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# Experimental study of the spatial distribution of quantum correlations in a confocal Optical Parametric Oscillator

## I Introduction

To date, almost all the experiments investigating the quantum properties of the states of light produced by Optical Parametric Oscillators (OPO) have been performed through the measurement of the total intensity of the generated fields, obtained by integrating on the detector the whole wavefront intensity distribution. Such measurements have put in evidence the squeezed vacuum character of the output of a degenerate OPO below threshold Kimble , the quantum intensity correlations between the signal and idler beams (twin beams)Mertz , and the bright squeezing of the output of an optical parametric amplifier (OPA) Schiller  and of the pump beam reflected by an OPO Gao .

In the last years, the interest has turned to the spatial aspects of quantum fluctuations, in particular because they open new perspectives in the quantum information field : spatial features offer the possibility of parallel processing and multichannel operation, each part in a transverse section of a beam playing the role of a channel. The concepts of temporal squeezing and correlations of light beams as a whole have been extended to spatio-temporal properties for the local quantum fluctuations in the plane perpendicular to the propagation : squeezing of the temporal fluctuations inside a small part of the transverse plane, or temporal quantum correlations between different transverse areas of the beam are some of the manifestations of the transverse quantum properties of light. It has been shown that, in order to obtain strong spatial quantum effects, one needs to use multimode nonclassical states of light, in contrast to the single mode operation of the experiments quoted above. It has also been shown that such nonclassical multimode states can be used to improve the optical resolution Optical Resolution  and to measure small transverse displacements of a light beam below the standard quantum limit Small Disp ; Prl .
Our investigations of the spatial distribution of multimode states of light produced by OPOs are related to the pioneer studies of the stochastic spatial noise performed in gas lasers laserStochast , and more recently in semiconductor lasers (diode lasers and VCSELs) diodeMode , for which the spatial distribution of the quantum fluctuations of the output beam has been studied and interpreted in terms of a superposition of several Hermite-Gauss modes. They must also be connected to the studies of spatial quantum effects for the photons generated by spontaneous parametric down-conversion, at the photon counting level, for example to the recent demonstration of spatial antibunching Monken .
Parametric interaction in a non-linear crystal has been theoretically shown to be a very efficient source of multimode nonclassical states of light. Many theoretical studies Kolobov ; KolobovSokolov  have shown in particular that Optical Parametric Amplifiers (OPA) generate multimode squeezed states. OPOs have also been shown to be a source of multimode squeezed states provided that they use optical cavities with degenerate transverse modes : in particular, detailed theoretical investigations have been performed on sub-threshold OPOs in planar LugiatoGatti ; GattiLugiato , or quasi-planar cavities LugiatoMarzoli ; Spherical OPO .
From an experimental point of view, such cavities, which are close to instability, are quite difficult to handle and have very high oscillation thresholds. Confocal cavities are much easier to operate, and still exhibit interesting nonclassical transverse effects, such as multimode squeezing in the degenerate case below threshold Confocal Sqz . The multimode transverse operation of confocal OPOs above threshold has been theoretically investigated at the classical level Transv OPO , and experimentally put in evidence in Matthias , where it has been shown that the field emitted by a confocal OPO above threshold can be described as a superposition of a great number of $`TEM_{pq}`$ modes. The quantum description of this regime is unfortunately a difficult task, as the device switches from an uncoupled regime of the different transverse modes to a strongly coupled regime when passing from the sub-threshold emission to the regime of intense output.
This paper is devoted to the study of the spatial distribution of quantum fluctuations of such a device, and shows that it generates multimode nonclassical states of light. In section II, we give the precise definition of multimode quantum states of light. We present in section III a criterion unambiguously characterizing such states in our experimental configuration, namely the measurement of the spatial distribution of the intensity correlations between the signal and idler beams. Section IV presents the experimental setup and the procedure for measuring these correlations. Finally, section V presents the experimental results proving that the signal and idler beams emitted by the confocal OPO are multimode and spatially quantum correlated.

## II Intrinsic characterization of multimode and single mode beams

### II.1 Definition of single mode and multimode beams

In the studies on optical patterns, a beam is said to be multimode (in the $`TEM_{pq}`$ basis), when the far field patterns appear to be different from the near field patterns. Actually, this feature is a proof that the beam consists of a superposition of several $`TEM_{pq}`$ modes. The electric field positive frequency envelope of such a light beam, $`E^{(+)}(\stackrel{}{r},z)`$, expanded in the basis of $`TEM_{pq}`$ modes $`u_{p,q}(\stackrel{}{r},z)`$, writes :

$$E^{(+)}(\stackrel{}{r},z)=\underset{p,q}{}\alpha _{p,q}u_{p,q}(\stackrel{}{r},z).$$
(1)
with more than one $`\alpha _{p,q}`$ coefficient different from zero. Nevertheless, if the $`\alpha _{p,q}`$ coefficients are fixed (i.e. if we deal with a coherent superposition of modes and not a statistical one), one can always define a new mode $`v_0(\stackrel{}{r},z)`$ :

$$v_0(\stackrel{}{r},z)=\frac{E^{(+)}(\stackrel{}{r},z)}{E^{(+)}(\stackrel{}{r},z)^2d^2r}$$
(2)
and construct a new orthonormal basis of modes $`\{v_i(\stackrel{}{r},z)\}`$ in which $`v_0`$ is the first element. In this new basis, the field which appeared multimode in the Gauss-Laguerre basis, is proportional to $`v_0`$ and is then single mode. This simple reasoning at the classical level seems to show that the single or multimode character of a beam having a well defined and fixed amplitude distribution depends on the choice of the basis, and is not an intrinsic property. A $`TEM_{00}`$ laser beam is single mode in the Laguerre-Gauss basis, and multimode in the basis of transverse plane waves. We will show here that this statement is no longer true when one describes the beam at the quantum level.
We will now define a single mode quantum state of light in the following way : $`\mathrm{\Psi }>`$ is a single mode quantum state of light if there exists a basis of modes $`\{v_i(\stackrel{}{r},z)\}`$ in which it can be written as

$$\mathrm{\Psi }>=\mathrm{\Psi }_0>0>0>\mathrm{}$$
(3)
where the first transverse mode $`v_0`$, whatever its shape, is a non-vacuum state $`\mathrm{\Psi }_0>`$, and all the other modes are in the vacuum state. We will call intrinsic multimode states all states defined by a ket $`\mathrm{\Psi }>`$ which cannot be written as (3) in any basis. We will give in the next subsection a characterization of such single mode or multimode states which is independent of the basis used to describe it.
This striking difference between the classical and quantum description of a multimode state comes from the fact that a quantum state gives information on the mean electric field, but also on the statistical distribution of quantum fluctuations : a single mode beam is characterized by a well defined transverse variation which carries all its transverse information. Consequently, in such a state the transverse distribution of quantum fluctuations can be deduced from the transverse variation of the mode itself. In contrast, in intrinsic multimode states, the spatial distribution of fluctuations and correlations cannot be deduced from the structure of the mean field.
Let us finally mention that this problem is modified if one considers stochastic fields, i.e. having classical fluctuations. In this case also, the comparison between the spatial (or temporal) distribution of the mean field and of the classical fluctuations is still an intrinsic tool to determine whether the field can be considered as single mode or multimode diodeMode . We will not consider further this problem here.

### II.2 Characterization of a single mode quantum state

Let us consider a single mode state of light $`\mathrm{\Psi }>`$, written in the adapted basis $`\{v_i\}`$ as (3), and let us call $`\widehat{a}_i`$ the annihilation operator of photons in the mode $`v_i`$. Let us now introduce any other mode basis of the transverse plane $`\{w_j\}`$, and the corresponding annihilation operators $`\widehat{b}_j`$. There is a unitary transformation relating the two basis, and correspondingly the two sets of annihilation operators :

$$\widehat{b}_i=\underset{j}{}U_{ij}\widehat{a}_j$$
(4)
From equations (3) and (4), one deduces that :

$$\widehat{b}_i\mathrm{\Psi }>=U_{i0}\widehat{a}_0\mathrm{\Psi }_0>$$
(5)
We thus obtain a specific property of a single mode quantum state : the action on it of all the annihilation operators of any given basis of transverse modes gives vectors which are all proportional. One can show that this feature is a necessary and sufficient condition to be a single mode state TrepsThese . In contrast, for an intrinsic multimode state, there exists at least one basis of modes in which this property is not true. The condition for single mode states being very restrictive, the set of single mode states is a very small subset of the general Hilbert space. The complementary of this subspace, namely the set of intrinsic multimode states, is therefore much larger.
This characterization of single and multimode states appears to be quite mathematical, and seems difficult to implement experimentally. We give in the following a more convenient property of single mode states, which is not a necessary and sufficient condition, but which can be submitted to an experimental check with our set-up.

## III Characterization of single mode and multimode twin beams

### III.1 Partial measurement of intensity fluctuations on a single mode beam

Let us consider an intensity, or photon number, measurement using a detector of variable transverse area $`S_A`$. We have shown in reference Small Disp  that if the light is in a single mode state, the variance of the photon number fluctuations measured with this partial detector is given by :

$$\mathrm{\Delta }N_A^2=<N_A>+\frac{<N_A>^2}{<N_{tot}>^2}(\mathrm{\Delta }N_{tot}^2<N_{tot}>)$$
(6)
where $`<N_A>`$ is the mean number of photons detected on the area $`S_A`$, $`<N_{tot}>`$ the mean number of photons detected on the whole transverse plane, and $`\mathrm{\Delta }N_{tot}`$ the corresponding variance. One sees that the intensity noise normalized to shot noise, $`\frac{\mathrm{\Delta }N_A^2}{<N_A>}`$ varies linearly with the quantity $`T=\frac{<N_A>}{<N_{tot}>}`$. This formula can be understood by considering that in a single mode state the photons are randomly distributed in the transverse plane, so that a partial detection will introduce sorting noise in the detection of the photon number, exactly like when one introduces a linear loss of value $`T`$ in front of the detector. This intuitive picture is no longer true for multimode beams.

### III.2 Partial measurement of intensity correlations on single mode twin beams

In a non degenerate OPO, the emitted signal and idler fields present strong intensity correlations at the quantum level (“twin beams”). In particular, the variance of the difference $`N_{dif,tot}=N_{1,tot}N_{2,tot}`$ between the signal (labeled 1) and idler (labeled 2) intensities detected over the whole transverse plane is smaller than $`<N_{1,tot}>+<N_{2,tot}>`$, which is the shot noise for the sum of the signal and idler beams. When the beams produced by the OPO are both single mode, one can easily show from Small Disp  that the following formula, similar to (6), holds in case of a partial photodetection of signal and idler beams by two detectors having the same areas and positions $`S_A`$ in the two beams :

$$\mathrm{\Delta }N_{dif,A}^2=(<N_{1,A}>+<N_{2,A}>)+\frac{(<N_{1,A}>+<N_{2,A}>)^2}{(<N_{1,tot}>+<N_{2,tot}>)^2}(\mathrm{\Delta }N_{dif,tot}^2(<N_{1,tot}>+<N_{2,tot}>))$$
(7)
Similarly to the interpretation of formula (6), this formula can be understood by considering that in single mode twin beams there is no spatial correlations between the twin photons inside the signal and idler beams, the photons being randomly distributed inside the two beams. If, instead of small detectors, we use detectors with a broad enough area to detect the whole beams, but preceded by a diaphragm, or iris, of variable transmission $`T`$, expression (7) shows that in single mode twin beams the relative noise on the intensity difference, $`n_A=\frac{\mathrm{\Delta }N_{dif,A}^2}{<N_{1,A}>+<N_{2,A}>}`$, is a linear function of the transmitted mean intensity. In contrast, a nonlinear variation of this quantity will be a signature for intrinsic multimode twin beams, for which the twin photons are not randomly distributed inside the two beams.

### III.3 Partial measurement of intensity correlations on single mode twin beams undergoing different losses

We have assumed so far that the detected mean intensities of the output beams are always equal, even in partial photodetection. In real experiments, this is not exactly the case, and imbalances of several percents are commonly measured, especially in confocal OPOs, where the patterns observed in the signal and idler beams are different. The imbalance will affect the intensity fluctuations of the two beams in a different way. The imbalance of the whole beams is due to the fact that the signal and idler beams, produced in exact equal amounts in the nonlinear crystal, experience different losses in their propagation. Furthermore, in the case of a partial photodetection, one must also take into account that the signal and idler beams may have different shapes. It is important to precise the way to define the “twin character” of such imbalanced beams in a partial measurement. We will first introduce the normalized intensity difference noise $`n`$ when the whole beams are measured (Fig.1a). We will then consider a partial measurement (Fig.1b) and define the direct normalized intensity difference noise $`n_d`$, with no corrections, as it can be directly calculated from the measurement. We will finally define the corrected normalized intensity difference noise $`n_{corr}`$, an attempt to recover the value of $`n`$ from $`n_d`$ assuming that the beams are single mode.

Assuming that the mean signal and idler fields are real, we can write the field intensity operator, in the small fluctuation approximation, as :

$$\delta \widehat{i}_m=2E_m\delta \widehat{E}_mm\{1,2\}$$
(8)
where $`\delta \widehat{E}_m`$ is the quadrature fluctuation operator in the amplitude direction. We now introduce the normalized quantity $`n`$, which is the variance of the intensity difference fluctuations normalized to the total shot noise, and can be written as :

$$n=\frac{(\delta \widehat{i}_1\delta \widehat{i}_2)^2}{4(i_1+i_2)\mathrm{\Delta }^2E_v}$$
(9)
where $`\mathrm{\Delta }^2E_v`$ is the noise variance of the vacuum field. $`n>1`$ for beams with classical correlations (obtained for example by using beamsplitters) and $`n<1`$ for quantum correlated beams (“twin beams”). Let us now assume that the two beams are subject to losses before being incident on the photodetectors (Fig.1b). We call $`E_m^{out}`$ the fields which are incident on the photodetectors and $`i_m^{out}`$ their intensities, and $`n_d`$ the normalized variance of their intensity difference :

$$n_d=\frac{\mathrm{\Delta }^2i_d^{out}}{4(i_1^{out}+i_2^{out})\mathrm{\Delta }^2E_v}=\frac{(\delta \widehat{i}_1^{out}\delta \widehat{i}_2^{out})^2}{4(i_1^{out}+i_2^{out})\mathrm{\Delta }^2E_v}$$
(10)
In the transverse single mode case, losses of any origin and partial photodetection have the same effect on the fluctuations mechanism, identical to the effect of a beam splitter of transmission $`t_m`$ (m=1,2) (with $`t_m^2=i_m^{out}/i_m`$). The field intensity $`\widehat{i}_m^{out}`$ measured by the photodetectors present fluctuations $`\delta \widehat{i}_m^{out}`$(t) given by:

$$\delta \widehat{i}_m^{out}(t)=2t_n^2E_m\delta \widehat{E}_m+2t_m\sqrt{(1t_m^2)}E_m\delta \widehat{E}_{vm}m\{1,2\}$$
(11)
Knowing the effective loss coefficient $`t_m`$, it is possible to adjust the gain $`g_m`$ on the acquisition channels at the value $`1/t_m^2`$, as shown in fig. 1, so that the mean values of the corrected intensities $`g_m\widehat{i}_m^{out}`$ are equal to their value without losses $`\widehat{i}_m`$. If one assumes that the two beams are single transverse mode, it is possible to recover the original normalized intensity difference noise $`n`$ of eq. (9) by subtracting the effect of the vacuum fluctuations $`\delta \widehat{E}_{vm}`$. Writing $`\mathrm{\Delta }^2i_g^{out}`$ the fluctuations of the difference between the two acquisition channels :

$$\mathrm{\Delta }^2i_g^{out}=(g_1\delta \widehat{i}_1^{out}g_2\delta \widehat{i}_2^{out})^2$$
(12)
One easily shows that the quantity

$$n_{corr}=\frac{\mathrm{\Delta }^2i_g^{out}}{4(g_1i_1^{out}+g_2i_2^{out})\mathrm{\Delta }^2E_v}+1\frac{g_1^2i_1^{out}+g_2^2i_2^{out}}{g_1i_1^{out}+g_2i_2^{out}}$$
(13)
is equal to $`n`$ in the single transverse mode case. The two last terms of (13) correspond to the corrections arising from vacuum fluctuations introduced by the losses or the partial detection.

### III.4 Multimode twin beams

Since for single mode signal and idler beams $`n_{corr}=n`$, a constant value $`n_{corr}`$ with the transmittance $`t_m`$ for a partial measurement (or a linear variation of $`n_d`$) is a good indication (but not a proof) of the single mode character of the signal and idler mode beams. In contrast a non constant value of $`n_{corr}`$, or a nonlinear variation of $`n_d`$, with respect to the losses is a an unambiguous signature of the multimode character of the two beams generated by the OPO. Furthermore, if these quantities are smaller than 1, we can conclude that we are in presence of multimode nonclassical beams. Strictly speaking, as the vacuum correction in $`n_{corr}`$ has been derived assuming single mode beams, $`n_{corr}`$ do not anymore correspond exactly to a noise correlation in the case of multimode beams. Moreover, for a partial measurement, the mean intensity of both beams may be different, and neither $`n_d`$ nor $`n_{corr}`$ are perfectly suited for the exact characterization of quantum intensity correlation. For these reasons, in the case of a partial measurement of a multimode beam, more sophisticated criteria should be investigated, that will be developed in a forthcoming publication.

## IV Experimental setup

For OPOs operating in cavities with degenerate transverse modes, the formation of complex spatial structures has been theoretically Lugiato ; Maxi  and experimentally Matthias ; Sara Ducci  studied. Furthermore, quantum multimode operation of OPO has been already theoretically predicted LugiatoGatti . But, up to now, to our knowledge, there has been no experimental demonstration that the emission of an OPO is intrinsically multimode. The experiment presented here investigates the spatial distribution of the intensity correlation between the signal and idler beams emitted by a confocal OPO above threshold in order to identify their single mode or multimode character.

The setup, shown in Fig.2, can be divided in two parts: the triply resonant OPO and the acquisition system of the intensity fluctuations of the beams.

### IV.1 The triply resonant OPO

In order to match the desired requirements of power and stability of the experiment, a dedicated setup was made for the generation of the pump beam for the OPO. We used an ultrastable single mode Nd:YAG (yttrium aluminum garnet) laser with 350 mW of output power to lock a flash-lamp-pumped Nd:YAG laser operating in a ring cavity. This configuration Matthias ; Sara Ducci  gives a stable single mode beam with an output power of 3.5 W at 1064 nm. This beam is injected in a semi-monolithic frequency doubler, using a MgO:LiNbO<sub>3</sub> crystal and a concave mirror. The output of the second harmonic generator reproduces the frequency stability of the injected Nd:YAG laser and gives a total output power of 1.3 W at 532 nm. The pump is then injected inside the OPO with a waist equal to twice the $`TEM_{00}`$ waist of the OPO cavity mode like in reference Matthias .
The nonlinear crystal used inside the OPO is a walk-off compensated KTP (potassium titanyl phosphate) cut for type II phase matching. It is made by two 5 mm long crystals that are optically contacted, with their orientations compensating the walk-off effect. The triply resonant OPO uses two plane-concave mirrors, whose curvature is R = 100 mm. The input coupler (IC) has a transmittance of 10% for the pump (532 nm) and high reflectance for the Nd:YAG wavelength (1064 nm). The output coupler (OC) has a high reflectance at 532 nm and 1% transmittance at 1064 nm. Measured finesse value of the cavity with the crystal is 40 at 532 nm and 300 at 1064 nm and temperature is controlled such that signal (o-polarization) and idler (e-polarization) emitted by the OPO are close to frequency degeneracy. The cavity length can be tuned over a few free spectral ranges with a piezo-electric ceramic (PZT) attached to the input coupler. A coarse control of the length of the OPO is performed by means of translation stages fixed on both cavity mirrors. A fraction of the infrared output of the Nd:YAG laser can also be injected into the cavity for alignment purposes and to check the transverse mode separation. The OPO works close to the confocal configuration. In order to define the region of confocality, it is useful to remember that the distance L between two spherical mirrors for a confocal cavity depends not only on the ray of the concave surface but also on the refractive index of the medium inside the cavity. Therefore, considering the diffraction effects inside a crystal of length $`\mathrm{}`$ and refractive index $`n`$ in a cavity made by two spherical mirrors of ray $`R`$, the distance L between the mirrors for the confocality will be cavityLength

$$L_{conf}=R+\mathrm{}(11/n)$$
(14)
Since the refractive index for pump, signal and idler are different (respectively 1.7881, 1.8296 and 1.7467 xtalData ), the length of the cavity $`L_{conf}`$ for which the exact confocality is obtained, is different for each of the three modes (104.41, 104.28 and 104.53 mm). Transverse degeneracy is achieved when different transverse modes are resonant for the same cavity length. Due to the width of the resonance peaks, transverse degeneracy can be obtained even if the cavity is not exactly confocal. The range of confocality can be defined as the region of the cavity length where the fundamental and the first transverse even mode separation is smaller than the cavity bandwidth, and, following siegman , can be expressed as

$$|LL_{conf}|<\frac{\pi R}{2F}$$
(15)
where F is the finesse of the cavity. In our case, the range of confocality for signal, idler (and pump) is larger than the difference between the confocal lengths for the signal, idler and pump modes. Transverse degeneracy, essential for multimode emission, is then achievable at the same time for the three modes. Taking the average of the confocal length for signal and idler, we will consider the confocal length as $`L_{conf}=104.41mm`$, and express the cavity length in terms of $`\mathrm{\Delta }L=LL_{conf}`$.
Although the threshold for oscillation is quite low and around 30mW, significant thermal effects take place inside the cavity even close to threshold, because of the non-negligible absorption of the green light(3% at 532nm) and of infrared light (0,45% at 1064nm) : thermal lensing changes the total Gouy phase shift added to the wave in a round trip siegman  and even a sub-confocal cavity can become transverse degenerate if the pump power injected into it is sufficiently high. Therefore the confocality Matthias  is obtained for cavity lengths which are shorter than the confocal length $`L_{conf}`$, defined above for a ”cold” OPO with no thermal effects.

### IV.2 Detection and acquisition

The details of the setup used for studying the transverse distribution of noise in twin beams cavity can be seen in Fig.2. Near the output coupler, a dichroic mirror (DM1) is used to eliminate the residual green light transmitted through the OPO cavity. A small fraction (2%) of the infrared light that is reflected by this mirror and transmitted by a second dichroic mirror (DM2) is monitored by an InGaAs infrared photodetector $`D_{IR}`$. It is used to stabilize the OPO cavity by a servo-loop made by a high-voltage amplifier connected to the PZT, controlling the output power of the IR beam and stabilizing it during a time ranging from seconds to minutes of continuous operation. The green light reflected by DM1 and DM2 is detected by a visible photodetector $`D_G`$.
After the dichroic mirror (DM1) at the OPO output, a flipping mirror (M) allows either the imaging of signal and idler far and near fields on a screen, or the recording of their intensities by two InGaAs infrared four-quadrants photodetectors D1 and D2 (ETX505Q from Epitaxx). In this experiment, only one quadrant of each photodetector is used. Their quantum efficiency are very close (less than 1% difference) and equal to 90% $`\pm `$ 5%. In both configurations, polarizing beamsplitters (PBS) separate the signal and idler beams. Depending of the orientation of the half wave plate (HWP) placed before PBS1, signal and idler can be sent either to D1 or D2. During the measurement process, two irises of variable diameter are used to select in the far field a circular region of the output beam. Iris I1 is used to select a narrow circular region on both signal and idler, while iris I2 acts only on a single beam, either signal or idler. The lenses L1 and L2 are adjusted for each experiment in order to project the far field of the beam into the iris plane. The transmitted intensities are recorded and their fluctuations are monitored by a dedicated data acquisition system that is described below.
The data acquisition system used for the noise measurement differs from the usual method of direct measurement and subtraction of noise fluctuations (e.g. Ref.twinOPO ). The high frequency part of the photocurrent of each photodetector is amplified by a transimpedance amplifier and a broadband 36 dB amplifier. This signal is then mixed in an electronic demodulator at a frequency $`f_0`$ equal to 3.5 MHz which lies inside the cavity bandwidth for the infrared modes and above the excess noise frequencies of the output beams. The output of the mixer has an active low-pass filter, working at 100 kHz. This signal is registered by a fast Analog-to-Digital acquisition card for measuring the noise correlation of the photocurrents. We used two acquisition cards (PCI6110E from National Instruments) with four simultaneous measurement channels each and 12 bits for signal conversion. The signal is measured with a repetition rate of 200 kHz and registered in the computer. Remaining channels of the data acquisition system are used for the measurement of the average value of the photocurrent of each detector, as well as the photocurrents of detectors $`D_G`$ and $`D_{IR}`$. From the stored information of the average value and noise fluctuations of the photocurrent we can calculate the noise correlation of the intensity, and compare it to a previous calibration of the shot noise level made with a single output of the OPO or with the injected IR light from the Nd:YAG laser. This technique allows us to acquire in a very short time interval both the temporal fluctuations of a given Fourier component of the photocurrents and of their mean values, and then to postprocess the stored data. We can thus determine the different normalized quantities that we have defined earlier in that paper.

### IV.3 Experimental procedure

When the OPO oscillation is stabilized for a given cavity length, we perform two kinds of experiments. In the first experiment, we record the simultaneous noise distribution of the signal and idler beams by using the iris I1. We continuously close the iris I1 in 2s, while acquiring a long series of values of $`\delta i_s`$, $`\delta i_i`$, $`i_s`$, $`i_i`$, $`i_{IR}`$ and $`i_G`$ (6 series of 400,000 simultaneous values). We analyze the data by groups of 10,000 values, calculating for each group the average photocurrent value $`i_m`$ (m=1,2) and the normalized variances $`n_{corr}`$ and $`n_d`$. The corresponding vacuum fluctuation $`\mathrm{\Delta }^2E_v`$ was previously calibrated, and the electronic noise level is subtracted in the calculation of the variances. The transmittance of the iris for each series of 10000 points is defined as $`T=\frac{r}{r_{open}}`$ where $`r`$ is the ratio $`r=\frac{i_s+i_i}{i_{IR}}`$, and $`r_{open}`$ corresponds to the initial value of $`r`$ when the diaphragm is open. The normalized intensity difference noise variances $`n_{corr}`$ and $`n_d`$ are then plotted as a function of the transmission of the iris.
The second kind of experiments consists in setting iris $`I_2`$ on either the signal or the idler beam path and taking the unaffected beam as a reference. The procedure is identical to the previous one, except that $`r`$, for the iris on the signal beam, is defined as $`r=\frac{i_s}{i_{IR}}`$. Closing the iris $`I_2`$ attenuates only one of the beams, and produces a strong imbalance between the photocurrents of the two photodetectors, with a ratio ($`i_s/i_i`$) well out of the range 90% to 110%, which was typical in the previous conditions. With such a large imbalance, the value of $`n_d`$ deduced from the experiment does not give any quantitative information on the quantum correlations between the two beams. On the other hand, the calculation of the corrected value of the normalized noise $`n_{corr}`$ allows one to recover the information on the quantum correlation only in the case where the two beams are single mode. Therefore, in this second kind of experiments, we only calculate $`n_{corr}`$ as a function of the transmittance $`T`$.

## V Spatial distribution of the intensity correlation

### V.1 Experiments with the iris on both signal and idler beams

As described in the previous subsection, only iris $`I_1`$ is present. We have realized in this configuration two series of measurements: in the first one, the OPO oscillation is stabilized for a cavity length outside the confocality range, ensuring a $`TEM_{00}`$ output mode for signal and idler beams (ref.Matthias ; Sara Ducci ) ; in the second one, the cavity length is set to a shorter value, inside the confocality range, where complicated patterns can be observed in the signal and idler beams. While closing continuously the iris $`I_1`$, we record the transmitted intensity of the signal and idler modes and the normalized intensity noise difference variance $`n_d`$. The different normalized variances are then plotted as a function of the transmittance $`T`$. In the figures (3), the straight line represents the value of $`n_d`$ that could be calculated with a single mode beam having the same intensity correlation as the whole beam.

One observes that outside the confocality range, where the signal and idler fields are close to $`TEM_{00}`$, the calculated straight line fits well the experimental points. Moreover, for an open diaphragm, the normalized intensity difference noise variance is equal to 0.8, demonstrating significant quantum intensity correlations between signal and idler.
In the confocality range, where the signal and idler fields have more complicated, and different, transverse variations, one observes that the variation of $`n_d`$ is no longer linear with the transmittance, demonstrating that the emission of the OPO is multimode. Moreover, when the iris is open in that confocal configuration, the noise correlation is still below shot noise and close to the value obtained for the single mode emission: the quantum intensity correlations for the whole beams are preserved even for multimode beams. The increase of noise when the iris is closed shows that the intensity correlation is stronger in the outer parts of the beams than in the center. Unfortunately, with such an experiment it is difficult to describe more precisely the transverse distribution of correlations between the signal and idler beams.

### V.2 Experiments with the iris either on signal or idler beam

#### V.2.1 Single mode beams

For a length of cavity $`L=L_{conf}+5,6mm`$, where the OPO is supposed far from transverse degeneracy, we compared the results of the two kinds of experiments for the values of $`n_{corr}`$ as a function of the transmittance. The results are plotted in Fig.4.

For all those experiments, as the beam intensity on the photodetector is reduced, the fluctuations of the photocurrent approaches the electronic level. The dispersion in the calculated data increases when we close the iris. Typically, the variance of the intensity noise reached the dark noise level for an incident power of 0.2 mW, obtained with a typical iris transmittance of 10%.
One observes that all the experimental points are aligned on a horizontal straight line, with a mean value around 70%, which shows that the signal and idler beams are single mode, quantum-correlated, beams. The difference in the obtained level of noise for in fig 4b (69% and 75%) is certainly due to the fact that both experiments are performed at different moments, and therefore on possibly different longitudinal modes. The values of $`n_{corr}`$ remain stable during a single series of measurements when we close the iris.

#### V.2.2 Beams emitted by an OPO close to confocality

The length for the cavity is chosen to be very close to the exact confocal length $`L_{conf}`$. In this configuration complex structures appear in far and near fields of the signal and idler beams Matthias . We performed the same experiments and analysis as in the previous subsection, adding the image of the near field and the far field of the beam obtained with the CCD cameras. Fig.5a, b and c display respectively the results obtained for $`LL_{conf}=0.38,0.37`$ and $`0.62mm`$.

In the configuration of Fig.5a, one observes a nearly gaussian distribution of the idler beam and a non-gaussian distribution of the signal beam. When the iris $`I_2`$ is placed on the idler beam, $`n_{corr}`$ does not deviate in a clear way from a flat line, except for lower values of the iris transmittance. In this situation, the dispersion in the results increases, following the attenuation of the idler field intensity. When we set the iris on the signal path, the corrected noise deviates slightly from a constant value for values of the transmittance close to 50%. The same behavior can be observed when we perform the experiment with iris 1 on both signal and idler.
In the configuration of Fig.5b, more complex structures appear : a ring pattern can be seen in the outer part of the idler far field image. In the near field, complex structures appear for both signal and idler beams. In this situation, when iris $`I_1`$ is put on both beams, the corrected correlation noise $`n_{corr}`$ goes up to the shot noise level and stabilizes around this value. It is interesting to observe that the level of squeezing obtained is reduced, and the normalized noise for open iris starts at 85%. When the iris $`I_2`$ is put on the signal path and closed, $`n_{corr}`$ remains constant: from these observations, one can infer that the photons in the signal beams which are correlated to the idler photons are uniformly distributed inside the signal beam. On the contrary, when the diaphragm $`I_2`$ is set on the idler beam, the plot of $`n_{corr}`$ deviates from a flat line. In that case the results are very close to those obtained when the iris $`I_1`$ is set on both signal and idler, showing that most of the correlated photons in the idler are concentrated in the external part of the beam. The center part of the idler is constituted essentially of non-correlated photons.
In the configuration of Fig.5c, both signal and idler beams present a faint external ring out of the central maximum. In that case, the evolution of the noise when closing iris 1 or closing iris 2 for signal or idler are very close. Both signal and idler corrected noises $`n_{corr}`$ are reduced when one closes iris I2, showing that unlike the centers of signal and idler beams, their outer parts are quantum correlated. We see that these experiments give interesting indications on the details of transverse distribution of the correlations inside the beams. Unfortunately, the great quantity of modes oscillating simultaneously in a confocal cavity, which makes a theoretical approach of the system very difficult, and the lack of long term stability of the setup, which induces a large dispersion on the experimental results, prevent us from a more quantitative comparison between theory and experiments, which has been tackled in the case of the multimode VCSEL for example diodeMode .

## VI Conclusion

The results presented in this paper show that the intensity correlations in a confocal OPO are at the same time below the standard quantum limit and not uniformly distributed inside the beams, which is a clear evidence that the quantum state generated by such an OPO is a multimode nonclassical state of light. This experiment showed also that even in the multimode case, the intensity fluctuations of the signal and idler beams remain quantum correlated. It would be very interesting to find a theoretical explanation, even qualitative, to the fact that, in our experimental configuration, the central part of the beams seem to be less quantum correlated than the outer parts. We plan to extend this study in the case of an OPO working in a lower degeneracy cavity, where only some few modes are allowed to oscillate simultaneously. The small number of oscillating modes can lead to a detailed theoretical description of the system. Another interesting regime is the operation below threshold, where the comparison with theory is somehow simpler, but which requires a spatially resolved homodyne detection. For a more general point, this demonstration of an intrinsic multimode emission of signal and idler beams in the quantum regime of the above threshold OPO, opens interesting prospects for the study and use of transverse quantum effects in bright beams.

###### Acknowledgements.

Laboratoire Kastler-Brossel, of the Ecole Normale Supérieure and the Université Pierre et Marie Curie, is associated with the Centre National de la Recherche Scientifique.
This work was supported by the European Commission in the frame of the QUANTIM project (IST-2000-26019).
M. Martinelli, on leave from the Instituto de Fisica, Universidade de São Paulo, PO Box 66318 CEP, São Paulo-SP Brazil, wishes to thank Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES-BR) and Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP-BR) for funding. Agnès Maître and Sara Ducci are also at the pôle Matériaux et phénomènes quantiques FR CNRS 2437 Université Paris 7 Denis Diderot.


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# A low-dimensional spin 𝑆=1/2 system at the quantum critical limit: Na2V3O7

## Abstract

We report the results of measurements of the dc-susceptibility and the 23Na-NMR response of Na2V3O7, a recently synthesized, non metallic low dimensional spin system. Our results indicate that upon reducing the temperature to below 100 K, the V4+ moments are gradually quenched, leaving only one moment out of 9 active. The NMR data reveal a phase transition at very low temperatures. With decreasing applied field $`H`$, the critical temperature shifts towards $`T=0`$ K, suggesting that Na2V3O7 may be regarded as an insulator reaching a quantum critical point at $`H=0`$.

Low dimensional spin systems have recently been the subject of interest in a large number of research projects. The interest in these systems is manifest in many theoretical studies and much progress has been made in the synthesis of new compounds, which may be considered to be physical realizations of systems with one- and two-dimensional arrays of spins in the form of spin chains and ladders. Prominent examples include Cuprates and ternary Vanadium oxides. The physical properties of ladder compounds are largely determined by the number of legs of the individual ladders. Less clear is the influence of the topology of a system on its physical properties. It has been suggested that the topology, specifically the periodic boundary conditions in the rung direction, is essential for the low temperature properties of some ladder compounds.

In this respect, new opportunities emerged from recognizing that variations in the composition of some two-dimensional layered compounds result in microscopic tubular structures. In 1999 Millet and coworkers reported the synthesis of Na2V3O7, a material whose structure may be considered as composed by nanotubes oriented along the c-axis of the crystal lattice (space group P31c). The individual nanotubes, with an inner diameter of approximately 5 $`\AA `$, are formed by VO5 square pyramids, joined at their edges and corners. The Na ions, occupying different sites inside and around individual nanotubes, are bonded to the O ions of up to three nanotubes. From our experimental data we infer that, upon reducing the temperature from 100 to 10 K, the effective moment of the V4+ ions in Na2V3O7 is reduced by one order of magnitude. Below 20 K our data reveal that for $`H=0`$, this material is close to a phase transition at $`T=0`$ K.

Our Na2V3O7 samples consisted of ensembles of randomly oriented small crystals, with typical dimensions of 10$`\mu `$m$`\times `$10$`\mu `$m$`\times `$1mm. The material was grown under vacuum from melts with a starting composition of Na1.9V3O7. The susceptibility was measured using a commercial SQUID magnetometer and the NMR measurements employed standard spin-echo techniques. In Fig. 1 we display the temperature dependence of the molar magnetic susceptibility $`\chi (T)`$ of Na2V3O7, at temperatures between 1.9 and 315 K. Curie-Weiss type features of $`\chi (T)`$ of the form

$$\chi (T)=\chi _{dia}+\frac{C}{(T\mathrm{\Theta })}.$$
(1)
are discernible in two different temperature regimes. The background $`\chi _{dia}`$ was extracted from the high temperature data. Above 100 K, the best fit to the data, represented by the broken line in Fig. 1, yields $`C1.4`$ emu$``$K/mol and $`\mathrm{\Theta }=200\pm 30`$ K. These values imply an effective magnetic moment of 1.9 $`\mu _B`$ per V ion, close to the expected value for V ions in their tetravalent configuration, and substantial antiferromagnetic interactions between them. Below approximately 100 K, $`\chi (T)`$ changes gradually and at much lower temperatures, between 20 K and 1.9 K, the straight solid line in Fig. 1 implies that, with respect to the high-temperature values, $`C`$ and $`\mathrm{\Theta }`$ are reduced by approximately one and two orders of magnitude, respectively. These results confirm those obtained previously in higher external fields. Considering these data and magnetization curves $`M(H)`$ displayed in the inset of Fig. 1, Na2V3O7 exhibits neither a phase transition to a magnetically ordered state nor spin freezing phenomena at temperatures above 2 K. The reduction of the effective magnetic moment is most likely due to a gradual process of moment compensation via the formation of singlet spin configurations with most but not all of the ions taking part in the process. This may be the result of antiferromagnetic interactions and geometrical frustration. It is tempting to conjecture the compensation of 8 out of the 9 V spins along the “circumference” of the individual nanotubes of Na2V3O7. This is natural if the dominant interactions are between edge-sharing VO5 pyramids, but more difficult to understand if the dominant interactions are between corner-sharing pyramids, as suggested in Ref..

The 23Na-NMR response of Na2V3O7 was measured in different external magnetic fields. An example of the 23Na-NMR spectra is displayed in the inset of Fig. 2, measured at a fixed Larmor frequency of 31.728 MHz. No quadrupolar wings appear in our data because their intensity is distributed over a broad frequency range. In the inset of Fig. 2, only the unresolved signals of the Zeeman central transitions $`(+1/21/2)`$ from the 4 Na sites are observed near 2.825 T, suggesting rather modest differences, if any, in the hyperfine fields at the different Na sites. This is is consistent with a direct dipolar coupling between the V4+ moments and the Na nuclei (see below).

In the main frame of Fig. 2 we display the temperature evolution of the 23Na-NMR linewidth ($`FWHM`$), measured at a fixed frequency of 31.728 MHz. Between 50 to 150 K the NMR linewidth increases gradually with decreasing temperature by approximately a factor of 2. A more dramatic change occurs at lower temperatures where an increase of more than one order of magnitude is observed as the temperature is reduced to below 1 K. This type of behavior usually reflects magnetic-ordering or spin-freezing phenomena. In our case, the temperature-independent linewidth at low temperatures increases with increasing applied field (data not shown), not consistent with either a simple ferro- or antiferromagnetic order.

In Fig. 3 we display the full 23Na NMR linewidth at half maximum ($`FWHM`$) as a function of the molar magnetization $`M`$ for temperatures above 3.5 K. Note the linear relation $`FWHM=(16+0.308M)`$ Gauss. The NMR linewidth is caused by a distribution of internal static fields at the four inequivalent Na sites in randomly oriented grains. These fields arise from the polarization of the V moments in an external field and therefore, we assume $`FWHM\mathrm{\Delta }A_{hf}(M/\mu _BN_A)`$ where $`M`$ is the molar magnetization, $`\mathrm{\Delta }A_{hf}`$ is the width of the distribution of hyperfine field couplings, $`\mu _B`$ and $`N_A`$ are the Bohr magneton and Avogadro’s number, respectively. From the slope of the straight solid line in Fig. 3 we infer that $`\mathrm{\Delta }A_{hf}=1.7`$ kOe per $`\mu _B`$ of V moment.

In order to gain a numerical estimate we have calculated the dipolar fields at the 4 Na sites generated by equally polarized V moments of 1 $`\mu _B`$, with the polarization along several directions. The results suggest that for a randomly oriented powdered sample, the total width of the 23Na-NMR signal ought be of the order of 2.5 kOe. The experimental value $`\mathrm{\Delta }A_{hf}=1.7`$ kOe per $`\mu _B`$ of V moment is thus consistent with a direct dipolar hyperfine coupling between the V moments and the Na nuclei. The quoted result still applies, if the formation of singlet states occurs for most of the V moments in clusters of ions, as long as the uncompensated spins are mobile in these clusters. The characteristic frequencies of this motion need to exceed the NMR Larmor frequencies. If, however, after the singlet formation the arrangements of spins are static, the dipolar fields are expected to vary depending on the details of the arrangement. Preliminary estimates indicate that although the fields at individual Na sites change substantially, the spread of their values is of the same order of magnitude as mentioned above. This analysis suggests that the S=1/2 ground-state of the 9-spin ring, with one S=1/2 spin delocalized into a sea of four singlets, is the relevant effective degree of freedom at low energy.

We now turn to the results of measurements of the spin-lattice relaxation rate $`T_1^1`$ as a function of temperature in various external fields. The values of $`T_1^1`$ were extracted from fits to nuclear magnetization recovery curves $`m(t)`$, obtained as follows. First the populations of the central 23Na nuclear Zeeman levels ($`I=+1/2,1/2`$) were equalized by applying a long comb of rf-pulses. After a variable delay $`t`$ a $`\pi /2\pi `$ spin-echo sequence was applied and the corresponding spin-echo intensity, $`m(t)`$, was recorded. In the main frame of Fig. 4 we display $`T_1^1(T)`$ measured in a magnetic field of 68.13 kOe below 40 K. The complete data set, covering temperatures up to 300 K gives no indication of a gap in the spin excitation spectrum at temperatures above the liquid He temperature range. Besides the peak at $`T_a=2.3`$K (see Fig. 4), two additional significant anomalies in $`T_1^1(T)`$ appear at $`T_b=1`$ K (left inset) and at $`T_c=0.43`$ K (right inset). Below $`T_b`$, $`T_1^1(T)exp(\mathrm{\Delta }/k_BT)`$ with values $`\mathrm{\Delta }/k_B`$ of 3.8 and 0.28 K above and below $`T_c`$, respectively. The evolution of these features with magnetic field below 10 K is depicted in Fig. 5. This suggests a small gap in the spin excitation spectrum at these temperatures. Since we are dealing with an $`S=1/2`$ spin system any anisotropy indicates some coupling to other degrees of freedom. The anomalies in $`T_1^1(T)`$ are indicated by arrows at $`T_a`$, and by the two dotted lines for $`T_b`$ and $`T_c`$. Substantial field-induced changes in $`T_1^1(T)`$ are observed at low temperatures, confirming that the state below $`T_a`$ involves spin degrees of freedom. As is shown in the inset of Fig. 5, the transition temperature $`T_a`$, the onset of the spin gap at $`T_b`$ and the manifestation of the anisotropy by the feature at $`T_c`$ are all smoothly shifting to zero upon reducing the external field to zero. This indicates that Na2V3O7, an insulator, may be considered as being close to or at a quantum critical point at $`H=0`$.

Features of $`T_1^1(T)`$ as those shown in the main frame of Fig. 4 are usually associated with a cooperative phase transition which, in magnetic systems, involves spin (and in some cases lattice) degrees of freedom. At this point we assume that a cooperative phase transition occurs at $`T_a`$. From $`\chi (T)`$ at temperatures between 2 and 20 K, the related paramagnetic Curie temperature for Na2V3O7 is $`\mathrm{\Theta }=2.5`$ K. Hence it is tempting to conclude that a transition to an antiferromagnetic state occurs at $`T_a`$. However, as stated above, the behaviour of the line width is not consistent with antiferromagnetic ordering. Besides, the temperature dependence of $`T_1^1`$ below $`T_a`$ is not consistent with expectations for a common magnetically ordered system. In particular, the change of slope in $`T_1^1(T)`$ at $`T_b`$ suggests that the formation of a gap in the spin excitation spectrum of the ordered state does not occur at the transition, $`T_a`$, but only at the lower temperature $`T_b`$. This clearly does not match with $`T_1^1(T)`$ of ordinary varieties of ferro- or antiferromagnetically ordered systems.

These and previous arguments lead to the conclusion that in the observed phase transition, degrees of freedom other than those of the spin system are involved. The coupling of spins to lattice distortions often leads to complications. A recent example is Cu2(C5H12N2)2Cl4, a spin ladder system where magnetoelastic effects are believed to influence a rather rich $`[H,T]`$ phase diagram at low temperatures. In this case, two quantum critical points at two different external magnetic fields $`H_{c1}`$ and $`H_{c2}`$ have been identified. Since our data suggest a quantum critical point at or very close to $`H=0`$, any intrinsic gap in the V spin excitation spectrum of the paramagnetic phase ought to be tiny. This is compatible with the topology of the spin arrangement in Na2V3O7 and the observed reduction to one effective spin 1/2 per turn around the tubes at low temperatures. This type of spin tubes is generically expected to have a much smaller gap than even-leg ladders. This is particularly clear in the limit where the rung coupling $`J_{}`$ is much larger than the leg coupling $`J_{}`$, presumably the relevant one for both systems: In two-leg ladders, the gap opens on each rung and scales with $`J_{}`$, while in odd-leg ladders with periodic boundary conditions, the gap opens due to a dimerization along the tube and scales with $`J_{}`$.

In summary, from the results of our dc-susceptibility and 23Na-NMR measurements on Na2V3O7, we conclude that at high temperatures, all the V ions are in a tetravalent state and all related moments contribute to the magnetic susceptibility. This situation changes gradually below 100 K. Below 20 K a different paramagnetic state is established with only 1 out of 9 of the V magnetic moments contributing to the susceptibility. At much lower temperatures and in the presence of modest external magnetic fields, a phase transition occurs at a field-dependent transition temperature $`T_a`$. In the ordered phase, an anisotropic gap $`\mathrm{\Delta }`$ forms at temperatures distinctly below $`T_a`$. All energy scales characterizing this ordered state, $`i.e.`$, $`T_a`$, $`T_b`$ and $`T_c`$, shift towards $`T=0`$ K with decreasing external field $`H`$. We therefore conclude that Na2V3O7 may be considered as being very close to or at a quantum critical point at $`H=0`$. It is conceivable that this quantum critical point is analogous to the one that appears in gapped systems when the field is large enough to close the gap.

This work was financially supported by the Schweizerische Nationalfonds zur Förderung der Wissenschaftlichen Forschung.


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# Light quark masses from Domain Wall Fermions

## 1 INTRODUCTION

We report here results for the light and strange quark masses extracted from the quark mass dependence of the meson spectrum calculated using domain wall fermions  (DWF), see  for our notation and conventions, in the quenched approximation and renormalised using the non-perturbative renormalisation (NPR) technique developed by the Rome-Southampton group .

All the results presented will be from simulation using a lattice with spatial dimensions $`16^3\times 32`$ and a fifth dimension of size 16. The new results use the DBW2 gauge action  at $`\beta =0.87`$ and $`\beta =1.04`$ corresponding to $`a^11.3\mathrm{GeV}`$ and $`a^12\mathrm{G}\mathrm{e}\mathrm{V}`$ respectively. This action is chosen for its much smaller explicit chiral symmetry breaking when compared to other actions. The results will be compared with those of previous studies using the Wilson gauge action with $`\beta =6.0`$ . For $`\beta =0.87`$, $`M_5=1.8`$ was used and 53 and 100 configurations were collected for the NPR and hadron spectrum respectively, whereas for $`\beta =1.04`$, $`M_5=1.7`$ was used and 51 and 405 configurations were collected.

## 2 RENORMALISATION

Our final result will be the renormalised mass in the $`\overline{MS}`$-scheme at 2 GeV. The relation between this value and the bare mass, $`m_f`$, consists of several factors and may be written

$$m_{\mathrm{ren}}=Z^{\mathrm{match}}Z_m^{RI}\left(m_f+m_{\mathrm{res}}\right).$$
(1)
The residual mass, $`m_{\mathrm{res}}`$, occurs because of small explicit chiral symmetry breaking effects due to the finite extent of the fifth dimension. This we determined from the breaking term of the axial Ward-Takahashi identity . $`Z_m^{RI}`$ is the mass renormalisation factor in the RI/MOM-scheme which is calculated directly on the lattice using the method of the Rome-Southampton group  and then matched to the $`\overline{MS}`$-scheme at 2 GeV using a two-loop perturbative matching factor, $`Z^{\mathrm{match}}`$ .

For the NPR technique to be successful a “window” of momenta must exist for which contamination due to (low-momenta) condensate effects are small but also for which (high-momenta) lattice artifacts are suppressed. Previous work shows that when using DWF with the Wilson action at $`a^12\mathrm{G}\mathrm{e}\mathrm{V}`$ this window exists. In this work we confirmed that this is also the case for the DBW2 action and checked the feasibility of NPR at $`a^11.3\mathrm{GeV}`$.

While $`Z_m`$ may be calculated directly from the momentum-space quark propagator this approach has large systematic errors. Instead we consider the renormalisation of the flavour non-singlet local quark bilinear operator, $`\overline{u}\mathrm{\Gamma }d`$. The NPR technique provides a clean extraction of the ratio $`Z_\mathrm{\Gamma }/Z_q`$, where $`Z_q`$ is the quark renormalisation factor. Putting the value of $`Z_S/Z_q`$ (scalar) and $`Z_A/Z_q`$ (axial) together with the value of $`Z_A`$ calculated from the hadronic matrix element of the local and conserved axial currents with the pseudo-scalar density gives our final value for $`Z_S`$. This can then be used to calculate $`Z_m`$ as $`Z_S=1/Z_m`$.

An important check of the existence of a “window” may be made by dividing $`Z_S/Z_q`$ by the predicted running from 3-loop perturbation theory to produce a renormalisation group invariant (RGI) value. Fig. 1 shows this for $`\beta =1.04`$ DBW2 where the RGI and bare data are constrained to agree at $`(ap)^2=1`$.

Fig. 2 show this for $`\beta =0.87`$ DBW2 (in this case the bare and RGI are constrained to agree at $`(ap)^2=1.5`$). There is both more evidence of curvature at low-momenta due to condensate effects and a noticeable slope versus $`(ap)^2`$ at high momenta. Interpreting this slope as $`O(a^2)`$ contamination and fitting the RGI value to $`A+B(ap)^2`$ allows the final value for $`Z_S/Z_q`$ to be extracted.

Table 1 collects together the (preliminary) DBW2 results for $`Z_A`$ and $`Z_S/Z_A`$ (the latter in the $`\overline{MS}`$-scheme at 2 GeV), and the results for Wilson gauge results already quoted in .

## 3 MESON MASSES

For the pseudo-scalar meson masses chiral perturbation theory to first order tells us that

$`m_\pi ^2a^2`$ $`=`$ $`B_\pi a\overline{m}`$ (2)
$`m_K^2a^2`$ $`=`$ $`B_\pi a(m_s+\overline{m})/2`$ (3)
where $`\overline{m}=\frac{1}{2}\left(m_u+m_d\right)`$, while for the vector mesons the leading dependence should be linear in the quark masses

$`m_\rho a`$ $`=`$ $`A_\rho +B_\rho \overline{m}.`$ (4)
Our approach to calculating the quark masses is to first fit the meson spectrum for the coefficients $`B_\pi `$, $`A_\rho `$ and $`B_\rho `$ and then to use the physical values for $`m_\pi `$, $`m_K`$ and $`m_\rho `$ to calculate $`a`$, $`\overline{m}`$ and $`m_s`$.

In extracting the meson masses we must deal with two systematic effects due to working in the quenched approximation: the contamination of meson correlators due to the presence of un-suppressed topological near zero-modes , and significant deviations from Eq. 2 at light masses due to quenching effects.

The effects of zero-modes are most apparent at light masses and small volumes, but also are strongly dependent on which correlators are used to calculate the mass. In particular when extracting the pseudo-scalar meson mass the zero-mode effects may be reduced (but not completely avoided) by calculating the mass from axial correlators rather than the more usual pseudo-scalar correlators. In addition to using the axial correlator for the pseudo-scalar mass extraction, we only use bare masses greater than $`m_f=0.01`$ in our analysis.

Using the mass extracted from the axial correlator, the consistency of our different data-sets with each other and the NPR calculation may be tested. Fig. 3 shows the pseudo-scalar mass versus $`\stackrel{~}{m}=m_f+m_{\mathrm{res}}`$, both measured in MeV, whereas Fig. 4 shows the same data versus renormalised mass. As can be seen once the renormalisation factors are taken into account the data-sets show excellent consistency both between the two gauge action at the same lattice spacing and the two different lattice spacing with the same gauge action.

The deviation from Eq. 2 is very apparent in our data with a simple linear fit of

$$(am_\pi )^2=A_\pi +B_\pi a\stackrel{~}{m}$$
(5)
for the $`\beta =1.04`$ DBW2 data having a constant term, $`A_\pi `$, inconsistent with zero by 3 standard deviation whereas the intercept of a more general quadratic fit misses zero by 7 standard deviations.

As this is the case we include a quenched chiral logarithm in our fitting formula (but drop its effects for the final calculation of the quark masses).

$$\left(am_\pi \right)^2=B_\pi \stackrel{~}{m}\left(1\delta \mathrm{log}\left(\frac{B_\pi \stackrel{~}{m}}{\mathrm{\Lambda }^2}\right)\right)$$
(6)
where we use a chiral scale of $`\mathrm{\Lambda }=1\mathrm{G}\mathrm{e}\mathrm{V}`$ . This gives very consistent values of $`\delta =5.1(19)\times 10^2`$ and $`\delta =4.6(18)\times 10^2`$ for Wilson and DBW2 at 2GeV and $`\delta =2.28(12)\times 10^2`$ at 1.3GeV. However, none of the fits are of high quality and the best treatment of the quenching effects is an issue that requires further study.

## 4 RESULTS

Putting together the NPR results and the fits to the meson spectrum gives values for the quark masses in $`\overline{MS}`$-scheme at 2 GeV. Using Equations 2 to 4 implies that

$$m_s/\overline{m}=2m_K^2/m_\pi ^2126$$
(7)
exactly for our results so we only quote the strange quark mass. For this we get $`132.5(31)`$ MeV ($`\beta =0.87`$, DBW2), $`132.6(21)`$ MeV ($`\beta =1.04`$, DBW2), and $`m_s=125.6(28)`$ MeV ($`\beta =6.0`$, Wilson) where the errors quoted are purely statistical.


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# Four-body Faddeev-Yakubovsky calculation of polarization transfer coefficient 𝑲_𝑦^𝑦' in the 2H(𝒅⃗,𝒑⃗)³H reaction at very low energies

## Abstract

The polarization transfer coefficient $`K_y^y^{}`$ for the 2H$`(\stackrel{}{d},\stackrel{}{p})^3`$H reaction at energies $`E_{\mathrm{lab}.}=30`$, 50, 70, and 90keV is calculated using the four-body Faddeev-Yakubovsky equation. We employ a separable type of the Paris potential. The experimental data \[Phys. Rev. C64, 047601 (2001)\] agrees with our solution at the scattering angle $`\theta _{\mathrm{c}.\mathrm{m}.}=0^{}`$, and there is no discrepancy pointed out in that paper. We found that the $`K_y^y^{}`$ is sensitive to the incident deuteron energy at this angle.

Since Kulsrud et al. proposed the idea of a neutron-lean fusion reactor KFVG , low energy 2H$`(d,p)^3`$H and 2H$`(d,n)^3`$He reactions have attracted much attention. Subjects of discussions are mainly about suppression of the reaction by the polarized beam and target deuterons in the same direction ($`\stackrel{}{d}+\stackrel{}{d}`$), to that by the unpolarized ones ($`d+d`$). Experimentally there is no direct data for the $`\stackrel{}{d}+\stackrel{}{d}`$ reaction, however new data of the cross sections by the unpolarized 2H$`(d,p)^3`$H and 2H$`(d,n)^3`$He reactions LosAla  and the vector and tensor analyzing powers by the polarized beam Koeln ; Tsuku  at several 10keV energies.

On the other hand there are many theoretical approaches to the suppression problem, with models HFsup ; LZSsup ; KIJTsup  and analyses of the experimental data LSsup ; FABsup ; ZLS2sup . But their solutions are all different each other depending the applied models or analyses methods, and there is no conclusion.

To obtain more accurate solution, we employ the four-body Faddeev-Yakubovsky (FY) equation FaYa  which is able to calculate the system in microscopic way. The FY theory is a direct extension of the three-body Faddeev theory to the four-body system, and it includes all kinematics of four nucleons. There are many vigorous studies in this field. For recent example, the analyzing powers for 4N system FON1 ; FON2 ; FON3 , and the cross section and low energy resonance for $`n^3`$He elastic scattering FON3 ; carbo  are reported. And the FY equation is applied to the 4He bound state KMD  and hypernuclei hyper1 ; hyper2 . In regard to the 4He ground state, our numerical result for the binding energy agrees with that by Fonseca PrCom  within a limited number of state channels and employing Yamaguchi potential.

In this decade, our investigations were mainly on the analyses of the experimental data of the cross section and analyzing powers, together with prediction of the suppression ratio uzu1 ; uzu2 ; uzu3 ; uzu4 ; uzu5 ; uzu6 . It began from Ref. uzu1  and estimation of the suppression by the invariant amplitude method IAM  is compared with our prediction using the FY equation in Ref. uzu2 . The final result employing the Yamaguchi-type nucleon-nucleon (NN) interaction are presented in Ref. uzu3 ; uzu4 . And the first step using the realistic potential is discussed in Ref. uzu5 . We think that a study of the S-factor is one of our important subject uzu6  to present a data for the astrophysics.

Recently Katabuchi et al. measured the polarization transfer coefficient $`K_y^y^{}`$ for the 2H$`(\stackrel{}{d},\stackrel{}{p})^3`$H reaction Kata . The incident deuteron laboratory energy ($`E_d`$) is 90keV, however, the data included those for all energies between 0 - 90keV with the energy loss in the target. The acceptance angle of the detector was $`\pm 6.5^{}`$ around the scattering angle $`0^{}`$ in the laboratory system. The obtained data was $`K_y^y^{}=0.09\pm 0.10`$.

In the same paper, they reported numerical results of the $`K_y^y^{}`$ using the amplitudes determined by Lemaître and Schieck LSsup , where the amplitudes are expressed as a production of the Coulomb penetrability function and “internal” reaction amplitudes in the NN interaction without the Coulomb force. The “internal” amplitudes are treated as parameters independent of the incident deuteron energy, and fitted to many experimental data for the $`d+d`$ reactions. The energy dependence is kept merely in the Coulomb penetrability function. Obtained $`K_y^y^{}`$ has very small energy dependence in all scattering angles, and the mean value over $`E_{\mathrm{lab}.}`$ is different from the measured data by 1.5 standard deviation. Thus they concluded that the other models should be compared with the data.

Complying to the discussion, we calculate the $`K_y^y^{}`$ at energies $`E_{\mathrm{lab}.}=`$30, 50, 70, and 90keV using the FY equation with following conditions. As the NN interaction, the Ernst, Shakin, and Thaler separable expansion EST  of the Paris (PEST) potential PEST  are employed for the following two-body states: 1S0 (3), 3S1-3D1 (4), 3P0 (2), 1P1 (2), 3P1 (2), and 3P2 (3). The numbers in the braces are ranks for each states. In the \[3+1\] sub-amplitude, the three-body total spin and parity $`j^\pi `$ considered are within the range $`1/2^\pm `$ to $`7/2^\pm `$. For the \[2+2\] sub-amplitude, all possible quantum states, which are automatically driven by two-body states, are taken into account. As for the four-body total spin and parity states $`J^\pi `$ these are taken from $`0^\pm `$ to $`4^\pm `$ and the convergence is confirmed.

The \[3+1\] and \[2+2\] subamplitudes are expanded in separable form adopting the energy dependent pole expansion (EDPE) EDPE  method with following modification. It is convenient to describe an outline of the technique with the expressions in Ref. NLAH . The original EDPE method requires to solve the eigenequations (15) with fixed energies $`E_x`$ and $`E_y`$ which are usually chosen below the $`d+p+n`$ threshold Energy. We adopt the numerical results of the binding energies for the triton as $`E_x`$ and two deuterons as $`E_y`$ in our calculation, and they are used in all states of the \[3+1\] and \[2+2\] subsystem. The form factors and propagators are obtained from the third through sixth equations in Eqs. (14) with required energy $`z`$ on the FY calculation. In case for the mixed channels of the repulsive and attractive forces or the multi-rank separable potentials in the 2-body subsystem, Eqs. (15) have many complex solutions and the convergence of the FY calculation become poor. The modification intends to improve this difficulty.

First the 2-body propagator $`\stackrel{~}{\tau }`$ is diagonalized with a unitary matrix $`U`$ as

$$\stackrel{~}{\tau }^D=U\stackrel{~}{\tau }U^1.$$
(1)
Next all the positive diagonal elements are set by negative but the same absolute values as

$$\stackrel{~}{\tau }_{jj}^{RD}=|\stackrel{~}{\tau }_{jj}^D|.$$
(2)
Thus the reduced propagator $`\stackrel{~}{\tau }^R`$ is obtained with $`U`$ as

$$\stackrel{~}{\tau }^R=U^1\stackrel{~}{\tau }^{RD}U.$$
(3)
and $`\stackrel{~}{\tau }^R`$ is used in the eigenequations (15) except for $`\stackrel{~}{\tau }`$. In this case all the eigenvalues and eigenfunctions become real, and the FY calculation keeps good convergence. After obtaining the form factor, the \[3+1\] and \[2+2\] propagators are calculated with the original $`\stackrel{~}{\tau }`$. Details of this technique will be described on the other paper.

As for the Coulomb force, exact calculation requires to distinguish the proton and neutron, and to include the pure Coulomb potential between two protons. However nobody is successful to carry out this method in the FY integral equation within the momentum representation for the difficulty of the logarithmic singularity. An approximation method is proposed in Ref. LSsup  but we adopt a different way of which basic idea is described as “Traditional” in Ref. uzu6 . In this approximation, the FY equation for 4-identical particles is solved without Coulomb force, and obtained amplitudes are regarded as solutions for a mixed channel 2-body problem where the two deuterons in the initial channel and proton and triton in the final are treated as point particles. The scattering amplitudes are described the operator of the T-matrix put between the plain wave functions for the initial and final channels. However in case for existence of the Coulomb repulsion, the Coulomb functions ought to be applied except for the plain waves. We modify this approximately with multiplying the amplitude by simple factors as

$$P_0^{}e^\delta _{\mathrm{}^{}}M_{\mathrm{}^{}\mathrm{}}P_0e^\delta _{\mathrm{}},$$
(4)
where $`M_{\mathrm{}^{}\mathrm{}}`$ is a reaction amplitude without Coulomb whose $`\mathrm{}`$ and $`\mathrm{}^{}`$ are the angular momentum in the initial and final channel, respectively. $`P_0`$s and $`\delta _{\mathrm{}}`$s are the damping effects and phase shifts corrections, respectively, where without and with prime indicates the initial and final channel, respectively. These factors are expressed as the ratio of the Coulomb wave function to the plain wave which is applied the limiting value of the radial valuable $`r`$ to be 0 since the range of the NN interaction is much smaller than that of the Coulomb force.

Thus we obtain $`P_0`$ as

$$P_0\underset{r0}{lim}\left|\frac{\psi _c(𝐫)}{\varphi _k(𝐫)}\right|=\left|\mathrm{exp}(\frac{1}{2}\pi \eta )\mathrm{\Gamma }(1+i\eta )\right|,$$
(5)
where $`\psi _c(𝐫)`$ and $`\varphi _k(𝐫)`$ are regular functions of the Coulomb and plain waves, respectively. $`\eta =0.1581/\sqrt{E_i}`$ is the Sommerfeld parameter where $`E_i`$ is a center of mass (c.m.) energy in the initial channel. $`P_0^{}`$ has the same expression except for changing $`\eta `$ into $`\eta ^{}=0.1369/\sqrt{E_f}`$ where $`E_f`$ is a c.m. energy in the final channel. It is easy to obtain the Gamow factor from $`P_0^2`$ in case for small energy which is described for instance in Ref. Schiff . This factor is cancelled in $`K_y^y^{}`$ due to independence of the partial waves.

The Coulomb phase shift $`\delta _{\mathrm{}}`$ is defined in the same manner as

$$\delta _{\mathrm{}}=\mathrm{arg}\mathrm{\Gamma }(\mathrm{}+1+i\eta )=\mathrm{arg}\left[\underset{r0}{lim}\frac{\psi _{\mathrm{}}(r)}{\varphi _{\mathrm{}}(r)}\right],$$
(6)
where $`\psi _{\mathrm{}}(r)`$ and $`\varphi _{\mathrm{}}(r)`$ are regular functions of the Coulomb and plain waves, respectively, represented by the partial wave decomposition. $`\delta _{\mathrm{}}`$ is represented in the same expression except for changing $`\mathrm{}`$ and $`\eta `$ into $`\mathrm{}^{}`$ and $`\eta ^{}`$, respectively. It is first introduced in Ref. CLBorg  for a two-body system and applied it to the three-body system in Ref. CLB3b .

One may think that the modification will be improved by changes of the functions $`\psi _c(𝐫)`$ and $`\varphi _k(𝐫)`$ in Eq. (5) for $`\psi _{\mathrm{}}(r)`$ and $`\varphi _{\mathrm{}}(r)`$. However in this case, the P-wave components in the initial channel are too much enhanced and the results for the differential cross sections and analyzing powers become worse. Then we did not adopt it.

FIG. 1 shows our solution of $`K_y^y^{}`$ together with the data in Ref. Kata . They are almost covering the error bar at $`\theta _{\mathrm{c}.\mathrm{m}.}=0^{}`$, thus the experimental data is described with the FY equation. The calculations are numerically converged enough for this discussion. The difference is about 2% between the present results and approximated ones including only 1S0, 3S1-3D1 states in the two-body subsystem. We expect that the influence to the results is small with inclusion of the higher spin states.

Once we reported similar calculations in Ref. uzu4 ; uzu5 , however, the graphs for the $`K_y^y^{}`$ show our results without the Coulomb modification. Then the discussions in the papers were based on these wrong results.

We found two discrepancies between our results and those in Ref. Kata . 1) Ours are sensitive to the incident deuteron energy at around $`\theta _{\mathrm{c}.\mathrm{m}.}=0^{}`$, where the larger the energy becomes, the smaller the value is. Then we expect if the target is as thin as the beam going through, the measured data will be small. 2) There are peaks at around $`\theta _{\mathrm{c}.\mathrm{m}.}=60^{}`$-$`90^{}`$. We suggest to measure at around those angles.

To find out an origin of the sensitivity to the energy at $`\theta _{\mathrm{c}.\mathrm{m}.}=0^{}`$, we compare the results for without Coulomb modification (FIG. 2) with the original (FIG. 1). The former case $`K_y^y^{}`$ is negative at around $`\theta _{\mathrm{c}.\mathrm{m}.}=0^{}`$ and positive at around $`\theta _{\mathrm{c}.\mathrm{m}.}=180^{}`$, which is totally different from the latter. And the difference between $`E_{\mathrm{lab}.}=30`$keV and 90keV for the former is smaller than the latter by about 1/3 at $`\theta _{\mathrm{c}.\mathrm{m}.}=0^{}`$. Thus we think that most of the energy dependence is due to the Coulomb force. This is against to the numerical results in Ref. Kata  since the energy variation of their amplitudes depends only on the Coulomb penetrability function.

We make another check on a connection between the energy dependence and partial waves. Since S- and P-waves are the main components in the initial channel of low energy 2H$`(d,p)^3`$H reaction, $`K_y^y^{}`$ becomes almost isotropic by disregard of the P-wave components from the reaction amplitudes (FIG.3). In this case the Coulomb effects are canceled within our modification by multiplication of an amplitude and one’s complex conjugation. Therefore the difference is small between FIG. 3 and 4 which is neglecting both of the P-waves and Coulomb. Then we find with comparison FIG. 1 \- 3 that the energy dependence in FIG. 1 comes from the Coulomb modification which affects to the mixing term of S- and P-wave components in the initical channel.

In case for neglecting P-waves, energy dependence at $`\theta _{\mathrm{c}.\mathrm{m}.}=0^{}`$ is small and our solutions are close to that by Katabuch et al. using the amplitudes in ref. LSsup . It is interesting to us and further investigation is in progress.

The author appreciates helpful discussions with professors S. Oryu and M. Tanifuji. The calculations for this article are carried out on computers in Research Center for Nuclear Physics, National Institute for Fusion Science, The Institute of Physical and Chemical Research (RIKEN), and Frontier Research Center for Computational Science in Tokyo University of Science.


text:
# Kinetics of charge inversion

## 1 Introduction

Colloidal suspensions and polyelectrolyte solutions containing multivalent counterions can exhibit some very curious electrostatic behavior . It is found that under some circumstances two like-charged polyions inside suspension can actually attract one another . The counterion mediated attraction is responsible for the $`DNA`$ compaction inside the bacteriophages, viruses that infect bacteria , and for the organization of eukaryotic cytoskeleton . Another “strange” electrostatic behavior which can occur in suspensions containing multivalent counterions is the reversal of the electrophoretic mobility . The first thing that is learned in a course on electrostatics is that the force produced by the electric field on a charged particle is

$$𝐅=Q𝐄.$$
(1)
Thus, a positively charged particle, $`Q>0`$, is expected to move in the direction of the applied field while a negatively charged particle, $`Q<0`$, will move in the direction opposite to the field. This simple picture, however, breaks down inside colloidal suspensions of low dielectric solvent or even in aqueous suspensions containing multivalent counterions. The reason for the violation of the “simple” physics learned in high-school are the strong electrostatic many-body interactions between the colloidal particles and the counterions. The reversal of electrophoretic mobility can be understood as a combination of two electrostatically driven mechanisms. Strong electrostatic interaction between colloids and counterions leads to formation of polyion-counterion complexes . The existence of counterion condensation has been known for over thirty years , the general phenomenon is, however, much older than this and can be traced to the pioneering work of Bjerrum on ionic association inside electrolyte solutions almost $`80`$ years ago . In aqueous suspensions with only monovalent counterions, the net charge of complexes is of the same sign as the bare charge of polyions.

If the solvent is water and the counterions are monovalent, the electrostatic interactions between the condensed counterions can be neglected , and the simplest Poisson-Boltzmann theory is sufficient to describe the polyion-counterion complexation . In aqueous suspensions containing multivalent counterions or in suspension of low dielectric solvents, the electrostatic energy between the condensed counterions is significantly larger than the thermal energy and the electrostatic correlations between the condensed counterions can no longer be neglected. These electrostatic correlations can lead to colloidal overcharging i.e. the net charge of the complex is of opposite sign to the charge of the bare polyion. The overcharged colloid will then move in the “wrong” direction with respect to the applied electric field .

## 2 Overcharging

To understand the phenomenon of overcharging we shall start by studying a very simple model. Consider a sphere of radius $`a`$ and fixed charge $`Zq`$ distributed uniformly over its surface. We would like to know how many point-like $`\alpha `$-valent counterions, each of charge $`\alpha q`$, should be placed on top of this sphere in order to minimize the total electrostatic free energy . When we say “counterions” we have in mind both simple multivalent ions such as $`Ca^{++}`$, as well as more complicated micelle-like aggregates with $`\alpha `$ significantly higher than one.

The free energy of a complex can be written as

$$E_n=\frac{Z^2q^2}{2ϵa}\frac{Z\alpha nq^2}{ϵa}+F_n^{\alpha \alpha }.$$
(2)
The first term is the self energy of the charged sphere, the second term is the electrostatic energy of interaction between the sphere and $`n`$ condensed $`\alpha `$-ions, and the last term is the electrostatic energy of repulsion between the condensed counterions. To calculate the free energy of repulsion, it is convenient to express $`F_n^{\alpha \alpha }`$ in terms of the free energy of a one component plasma ($`OCP`$), $`n`$ $`\alpha `$-ions on the surface of a sphere with a uniform $`neutralizing`$ background, $`F_n^{OCP}`$. The free energy of a spherical $`OCP`$ can be written as

$$F_n^{OCP}=F_n^{\alpha \alpha }\frac{\alpha ^2n^2q^2}{ϵa}+\frac{\alpha ^2n^2q^2}{2ϵa}.$$
(3)
Substituting Eq. (3) into Eq. (2) the electrostatic free energy of a polyion-counterion complex becomes,

$$E_n=\frac{(Z\alpha n)^2q^2}{2ϵa}+F_n^{OCP}.$$
(4)
In the strong coupling limit, corresponding to multivalent counterions or solvents of low dielectric permittivity, the free energy of the $`OCP`$ is well approximated by the free energy of the low temperature phase corresponding to a triangular Wigner crystal,

$`F_n^{OCP}=M{\displaystyle \frac{\alpha ^2q^2n^{3/2}}{2ϵa}}.`$ (5)
where $`M`$ is the Madelung constant. For weaker couplings, the expression for the $`F_n^{OCP}`$ can be obtained from the fits to the Monte Carlo data . For concreteness we shall use $`M=1.106`$, the value appropriate for a planar Wigner crystal .

The effective charge of a polyion-counterion complex, in units of $`q`$ is

$`Z_{eff}=Z\alpha n,`$ (6)
The optimum number of condensed counterions is determined from the minimization of the total electrostatic free energy. We find

$`Z_{eff}^{}={\displaystyle \frac{1+\sqrt{1+4\gamma ^2Z}}{2\gamma ^2}}{\displaystyle \frac{\sqrt{Z}}{\gamma }},`$ (7)
where

$`\gamma ={\displaystyle \frac{4}{3M\sqrt{\alpha }}}.`$ (8)
We see that the optimal charge of a polyion-counterion complex is of opposite sign to the bare colloidal charge, i.e. the complex is overcharged. Inside the colloidal suspension containing multivalent counterions or solvents of low dielectric permittivity the electrophoretic mobility can, therefore, be reversed.

Some care, however, must be taken in extrapolating the results of this simple model to real systems. While we have treated the counterions as condensed on top of the sphere, this is clearly not the case for real colloidal suspension. Instead the associated counterions form a layer around a colloidal particle which can be some nanometers wide. The presence of simple electrolyte also strongly affects the net charge of the polyion-$`\alpha `$-ion complex. Furthermore, the complex formation is a kinetic phenomenon requiring a counterion to overcome an energy barrier in order to join the already overcharged complex.

## 3 The overcharging potential

In the previous section we found that the minimum of the total electrostatic free energy of a polyion-$`\alpha `$-ion complex corresponds to an overcharged state. However, for a counterion to join an already overcharged complex it must overcome an energy barrier. The waiting time for a thermal fluctuation of sufficient strength necessary to drive a counterion over an activation barrier scales exponentially with the height of the barrier. There is, therefore, a kinetic limitation to the degree of overcharging which can prevent a thermodynamically optimum state from being reached on experimental time scale. To explore this further we have to construct an effective interaction potential between a complex and a counterion separated by distance $`r`$.

The work necessary to bring a counterion from infinity to join a complex containing $`n`$ $`\alpha `$-ions is

$`W={\displaystyle \frac{dE_n}{dn}}.`$ (9)
We define the reduced electrostatic potential of a counterion on the surface of the complex as $`\phi (a)=\beta W`$, where $`\beta =1/k_BT`$. Differentiating Eq. (4) we find

$`\phi (a)={\displaystyle \frac{(Z\alpha n)\lambda _B\alpha }{a}}{\displaystyle \frac{3M\alpha ^2\sqrt{n}}{4a}},`$ (10)
where $`\lambda _B=q^2/ϵk_BT`$. The first term of Eq. (10) is the electrostatic energy of interaction between a uniform spherical charge and an $`\alpha `$-ion, while the second term is due to electrostatic correlations between the $`\alpha `$-ions. In the strong coupling limit correlational contribution to the interaction potential decay exponentially fast with the separation from the polyion surface . The characteristic length is set by the average separation between the condensed counterions. More specifically we can approximate the reduced interaction potential by

$`\phi (r)={\displaystyle \frac{(Z\alpha n)\lambda _B\alpha }{r}}{\displaystyle \frac{3M\alpha ^2\sqrt{n}}{4a}}e^{(ra)/\xi }.`$ (11)
The decay of the correlational contribution is governed by the characteristic length $`\xi `$ which in the strong coupling limit is well approximated by ,

$`\xi ={\displaystyle \frac{1}{|𝐆|}},`$ (12)
where $`𝐆`$ is the reciprocal lattice vector of a triangular Wigner crystal of condensed counterions. Due to strong coupling between the condensed counterions, Eq. (12) should remain a good approximation even significantly above the crystallization temperature. For a triangular Wigner crystal,

$`|𝐆|={\displaystyle \frac{4\pi }{\sqrt{3}b}},`$ (13)
where $`b`$ is the lattice spacing

$`b={\displaystyle \frac{1}{3^{1/4}\sqrt{\sigma }}}`$ (14)
and $`\sigma =n/4\pi a^2`$ is the surface density of condensed counterions. Substituting Eqs. (13) and (14) into Eq. (12), the decay length is found to be

$`\xi ={\displaystyle \frac{3^{1/4}}{2\sqrt{\pi }}}{\displaystyle \frac{a}{\sqrt{n}}}.`$ (15)
We are now in possession of the electrostatic potential which will allow us to study the kinetics of overcharging.

## 4 Kinetics of overcharging

For $`n<Z/\alpha `$, the electrostatic potential between a counterion and a complex is purely attractive favoring further counterion condensation. Inside an electrolyte solution this tendency towards polyion-counterion association is opposed by the loss of entropy resulting from the confinement of condensed counterions near the colloidal surface. Here, however, we shall not be concerned with the role of entropy .

For $`n>Z/\alpha `$ the interaction potential has two minima, one located at $`r=a`$ and the second at $`n=\mathrm{}`$. For $`Z/\alpha <n<n^{}`$ the $`r=a`$ minimum is the dominant one, while for $`Z>n^{}`$ the global minimum changes to $`r=\mathrm{}`$. The value of $`n^{}`$ corresponds to the number of condensed counterions which minimize the electrostatic free energy of the complex Eq. (4),

$`n^{}={\displaystyle \frac{ZZ_{eff}^{}}{\alpha }}.`$ (16)
In the case of trivalent counterions the energy barrier that a counterion needs to overcome in order to join a complex which already contains $`n^{}`$ condensed $`\alpha `$-ions is less than $`2k_BT`$, Fig 1. Thus, for trivalent counterions there is no kinetic hindrance to reaching the optimum overcharged state.

We next look at the height of the activation barrier as a function of the counterion valence, Fig. 2.

It is clear that the height of the activation barrier grows rapidly with the increased valence of the $`\alpha `$-ions. In particular we see that for $`\alpha =10`$ the activation barrier is already some $`10k_BT`$ which is probably the maximum height that a counterion can overcome on a reasonable experimental time scale. Thus, the process of overcharging by the $`\alpha `$-ions with $`\alpha >10`$ will be kinetically controlled. For example, from Eq. (7) we see that the optimal state of overcharging of a colloidal particle of $`Z=4000`$ and radius $`a=1000`$ Å by micelles with $`\alpha =25`$ corresponds to $`Z_{eff}^{}=271`$. In practice, though, the process of overcharging will come to a stop when the barrier height reaches about $`10k_BT`$, implying that the complex will stop growing when the net charge is only $`Z_{eff}=70`$.

## 5 Conclusion

In this contribution we have explored the kinetic limitation to overcharging. We find that kinetics does not play an important role for overcharging by simple multivalent counterions, so that the state of optimal overcharging, Eq. (7), is accessible within an experimental time scales. On the other hand, we find that the activation barrier grows rapidly with the valence of counterions, suggesting that the extent of overcharging by micelle-like aggregates is largely kinetically controlled.

The kinetic limitation to overcharging might also be important for the formation of the DNA-cationic lipid complexes. The problem of a reliable and safe mechanism for gene delivery is particularly pressing in view of the current medical applications. Strong electrostatic repulsion between a DNA and a cellular membrane inhibits transfection of a naked DNA into the cell. A way to overcome this difficulty is through the formation of overcharged complexes between the DNA and the cationic liposomes . These lipoplexes having a net positive charge are attracted to the cellular membrane, facilitating the genetic transfection.

Finally, the presence of a simple electrolyte will have a strong influence on the overcharging. It has been demonstrated that for sufficient concentration of $`\alpha `$-ions, monovalent salt favors overcharging . In fact in the presence of simple electrolyte the thermodynamic state of optimum overcharging corresponds to the charge inversion of as much as $`100\%`$. This should be contrasted with the result of Eq. (7), which shows that in the absence of salt, the effective charge of a complex scales as a square root of the bare charge. The presence of salt will also lower the height of the activation barrier reducing the kinetic hindrance to overcharging.