorded after $`50h`$ when the system satisfies FDT.

The evolution of the intermittent properties of the noise can be characterized by studying the probability density function(PDF) of the signal as a function of time. To compute the PDF, the time series are divided in several time windows and the PDF are computed in each of these window. Afterwards the result of several experiments are averaged. The PDF computed at different times are plotted in fig.7. We see that at short $`t_w`$ the PDF presents very high tails which slowly disappear at longer $`t_w`$. Finally a Gaussian shape is recovered at $`t_w=16h`$. This kind of evolution of the PDF clearly indicate that the signal is very intermittent at the very beginning and it relaxes to the Gaussian noise at very long times.

The comparison of these results with aging models will be done in the conclusions. We prefer to describe now another experiment in a completely different material.

## 3  Polycarbonate dielectric properties

In order to give more insight into the problem of the violation of FDT and of the intermittent beahvior discussed in the previous section we have done wide band ($`20mHz100Hz`$) measurements of the dielectric susceptibility and of the polarization noise in a polymer glass: polycarbonate. We present in this article several results which show a strong violation of the FDT when this material is quenched from the molten state to below its glass-transition temperature. The effective temperature defined by eq.2 slowly relaxes towards the bath temperature. The violation is observed even at $`\omega t_w1`$ and it may last for more than $`3h`$ for $`f>1Hz`$.

### 3.1 The experimental apparatus

The polymer used in this investigation is Makrofol DE 1-1 C, a bisphenol A polycarbonate, with $`T_g419K`$, produced by Bayer in form of foils. We have chosen this material because it has a wide temperature range of strong aging . This polymer is totally amorphous: there is no evidence of crystallinity . Nevertheless, the internal structure of polycarbonate changes and relaxes as a result of a change in the chain conformation by molecular motions,,. Many studies of the dielectric susceptibility of this material exist, but no one had an interest on the problem of noise measurements.

In our experiment polycarbonate is used as the dielectric of a capacitor. The capacitor is composed by $`14`$ cylindrical capacitors in parallel in order to reduce the resistance of the sample and to increase its capacity. Each capacitor is made of two aluminum electrodes, $`12\mu m`$ thick, and by a disk of polycarbonate of diameter $`12cm`$ and thickness $`125\mu m`$. The experimental set-up is shown in fig.8a). The $`14`$ capacitors are sandwiched together and put inside two thick aluminum plates which contain an air circulation used to regulate the sample temperature. This mechanical design of the capacitor is very stable and gives very reproducible results even after many temperature quenches. The capacitor is inside two Faraday screens to insulate it from external noise. The temperature of the sample is controlled within a few percent. Fast quench of about $`50K/min`$ are obtained by injecting Nitrogen vapor in the air circulation of the aluminum plates. The electrical impedance of the capacitor is $`Z(\omega ,t_w)=R/(1+i\omega RC)`$, where $`C`$ is the capacitance and $`R`$ is a parallel resistance which accounts for the complex dielectric susceptibility. It is measured using a Novocontrol Dielectric Analyzer. The noise spectrum of this impedance $`S_Z(\omega ,t_w)`$ is:

$$S_Z(f,t_w)=4k_BT_{eff}(f,t_w)Re[Z(\omega ,t_w)]=\frac{4k_BT_{eff}(f,t_w)R}{1+(\omega RC)^2}$$
(4)
where $`T_{eff}`$ is the effective temperature of the sample. In order to measure $`S_Z(f,t_w)`$, we have made a differential amplifier based on selected low noise JFET(2N6453 InterFET Corporation), whose input has been polarized by a resistance $`R_i=4G\mathrm{\Omega }`$. Above $`2Hz`$, the input voltage noise of this amplifier is $`5nV/\sqrt{Hz}`$ and the input current noise is about $`1fA/\sqrt{Hz}`$. The output signal of the amplifier is analyzed either by an HP3562A dynamic signal analyzer or directly acquired by a NI4462 card. It is easy to show that the measured spectrum at the amplifier input is:

$`S_V(f,t_w)`$ $`=`$ $`{\displaystyle \frac{4k_BRR_i(T_{eff}(f,t_w)R_i+T_RR+S_\xi (f)RR_i)}{(R+R_i)^2+(\omega RR_iC)^2}}+S_\eta (f)`$ (5)
where $`T_R`$ is the temperature of $`R_i`$ and $`S_\eta `$ and $`S_\xi `$ are respectively the voltage and the current noise spectrum of the amplifier. In order to reach the desired statistical accuracy of $`S_V(f,t_w)`$, we averaged the results of many experiments. In each of these experiments the sample is first heated to $`T_i=433K`$. It is maintained at this temperature for 4 hours in order to reinitialize its thermal history. Then it is quenched from $`T_i`$ to $`T_f=333K`$ in about 2 minutes. A typical thermal history of the quench is shown in fig.8(b). The reproducibility of the capacitor impedance, during this thermal cycle is always better than $`1\%`$. The origin of aging time $`t_w`$ is the instant when the capacitor temperature is at $`T_g419K`$, which of course may depend on the cooling rate. However adjustment of $`T_g`$ of a few degrees will shift the time axis by at most $`30s`$, without affecting our results.

### 3.2 FDR measurements

In fig.9(a) and (b), we plot the measured values of $`R`$ and $`C`$ as a function of $`f`$ at $`T_i`$ and at $`T_f`$ for $`t_w200s`$. We see that lowering temperature $`R`$ increases and $`C`$ decreases. At $`T_f`$ aging is small and extremely slow. Thus for $`t_w>200s`$ the impedance can be considered constant without affecting our results. From the data plotted in fig.9 (a) and (b) one finds that $`R=10^{10}(1\pm 0.05)f^{1.05\pm 0.01}\mathrm{\Omega }`$ and $`C=(21.5\pm 0.05)nF`$. In fig.9(a) we also plot the total resistance at the amplifier input which is the parallel of the capacitor impedance with $`R_i`$. We see that at $`T_f`$ the input impedance of the amplifier is negligible for $`f>10Hz`$, whereas it has to be taken into account at slower frequencies.

fig.10(a) represents the evolution of $`S_V(f,t_w)`$ after a quench. Each spectrum is obtained as an average in a time window starting at $`t_w`$. The time window increases with $`t_w`$ so to reduce error for large $`t_w`$. Then the results of 7 quenches have been averaged. The longest time ($`t_w=1day`$) the equilibrium FDT prediction (continuous line) is quite well satisfied. We clearly see that FDT is strongly violated for all frequencies at short times. Then high frequencies relax on the FDT, but there is a persistence of the violation for lower frequencies. The amount of the violation can be estimated by the best fit of $`T_{eff}(f,t_w)`$ in eq.5 where all other parameters are known. We started at very large $`t_w`$ when the system is relaxed and $`T_{eff}=T`$ for all frequencies. Inserting the values in eq.5 and using the $`S_V`$ measured at $`t_w=1days`$ we find $`T_{eff}333K`$, within error bars for all frequencies (see fig.10b). At short $`t_w`$ data show that $`T_{eff}(f,t_w)T_f`$ for $`f`$ larger than a cutoff frequency $`f_o(t_w)`$ which is a function of $`t_w`$. In contrast, for $`f<f_o(t_w)`$ we find that $`T_{eff}`$ is: $`T_{eff}(f,t_w)f^{A(t_w)}`$, with $`A(t_w)1`$. This frequency dependence of $`T_{eff}(f,t_w)`$ is quite well approximated by

$$T_{eff}(f,t_w)=T_f[1+(\frac{f}{f_o(t_w)})^{A(t_w)}]$$
(6)
where $`A(t_w)`$ and $`f_o(t_w)`$ are the fitting parameters. We find that $`1<A(t_w)<1.2`$ for all the data set. Furthermore for $`t_w250`$, it is enough to keep $`A(t_w)=1.2`$ to fit the data within error bars. For $`t_w<250s`$ we fixed $`A(t)=1`$. Thus the only free parameter in eq.6 is $`f_o(t_w)`$. The continuous lines in fig.10(a) are the best fits of $`S_V`$ found inserting eq.6 in eq.5.

In fig.10(b) we plot the estimated $`T_{eff}(f,t_w)`$ as a function of frequency at different $`t_w`$. We see that just after the quench $`T_{eff}(f,t_w)`$ is much larger than $`T_f`$ in all the frequency interval. High frequencies rapidly decay towards the FDT prediction whereas at the smallest frequencies $`T_{eff}10^5K`$. Moreover we notice that low frequencies decay more slowly than high frequencies and that the evolution of $`T_{eff}(f,t_w)`$ towards the equilibrium value is very slow. From the data of fig.10(b) and eq.6, it is easy to see that $`T_{eff}(f,t_w)`$ can be superposed onto a master curve by plotting them as a function of $`f/f_o(t_w)`$. The function $`f_o(t_w)`$ is a decreasing function of $`t_w`$, but the dependence is not a simple one, as it can be seen in the inset of fig.10(b). The continuous straight line is not fit, it represents $`f_o(t_w)1/t_w`$ which seems a reasonable approximation for these data. For $`t_w>10^4s`$ we find the $`f_o<1Hz`$. Thus we cannot follow the evolution of $`T_{eff}`$ anymore because the contribution of the experimental noise on $`S_V`$ is too big, as it is shown in fig.10(b) by the increasing of the error bars for $`t_w=1day`$ and $`f<0.1Hz`$.

Before discussing these experimental results we want to compare them to the single frequency experiment performed on glycerol . In this experiment, $`T_{eff}`$ has been measured only at $`7Hz`$. Thus we studied how $`T_{eff}(7Hz,t_w)`$ depends on $`t_w`$ at $`7Hz`$ in our experiment. The time evolution of $`T_{eff}(7Hz,t_w)`$ is plotted as a function of $`t_w`$ in fig.11a). The time evolution of $`T_{eff}(2Hz,t_w)`$ is also plotted just to show the large temperature difference between two frequencies. Let us consider the evolution at $`7Hz`$ only. As in the experiment of ref., we confirm the fact that the violation is observed even if $`\omega t_w>>1`$, which is in contrast with theoretical predictions. The biggest violation is for short times after the quench where the effective temperature is surprisingly huge: around 800K at 7Hz and $`t_w=300s`$. In the experiment on glycerol the first data reported are for $`t_w>1000s`$. Thus if we consider only data at $`t_w>1000s`$ in fig.11a) we see that our results are close to those of ref.. Indeed at $`t_w=1000s`$ we find in our experiment $`(T_{eff}T_f)/(T_gT_f)2.4`$ The glycerol data give $`(T_{eff}T_f)/(T_gT_f)1`$. Thus the relative violations of FDT at $`7Hz`$ are very close in glycerol and polycarbonate. However it would be interesting to check whether at shorter times and at lower frequencies large $`T_{eff}`$ could be observed in glycerol too.

In order to compare with theoretical predictions  and recent spin glass experiment  we may plot the integrated response $`R(t,t_w)`$ as a function of the correlation $`C(t,t_w)`$. The latter is obtained inserting measured $`T_{eff}(f,t_w)`$ in eq.4 and by Fourier transforming this equation. $`R(t,t_w)`$ can be computed by Fourier transforming $`Real[Z(\omega ,t_w)]`$. FDR now takes the form :

$$C(t,t_w)+C(t_w,t_w)=k_BT_{eff}(t,t_w)R(t,t_w)$$
(7)
In the inset of fig.11b), we see that for $`t_w>300s`$ the shape of the decay of $`C(t_w,t)`$ remains essentially the same. Indeed data for different $`t_w`$ can be scaled onto a single master curve by plotting $`C(t_w,t)`$ as a function $`(tt_w)/t_o(t_w)`$, where $`t_o(t_w)`$ is an increasing function of $`t_w`$: approximately $`t_o(t_w)log(t_w)`$ for $`t_w>500s`$. The self-similarity of correlation functions, found on our dielectric data, is a characteristic of the universal picture of aging , which has been also observed in spin-glass experiment  and in the structure function of the dynamic light scattering of colloidal gels . Thus our results confirm that this picture of aging applies also to the polymer dielectric measurements. To further investigate this aging, we plot, in fig.11b), $`R(t,t_w)`$ as a function $`(C(t,t_w)+C(t_w,t_w))/k_B`$ at different $`t_w`$. The slope of this graph gives $`1/T_{eff}`$. The symbols correspond to the data whereas the dashed line are obtained by inserting the best fit of $`T_{eff}`$ in eq.6, in eq.4. We clearly see that data at small $`C(t,t_w)`$ asymptotically converge to an horizontal straight line, which means that the system has an infinite temperature. At short time, large $`C(t,t_w)`$, FDT prediction is recovered (continuous straight line of slope $`1/T_f`$). This result is quite different to what has been observed in recent experiments on spin glasses where $`T_{eff}5T_g`$ has been measured. In contrast infinite $`T_{eff}`$ has been observed during the sol gel transition  and in numerical simulation of domain growth phenomena.

### 3.3  Statistical analysis of the noise

In order to understand the origin of such large deviations in our experiment we have analyzed the noise signal. We find that the signal is characterized by large intermittent events which produce low frequency spectra proportional to $`f^\alpha `$ with $`\alpha 2`$. Two typical signals recorded at $`1500s<t_w<1900s`$ and $`t_w>75000s`$ are plotted in fig.12. We clearly see that in the signal recorded at $`1500s<t_w<1900s`$ there are very large bursts which are on the origin of the frequency spectra discussed in the previous section. In contrast in the signal (fig.12b), which was recorded at $`t_w>75000s`$ when FDT is not violated, the bursts are totally disappeared.

As for Laponite we have studied the PDF of the signal as a function of $`t_w`$ for polycarbonate. The results are shown in fig.13. We clearly see that the PDF, measured at small $`t_w`$, has very high tails which becomes smaller and smaller at large $`t_w`$. Finally the Gaussian profiles is recovered after $`24h`$. This strongly intermittent dynamics is reminiscent of the intermittence observed in the local measurements of polymer dielectric properties  and in the slow relaxation dynamics of a colloidal gel

## 4 Discussion and conclusions

Let us resume the main results of the two experiments described in the previous sections. We have seen that dielectric measurements of Laponite, during the sol-gel transition, and of polycarbonate, after a temperature quench, show a strong violation of FDT. The effective temperature defined by eq.2 is huge at small $`t_w`$ and slowly relaxes towards the bath temperature. In contrast to theoretical predictions the violation is observed even at $`\omega t_w1`$ and it may last for more than $`3h`$ for $`f>1Hz`$. We have then investigated the beahvior of the noise signals and we have shown that the huge $`T_{eff}`$ is produced by very large intermittent bursts which are at the origin of the low frequency power law decay of noise spectra. Furthermore we have also shown that for both materials the statistic of this event is strongly non Gaussian when FDT is violated and slowly relaxes to a Gaussian one at very long $`t_w`$. Thus these two very different materials have a very similar relaxation dynamics, characterized by a strong intermittency. This strongly intermittent dynamics is reminiscent of the intermittence observed in the local measurements of polymer dielectric properties. . Furthermore recent measurements done, using time resolved correlation in diffusing wave spectroscopy, have shown a strong intermittency in the slow relaxation dynamics of a colloidal gel . This kind of beahvior can indeed be interpreted on the basis of the trap model , which predicts non trivial violation of FDT associated to an intermittent dynamics. The system evolves in deeper and deeper valleys on the energy landscape. The dynamics is fundamentally intermittent because either nothing moves or there is a jump between two traps. In our case these jumps could explain the presence in the dielectric voltage noise of very large and rare peaks with a slow relaxation after the jump. Clear answers to this question can be given by a detailed study of the statistics of the time intervals between large peaks. This work is in progress.

This work clearly shows the importance of associating thermal noise and response measurements. Many questions remain opened on the subject of FDR in out of equilibrium systems. One may wonder whether different couples of conjugated variables give the same $`T_{eff}`$ as defined by eq.2. For example FDR measured on the rheological properties of Laponite show no violation of FDT . The reasons of these differences between electrical and mechanical measurements are unclear and much work is necessary to give new insight on these problems.

Acknowledgments

We acknowledge useful discussion with J. Kurchan and J.P. Bouchaud. We thank P. Metz and F. Vittoz for technical support. This work has been partially supported by the Région Rhône-Alpes contract “Programme Thématique : Vieillissement des matériaux amorphes”.


text:
# Polarization dependence of spin excitations in BaCu2Si2O7.

## I Introduction

Excitations in weakly ordered quasi-one-dimensional (quasi-1D) antiferromagnets (AFs) are a topic of considerable current interest in the field of quantum magnetism. Particularly intriguing is the problem of the so-called longitudinal mode (LM), a magnon excitation polarized parallel to the direction of ordered moment. The discovery of a coherent LM in KCuF3 (Refs. Lake et al., 2000; Lak, ) confirmed previous theoretical predictions,Ess  based on the chain-Mean FieldSca  (chain-MF) and Random Phase Approximation (RPA) theories.Sch ; Ess  Currently chain-MF/RPA indeed appears to be the most versatile analytical framework for treating weakly-coupled quantum spin chains. However, the KCuF3 experiments also highlighted certain limitations of this approach. In particular, the chain-MF/RPA can not, by its very definition, account for the experimentally observed finite lifetime (broadening) of the LM.

In a recent short paperZhe (a) we reported polarization-sensitive neutron scattering measurements of the dynamic spin structure factor in another model quasi-1D antiferromagnet, namely BaCu2Si2O7. This $`S=1/2`$ system has much weaker inter-chain interactions and low-temperature ordered moment than KCuF3. Preliminary results indicated that, unlike in KCuF3, in BaCu2Si2O7 there is no well-defined longitudinal mode. Instead, the longitudinal spectrum is best described as a single broad asymmetric continuum feature. This stark discrepancy with the predictions of the chain-MF/RPA model came as surprise. Indeed, for the transverse-polarized spectrum of BaCu2Si2O7, earlier neutron scattering work confirmed excellent agreement with chain-MF/RPA theory, at least as far as excitation energies were concerned.Zheludev et al. (2001a); Zhe (b) The apparent paradox is not fully resolved to date. This is in part due to that only very limited data are available for longitudinal-polarized excitations. Even for the transverse-polarized spectrum, the existing wealth of high-resolution neutron data could not be quantitatively compared to theoretical predictions, for lack of calculations based on the specific geometry of inter-chain interactions in BaCu2Si2O7. The present work addresses both these issues and involves a detailed experimental and theoretical study of the polarization dependence of magnetic excitations in this compound. First, we further exploit the technique of polarization analysis described in Ref. Zhe, a to investigate the wave vector dependence of longitudinal excitations. We then perform chain-MF/RPA calculations of the dynamic structure factor for the exchange topology and constants of BaCu2Si2O7. This enables us to perform a direct quantitative comparison between theory and experiment for both energies and intensities of the coherent and diffuse components of the dynamic spin correlation functions.

Magnetic interactions in BaCu2Si2O7 have been previously thoroughly studied using bulk methods, Tsu ; Tsukada et al. (2001) neutron diffraction,Tsu ; Zheludev et al. (2002) and inelastic neutron scattering. Tsu ; Zhe (c); Ken ; Zhe (b)

The silicate BaCu2Si2O7crystallizes in an orthorhombic structure (space group $`Pnma`$, $`a=6.862`$ Å, $`b=13.178`$ Å, $`c=6.897`$ Å) with slightly zigzag AF $`S=1/2`$ chains of Cu2+ ions running along the $`c`$ axis. The in-chain exchange constant is $`J=24.1`$ meV. Interactions between the chains are much weaker, and the characteristic bandwidth of spin wave dispersion perpendicular to the chain direction is $`\mathrm{\Delta }=2.51`$ meV. BaCu2Si2O7 orders antiferromagnetically at $`T_N=9.2`$ K$`=0.033J/k_\mathrm{B}`$ with a zero-$`T`$ saturation moment of $`m_0=0.15`$ $`\mu _\mathrm{B}`$ parallel to the crystallographic $`c`$ axis.

## II Experimental procedures

In the present study we employed the same basic principle of using a tuneable horizontal magnetic field to determine the polarization of magnetic excitations in BaCu2Si2O7 with unpolarized neutrons, as described in Ref. Zhe, a. However, the new experimental setup included several significant improvements compared to that used previously. First, we utilized a different horizontal field magnet with a much more open coil construction, that allowed almost unrestricted scattering geometries within the horizontal plane. This enabled us to collect the data in a series of conventional constant-$`Q`$ and constant-$`E`$ scans, which was not possible in the highly restrictive geometry used before. Second, the larger diameter of the magnet bore made it possible to mount the sample with a high-symmetry reciprocal-space crystallographic $`(a,c)`$ plane horizontal, rather than having a scattering plane defined by some low-symmetry vectors as in previous studies. Third, the experiments were carried out at the IN22 instrument installed at Institut Laue Langevin in Grenoble, France. This instrument boasts a much higher neutron flux which accelerated the data collection rate considerable, while reducing statistical errors.

All data were collected using a 14.7 meV fixed-final energy configuration with PG (pyrolitic graphite) $`(002)`$ reflections employed in the vertical-focusing monochromator and flat analyzer. A PG filter was installed after the sample to eliminate higher-order beam contamination. The supermirror neutron guide provided effective pre-monochromator beam collimation. Soller collimators with a horizontal acceptance of $`60^{}`$ were installed before and after the sample. No dedicated collimation devices were used between analyzer and detector. The measurements were performed at momentum transfers $`(0,k,l)`$ in the vicinity of the 1D AF zone-center $`l=1`$, for $`k=1\mathrm{}0`$. The main advantage of working around $`l=1`$ (as opposed to $`l=3`$, as in previous studies) is a smaller intensity penalty due to the magnetic form factor of Cu2+, and the negligible small 3D modulation of the dynamic structure factor due to the slightly zigzag structure of the spin chains.222In other words, only the first term in Eq. (3) of Ref. Zhe, b is of any importance in the studied $`𝐪`$-range. The tradeoff is limitations on the energy transfer (up to 12 meV in the present experiment) imposed by kinematic constraints on the scattering geometry.

Each data set was measured for two values of magnetic field applied along the crystallographic $`c`$ axis, $`H_1=1.5`$ T and $`H_2=2.2`$ T. These field values were chosen to be below and just above a spin-flop transition at $`H_c=2.0`$ T, respectively.Tsukada et al. (2001); Zheludev et al. (2002) The transition involves a re-orientation of the ordered staggered magnetization in the system.Zheludev et al. (2002) As explained in Ref. Zhe, a, this leads to a drastic change in the polarization-dependent part of the scattering cross section for unpolarized neutrons. The effect on the scattering intensity from longitudinal (parallel to the ordered moment) and transverse (perpendicular to the ordered moment) spin fluctuations is different, which allows us to separate the two components. In general, the measured intensity can be expanded as:

$`I(𝐪,\omega )`$ $``$ $`S^{}(𝐪,\omega )(1+\mathrm{cos}^2\alpha _𝐪)`$ (1)
$`+`$ $`S^{}(𝐪,\omega )\mathrm{sin}^2\alpha _𝐪+(𝐪,\omega ).`$
In this equation $`S^{}(𝐪,\omega )`$ and $`S^{}(𝐪,\omega )`$ are the magnetic dynamic structure factors for transverse and longitudinal polarizations, respectively. The wave vector dependent angle $`\alpha _𝐪`$ is measured between the momentum transfer $`𝐪`$ and the direction of ordered moment. The orientations of the latter was previously determined using neutron diffraction in both the low-field (along the $`c`$ axis) and in the spin-flop states (roughly along $`a`$), so $`\alpha _𝐪`$ is a known quantity for every scan measured. The quantity $`(𝐪,\omega )`$ is the polarization-independent background determined separately, as discussed below. In our measurements $`S^{}(𝐪,\omega )`$ and $`S^{}(𝐪,\omega )`$ could thus be extracted from pairs of scans at $`H_1`$ and $`H_2`$ by solving a set of two coupled linear equations for each point.

For this procedure to work, the exact knowledge of $`(𝐪,\omega )`$ is required. $`(𝐪,\omega )`$ includes both intrinsic (coherent and incoherent nuclear scattering in the sample) and extrinsic (scattering in the sample holder, magnet, etc.) contributions. In our previous experiments only the latter part was measured. This was accomplished by repeating all scans on an empty sample container. In the present work we adopted a different approach to measure both components. With the sample in place, background scans were collected at wave vectors far from the 1D AF zone-center, at $`l=1.2`$ or $`l=0.8`$. Due to the very steep dispersion of magnetic excitations along the chain axis, no magnetic signal is expected at these positions in the energy range covered in our experiments. In all cases the background signal was measured at both field values $`H_1`$ and $`H_2`$, but was found to be field-independent, as expected.

The main assumption behind the “spin flop” polarization analysis is that the magnetic field needed to induce the transition is weak on the energy scale set by the strength of relevant inter-chain interactions, the experimental energy range, and the energy resolution of the spectrometer. In other words, in Eq. (1), it is only the angle $`\alpha _𝐪`$ that changes on going through the spin-flop transition, while the structure factors $`S^{}(𝐪,\omega )`$ remain unaffected. The validity of this assumption for the type of measurements performed in this work was argued in detail in Ref. Zhe, a.

## III Experimental results

Typical raw data sets measured in constant-$`Q`$ and constant-$`E`$ modes at $`T=1.5`$ K are shown in Fig. 1. At energies in excess of about $`2\mathrm{\Delta }`$ the scattering is practically unaffected by the phase transition (Fig. 1b). The contrast in inelastic intensity measured at two different field values is most apparent at energy transfers of about $`\mathrm{\Delta }`$( Fig. 1a and c). Separating the longitudinal and transverse contributions as described in the previous section yields the constant-$`Q`$ scans shown in Figs. 24. The evolution of the instrumental FWHM resolution ellipsoid in the course of each scan is shown in the right part of each figure. Typical constant-$`E`$ data are shown in Fig. 5. A contour and false color plot based on a series of 10 such scans taken with 1 meV energy step is shown in Fig. 6.

Certain important features of the measured transverse and longitudinal dynamic structure factors can be identified even without a quantitative data analysis. An important experimental observation is that longitudinal excitations show a steep dispersion along the chains. As can be seen in Fig. 6, the corresponding spin velocity is the same as for transverse-polarized spin waves. Furthermore, at high energy transfers (above $`7`$ meV) the scattering is almost polarization-independent to within experimental accuracy and resolution (Figs. 25). Such behavior is consistent with our general expectation that inter-chain interactions become almost irrelevant at energies well above the gap energy $`\mathrm{\Delta }`$. The dynamic structure factor in this regime is as in isolated chains, and is therefore almost isotropic.

At smaller energy transfers the structure factors for longitudinal and transverse polarizations are noticeably different. As observed in previous detailed studies,Zhe (b) transverse-polarization constant-$`Q`$ scans are characterized by a sharp spin wave peak, whose position and intensity is strongly dependent on momentum transfer $`𝐪_{}`$ in the direction perpendicular to the spin chains. The effect of this pronounced dispersion can be seen in Figs. 2a–4a. In contrast, longitudinal-polarized scans lack the sharp component and are almost independent of $`𝐪_{}`$ (Figs. 2b–4b). Such behavior is reminiscent of that for the transverse-polarized continuum that also shows very little variation with $`𝐪_{}`$.Zhe (b)

## IV Theory

Before discussing the quantitative analysis of the experimental data we shall describe the application of the chain-MF/RPA approach to the problem of weakly coupled chains in BaCu2Si2O7.

### IV.1 Hamiltonian and definitions

Following Refs. Ken, ; Zhe, b the spin Hamiltonian for BaCu2Si2O7 is written as:

$`H`$ $`=`$ $`H_{\mathrm{chains}}+H^{},`$
$`H_{\mathrm{chains}}`$ $`=`$ $`J{\displaystyle \underset{i,j,n}{}}𝐒_{i,j,n}𝐒_{i,j,n+1},`$
$`H^{}`$ $`=`$ $`{\displaystyle \underset{i,j,n}{}}J_x𝐒_{i,j,n}𝐒_{i+1,j,n}+J_y𝐒_{i,j,n}𝐒_{i,j+1,n}`$ (2)
$`+J_3𝐒_{i,j,n}\left(𝐒_{i+1,j+1,n}+𝐒_{i+1,j1,n}\right).`$
The Fourier transform of the inter-chain coupling is defined as

$`J^{}(𝐪)`$ $`=`$ $`J_x\mathrm{cos}(q_x)+J_y\mathrm{cos}(q_y)`$ (3)
$`+J_3\left[\mathrm{cos}(q_x+q_y)+\mathrm{cos}(q_xq_y)\right].`$
In order to comply with the formalism of Refs. Sch, ; Ess,  it is convenient to introduce new spin variables $`\stackrel{~}{S}^\alpha `$:

$`S_{i,j,n}^x=\stackrel{~}{S}_{i,j,n}^x,S_{i,j,n}^\alpha =(1)^j\stackrel{~}{S}_{i,j,n}^\alpha ,\alpha =y,z.`$ (4)
The transformation (4) leaves $`H_{\mathrm{chains}}`$ invariant, but flips the signs of $`J_y`$ and $`J_3`$ in the interaction of the $`y`$ and $`z`$ components of the spin operators in $`H^{}`$. The staggered magnetization at $`T=0`$ is defined as

$`\stackrel{~}{S}_{i,j,n}^\alpha `$ $`=`$ $`\delta _{\alpha ,z}(1)^nm_0.`$ (5)
### IV.2 Chain-MF and field-theoretical results for a single chain

The first step in the chain-MF/RPA is a mean-field decoupling of the inter-chain interaction $`H^{}`$:Sca

$`\stackrel{~}{S}_{i,j,n}^\alpha =\stackrel{~}{S}_{i,j,n}^\alpha +\delta \stackrel{~}{S}_{i,j,n}^\alpha ,`$ (6)
where $`\delta \stackrel{~}{S}_{i,j,n}^\alpha `$ denote (small) fluctuations around the expectation value. Substituting (6) in $`H^{}`$ we obtain a mean-field Hamiltonian

$`H_{\mathrm{MF}}`$ $`=`$ $`{\displaystyle \underset{i,j}{}}{\displaystyle \underset{n}{}}J\stackrel{~}{𝐒}_{i,j,n}\stackrel{~}{𝐒}_{i,j,n+1}+h(1)^n\stackrel{~}{S}_{i,j,n}^z,`$
$`h`$ $`=`$ $`2(J_xJ_y2J_3)m_0J^{}m_0.`$ (7)
The Hamiltonian (7) describes an ensemble of uncoupled spin-$`\frac{1}{2}`$ Heisenberg chains in a staggered magnetic field

$$H_{1\mathrm{d}}=\underset{n}{}J\stackrel{~}{𝐒}_n\stackrel{~}{𝐒}_n+h(1)^n\stackrel{~}{S}_{n+1}^z.$$
(8)
The next step is to find a solution for an isolated chain in an external field $`h`$. Since in the limit of weak inter-chain coupling the latter is expected to be small compared to $`J`$, it is possible to determine dynamical correlation functions at low energies $`\mathrm{}\omega J`$ by means of field theory methods. A standard bosonization analysis gives the following scaling limit of (8):

$`_{1\mathrm{d}}`$ $`=`$ $`{\displaystyle 𝑑x\left[\frac{v}{2}\left(_x\varphi \right)^2+\frac{1}{2v}\left(_t\varphi \right)^2+Ch\mathrm{cos}(\sqrt{2\pi }\varphi )\right]}.`$
In this formula $`v=\pi Ja_0/2`$ is the spin velocity of the spin-1/2 Heisenberg chain333$`a_0`$ is the period of the spin chains that for BaCu2Si2O7 is equal to $`c/2`$. and $`C`$ is a non-universal constant that was calculated in Ref. Lukyanov and Zamolodchikov, 1997. The model (LABEL:SGM) is known as the quantum Sine Gordon model (SGM) and is exactly solvable. The spectrum is formed by scattering states of four particles, called soliton $`s`$, antisoliton $`\overline{s}`$, breather $`B_1`$ and breather $`B_2`$. The breathers themselves are soliton-antisoliton bound states. All four particles have gapped relativistic dispersion relations:444In Ref. Ess,  the mass gap $`\mathrm{\Delta }`$ is denoted as $`M`$.

$`E_\alpha `$ $`=`$ $`\mathrm{\Delta }\mathrm{cosh}\theta ,P_\alpha ={\displaystyle \frac{\mathrm{\Delta }}{v}}\mathrm{sinh}\theta ,\alpha =s,\overline{s},B_1,`$
$`E_{B_2}`$ $`=`$ $`\sqrt{3}\mathrm{\Delta }\mathrm{cosh}\theta ,P_{B_2}={\displaystyle \frac{\sqrt{3}\mathrm{\Delta }}{v}}\mathrm{sinh}\theta .`$ (10)
Using the integrability of the SGM it is possible to determine correlation functions by exact methods. As described in Ref. Affleck and Oshikawa, 1999, the expectation value of the staggered magnetization can be calculated from the results of Ref. Lukyanov and Zamolodchikov, 1997:

$`m_0`$ $`=`$ $`C\mathrm{cos}\sqrt{2\pi }\varphi c\left({\displaystyle \frac{h}{J}}\right)^{\frac{1}{3}}\left[\mathrm{ln}\left({\displaystyle \frac{J}{h}}\right)\right]^{\frac{1}{3}},`$
$`c`$ $`=`$ $`{\displaystyle \frac{2^{\frac{2}{3}}}{3\sqrt{3}\pi }}\left[{\displaystyle \frac{\mathrm{\Gamma }(\frac{3}{4})}{\mathrm{\Gamma }(\frac{1}{4})}}\right]^{\frac{4}{3}}\left[{\displaystyle \frac{\mathrm{\Gamma }(\frac{1}{6})}{\mathrm{\Gamma }(\frac{2}{3})}}\right]^2.`$ (11)
Equation (11) is the self-consistency equation of the MF approximation (recall that $`h=m_0J^{}`$) and is easily solved for $`m_0`$:

$`m_0`$ $``$ $`A_1\left[{\displaystyle \frac{J^{}}{J}}\mathrm{ln}\left({\displaystyle \frac{2.58495J}{J^{}}}\right)\right]^{\frac{1}{2}},`$
$`A_1`$ $`=`$ $`{\displaystyle \frac{\sqrt{2}}{3^{\frac{7}{4}}\pi ^{\frac{3}{2}}}}\left[{\displaystyle \frac{\mathrm{\Gamma }(\frac{3}{4})}{\mathrm{\Gamma }(\frac{1}{4})}}\right]^2\left[{\displaystyle \frac{\mathrm{\Gamma }(\frac{1}{6})}{\mathrm{\Gamma }(\frac{2}{3})}}\right]^30.294691.`$ (12)
We note that the constant $`2.58495`$ should not be taken seriously as we have ignored subleading logarithmic corrections. The result (12) is found to be in good agreement (for small $`J^{}/J`$) with a phenomenological expression obtained from quantum Monte-Carlo simulations in Ref. Sandvik, 1999. The soliton gap as a function of the staggered field $`h`$ has been calculated in Refs. Essler, 1999; Affleck and Oshikawa, 1999. Expressing $`h`$ in terms of $`m_0`$ by (7) and then using (12) we obtain

$`{\displaystyle \frac{\mathrm{\Delta }}{J}}`$ $``$ $`A_2{\displaystyle \frac{J^{}}{J}}\left[\mathrm{ln}\left({\displaystyle \frac{2.58495J}{J^{}}}\right)\right]^{\frac{1}{2}},`$
$`A_2`$ $`=`$ $`{\displaystyle \frac{1}{3\pi }}\left[{\displaystyle \frac{\mathrm{\Gamma }(\frac{3}{4})}{\mathrm{\Gamma }(\frac{1}{4})}}\right]^2\left[{\displaystyle \frac{\mathrm{\Gamma }(\frac{1}{6})}{\mathrm{\Gamma }(\frac{2}{3})}}\right]^30.841916.`$ (13)
Note that this result is at variance with that of Ref. Sch, , where it was reported that (in our notations)

$$\mathrm{\Delta }\frac{6.175}{4}J^{}=1.544J^{}.$$
(14)
The polarization-dependent dynamic structure factors of interest to us in the present study are directly related, through the fluctuation-dissipation theorem, to the imaginary parts of the corresponding dynamic susceptibilities. For a single spin chain in a self-consistent staggered mean field the latter were derived in Ref. Ess, , and are expressed in terms of a spectral sum over intermediate states with one, two, three, etc. particles. In the energy range that we are interested in here ($`\mathrm{}\omega 5\mathrm{\Delta }`$), the contributions due to intermediate states with three or more particles are negligible. With all contributions from intermediate states with at most two particles taken into account, the expressions for the dynamic susceptibilities are:

$`\stackrel{~}{\chi }_{1\mathrm{d}}^{}(\omega ,\pi +q)={\displaystyle \frac{2|F_1|^2}{\mathrm{\Delta }^2s^2iϵ}}`$
$`{\displaystyle _0^{\mathrm{}}}{\displaystyle \frac{d\theta }{\pi }}{\displaystyle \frac{2|F_+^{\mathrm{cos}}(\theta )|^2+|F_{11}^{\mathrm{cos}}(\theta )|^2}{s^2[2\mathrm{\Delta }\mathrm{cosh}(\theta /2)]^2+iϵ}},`$
$`{\displaystyle _0^{\mathrm{}}}{\displaystyle \frac{d\theta }{\pi }}{\displaystyle \frac{|F_{22}^{\mathrm{cos}}(\theta )|^2}{s^2[\sqrt{12}\mathrm{\Delta }\mathrm{cosh}(\theta /2)]^2+iϵ}},`$ (15)
$`\stackrel{~}{\chi }_{1\mathrm{d}}^{}(\omega ,\pi +q)={\displaystyle \frac{2|F_2|^2}{3\mathrm{\Delta }^2s^2iϵ}}`$
$`{\displaystyle _0^{\mathrm{}}}{\displaystyle \frac{d\theta }{\pi }}{\displaystyle \frac{2|F_+^{\mathrm{sin}}(\theta )|^2}{s^2[2\mathrm{\Delta }\mathrm{cosh}(\theta /2)]^2+iϵ}}`$
$`{\displaystyle _0^{\mathrm{}}}{\displaystyle \frac{d\theta }{\pi }}{\displaystyle \frac{2|F_{12}^{\mathrm{sin}}(\theta )|^2}{s^24\mathrm{\Delta }^2(1+\frac{\sqrt{3}}{2}\mathrm{cosh}\theta )+iϵ}}.`$ (16)
Here $`s^2=\mathrm{}^2\omega ^2v^2q^2/a_0^2`$ and the functions $`F_{ϵ_1ϵ_2}^{\mathrm{sin}}(\theta )`$, $`F_{ϵ_1ϵ_2}^{\mathrm{cos}}(\theta )`$ are determined in Ref. Ess,  up to an overall constant factor denoted by $`Z`$. Analytic expressions for the constants $`|F_{1,2}|^2`$ are also given in Ref. Ess,  and have the numerical values of

$`|F_1|^20.0533Z,|F_2|^20.0262Z,`$ (17)
Using recent theoretical advances Lukyanov and Zamolodchikov (1997); Affleck and Oshikawa (1999) it is possible to calculate the normalization $`Z`$ with good accuracy although we do not need it in the present calculation (see below). Note that both the longitudinal and transverse dynamic susceptibilities feature single-mode and continuum contributions. In the transverse polarization channel the single-mode excitations have the energy $`\mathrm{\Delta }`$, while the energy of the longitudinal mode is $`\sqrt{3}\mathrm{\Delta }`$. Regardless of polarization, the continuum has a gap of $`2\mathrm{\Delta }`$. While the transverse continuum is singular on its lower bound, the one in the longitudinal polarization channel is not.

### IV.3 Coupled chains and the RPA

In the final stage of the described approach the dynamic susceptibilities of coupled chains (in the original spin variables) are expressed as

$`\chi _{3\mathrm{d}}^\alpha (\omega ,𝐪)`$ $`=`$ $`{\displaystyle \frac{\stackrel{~}{\chi }_{1\mathrm{d}}^\alpha (\omega ,q_{})}{1J^{}(𝐪)[\stackrel{~}{\chi }_{1\mathrm{d}}^\alpha (\omega ,q_{})+\mathrm{\Sigma }^\alpha (\omega ,𝐪)]}},`$
where $`\alpha =,`$. In Eq. (LABEL:RPA) $`\mathrm{\Sigma }^{}`$ and $`\mathrm{\Sigma }^{}`$ are the self-energies that are expressed in terms of integrals involving three-point, four-point etc correlation functions of spin operators. The analogous expressions in the disordered phase were derived in Refs Bocquet, 2002; Irkhin and Katanin, 2000. To date, the relevant multipoint correlation function have not been calculated for the Sine-Gordon model. The essence of the RPA is to simply neglect the self-energies.Sca ; Sch  In other words, one sets

$`\mathrm{\Sigma }^{}=\mathrm{\Sigma }^{}=0.`$ (19)
One problem is that in this approximation the transverse susceptibility will not have a zero-frequency spin wave pole at the 3D magnetic zone-center, as it should, spin waves being the Goldstone modes of the magnetically ordered state. In order for the pole to be exactly at $`\omega =0`$ the full self-energy $`\mathrm{\Sigma }^{xx}`$ must, in fact, be included. A work-around was suggested by Schulz.Sch  Assuming the RPA is a reasonably good approximation, the pole in $`\chi _{3\mathrm{D}}^{}(\omega ,0,\pi ,\pi )`$ will occur at a very small frequency. As a result,

$`1J^{}(0,\pi )\stackrel{~}{\chi }_{1\mathrm{d}}^{}(0,\pi ).`$ (20)
The idea is to replace (20) by an equality

$`1=J^{}(0,\pi )\stackrel{~}{\chi }_{1\mathrm{d}}^{}(0,\pi ),`$ (21)
and then use (21) to fix the overall normalization of $`\stackrel{~}{\chi }_{1\mathrm{d}}^{}(\omega ,q)`$. Following this logic, we may carry out the integral in (15) numerically and obtain

$`Z7.994{\displaystyle \frac{M^2}{J^{}(0,\pi )}}.`$ (22)
Now it is a simple matter to determine $`\chi _{3\mathrm{d}}^\alpha (\omega ,𝐤,q)`$ by evaluating the 1D susceptibilities numerically and then inserting them into (LABEL:RPA).

As explained in Ref. Ess, , the resulting dynamic susceptibility for transverse spin fluctuations in coupled chains contains a pair of spin wave excitations that disperse perpendicular to the spin chains, and are, by design, gapless. The longitudinal mode also disperses in the direction perpendicular to the chains, but retains a non-zero gap at the 3D magnetic zone-center. Under the approximations made, the lower bounds of the continua remain at $`2\mathrm{\Delta }`$ and are independent of $`𝐪_{}`$, regardless of polarization. The singularity at the lower bound of the transverse-polarized continuum vanishes and persists only at the “magic” wave vector $`𝐪_0`$, such that $`J^{}(𝐪_0)0`$. For BaCu2Si2O7 $`𝐪_0=(0.5,0.5,1)`$. At $`𝐪_0`$ the dynamic structure factor is as for uncoupled chains in a staggered field and the gap $`\mathrm{\Delta }`$ can be observed directly.

### IV.4 Results for BaCu2Si2O7

The exchange parameters $`J`$, $`J_x`$, $`J_y`$ and $`J_3`$ for BaCu2Si2O7 are known with very good accuracy from the previously measured spin wave dispersion relation. Zhe (b) Using these numerical values the low-energy part of transverse and longitudinal structure factors were calculated for several wave vectors on the $`(0,k,1)`$ reciprocal-space rods using the chain-MF/RPA approximation described above. The results are visualized in Fig. 7. To improve the visual effect, any singularities in these plots were eliminated by convoluting the calculated profiles with a Gaussian kernel of a fixed FWHM of 0.2 meV. Note that this width is still considerably narrower than the typical resolution of a 3-axes instrument in our experiments. A comparison of these calculation results to actual neutron scattering data is the subject of the next section.

## V Analysis of experimental data

To better understand the experimental results and perform a quantitative comparison between measured and calculated dynamic structure factors one has to take into account the effects of experimental resolution. This is best done by fitting the data to a parametrized model cross section function numerically convoluted with the 4-dimensional resolution function of the instrument.

### V.1 A model cross section

In Ref. Zhe, b for this purpose we have successfully employed a model cross section designed to reproduce the main features of the chain-MF/RPA calculations. The first component of the fit function for transverse excitations represents the long-lived spin-waves and is written exactly as in chain-MF/RPA theory:

$`S_{\mathrm{SM}}^{}(𝐪,\omega )`$ $`=`$ $`A{\displaystyle \frac{[1\mathrm{cos}(\pi l)]}{2\omega _{}(𝐪)}}\times `$ (23)
$`\times `$ $`\left\{\delta \left[\omega \omega _{}(𝐪)\right]+\delta \left[\omega +\omega _{}(𝐪)\right]\right\}.`$
Here $`\omega _{}^2(𝐪)`$ is the spin wave dispersion relation given by:

$$\omega _{}^2(𝐪)=\frac{\pi ^2}{4}J^2\mathrm{sin}^2(\pi l)+\frac{\mathrm{\Delta }^2}{|J^{}|}\left[|J^{}|+2J^{}(𝐪)\right],$$
(24)
where $`J^{}(𝐪)`$ is defined by Eq. 3.

The second component of the fit function for transverse excitations approximates the continuum. We have previously found that, at least for wave vectors on the $`(0,k,1)`$ reciprocal-space rod, continuum scattering can be very well approximated by the “truncated Müller ansatz” (TMA) function:555In Ref. Zhe, b there is a a factor of 2 mistake in the quoted value of $`\alpha `$. Note also that $`\alpha `$ is measured in reciprocal energy units.

$`S_\mathrm{c}^{}(𝐪,\omega )`$ $`=`$ $`{\displaystyle \frac{\alpha A}{2}}{\displaystyle \frac{[1\mathrm{cos}(\pi l)]}{\sqrt{\omega ^2\frac{\pi ^2}{4}J^2\mathrm{sin}^2(q_{})}}}\times `$ (25)
$`\times `$ $`\theta \left(\omega ^2\mathrm{\Delta }_{c,}^2{\displaystyle \frac{\pi ^2}{4}}J^2\mathrm{sin}^2(\pi l)\right)`$
The TMA is plotted in a thin dotted lined in Figs. 7a–c for a direct comparison to our chain-MF/RPA result. Conveniently, given the experimental resolution width, the two functional forms are almost indistinguishable. This fact is illustrated in Fig. 8 that shows the transverse continuum obtained in the actual chain-MF/RPA calculation for $`𝐪=(0,0,1)`$ (solid line), along with the form 25 (dotted line), both profiles being numerically convoluted with the resolution function of the instrument. Resolution effects taken into account, an almost perfect match between the chain-MF/RPA calculation for BaCu2Si2O7 and Eqs. (23) and (25) can be obtained for the entire range of energy and momentum transfers covered in our experiments by choosing $`\mathrm{\Delta }_{c,}=5.0`$ meV and $`\alpha =0.17`$ meV-1.

Just like the transverse-polarized part, the fit function for longitudinal scattering is composed of a single-mode and a continuum components. The dispersion relation and dynamic structure factor for the single-mode contribution are written as:

$`S_{\mathrm{SM}}^{}(𝐪,\omega )`$ $`=`$ $`{\displaystyle \frac{\gamma }{2}}A{\displaystyle \frac{[1\mathrm{cos}(\pi l)]}{2\omega _{}(𝐪)}}{\displaystyle \frac{\mathrm{\Gamma }/\pi }{\left[\omega \omega _{}(𝐪)\right]^2+\mathrm{\Gamma }^2}},`$ (26)
$`\omega _{}^2(𝐪)`$ $`=`$ $`{\displaystyle \frac{\pi ^2}{4}}J^2\mathrm{sin}^2(\pi l)+\mathrm{\Delta }_{}^2+{\displaystyle \frac{\mathrm{\Delta }^2J^{}(𝐪)}{|J^{}|}}`$ (27)
These equations are a generalization of Eqs. (12) and (13) in Ref. Zhe, b, that allow for a damping of the longitudinal mode. The adjustable parameter $`\mathrm{\Delta }_{}`$ is the the energy of the longitudinal mode at the RPA “magic” point. The coefficient $`\gamma `$ is an adjustable parameter that determines the intensity ratio of longitudinal and transverse excitations, while $`A`$ is an overall intensity prefactor used for both polarizations (see Eqs. (4), (5), and (10) in Ref. Zhe, b). In Eq. (26) the $`\delta `$-function is replaced (for positive energy transfers) by a Lorentzian profile with a half-width at half height of $`\mathrm{\Gamma }`$.

The longitudinal-polarized excitation continuum was modelled using the same truncated Müller-ansatz cross section function as previously done for the transverse case:

$`S_\mathrm{c}^{}(𝐪,\omega )`$ $`=`$ $`{\displaystyle \frac{\beta A}{2}}{\displaystyle \frac{[1\mathrm{cos}(\pi l)]}{\sqrt{\omega ^2\frac{\pi ^2}{4}J^2\mathrm{sin}^2(q_{})}}}\times `$ (28)
$`\times `$ $`\theta \left(\omega ^2\mathrm{\Delta }_{c,}^2{\displaystyle \frac{\pi ^2}{4}}J^2\mathrm{sin}^2(\pi l)\right)`$
Note that, unlike in Ref. Zhe, b, we use separate relative intensity prefactors and (pseudo)gap energies for the transverse and longitudinal continua. By choosing $`\mathrm{\Delta }_{c,}=\mathrm{\Delta }_{c,}`$ and $`\beta =\alpha `$ one can accurately reproduce the chain-MF/RPA result for BaCu2Si2O7 to within resolution effects in the energy and momentum transfer range covered in the present study.

### V.2 Transverse polarization

As a first step in the quantitative data analysis, the two-component model cross section for transverse polarization was numerically convoluted with the calculated spectrometer resolution function and fit to the transverse components of all scans measured in this work (429 total scan points). The relevant parameters of the model, including the mass gap $`\mathrm{\Delta }=2.51(2)`$ meV, the inter-chain exchange constants $`J_x=0.460(7)\mathrm{meV}`$, $`J_y=0.200(6)\mathrm{meV}`$, $`2J_3=0.152(7)\mathrm{meV}`$, the in-chain exchange parameter $`J=24.1`$ meV, the continuum gap $`\mathrm{\Delta }_{c,}=4.8(2)`$ meV, and the ratio $`\alpha =0.20(3)`$ meV-1 of single-mode and continuum intensities, were determined previously with very good accuracy.Ken ; Zhe (b) In analyzing the present data, only the overall scaling factor was treated as an adjustable parameter. A good ($`\chi ^2=2.7`$) 1-parameter global fit to all the measured scans was obtained (heavy solid lines in Figs. 2a–4a and Figs. 5a–g. The hatched and greyed areas represent the continuum and single-mode components, respectively.

As mentioned in the previous section, our chain-MF/RPA theoretical result for BaCu2Si2O7 corresponds to fitting function parameters $`\mathrm{\Delta }_{c,}=2\mathrm{\Delta }=5.0`$ meV and $`\alpha =0.17`$ meV-1, which is in a remarkably good agreement with previous and current experiments. We conclude that for transverse polarization the chain-MF/RPA not only predicts the correct spin wave dispersion relation and continuum gap energy, but provides an accurate estimate for the intensity of the lower-energy part of the continuum.

### V.3 Longitudinal polarization

The agreement with theory is not nearly as good in the longitudinal polarization channel. In the chain-MF/RPA the LM is infinitely sharp and corresponds to $`\mathrm{\Gamma }0`$ in Eq. (26). The LM’s energy and intensity are given by $`\mathrm{\Delta }_{}=\sqrt{3}\mathrm{\Delta }`$, and $`\gamma 0.49`$. Our chain-MF/RPA calculation for the longitudinal continuum in BaCu2Si2O7 is very well approximated by Eq. (28) with $`\mathrm{\Delta }_{c,}=\mathrm{\Delta }_{c,}`$ and $`\beta =\alpha `$. Using these values in the model cross section convoluted with the resolution function of the spectrometer, we can simulate the measured scans as expected in the chain-MF/RPA model. These simulations are shown in solid lines in Figs. 2b–4b. The dark greyed area represents the longitudinal mode, and the hatched area is the continuum contribution. It is clear that at all values of $`𝐪_{}`$ the model fails to reproduce the observed longitudinal spectrum. The discrepancy is greatest at energy transfers below $`2\mathrm{\Delta }`$, where the chain-MF/RPA model predicts no scattering except that by the LM. At higher energy transfers the agreement between theory and experiment becomes progressively better.

Of course, much better fits to the experimental data can be obtained if the central energy $`\mathrm{\Delta }_{}`$, intensity prefactor $`\gamma `$ and intrinsic energy width $`\mathrm{\Gamma }`$ of the longitudinal mode are allowed to vary. The result of fitting this “damped LM” model globally to the entire data set for longitudinal polarization (358 data) is shown in Figs. 2b–4b in a dotted line, and corresponds to $`\chi ^2=1.5`$. The fit yields $`\mathrm{\Delta }_{}=2.1(1)`$ meV, $`\gamma =1.2(2)`$ and $`\mathrm{\Gamma }=1.5(2)`$ meV. This analysis confirms the main conclusion of the preliminary study of Ref. Zhe, a: to adequately describe the longitudinal scattering in BaCu2Si2O7 in terms of a “longitudinal mode” one has to assume a substantial intrinsic width, comparable to the mode’s central energy and to its separation from the continuum threshold. The “longitudinal mode” can therefore be no longer considered a separate feature, as it is merged with the strong continuum at higher energy transfers. The energy separation of single-mode and continuum excitations previously observed for transverse polarization is absent in the longitudinal channel. It is important to emphasize that the mismatch between theory and experiment involves more than simply a broadening of the LM. Experimentally one observed considerably more scattering below $`2\mathrm{\Delta }`$ energy transfer than the LM could provide in the chain-MF/RPA model. As a result, the refined value of $`\gamma `$ is almost 4 times larger than expected, and the “LM” is almost equal in intensity to a transverse spin wave.

The measured data can, in fact, be reproduced without including a single-mode longitudinal component in the cross section. This “continuum-only” model corresponds to $`\gamma =0`$, while $`\mathrm{\Delta }_{c,}`$ and $`\alpha _{}`$ are the adjustable parameters. Rather good global fits to 249 data points at $`k=0`$ are obtained with $`\mathrm{\Delta }_{c,}=2.0(1)`$ meV, $`\alpha _{}=0.22(0.01)`$ and $`\chi ^2=1.16`$. Scan simulations based on these parameter values are plotted in heavy solid lines in Fig. 5b,d,f, and h, and in a dash-dot line in Fig. 2b. The parameter $`\mathrm{\Delta }_{c,}`$ was fit separately for the constant-$`Q`$ scans at $`k=0.5`$ and $`k=1`$, yielding $`\mathrm{\Delta }_{c,}=1.8(1)`$ meV and $`\mathrm{\Delta }_{c,}=1.5(1)`$ meV, respectively. The results are shown in dash-dot lines in Figs. 3b and 4b. The variation of $`\mathrm{\Delta }_{c,}`$ as a function of $`𝐪_{}`$ corresponds to the dispersion of the longitudinal mode built into the “damped LM” model.

## VI Concluding remarks

Based on the neutron scattering results we can now give phenomenological description of the longitudinal excitations in weakly interacting quantum spin chains. There is no sharp longitudinal mode, but a broad asymmetric peak that is inseparable from the continuum at higher frequencies. This feature is practically independent of $`𝐪_{}`$, but has a steep dispersion along the chain axis. The scattering starts at energies well below $`2\mathrm{\Delta }`$, and its intensity at low energies is considerably greater than predicted by the chain-MF/RPA.

It appears that the established chain-MF/RPA model is at the same time remarkably good in predicting the transverse correlations of weakly-coupled chains, and sourly inadequate as far as longitudinal fluctuations are concerned. Admittedly, one can never entirely dismiss the possibility that the disagreement between theory and experiment in the latter case may, in fact, be due to some intrinsic flaw in the unconventional technique that we used for polarization analysis. However, having repeatedly scrutinized the measurement procedure, we were unable to identify any potential sources of systematic error that could account for the observed discrepancies with theoretical calculations. We thus conclude that the discrepancies stem from limitations of the theoretical method itself. Among the assumptions and approximations associated with the chain-MF/RPA approach, the most likely source of errors is the uncontrolled discarding of the self-energies in the RPA. The RPA, by definition, acts on bare (purely 1D) dynamic susceptibilities at particular wave vectors. It excludes interactions between particles, such as processes that involve a decay of a particle with momentum $`𝐪`$ into a pair of particles with momenta $`𝐪_1+𝐪_2=𝐪`$. The contributions of such processes to the susceptibility involve 1D correlation functions of three or more spin operators. For spin chains that are intrinsically gapped such processes are expected to be suppressed, in which case the RPA will be fully justified. We can expect the RPA to be an almost perfect description of weakly coupled ladders or Haldane spin chains. For weakly coupled $`S=1/2`$ chains however the mean-field gap $`\mathrm{\Delta }`$ is itself determined by $`J^{}`$. As a result, the transverse spectrum in RPA is gapless, regardless of $`J^{}/J`$. Hence a longitudinal excitation can always decay into a pair of transverse-polarized spin waves. The RPA fails by excluding this effect. Comparing the results of the present study to the ones reported in Ref.Lake et al., 2000 for $`\mathrm{KCuF}_3`$, the question arises why there is a longitudinal mode, albeit damped, in the latter material but not in $`\mathrm{BaCu}_2\mathrm{Si}_2\mathrm{O}_7`$. The main difference between the two materials is the strength of the interchain coupling: in BaCu2Si2O7 the ratio of the bandwidths perpendicular to the chains and along the chains is $`2\mathrm{\Delta }/\pi J0.066`$, whereas it is approximately $`0.2`$ for $`\mathrm{KCuF}_3`$. This may suggest that a sufficiently strong dispersion perpendicular to the chains is necessary in order to stabilize a damped longitudinal mode. It would be interesting to investigate this issue by determining the damping of the longitudinal mode in MF/RPA.

###### Acknowledgements.

Work at the University of Tokyo was supported in part by the Grant-in-Aid for COE Research “SCP coupled system” of the Japanese Ministry of Education, Culture, Sports, Science, and Technology. Oak Ridge National Laboratory is managed by UT-Battelle, LLC for the U.S. Department of Energy under contract DE-AC05-00OR22725. FHLE is supported by the DOE under contract number DE-AC02-98 CH 10886. We would like to thank S. Maslov, I. Zaliznyak and A. Tsvelik for illuminating discussions.