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# Studies of transverse and longitudinal relaxations of 55Mn in molecular cluster magnet Mn12Ac

## I Introduction

Recently there has been a great interest in nano-scale molecular cluster magnets in view of the microscopic quantum nature appearing in the macroscopic properties of the system. The synthesis of the molecular cluster magnets have solved the most serious problem of the particle size, because the cluster size of the cluster magnet is exactly same and known. As a typical candidate compound, the molecular cluster magnet Mn12O12(CH3COO)6(H2O)4 (abbreviated as Mn12Ac), which was synthesized and whose crystal structure was studied using X-ray diffraction by Lis, L  has been studied so far most extensively. Magnetic properties of Mn12Ac have been explained satisfactorily by treating the strongly-coupled cluster spins as a single quantum spin of $`S`$=10. The prominent features have been demonstrated in very long relaxation time of the magnetization at low temperatures, SGCN ; VBSP  and the step-wise recovery of the magnetization in the external field at every interval of about 0.45 T, which is associated with the quantum tunneling which occurs with coincidence in the Zeeman levels of oppositely directed magnetization of the cluster spins. TLBGSB ; FSTZ  Such a tunneling phenomenon was interpreted as thermally-assisted and/or field-tuned processes associated with the spin-phonon interaction. PRHV

Another molecular compound \[(tacn)6Fe8O2(OH)12\]8+ (abbreviated as Fe8) with a large cluster-spin of $`S`$=10 has been the subject of investigations on the same viewpoint. SOPSG ; WSG  On contrary to Mn12Ac and Fe8 in which the tunneling is due to “spin-bath”, a molecular cluster magnet K8\[V$`{}_{}{}^{\mathrm{IV}}{}_{15}{}^{}`$As6O42(H2O)\]$``$8H2O (so called V15) has been studied as a system with a lowest cluster spin of $`S`$=1/2, which shows a hysteresis curve associated with “phonon-bath”, although there is no energy barrier against the spin reversals. CWMBB

A great deal of experimental and theoretical works related to Mn12Ac has been reviewed in some books and review papers. GB ; CT ; HPV ; TPS ; TB

In order to understand the magnetic properties of these molecular cluster magnets more thoroughly, it is worthwhile to examine the dynamical behavior as well as statistical nature of each magnetic ion which constitutes the cluster spin. One of the most promising experimental procedures for this purpose will be to use an NMR with respect to the relevant magnetic ions. In view of this, we have been studying 55Mn NMR in Mn12Ac. As reported in our preliminary paper, we first succeeded, using powder sample, in observing all of 55Mn NMR signals belonging to Mn4+ and two in-equivalent Mn3+ ions in zero field, and measured the temperature dependence of the transverse relaxation time $`T_2`$ at liq. Helium temperatures. GKKFOATA  In the recent paper, we have determined the hyperfine interaction tensors of 55Mn nuclei in Mn12Ac by analyzing the more detailed 55Mn NMR spectra on the basis of the ground-state spin-configuration. KGKTA

In the present work, we have measured, using oriented powder sample, the transverse relaxation time $`T_2`$ and the spin-lattice relaxation time $`T_1`$ of 55Mn in Mn12Ac. The measurements have been done in the wide temperature range from 2.5 K down to 200 mK in zero field and at liq. Helium temperatures with an applied field up to 9T. As for the nuclear-spin lattice relaxation in Mn12Ac, the proton spin- and muon spin-lattice relaxation times have been measured by Lascialfari et al. at the temperature range of 4.2-400 K and at the field range of 0-9.4 T, LGBSJC  and subsequently at the lower temperatures down to around 2 K below 1.6 T. LJBCG  In Ref. LJBCG,  the field dependence of the proton relaxation rate $`T_1^1`$ and the temperature dependence of the muon relaxation rate have been analyzed on the basis of the standard perturbation method, that is, weak collision model. Then the fluctuating local fields at the proton or the muon site have been taken to originate from the random change between the adjacent Zeeman-energy levels of the ground-state configuration of the total spin of $`S`$=10, which is caused by the spin-phonon interactions. Quite recently Furukawa et al. have reported on the experimental results for the temperature and field dependence of $`T_1^1`$ of 55Mn in Mn12Ac above 1.2 K and below 1 T. FWKBG , and the analysis has been made on the basis of essentially the same treatment given in Ref. LJBCG, .

The analysis for our experimental results are made on the basis of the concept as presented in Ref. LJBCG,  such that the fluctuating local field at each of 55Mn sites in Mn4+ and Mn3+ ions is originated from the thermal excitations in the Zeeman-energy levels due to the spin-phonon interaction. Then, in order to proceed the analytical treatment, we simplify the problem by taking into account only the lowest two levels of the cluster spin $`S`$=10, the ground-state and the first excited state which lies above about 12 K. This simplification will be reasonable, since the data for the 55Mn NMR are available only below about 2.5 K, thus the statistical weight of higher excited states being extremely small. For the interpretation for $`T_2`$, which was measured by observing the spin-echo decay time, we employ the general treatment based on non-linear theory. As we shall explain, it turns out that the transverse relaxation rate $`T_2^1`$ is reasonably understood in terms of the strong collision regime instead of weak collision regime. On the other hand, the results of $`T_1`$ is interpreted satisfactorily by the standard perturbation formalism. However, our standpoint for the interpretation for $`T_1`$ is somewhat different from that presented in Ref. FWKBG,  apart from the simplification of the problem. The essential part has already been reported in our recent brief publication. KGKA

The constitution of the present article is as follows. In the next section, we explain briefly the magnetic structure and hyperfine coupling tensors of 55Mn in Mn12Ac determined by analysis of 55Mn NMR spectra. The experimental results are presented in Sec. III. Section IV is devoted to the derivation of the theoretical equations for interpretations for the experimental results. Subsequently we show that the experimental results of $`T_2`$ and $`T_1`$ are interpreted reasonably in terms of the present theoretical treatment. In Sec. V we discuss on the quantitative considerations. The final section yields the summaries of this article.

## II Properties of $`\text{Mn}_{12}\text{Ac}`$

### II.1 Crystal Structure and magnetic properties

The crystal and magnetic structures of the cluster of Mn12Ac are shown in Fig. 1(a). Each cluster, which constitutes a tetragonal symmetry with the lattice constants of $`a=b=17.3`$ Å, and $`c=12.4`$ Å, is constructed from four Mn4+ ions ($`S=3/2`$) in a central tetrahedron (denoted by Mn(1)) and surrounding eight Mn3+ ($`S=3/2`$) with two in-equivalent sites (denoted by Mn(2) and Mn(3)) located alternately. The Mn atoms are linked by triply bridged oxo oxygens and by carboxylate bridges from acetate anions. The Mn(1) and Mn(2) have distorted octahedral coordination of oxygens due to above links. In Mn(3), one water molecule completes the octahedral environment of oxygens. L

There exist four kinds of exchange interactions among these manganese ions, as shown schematically in Fig. 1(b). Quite recently, a set of the magnitudes and signs of these exchange couplings has been determined, using exact diagonalization of the spin Hamiltonian of the cluster spin by a Lanzcos algorism, so as to explain the high-field magnetization and the realization of the ground state of $`S=10`$. These values are $`J_1/k_B=119`$ K, $`J_2/k_B=118`$ K (antiferromagnetic), $`J_3/k_B=8`$ K (ferromagnetic) and, $`J_4/k_B=23`$ K, RJSGV  and except the value of $`J_1/k_B`$, they are different largely from the previously available values. STSWVFGCH

As a combined effect of the above exchange interactions, the ground-state configuration of the total spin of $`S=10`$ is established CGSBBG  in such a way that the assemblies of outer eight Mn3+ ions and the inner Mn4+ ions, which have respectively resultant ferromagnetic spins of $`S=16`$ ($`8\times 2`$) and $`S=6`$ ($`4\times 3/2`$), are coupled anti-ferromagnetically to each other at low temperatures. CGSBBG  Because of the anisotropy due to Jahn-Teller distortion of Mn3+ ions, there appears a single-ion type anisotropy $`D`$ along the $`\pm c`$-axis. Thus the total magnetic moments of each cluster are either parallel or anti-parallel to the $`c`$-axis. Henceforth these clusters are referred to respectively as ($`+`$) and ($``$) cluster, with respect to the $`c`$-axis taken as the $`z`$-axis. The inter-cluster interaction is only due to dipolar origin of the order of 0.5 K. In the presence of an external field $`H_0`$ applied along the $`c`$-axis, the effective exchange Hamiltonian for each cluster is given by

$$=DS_z^2BS_z^4\pm g_{}\mu _BH_0S_z,$$
(1)
where the exchange parameters have been evaluated from recent high-field ESR BGS  and neutron spectroscopy MHCAGIC  as $`g_{}=1.93`$BGS  $`D/k_B=0.67`$ K, BGS  and 0.66 K, MHCAGIC  and $`B/k_B=1.1`$-$`1.2\times 10^3`$ K, BGS  and the sign $`\pm `$ correspond to the ($`+`$) and ($``$) clusters, respectively. According to this Hamiltonian, the discrete energy levels $`|S,m`$ are well defined along the $`z`$-axis in the ground-state spin configuration of $`S=10`$. This gives satisfactory understandings for the most of magnetic properties of Mn12Ac such as an energy barrier of about 60 K in zero field from the ground level of $`m=\pm 10`$ up to the highest level of $`m=0`$, and the step-wise recovery of the magnetization at each step of about 0.45 T which occurs corresponding to the coincidence of the energy levels between $`S_z=m(<0)`$ in the ($`+`$) cluster and $`S_z=m(>0)`$ in the ($``$) cluster. In addition to the above main Hamiltonian, there exists the perturbing Hamiltonian $`^{}`$ including the terms such as higher-order transverse anisotropy and the transverse external field. These terms do not commute with $`S_z`$, thus playing a crucial role for the mechanism of the tunnelling. In particular, the transverse external field gives rise to a drastic change in the tunnel-splitting at the level-crossing fields, which may promote the tunneling appreciably. PS

### II.2 Hyperfine interaction tensor

Next we review the 55Mn hyperfine interaction tensor determined from the NMR spectra in zero field in Ref. KGKTA,  for the numerical evaluation of the present experimental results. Figure 2 shows the NMR spectra of 55Mn ($`I=5/2`$) in Mn12Ac obtained at 1.45K in zero field. The three completely separated lines with the central frequencies of $`\nu _N=`$230, 279, and 364 MHz, were identified to be due to Mn4+ ion (Mn(1)), and Mn3+ ion (Mn(2) and Mn(3)), respectively. The corresponding internal fields are $`H_{\mathrm{int}}=21.8,26.5,34.5`$ T. From now on, these three lines are referred to as L1, L2, and L3, respectively. The resonance lines L1, L2, and L3 involve the five-fold quadrupole-splitting with $`\mathrm{\Delta }\nu _q=0.72,4.3,2.9`$ MHz, respectively. KGKTA

The nuclear hyperfine Hamiltonian, which consists of Fermi-contact, dipolar, and orbital terms, is obtained by taking the expectation values for the corresponding Hamiltonians with respect to the ground-state wave-function of the magnetic ion. This Hamiltonian is expressed as,

$$_N=𝐈A𝐒=\gamma _N\mathrm{}𝐈(𝐇_F+𝐇_d+𝐇_l),$$
(2)
where $`A`$ is the hyperfine coupling tensor between the nuclear spin $`𝐈`$ and the electronic spin $`𝐒`$, and $`𝐇_F`$, $`𝐇_d`$, $`𝐇_l`$ are the corresponding hyperfine fields. Each of manganese ions in Mn12Ac is subject to the crystalline field with dominant cubic symmetry due to the surrounding distorted octahedral coordination of oxygens.

The ground-state of the Mn4+ ion (3d3, 4F) is the orbital-singlet. So the dipolar and the orbital terms in Eq. (2) vanishes primarily, and only the isotropic Fermi-contact term is important. The corresponding Fermi-contact field $`𝐇_F`$ is given, using the conversion factor of 1 atomic unit ( $`a.u.`$) = 4.17 T, as

$$𝐇_F=\frac{A_f𝐒}{\gamma _N\mathrm{}}=2\times 4.17\chi 𝐒,$$
(3)
where $`A_f`$ is the component of the tensor $`A`$, and $`\chi `$ is the effective field per unpaired electron in atomic unit. According to Freeman and Watson, FW  the value of $`\chi `$ is calculated to be 2.34 for the free Mn4+ ion, by taking into account the contributions from three inner electron spins (1$`s`$, 2$`s`$, and 3$`s`$). The minus sign in $`𝐇_F`$ indicates that the direction of $`𝐇_F`$ is opposite to the magnetic moment. Thus for the free Mn4+ ion, the values of $`𝐇_F`$ is estimated to be $`H_F=29.3`$ T. The effect of the admixture of the higher triplet state to ground-state and distorted crystalline field may be extremely small. In fact, for the diluted ion in the trigonal symmetry, the hyperfine anisotropy is of the order of 0.1%. FW . It is noted that the experimental internal field of 21.8 T is smaller by 26% as compared with calculated value of 29.3 T for the free ion. This is understood by considering a large amount of reduction of the magnetic moment. The recent polarized neutron diffraction measurement yields the presence of 22% reduction from the full value of 3$`\mu _B`$ in the magnitude of the Mn4+ magnetic moment. RBAHA  Since the reduction of the magnetic moment due to 3$`d`$-electrons reflects the contact term, the present result is consistent with the neutron results. Such a large amount of reduction may be ascribed to the presence of the covalence and strong exchange interactions, as observed usually in the condensed matter.

On the other hand, the ground state of the Mn3+ ion (3d4, 5D) is orbital doublet denoted by $`E_g`$ in the cubic crystalline field. As in the case of Mn4+ ion, the Fermi-contact field $`HF`$ is obtained for the free Mn3+ to be 48.5 T using the calculated value of $`\chi `$=2.91. FW  Because of the additional elongated tetragonal symmetry of the crystalline field caused by Jahn-Teller effect and low-symmetric carboxylate ligands, the orbital degeneracy is removed to the lower and higher states with the wave functions expressed as $`|\mathrm{\Psi }_1=|X^2Y^2`$ and $`|\mathrm{\Psi }_2=|3Z^2r^2`$, respectively. Here we defined the rectangular coordinate system ($`XYZ`$) with the tetragonal $`Z`$-axis and the $`X`$-axis along one of the principal axes in the tetragonal plane. Further, the orthorhombic distortion of the crystalline field gives rise to the admixture of $`|\mathrm{\Psi }_2`$ to $`|\mathrm{\Psi }_1`$, thus the ground-state wave-function being expressed as $`|\mathrm{\Psi }_g=\mathrm{cos}\varphi |\mathrm{\Psi }_1+\mathrm{sin}\varphi |\mathrm{\Psi }_2`$, where $`\mathrm{cos}\varphi `$ and $`\mathrm{sin}\varphi `$ are normalization factors. In Mn(2) and Mn(3), the $`Z`$-axis tilts from the $`c(z)`$-axis by the angles of $`\theta =11.7^{}`$ and $`36.2^{}`$, respectively. In the case of Mn3+ ion, the dipolar term in Eq. 2 contributes appreciably to the hyperfine tensor in addition to the dominant isotropic Fermi-contact term. By using the wave function $`|\mathrm{\Psi }_g`$ in the standard operator-equivalent method, the dipolar Hamiltonian $`_d`$=$`\gamma _N\mathrm{}𝐈`$$``$$`𝐇_d`$, which is expressed in terms of the principal terms with respect to the ($`XYZ`$) coordinate system, is given as,

$$_d=h_d\gamma _N\mathrm{}\mathrm{cos}(2\varphi )\left[S_ZI_Z\frac{1}{2}(S_XI_X+S_YI_Y)\right]$$
(4)
with

$$h_d=\frac{4}{7}\mu _Br^3_d,$$

where $`r^3_d`$ is the average for the orbital radius $`r`$ with respect to 3$`d`$ shell. It is useful to define the ($`xyz`$) rectangular coordinate system with the $`z`$-axis along the magnetic moment and the $`x`$-axis is taken in the $`Zz`$-plane. (See Fig. 4 in Ref. KGKTA, .) Then the above equation is expressed as KGKTA

$$_d=𝐈D𝐒$$

with

$$D=\frac{h_d}{4}\gamma _N\mathrm{}\mathrm{cos}(2\varphi )\left(\begin{array}{ccc}2(23\mathrm{cos}^2\theta )& 0& 3\mathrm{sin}2\theta \\ 0& 2& 0\\ 3\mathrm{sin}2\theta & 0& 2(3\mathrm{cos}^2\theta 1)\end{array}\right).$$
(5)
The principal terms are anisotropic, and there appear the off-diagonal terms. For the free Mn3+ ion which has $`r^3_d=4.8a.u.`$FW  $`h_d`$ is evaluated to be $`+`$17.1T.

The orbital contribution is in general evaluated from the equation, $`H_l=2\mu _Br^3_d\mathrm{\Delta }g`$, where $`\mathrm{\Delta }g`$ represents the deviation of the $`g`$-value from $`g_s=2.0023`$ due to admixture of the higher excited orbital state. Applying the value of $`g_z=1.95`$ and $`g_{}=1.97`$ for Mn3+ ion evaluated from high field EPR measurement, BGS  the value of $`H_d`$ is calculated, using $`r^3_d=4.8a.u.`$ for the free ion, to be about 2 T. So, we may neglect the orbital contribution as compared with the other terms. By taking into account the dipolar contribution to the internal field, which is given by the $`D_{zz}`$ component in the dipolar tensor $`D`$ (Eq. (5)), the total internal field is given by

$$H_{\mathrm{int}}=|𝐇_F|D_{zz}/\gamma _N\mathrm{}.$$
(6)
The identification of the L2 and L3 lines was made in view of Eq. (6). By considering that the increase in $`\theta `$ plays a role to deduce $`|𝐇_F|`$ as far as $`\theta <53^{}`$, it turns out that the line L2 with lower $`\omega _N`$ should be due to Mn(2), and thus the L3 line being due to Mn(3). As for the quadrupole splitting, the dominant term is expressed, for the axial-symmetry case, as $`\mathrm{\Delta }\nu _q=\frac{1}{2}(3\mathrm{cos}^2\theta 1)\nu _q,`$ where $`\nu _q`$ is the quadrupole-splitting parameter. The larger value of $`\theta `$ yields the larger splitting as far as $`\theta <53^{}`$. The above identification is then consistent with the observed difference in quadrupole splitting between 55Mn NMR for the L2 and L3 lines.

The determination of the components of the hyperfine tensors $`A`$ for Mn(2) and Mn(3) of Mn3+ ion was made in the following way. There are three unknown factors, the reduction factor for the contact term, the value of $`r^3_d`$, and the amount of the mixing of the two wave functions in the ground-state $`E_g`$, which is represented by the factor $`\mathrm{cos}2\varphi `$ in Eq. (5). According to Ref. RBAHA, , the reductions of the magnetic moments for the Mn(2) and Mn(3) ions are obtained to be 8% and 6%, respectively. First, by applying these reduction factors to the value of $`r^3_d`$ in Eq. (4) for each ion, we evaluated that $`h_d`$=$`+`$15.7 and $`+`$ 16.0 T, respectively. Secondly, referring to the crystal parameters given in Ref. L, , we assumed the tetragonal and orthorhombic symmetries of the crystalline field for Mn(2) and Mn(3), respectively. That is, we put $`\mathrm{cos}2\varphi =1`$ for Mn(2), and the coefficient $`\mathrm{cos}2\varphi `$ for Mn(3) was remained as an unknown factor. Then using $`\theta =11^{}`$ for Mn(2), we obtain the dipolar contribution $`D_{zz}/\gamma _N\mathrm{}=`$+$`1.6`$ T. Using the experimental value of 26.5 T for $`H_{\mathrm{int}}`$ in Eq. (6), we find $`H_F`$(Mn(2))=24.8 T. This corresponds to 85% of $`H_{\mathrm{int}}`$ for the free ion, thus reduction factor for the contact term being evaluated to be 15%. Next we adopted the same value of the contact field for Mn(3). Then using $`\theta =36^{}`$, the mixing parameter for Mn(3) was estimated to be $`\mathrm{cos}2\varphi =0.89`$. From the above considerations, we finally determined the following numerical values of the components of the 55Mn hyperfine-interaction tensors for each of three manganese ions, which are expressed in unit of MHz with respect to the ($`xyz`$)-coordinate frame with the $`z`$-axis of the $`c`$-axis;

$`A(\mathrm{Mn}(1))`$ $`=\mathrm{diag}(153,153,153),`$ (7a)
$`A(\mathrm{Mn}(2))`$ $`=\left(\begin{array}{ccc}254& 0& 24.7\\ 0& 176& 0\\ 24.7& 0& 140\end{array}\right),`$ (7b)
$`A(\mathrm{Mn}(3))`$ $`=\left(\begin{array}{ccc}221& 0& 53.0\\ 0& 181& 0\\ 53.0& 0& 182\end{array}\right).`$ (7c)
## III Experimental results for the relaxation rates

The transverse and longitudinal relaxation times $`T_2`$ and $`T_1`$ of the 55Mn were measured for the three resonance lines at the liq.Helium temperatures with the external field $`H_0`$ up to 9 T applied along the $`c`$-axis, and for the L1 line the measurement was extended down to 200 mK in zero field. Figure 3 shows the field dependence of the resonance frequencies of the central peaks of the three resonance lines, which was obtained at 1.65K by applying the external field $`H_0`$ along the $`c`$-axis ($`z`$-axis) after zero-field cooling. Within the experimental error, the slopes of these lines coincide with the gyromagnetic ratio $`\gamma _N`$ of the free manganese nuclei. As explained in Sec. II.2, the internal field $`H_{\mathrm{int}}`$ of 55Mn, which is mainly due to the Fermi-contact term, appears along the spin direction, that is, opposite to the magnetic moment. So when $`H_{\mathrm{int}}H_0`$ as in the present case, the resonance conditions for Mn4+ ion belonging to the ($`+`$) and ($``$) clusters are given by $`\omega _N=\gamma _N(H_{\mathrm{int}}\pm H_0)`$, and these are referred to as upper and lower branches, respectively. In the case of Mn3+ ion, the above relations are vice versa.

At lower temperatures than the blocking temperature of $`T_B3`$ K, we can observe the NMR signals and measure $`T_2`$ and $`T_1`$ for the ($``$) cluster in addition to those for the ($`+`$) cluster, as far as the relaxation time of the reorientation of the ($``$) clusters to the $`z`$-direction is enough longer as compared with $`T_1`$. The transverse relaxation time $`T_2`$ were obtained by measuring the decay of spin-echo amplitude as a function of the time interval between two $`rf`$-pulses. The decay was of single-exponential type. The longitudinal relaxation time $`T_1`$ is obtained in general by measuring the recovery of the nuclear magnetization after the saturation of the nuclear magnetization of the central line. Under the ideal condition of the complete saturation, the magnetization recovery for the nucleus of $`I=5/2`$ is obtained by the equation AT

$`m(t)`$ $`=1{\displaystyle \frac{M(t)}{M_0}}`$
$`=a\mathrm{exp}(t/T_1)+b\mathrm{exp}(6t/T_1)+c\mathrm{exp}(15t/T_1)`$ (8)
with the condition such that $`a+b+c=1`$. However, in the present case, it was difficult to attain complete saturation of the NMR signal because of the broadness of each quadrupole splitting resonance line. Then the relaxation rate $`T_1`$ was determined by doing the best-fitting of the experimental recovery curve to the Eq. (III). The value of $`T_1`$ obtained in such a way was almost the same as the value determined from the fitting of the slowest recovery region to the single exponential equation $`\mathrm{exp}(t/T_1)`$. Figure 4 shows a typical example of the best-fit recovery curve of the nuclear magnetization for the Mn4+ ion.

Figure. 5 show the temperature dependence of the transverse relaxation rate $`T_2^1`$ and the longitudinal relaxation rate $`T_1^1`$ measured in zero field for each central peak of the three resonance lines. As is seen, both rates exhibit qualitatively the same remarkable decrease with decreasing temperature above about 1.4 K, and the values of $`T_1^1`$ are smaller than that of $`T_2^1`$ by almost two orders of magnitudes. Below 1.4 K, $`T_2^1`$ becomes rather moderate, and it becomes almost constant around the value of 100 s-1 below about 0.5 K. The values of $`T_2^1`$ for Mn4+ ion and Mn3+ ions are almost the same, though the former is somewhat smaller only at the temperatures above about 2 K. On the other hand, the value of $`T_1^1`$ continues to decrease remarkably down to around 0.5 K, Thus, at very low temperatures there appears, between $`T_2^1`$ and $`T_1^1`$, a difference extending over four orders of magnitude. The values of $`T_1^1`$ for Mn3+ ion are larger by about twice than that for Mn4+ ion.

The field dependence of $`T_2^1`$ for Mn(1), Mn(2), and Mn(3). Mn4+ ion was measured at 1.65 K for the ($`+`$) cluster (upper branch) up to 9 T and for the ($``$) cluster (lower branch) up to 1.2T. The data were taken also at 1.45 K only for the ($`+`$) cluster up to 9 T. The field dependence of $`T_1^1`$ for Mn4+ ion was measured at 1.65 K for the ($`+`$) cluster (upper branch) up to 5 T, and for the ($``$) cluster (lower branch) up to 1.2 T. The data were taken also at 1.45 K for the ($`+`$) cluster up to 3 T. The experimental results are shown in Fig. 6 and 7. As is seen, $`T_2^1`$ for the ($`+`$) cluster (upper branch) decrease monotonously with increasing field down to the field at which $`T_2^1`$ reaches the value of around 150 s-1. This value is nearly close to the constant value obtained at very low temperature in the temperature dependence of $`T_2^1`$. The field dependence at 1.45 K is slightly remarkable than that for 1.65 K. The anomalous peak around $`H_0=6.8`$ T in $`T_2^1`$ may be due to cross-relaxation with 1H NMR. It should be noted that the field dependence of $`T_1^1`$ is slightly more remarkable than that of $`T_2^1`$. For the ($``$) cluster (lower branch), on the other hand, the values of $`T_2^1`$ increase with increasing field. However, the change is rather monotonous as in the case of the ($`+`$) cluster. No any appreciable change was observed at the level-crossing fields around $`H_0`$=0, 0.45, and 0.9T. Figure 8 represents the field dependence of $`T_2^1`$ for Mn4+ ion (Mn(1)) and for Mn3+ ion (Mn(2)) for the ($`+`$) cluster obtained at 1.45K. No appreciable difference was found.

## IV Analysis

In this section, we shall analyze the experimental results. The nuclear magnetic relaxations in Mn12Ac will be primarily caused by the fluctuating component $`\delta 𝐒(t)`$ of the on-site manganese ion via the hyperfine interaction $`\delta _N(t)=𝐈A\delta 𝐒(t)`$, where $`A`$ is the hyperfine interaction tensor given by Eq. 7. In view of the fact that an assembly of the strongly-coupled manganese spins in a cluster is established as the cluster spin of $`S=10`$, we may assume that each manganese spin is subject to the same fluctuation corresponding to thermal fluctuation of the cluster spin along the z-axis, which is caused by the spin-phonon interaction. Then, the effective perturbing hyperfine interaction is expressed as

$$\delta _N(t)=(I_xA_{xz}+I_yA_{yz}+I_zA_{zz})\delta S_z(t).$$
(9)
Lascialfari et al. treated the fluctuating local field due to the spin-phonon interaction in analyzing the proton and muon spin-lattice relaxation rates in Mn12Ac by considering all of Zeeman levels with statistical weight. LJBCG  Here, we simplify the problem by taking into account only the lowest two energy-levels of $`S=10`$ within each of the double-well potential, that is, the ground-state $`S_z=m=10`$ and the first excited state $`m=9`$ for the (+) cluster, and $`m=+10`$ and $`m=+9`$ for the (-) cluster. Such a simplification is reasonable since the present 55Mn NMR is available only at low temperatures below about 2.5 K where the statistical weights of the higher excited states are quite small. Then the average life-times $`\tau _0`$ and $`\tau _1`$ of the ground-state and the excited state are given as follows within the framework of the lowest two levels;

$$\frac{1}{\tau _0}=\frac{C\mathrm{\Delta }^3}{\mathrm{exp}(\mathrm{\Delta }/T)1}$$
(10a)
and
$$\frac{1}{\tau _1}=\frac{C\mathrm{\Delta }^3}{1\mathrm{exp}(\mathrm{\Delta }/T)},$$
(10b)
where $`C`$ is the coupling constant for the spin-phonon interaction, VBSR  and $`\mathrm{\Delta }`$ is the energy difference between the ground-state and the first excited state, which is given by

$$\mathrm{\Delta }=19D_I/k_B\pm g_{}\mu _BH_0/k_B.$$

Here the signs $`\pm `$ correspond to the upper and lower branches for Mn4+ ion, respectively, and vice versa for Mn3+ ion. By using the values of $`D/k_B=0.67`$ K, BGS  and $`g_{}=1.93`$BGS  $`\mathrm{\Delta }`$ is given as $`(12.7\pm 1.30\times H_0)`$ K, $`H_0`$ being expressed in T. In our present experimental condition for the applied field, the attained value of $`\mathrm{\Delta }`$ is at the least about 11 K. So, for the low temperatures below 2.5 K, it turns out, from the expressions given by Eqs. (10), that $`\tau _0`$ exhibits very remarkable temperature dependence, whereas $`\tau _1`$ remains almost constant with the relation such that $`\tau _0\tau _1`$. Then, the effective fluctuation at each of the 55Mn sites is regarded to be step-wise, and it is characterized by random sudden jumps between the ground-sate and the excited state, as shown schematically in Fig. 9. Here $`h_\alpha `$ ($`\alpha =z`$ or $``$) is the average magnitude of the effective fluctuating field along or perpendicular to the $`z`$-axis. These effective fluctuating fields are related to the components of the hyperfine interaction tensor $`A`$ as $`h_z=A_{zz}/\gamma _N\mathrm{}`$ and $`h_{}=A_{xz}/\gamma \mathrm{}`$. In the followings we find expressions for the nuclear magnetic relaxation rates on the basis of the above model to look at the experimental results.

### IV.1 Transverse relaxation rate

First we consider the transverse relaxation rate. In our experiment, the relaxation time $`T_2`$ was determined by measuring the time constant of the decay of the spin-echo amplitude $`E(2\tau )`$, that is, the macroscopic transverse nuclear magnetic moment, as a function of time interval $`\tau `$ between the two *rf*-pulses. This decay, which corresponds to the phase disturbance of the Larmor precessions caused by the longitudinal fluctuating local field, is represented as KA

$$E(2\tau )=E_0\mathrm{exp}[i_0^\tau \delta \omega (t)𝑑ti_\tau ^{2\tau }\delta \omega (t)𝑑t]$$
(11)
The spin-echo amplitude can be calculated from Eq. (11) by considering all possible pulse sequences of e fluctuations, the phase deviations and the statistical weight of the pulse sequence. This problem has been treated by Kohmoto et al. for the interpretation of 133Cs relaxation times $`T_2`$ and $`T_1`$ in the $`S=1/2`$ Ising-like linear chain antiferromagnet CsCoCl3.KGMFFKM  According to the procedure presented in Ref. KGMFFKM, , we obtain, for $`\tau _0\tau _1`$, the following final expression

$$E(2\tau )=E_0\mathrm{exp}(\frac{2\tau }{T_2})$$

with

$$\frac{1}{T_2}=\frac{1}{\tau _0}\frac{(\gamma _Nh_z\tau _1)^2}{1+(\gamma _Nh_z\tau _1)^2}.$$
(12)
Thus the relaxation rate depends on the number of the fluctuation pulse per second, $`\tau _0^1`$ and average phase change $`\gamma _Nh_z`$ for one fluctuating field. The above equation yields for $`\gamma _Nh_z\tau _11`$

$$\frac{1}{T_2}=\frac{1}{\tau _0}(\gamma _Nh_z\tau _1)^2\frac{\tau _1^2}{\tau _0},$$
(13a)
and for $`\gamma _Nh_z\tau _11`$
$$\frac{1}{T_2}=\frac{1}{\tau _0}.$$
(13b)
As we see in the following section, Eq. (13a) corresponds to the expression obtained on the basis of the standard perturbation method, that is, the weak collision regime. On the other hand, Eq. (13b) means that the relaxation rate is determined solely by the average number of the appearance of the thermal excitation per one second, and further it does not depend on the magnitude of the fluctuating field. This is the strong collision regime. As evaluated above, in the present experimental conditions, the temperature dependence of $`T_2^1`$ results predominantly through the term of $`\tau _0`$. Accordingly, as far as the temperature dependence is concerned, there is no appreciable difference between both regimes for $`T_2^1`$. On the other hand, since the term of $`\mathrm{\Delta }^3`$ in $`\tau _0`$ and $`\tau _1`$ contributes to the field dependence of $`T_2^1`$, the qualitative difference between Eqs. (13a) and (13b) is expected to appear in the field dependence of $`T_2^1`$. Thus it is worthwhile to look at the qualitative field dependence of $`T_2`$ to find the plausible regime. The field-dependence of the relevant terms of $`\tau _0`$ and $`\tau _1^2\tau _0^1`$ calculated for T=1.45 K are shown in Fig. 10 by the solid and dashed lines, respectively. Clearly the solid line in Fig. 10, which represents $`\tau _0^1`$, explains well the corresponding experimental curve given in Fig. 6. This means that the strong-collision regime is valid. The solid line in Fig. 5 represents the result for qualitative fitting of the calculated curve of Eq. (13b) for zero field to the experimental temperature dependence of $`T_2^1`$. It should be noted that there appears no definite dependence of $`T_2^1`$ on the site of the manganese nuclei, although there exists rather large difference in the $`A_{zz}`$ component of the hyperfine tensor as estimated in the previous section (see Eqs. (7)). This is well understood if we adopt Eq. (13b). The results for the similar fittings for the field dependence of $`T_2^1`$ are shown in Fig. 6 by the solid and dotted lines. The solid line in Fig. 8 represents the fitted curve of Eq. (13b). In both cases of the temperature and field dependence of $`T_2^1`$, the agreements are satisfactory. Thus it is concluded that the transverse relaxation is essentially determined by the phase disturbance associated with the average number of the appearance of the first excited state per one second (strong collision regime).

### IV.2 Longitudinal relaxation rate

Now let us turn to the longitudinal relaxation rate. if we pay attention to the experimental fact that $`T_2^1T_1^1`$ together with the validity of Eq. (13b), it is reasonable to assume that the longitudinal relaxation time $`T_1`$ is much longer than the characteristic times $`\tau _0`$ and $`\tau _1`$. Then, the longitudinal relaxation rate $`T_1^1`$ should be obtained, following to the conventional perturbation theory, by the spectral component at the 55Mn Larmor frequency $`\omega _N`$ of the time correlation function for the step-wise fluctuating field as given in Fig. 9. The time correlation function for such a fluctuating field is easily calculated to be

$$\{h_+(t)h_{}(0)\}=h_{\mathrm{eff}}^2\mathrm{exp}(\frac{t}{\tau _c})$$
(14)
with

$$h_{\mathrm{eff}}^2=\frac{\tau _o\tau _1}{(\tau _o+\tau _1)^2}h_{}^2\frac{\tau _1}{\tau _0}h_{}^2$$
(15)
and

$$\frac{1}{\tau _c}=\frac{1}{\tau _0}+\frac{1}{\tau _1}\frac{1}{\tau _1},$$
(16)
where $`\tau _c`$ is the correlation time. The approximation used in Eqs. (15) and (16) is valid under the condition that $`\tau _0\tau _1`$, which is the relevant case. Taking the Fourier transform of Eq. (14), we obtain for $`\tau _0\tau _1`$,

$$\frac{1}{T_1}=\frac{\tau _1}{\tau _0}(\gamma _Nh_{})^2\frac{2\tau _1}{1+(\omega _N\tau _1)^2}.$$
(17)
This equation yields for $`\omega _N\tau _11`$

$$\frac{1}{T_1}=\frac{2(\gamma _Nh_{}\tau _1)^2}{\tau _0}\frac{\tau _1^2}{\tau _0},$$
(18a)
and for $`\omega _N\tau _11`$
$$\frac{1}{T_1}=\frac{2(\gamma _Nh_{})^2}{\tau _0\omega _N2}\frac{1}{\tau _0\omega _N^2}.$$
(18b)
Here the resonance frequency is given by $`\omega _N=\gamma _N(H_{\mathrm{int}}\pm H_0)`$, where the signs $`\pm `$ correspond to the upper and lower branches for Mn4+ ion and vice versa for Mn3+ ion. As in the case of $`T_2^1`$, the temperature dependence of $`T_1^1`$ is almost determined by $`\tau _0`$, while the field dependence depends not only on $`\tau _0`$ but also on $`\tau _1^2`$ and $`\omega _N^2`$. The field dependence of $`T_1^1`$ is determined by $`\tau _1^2\tau _0^1`$ for the low-frequency limit $`\omega _Nh_z\tau _11`$, and by $`\tau _0^1\omega _N^2`$ for the high-frequency limit $`\omega _Nh_z\tau _11`$. The dotted line in Fig. 10 represents the field dependence of $`\tau _0^1\omega _N^2`$ calculated for $`T=1.45`$ K. It is found that the experimental field dependence obtained for $`T=1.45`$ K fits well the dotted line, but not the dashed line, thus suggesting the validity of the equation for the high-frequency limit instead of the other. The dot-dashed and dotted lines in Fig. 5 represent the results of the best fitting of the curve $`\tau _0^1`$ for zero field to the experimental results for temperature dependence for the L1-line (Mn4+ ion) and the L2-line (Mn3+ ion). The agreement is reasonable down to around 0.7 K. The results for the similar fittings for the field dependence of $`T_1^1`$ are shown in Fig. 6 by the solid and dotted lines. The agreement is also satisfactory. Thus it turns out that the longitudinal relaxation is governed by perturbing effect of the fluctuating field $`h_{}(t)`$ (weak collision model), and then the high-frequency limit for the $`\omega _N`$ component of the correlation function of $`h_{}(t)`$ holds. It should be noted that the slight difference in the field dependence between $`T_2^1`$ and $`T_1^1`$ results from the presence of the factor $`\omega _N^2`$ in the latter, which is approximated as ($`\gamma _NH_{\mathrm{int}})^2(12H_0/H_{\mathrm{int}}`$) for $`H_{\mathrm{int}}H_0`$.

## V Discussions

First we examine the above treatment numerically. The use of $`T_2`$ yields directly the value of $`\tau _0`$. Then we obtain the constant for the spin-phonon interaction, $`C5\times 10^3`$ s-1K-3, which lies reasonably in the range of the value of 10$`{}_{}{}^{3}10^5`$ s-1K-3predicted in Ref. VBSP, . Using this value, we obtain $`\tau _11.1\times 10^7`$ s. Here if we tentatively assume that the deviation of the cluster spin of $`\delta S_z`$=1 during $`\tau _1`$ is shared by the 12 manganese spins, the average deviation of each spin is taken to be $`\delta S_z=1/4`$. Then, for instance, the use of $`A_{zz}/\mathrm{}=154`$ MHz for Mn4+ ion yields $`\gamma _Nh_z\tau _1`$25, thus the condition for the strong collision regime for $`T_2^1`$ relaxation process being satisfied. The reason why there appears above about 2K the slight difference in the value of $`T_2^1`$ between Mn4+ and Mn3+ ions might be due to the cross-over from the strong-collision regime to the weak collision regime. In fact, in the latter, the difference in the coupling constant term, that is, $`\gamma _Nh_z`$ or $`A_{zz}/\mathrm{}`$ should reflects in the value of $`T_2`$. Nevertheless, as far as we are confined ourselves within the present simplified treatment, it is not realized because $`\tau _1`$ is almost temperature-independent.

As for $`T_1`$, for instance, using the evaluated value of $`A_{xz}/\mathrm{}=24.7`$ MHz (Mn(2)) and 53 MHz (Mn(3)), we obtain $`T_2^1/T_1^1500`$ and $`100`$, respectively, which agrees reasonably with the experimental result in relative order of magnitude. However, the following points remain not understood. First, as far as the hyperfine interaction for Mn4+ ion is taken to be isotropic and not to have off-diagonal terms as determined in the present analysis of the NMR spectra, it is difficult to understand that the relaxation rate for Mn4+ ion is of comparable order with that for Mn3+ ion. In order to understand the experimental results for $`T_1`$ for Mn4+ ion, the assumption of the presence of any off-diagonal term of the hyperfine interaction tensor will be necessary. Unless the anisotropic term is not effective, the possible relaxation mechanism may be inevitably ascribed to the isotropic interaction term like $`AI^+`$$`\delta `$$`S^{}(t)`$ as in the case of the three-magnon relaxation process in usual magnetic system. In this case, the relevant activation energy which determines the temperature dependence of $`T_1`$ should be at least twice of the gap energy so as to guarantee the energy conservation between the nuclear spin and the electronic spin system. However, in the cluster which involves only twelve electronic spins coupled strongly to each other by exchange interactions, it may be quite unreliable. Anyhow, the origin of the effective coupling constant for $`T_1`$ for Mn4+ ion is uncertain at the present.

Next we discuss on the present concept for obtaining the relevant equations for $`T_2`$ and $`T_1`$. As a starting point we considered only the two lowest levels, the ground-state and the first excited state. Then, if we follow the standard stochastic theory, the fluctuating local field responsible for the nuclear magnetic relaxation, which is caused by the thermal excitation to the excited state from the ground-state, is treated as a perturbation with respect to the nuclear quantization axis. In the cases of zero field and where the external field is applied along the c-axis, the nuclear quantization axis is taken to be along the internal field at the 55Mn site, that is, along the $`c`$-axis. The longitudinal and transverse relaxation rates are given by the Fourier spectrum of correlation function of such a fluctuating local field $`h_\alpha (t)`$ ($`\alpha =z`$ or $``$) at the resonance frequency $`\omega _N`$ as follows:

$$\frac{1}{T_1}=F_{}(\omega _N)\text{and}\frac{1}{T_2}=\frac{1}{2T_1}+F_z(0)$$

with

$$F(\omega _N)=\frac{\gamma _N^2}{2}_{\mathrm{}}^{\mathrm{}}\{\delta h_\alpha (t)\delta h_\alpha (t)\}\mathrm{exp}(i\omega _Nt)𝑑t.$$
(19)
As shown in Sec. IV, the correlation function for the pulse-like field given in Fig. 9, is calculated to have the exponential-typed form given by Eq. (14). The longitudinal relaxation rate has already been given by Eq. (17). On the other hand, we have found experimentally that $`T_2^1T_1^1`$. So $`T_2^1`$ should be ascribed to the zero-frequency term $`F(0)`$, which is given by

$$\frac{1}{T_2}=F(0)=\frac{\tau _1^2}{\tau _0}(\gamma _Nh_z)^2.$$
(20)
According to this equation, the temperature dependence of $`T_2^1`$ results only from $`\tau _0`$ as far as $`\tau _0\tau _1`$ because $`\tau _1`$ is taken to be almost independent on the temperature. However, the value of $`T_2^1`$ should have a large site-dependence through the coupling constant term $`(\gamma _Nh_z)^2`$, which is proportional to the hyperfine interaction term of $`A_{zz}^2`$. Furthermore, as already shown in Fig. 10, the field dependence of $`\tau _1^2\tau _0^1`$ differs from that of only $`\tau _0^1`$. Such features contradict with our experimental results. Instead, as we have already mentioned, the equation like $`T_2^1=\tau _0^1`$ obtained as a strong collision regime on the basis of more basic treatment explains satisfactorily our experimental results for $`T_2`$.

Finally, with respect to the longitudinal relaxation, we compare our present formalism with the equation adopted by Furukawa et al. in Ref. FWKBG, . They have taken into account all of the 21 energy levels ($`m=10+10`$) of $`S=10`$ as the candidates for the fluctuating field $`\delta h_{}`$ responsible for the nuclear magnetic relaxation. Then, it has been assumed that the correlation functions associated with each of these energy levels are the exponential-typed one with the correlation time equal to the corresponding average life time, which is determined by the spin-phonon interaction as discussed in Ref. VBSP, . The contributions from each level have been summed up with the statistical weight. However, in considering the low temperature results, only the term related to the lowest ground-state with $`m=10`$ with the predominant statistical weight was remained as an effective one, thus yielding the expression like $`T_1^1A_\pm ^2/\tau _0\omega _N^2`$ in the high-frequency limit for $`\tau _0\omega _N1`$. As is seen, our equation (18b) has the same form as this equation. However, the origins of each term are different. First, in Eq. (18b), the term $`\tau _0`$ results from the effective amplitude of the fluctuating field $`(\tau _1/\tau _0)(\gamma _Nh_{})^2`$ in the correlation function. Secondly the criterion for the high-frequency limit, which brings the term $`\omega _N`$ in the equation, is taken with respect to $`\tau _1\omega _N`$ instead of $`\tau _0\omega _N`$. Thirdly, as for the coupling constant, Eq. (18b) involves the transverse fluctuating field $`h_{}`$, that is, the off-diagonal term $`A_{xz}`$, since it is assumed that the the anisotropic perturbing interaction like $`I^+\delta S_z(t)`$ is responsible for the nuclear spin lattice relaxation. While, in Ref. FWKBG, , the coupling constants for Mn(1) , Mn(2), and Mn(3) have been taken to be proportional to the square of the internal static field in zero field, i. e., square of $`A_{zz}`$ in our notation. Then, in view of the large difference of the ratio of the coupling constants of $`T_1^1`$ for the three ions between experimental values and the above estimation, the presence of the coupling constants for non-zero mode have been suggested. Unfortunately the 55Mn NMR signal is observable only at low temperatures. So it is difficult to find experimentally the maximum point of the relaxation rate which appears in the BPP-typed equation under the condition $`\tau _1\omega _N=1`$. It may be possible for other nuclei with much lower resonance frequency. However, such a condition is realized at rather high temperatures. In this case, the present two-level model may fail. Further extension of the present treatment will be necessary by taking into account the higher excited levels.

## VI Conclusion

The nuclear magnetic relaxation times $`T_2`$ and $`T_1`$ of 55Mn for Mn4+ and Mn3+ ions in Mn12Ac have been measured using the oriented powder sample at low temperatures below 2.5 K down to 200 mK in the fields up to 9 T applied along $`c`$-axis. The relaxation rates $`T_2^1`$ and $`T_1^1`$ in zero field exhibited remarkable decreases with decreasing temperature with the relative relation like $`T_2^1/T_1^1=200`$ at the temperatures above about 1.5 K. At the lower temperatures the difference was more pronounced. The field dependence of $`T_2^1`$ and $`T_1^1`$ showed decrease with increasing field for the cluster whose magnetic moment is parallel to the $`c`$-axis. On the contrary, those for the cluster whose magnetic moment is antiparallel to the $`c`$-axis increase with increasing field. The analysis for the experimental results was made on the concept that the nuclear magnetic relaxation is caused by thermal excitations of the cluster spin. We simplified the problem by considering only the excitation from the ground-state to the first excited state within each well of the double-well potential with the average life times determined by the spin-phonon interaction. On basis of the nonlinear theory, we obtained general expression for the transverse relaxation rate $`T_2^1`$ for such a pulse-like fluctuating field. It turned out that $`T_2^1`$ is well understood in terms of the equation $`T_2^1=\tau _0^1`$, which corresponds to the strong collision regime. On the other hand, the experimental results for $`T_1^1`$ was interpreted well by the standard perturbation formalism. On the other hand, the results for $`T_1`$ have been well understood, on the basis of the standard perturbation method, by the equation for the the high-frequency limit like $`T_1^11/\tau _0\omega _N^2`$, where $`\omega _N`$ is the 55Mn Larmor frequency. The quantitative comparison between the experiment and the theoretical calculation was made by using the 55Mn hyperfine interaction tensors, which resulted in reasonable agreement.

## Acknowledgments

The authors wish to thank Professor T. Kohmoto for valuable discussions. Discussions with Professor F. Borsa and Dr. A. Lascialfari are greatfully appreciated. Thanks are also due to Dr. Y. Furukawa for giving us useful informations. This work is supported by the Grant-in-Aid for Scientific Research from Ministry of Education, Culture, Sports, and Technology.


text:
# A new Manifestation of Atomic Parity Violation in Cesium: a Chiral Optical Gain induced by linearly polarized 6S-7S Excitation

APV experiments are important because they probe the electron-hadron $`Z^0`$ exchange in conditions totally different from those encountered in high energy experiments . The Boulder group  has made quite an achievement by performing a calibrated  measurement of the parity violating 6S-7S transition amplitude $`\mathrm{E}_1^{pv}`$, at a level of precision better than one per cent. The importance of this work is illustrated by the abundant literature triggered by the result. An atomic physics calculation is required to arrive at a precise determination of the weak nuclear charge $`Q_W`$, measuring the interaction strength. Atomic theorists have met the real challenge of reducing their calculation uncertainty below the existing value of one per cent . Subtle Breit  and radiative  corrections, previously omitted, were found to contribute at the few tenths of a percent level. Several authors  have announced a deviation of 2.5 or 2.2$`\sigma `$ between the empirical determination of $`Q_W`$ and the theoretical value expected in the Standard Model. Therefore, particle physicists have searched for the possible implications of such a deviation when taken seriously. The best way to account for it, without causing conflict with high energy results, is to admit the existence of an additional neutral vector boson $`Z_0^{}`$, whose mass differs according to the models, but always falls around a fraction of TeV .

In view of such an important implication, an independent measurement obtained by a totally different method, offering a cross-check of the result, would be extremely valuable. Our experiment has been designed to achieve this. Our approach differs from the Boulder’s one in two respects: a different emphasis given to signal-to-noise ratio (SNR) versus background level, and the choice of a new APV physical observable. The idea arose after our first experiment  succeeded in illustrating the interest of measurements in the forbidden 6S-7S Cs transition. It became clear that a novel detection scheme was required to improve their sensitivity. The polarization analysis of the fluorescence light collected only one thousandth of the photons emitted by the excited 7S atoms. We proposed a more efficient scheme based on stimulated emission from 7S to 6P3/2. As shown in Fig.1, an intense pulsed laser excites the 6S - 7S transition in a time short compared to the 7S lifetime, in a longitudinal electric field $`\stackrel{}{E}_l`$, giving rise to a large population inversion and transient amplification of a probe beam tuned at resonance for the 7S - 6P3/2 transition. Thus, nearly all atoms contribute to the signal. The dependence of the amplification on the relative orientation of the linear excitation polarization $`\widehat{ϵ}_{ex}`$ and the linear probe one $`\widehat{ϵ}_{pr}`$, is the effect which demonstrates APV. In two mirror-image configurations the excited vapor exhibits different gains, depending on whether the trihedron formed by $`\stackrel{}{E}_l,\widehat{ϵ}_{ex}`$ and $`\widehat{ϵ}_{pr}`$, is either right or left. In the present paper, we report on the first APV manifestation via such a chiral optical gain which validates our approach.

The pseudo-scalar $`(\widehat{ϵ}_{ex}\widehat{ϵ}_{pr})(\widehat{ϵ}_{ex}\widehat{ϵ}_{pr}\stackrel{}{E}_l)`$ appearing in the gain leads to a tilt $`\theta ^{pv}`$ of its optical axes with respect to the symmetry planes of the experiment (Fig.1). This tilt is given by the ratio of the PV E1 amplitude to the vector part of the Stark induced amplitude , $`\theta ^{pv}=\mathrm{ImE}_1^{\mathrm{pv}}/\beta E_l`$, about one $`\mu `$rd in current experimental conditions. We note that it is odd under $`\stackrel{}{E}_l`$ reversal. In our experiment, two mirror-image configurations, associated with the beams coming out from the polarizing beam splitter (PBS), are observed simultaneously, as shown in Fig.1. At the cell input $`\widehat{ϵ}_{pr}`$ is aligned along one of the optical axes in absence of APV, either parallel ($``$) or perpendicular ($``$) to $`\widehat{ϵ}_{ex}`$. During propagation through the vapor, APV induces a small tilt of $`\widehat{ϵ}_{pr}`$ towards the direction of largest gain. This linear dichroism should not be confused with a true optical rotation! It gives rise to an imbalance, odd under $`\stackrel{}{E}_l`$ reversal, in our two channel polarization analyzer, operating in balanced mode in absence of APV. In an ideal configuration, the imbalance between the optical signals in the two channels, $`S_1`$ and $`S_2`$, yields a measurement of the left-right (L-R) asymmetry:

$$A_{LR}=\frac{(S_1S_2)}{(S_1+S_2)}=2\theta ^{pv}\left[\mathrm{exp}(\eta 𝒜)1\right].$$
(1)
Here $`𝒜`$ is the optical density for the probe and $`\eta `$ the gain anisotropy, equal to $`(\alpha _{}\alpha _{})/2\alpha _{}`$, where $`\alpha _{}`$ (resp. $`\alpha _{})`$ is the probe gain per unit length for $`\widehat{ϵ}_{ex}\widehat{ϵ}_{pr}`$ (resp. $`\widehat{ϵ}_{ex}\widehat{ϵ}_{pr})`$. In these APV measurements, we selected the hyperfine component of the probe transition, the $`7S_{1/2,F=4}6P_{3/2,F=4}`$ line, leading to the largest value of $`\eta `$, hence the largest L-R asymmetry. As Eq. 1 shows, the greater the optical density, the larger the amplification of both the probe beam and the L-R asymmetry. We took advantage of this by exploiting the high optical densities available in a vapor cell, and by increasing the excitation energy and the $`\stackrel{}{E}_l`$ field magnitude. The exponential growth of the asymmetry with the applied field is the attribute of detection by stimulated emission, contrasting with fluorescence detection where the asymmetry $`\mathrm{Im}\mathrm{E}_1^{\mathrm{pv}}/\beta E_l`$ decreases when $`E_l`$ is increased. It should be stressed that a precise calibration procedure, independent on line-shape, optical density and saturation, has been devised and carefully tested . This consists in deliberately tilting the direction of $`\widehat{ϵ}_{ex}`$ with respect to $`\widehat{ϵ}_{pr}`$ by a small precisely calibrated angle $`\theta _{cal}`$. It can be shown that this causes the probe polarization to rotate by an angle $`k\theta _{cal}`$, with the same proportionality factor k as the APV angle $`\theta ^{pv}`$. On the other hand, due to the absence of magnetic fields, all atoms belonging to a given hyperfine state contribute and line shape problems coming from overlapping Zeeman components are avoided. In addition, the suppression in the longitudinal $`E_l`$-field configuration of the $`M_1`$-Stark interference effect, which is a potential source of systematic effect, is welcome. A further attractive feature is the cylindrical symmetry exhibited by the experiment: the signal is expected to remain invariant under simultaneous rotations of the polarizations $`\widehat{ϵ}_{ex}`$ and $`\widehat{ϵ}_{pr}`$ about the common beam direction. This feature has enabled us to discriminate against possible systematics arising from stray fields.

Despite the fact that our scheme combines several attractive new features, the observation of the APV chiral optical gain remains an experimental challenge. To make the method work we have had to solve often unexplored experimental problems. Besides a high precision differential polarimeter operating in pulsed regime , our experiment requires both the pulsed excitation laser and the probe laser systems to satisfy uncommon specifications described elsewhere. For instance, it is crucial to restrict the detection to the short time interval ($``$ 20 ns) during which the vapor acts as an amplifier, with the help of a fast optical switch on the probe laser beam. Another major problem was actually to generate a pulsed longitudinal uniform $`\stackrel{}{E}_l`$-field of $``$ 2 kV/cm inside a Cs vapor cell at the useful atomic densities ($`10^{14}`$/cm-3) and over a length of 80 mm. Moreover, the initial glass cells  had to be replaced by alumina ones consisting of an alumina tube, closed by sapphire windows glued at both ends. The surface electrical conductivity of alumina being much lower than that of glass , stray magnetic fields induced by electric surface currents are thereby suppressed. With alumina, one can use external electrodes if need be . The sapphire windows, unlike glass ones, retain excellent transparency under intense laser illumination in presence of the Cs vapor. Finally, one can heat alumina cells to 250-300 C to thermodissociate troublesome Cs2 dimers. As a consequence, the $`\stackrel{}{E}`$-field map distorsions coming from dimer photoionization by the excitation laser beam  are strongly reduced. One remaining problem, however, arises from the photoelectrons emitted by the windows. We have shown that these are considerably amplified by secondary electron emission (SEE) from grazing collisions with the walls. An efficient solution has consisted in machining annular grooves with sharp tips in the alumina walls (1 mm apart), making grazing incidence unlikely . This modification of the internal surface has led to strong reduction of the $`\stackrel{}{E},\stackrel{}{B}`$ stray fields and enabled us to perform the APV measurements reported here.

The signature of the PV signal first relies on a doubly differential feature of the polarimeter output. The imbalance at each amplified probe pulse, $`D^{amp}=\frac{(S_1S_2)}{(S_1+S_2)}`$ is compared to that of four consecutive probe pulses, $`D^{ref}`$, measured when all 7S excited atoms have decayed. Thus the doubly differential signal, $`D^{amp}D^{ref}`$, selects at the laser repetition rate ($``$ 100 s-1) a true atomic effect, $`D_{at}`$, free from the probe polarization rotation (independent of the excited atoms) arising from polarization defects present on the probe beam path. Our measurement involves four different physical parameter reversals, listed in order of increasing period. 1) reversal of $`\theta _{cal}`$, every 0.25 s, providing for real time calibration; 2) reversal of the $`\stackrel{}{E}_l`$ field every 0.5 s (with 60 ms dead time); 3) switching of the half-wave plate $`(\frac{\lambda }{2})^{det}`$ in front of the polarimeter, which performs a symmetry of the outgoing probe polarization with respect to the symmetry plane of the experiment, every 2 s: it allows us to discriminate between true polarization rotations and instrumental imbalances ; 4) switching of another half-wave plate $`(\frac{\lambda }{2})^{pr}`$ which acts on the input probe polarization, from para ($`\widehat{ϵ}_{ex}\widehat{ϵ}_{pr}`$) to ortho ($`\widehat{ϵ}_{ex}\widehat{ϵ}_{pr}`$) configuration for discrimination between linear dichroism and optical rotation . Since performing twice a given reversal leaves the system unchanged, for each reversal we introduce one binary variable: $`\sigma _{cal},\sigma __E,\sigma _{det},\sigma _{pr}=\pm 1`$. Thus the complete signature of the APV signal involves an average over all the $`2^4`$ possible states. For a given $`f(\sigma `$), we define the average, $`<f(\sigma )>_\sigma =\frac{1}{2}(f(1)+f(1))`$, i.e. the $`\sigma `$-even part. This implies that $`<\sigma f(\sigma )>_\sigma =\frac{1}{2}(f(1)f(1))`$ yields the $`\sigma `$-odd part. The determination of the PV calibrated linear dichroism involves the construction of the following quantity:

$`G=\theta _{cal}\sigma __E\left[{\displaystyle \frac{<\sigma _{det}D_{at}(\{\sigma _j\})>_{\sigma _{det}\sigma _{cal}}}{<\sigma _{det}\sigma _{cal}D_{at}(\{\sigma _j\})>_{\sigma _{det}\sigma _{cal}}}}\right]_{\sigma __E\sigma _{pr}}`$ (2)
We stress that an imperfect $`\stackrel{}{E}_l`$ reversal leading to a $`\stackrel{}{E}_{l,odd}`$ contribution to $`𝒜`$ does not affect the RHS of Eq. 2.

Moreover, measurements with different orientations of $`\widehat{ϵ}_{ex}`$ provide important tests for systematic effects associated with stray transverse $`\stackrel{}{E}_T`$ and $`\stackrel{}{B}_T`$ fields (or beam misalignment), since they are related to two preferred directions in the transverse plane. In fact, four orientations suffice because of the structure of the Stark induced dipole. A set of four supplementary $`\lambda /2`$ plates (two on each beam) enables us to perform successive rotations of $`\widehat{ϵ}_{ex}`$ (and $`\widehat{ϵ}_{pr}`$) by steps of 45, (directions $`\widehat{i}=\widehat{x},\widehat{u},\widehat{y},\widehat{v}`$), while keeping the analyzer fixed . From the four measurements, $`G_i`$, we extract two values of the isotropic part, $`\frac{1}{2}(G_x+G_y)=\frac{1}{2}(G_u+G_v)`$, expected - and actually found - to be equal to within the noise and to average to $`\theta ^{pv}`$. The presence of an anisotropic part manifests itself through the differences $`D_{xy}=\frac{1}{2}(G_xG_y)`$ and $`D_{uv}=\frac{1}{2}(G_uG_v)`$. The isotropy test consists in plotting one point in the cartesian coordinate system $`D_{xy},D_{uv}`$, for each cycle of four orientations of $`\widehat{ϵ}_{ex}`$ and to look for a possible deviation of the center of gravity of the cloud of points associated to all data. Clear anisotropies were sometimes observed. However, since their correlation with the isotropic part is not significant, the latter is negligibly affected. The two isotropic values obtained for each PV cycle (every $``$ 8 mn) were averaged together over a number N of cycles.

Finally, for practical reasons, we are obliged to carry out a further reversal. Although the ideal configuration requires perfect alignment of both laser beams along the cell axis, we have to concede a small tilt angle of the cell axis ($`\psi `$ 3 mrd), in order to avoid an excess of noise in the polarimeter. Since such a tilt breaks the symmetry, we reverse its sign every few hours and we take the average of the results obtained with both tilts, affected in practice by similar statistical noise: $`\theta _{exp}^{pv}=\frac{1}{4}<_iG_i(\sigma _\psi )>_{N,\sigma _\psi }.`$

As a consistency check, we have reconstructed the APV signal in a different way. $`D_{at}`$ and $`𝒜`$ measured for each pulse, yield the probe polarization tilt, $`\theta =D_{at}/2(\mathrm{exp}(\eta 𝒜)1)`$. for $`D_{at}`$. Replacing $`D_{at}`$ by $`\theta `$ in Eq. 2 provides a second determination of the linear dichroism G. Both methods lead to practically identical final results.

The validity of the entire acquisition procedure has been tested by programming the reversal of an additional tilt $`\theta _0`$ of the input polarization $`\widehat{ϵ}_{ex}`$, willingly correlated with $`\stackrel{}{E}_l`$ reversal. It is intended to mimic the APV effect by optical means. More precisely, the tilt and the field are switched in accordance with the following pattern,

$`(\theta _0+\theta _{cal},\stackrel{}{E}_l)`$$`(\theta _0`$ \- $`\theta _{cal},\stackrel{}{E}_l)`$ (-$`\theta _0+\theta _{cal},`$ -$`\stackrel{}{E}_l)`$(-$`\theta _0`$ -$`\theta _{cal},`$ -$`\stackrel{}{E}_l)`$

expected to mimic $`\theta ^{pv}=\theta _0`$. We expect the reconstructed signal G (Eq. 2) to give $`\theta _0+\theta ^{pv}`$. This test performed with $`\theta _0/\theta _{cal}=10^1`$, has been successful within a precision of 2 $`\%`$. When $`\widehat{ϵ}_{ex}`$ was rotated by increments of 450, the same procedure enabled us to test the isotropy of the polarimetry method, with SNR $``$ 100. The $`\theta _0`$ tilt creates a large linear dichroism $`\gamma _1`$, with no optical rotation $`\alpha _2`$. Thus, we also test successfully the discrimination between $`\gamma _1`$ and $`\alpha _2`$, based on the para/ortho reversal. This is a verification of the reconstitution method (Eq. 2), which deals correctly with the problem of a large gain anisotropy.

This test also shows the importance of a continuous search for a possible unwanted $`\stackrel{}{E}_{l,odd}`$ tilt of the input excitation polarization during APV measurements. This has been implemented using a visible polarimeter of the same design as the probe polarimeter, with sensitivity about 2.5 times better. Up to now, a stray effect of this kind, which might have arisen from electromagnetic interferences associated with pulsed $`\stackrel{}{E}_l`$ field monitoring, remains buried in noise ($`3.5\times 10^8`$rd).

There is one more harmful effect which arises from a longitudinal magnetic field reversing with the $`\stackrel{}{E}_l`$-field, $`B_z(E_{l,odd})`$. This causes a Hanle precession ($`E_{l,odd}`$) of the axes of the atomic alignment responsible for the parity conserving linear dichroism, around the beam axis. In fact, such a $`B_z`$ field also gives rise to an optical rotation by Faraday effect. The $`B_z(E_{l,odd}`$) Faraday effect can thus be isolated and exploited to measure the field magnitude . For this measurement, we select the highly $`B_z`$-sensitive $`7S_{1/2,F=4}6P_{3/2,F=5}`$ line. Owing to the progress which has resulted from grooving the internal surface of the alumina cell , the $`B_z(E_{l,odd})`$ field has remained either practically absent or small ($`<50\mu `$G) during the measurements reported here and more importantly it has exhibited only very slow drifts. Thus it is possible to correct for its effect, with only slight increase of the statistical noise, by inserting field measurements between longer periods of APV data averaging. We have verified the exactitude of the correction by performing measurements on both transitions, while willingly applying a $`B_z(E_{l,odd})`$ field of known magnitude.

We have calibrated the magnitude of the $`E_l`$ field inside the alumina cell by exploiting the atomic signals. Using this calibration leading to $`E_l`$ = 1.619 kV/cm, with 2$`\%`$ accuracy, and the result given by the Boulder group  we expect to obtain for the $`6S_{1/2,F=3}7S_{1/2,F=4}`$ excitation line: $`\theta ^{pv}=\frac{\mathrm{ImE}_1^{\mathrm{pv}}}{\beta E_l}=0.962\pm 0.020\times 10^6`$ rd.

We have now accumulated 3200 experimental isotropic values of the $`E_{l,odd}`$ linear dichroism. Fig. 2 shows the results of successive runs. The final result is:

$$\theta _{exp}^{pv}(\mu \mathrm{rd})=1.082\pm 0.091(\mathrm{stat}),$$
(3)
which agrees with the expected value within statistical error. The chiral optical gain which manifests APV is thus clearly detected. This validates our method.

The experiment has not yet reached its ultimate sensitivity. The noise is about 2.5 times the shot noise limit. Its sensitivity to optical adjustments proves that extra noise arises from interferences inside the inhomogeneously thick sapphire plates mounted as windows. In our next Cs cell, their parallelism will be much improved. By temperature tuning , an excellent reflexion minimum $`10^3`$ can be achieved and should be accompanied by strong reduction of the interference noise. For further improvement of the SNR, magnification of polarization tilts using a dichroic optical component , is also a promising technique we plan to implement soon. In parallel, we are constructing a new type of cell with internal ring electrodes spaced by ceramic braces. This geometry inhibits SEE while the electrodes connected at fixed potentials tend to evacuate the electrons circulating inside the vapor. Hence, we expect a reduction of the transverse fields , still present during the work reported here. All in all combined with an increased acquisition time (now 210 h) by a factor of 3 or 4, these improvements should bring us to within reach of our $`1\%`$ precision objective.

We thank many colleagues, more particularly F. Laloë, D. Treille, C. Bouchiat, M. D. Plimmer, for their interest in this work and encouragements, L. Pottier for early contributions and A. Clouqueur for technical assistance. A.W. acknowledges support from CNRS (IN2P3) and S.S. from the European Commission. Laboratoire Kastler Brossel is a Unité de Recherche de l’Ecole Normale Supérieure et de l’Université Pierre et Marie Curie, associée au CNRS (UMR 8552).

a Present address: Laboratoire de Physique des Lasers Univ. Rennes 1, Campus de Beaulieu, 35700 Rennes, France.

b Also at E. Fermi Physics Department, Pisa Univ., Italy.