# Muon Spin Relaxation and Nonmagnetic Kondo State in PrInAg2

## I Introduction

In a seminal paper, Yatskar et al. reported evidence for unconventional heavy-fermion behavior in the praseodymium-based intermetallic PrInAg<sub>2</sub>. This compound is one of only a handful of Pr-based materials which exhibit heavy-fermion or Kondo-like properties. Specific heat, magnetic susceptibility, and neutron scattering experiments indicate a non-Kramers doublet ($`\mathrm{\Gamma }_3`$) ground state due to crystalline-electric-field (CEF) splitting of the Pr<sup>3+</sup> $`{}_{}{}^{1}H_{4}^{}`$ term. The $`\mathrm{\Gamma }_3`$ state is nonmagnetic, i.e., there are no matrix elements of the magnetic moment operator within its doubly degenerate manifold. A nonmagnetic ground state would make the heavy-fermion-like specific heat anomaly found below 1 K and the enormous low-temperature Sommerfeld specific heat coefficient $`\gamma (T)6.5`$ J mole<sup>-1</sup> K<sup>-2</sup> quite unexpected, and suggests that PrInAg<sub>2</sub> may be a system in which an unusual nonmagnetic path to heavy-fermion behavior is realized. But such a scenario depends crucially on the nonmagnetic nature of the ground state.

This paper reports two results of muon-spin-relaxation ($`\mu `$SR) experiments in PrInAg<sub>2</sub> which support the conclusion of Yatskar et al. that the Kondo effect in PrInAg<sub>2</sub> is nonmagnetic in origin. First, we observe no temperature dependence of the muon relaxation rate at low temperatures, contrary to what would be expected if the specific heat anomaly involved magnetic degrees of freedom. Second, the muon relaxation behavior indicates that the CEF ground state in PrInAg<sub>2</sub> is in fact nonmagnetic, since the low-temperature muon relaxation can only be understood in terms of strong hyperfine enhancement of the <sup>141</sup>Pr nuclear magnetism. Hyperfine enhancement is an effect of the hyperfine coupling between the nucleus and the Van Vleck susceptibility of $`f`$ electrons of a non-Kramers $`f`$ ion in a nonmagnetic ground state, and only occurs when the Pr<sup>3+</sup> CEF ground state is nonmagnetic. It has been used to attain very low temperatures by nuclear demagnetization of singlet-ground-state Pr-based intermetallics.

Both of our results confirm the unusual nonmagnetic correlated-electron behavior of PrInAg<sub>2</sub>, using for the first time a microscopic probe of the electronic structure. We argue below that $`\mu ^+`$ relaxation is dominated by dipolar coupling to nearby <sup>115</sup>In and <sup>141</sup>Pr nuclear magnetic moments (Ag nuclear moments are negligible in comparison); the Pr<sup>3+</sup> wave function enters only in the hyperfine enhancement of the <sup>141</sup>Pr nuclear magnetism. The fact that no direct Pr<sup>3+</sup> $`f`$-ion magnetism is observed in PrInAg<sub>2</sub> is strong evidence for a nonmagnetic Pr<sup>3+</sup> CEF ground state, and the fact that the specific heat anomaly of Yatskar et al. corresponds to a molar entropy of $`R\mathrm{ln}2`$ indicates that this ground state is a $`\mathrm{\Gamma }_3`$ doublet.

The remainder of this introduction contains three brief pedagogical sections: a description of the theoretical basis for a nonmagnetic Kondo effect (Sect. I A), an introduction to the elements of the $`\mu `$SR technique used in this study (Section I B), and a review of the important aspects of hyperfine enhancement (Sect. I C). In Sect. II we describe our experimental results in PrInAg<sub>2</sub>, which include the temperature dependence of the zero-field $`\mu `$SR relaxation and the longitudinal field dependence of the relaxation at low temperatures. The implications of these results for the nature of the low-temperature state of PrInAg<sub>2</sub> are discussed in Sect. III, where it is concluded that (a) the observed $`\mu `$SR behavior is due to nuclear magnetism rather than a magnetic Pr<sup>3+</sup> ground state, i.e., the ground state is nonmagnetic; and (b) the effect of the muon electric charge on its environment does not invalidate the analysis which leads to this conclusion. We summarize our results in Sect. IV.

### A Nonmagnetic Kondo effect

The only nonmagnetic mechanism for Kondo behavior proposed to date is the two-channel quadrupolar Kondo effect (QKE) of Cox. In this picture, which was developed to explain the unexpected lack of field dependence of heavy-fermion properties in uranium-based compounds, correlated-electron behavior occurs when a non-Kramers $`f`$ ion such as Pr<sup>3+</sup> possesses a nonmagnetic multiplet ground state. The fluctuating electric quadrupole moment of the ground state scatters conduction electrons, analogous to spin-fluctuation scattering in the usual Kondo effect. An important difference between the two effects is that in the QKE there are two conduction-electron channels (spin-up and spin-down); since spin plays no role in the nonmagnetic scattering, the spin directions serve only as labels. The QKE is therefore one of a class of multi-channel Kondo effects for which the low-temperature behavior is that of a “non-Fermi liquid” with unusual properties, e.g., logarithmic divergence of $`\gamma (T)`$ and nonzero residual entropy $`S(T=0)=\frac{1}{2}R\mathrm{ln}2`$.

In its original form the theory of the QKE considers isolated impurities only, and to our knowledge no treatment of a lattice of nonmagnetic QKE $`f`$ ions has appeared. In particular, it is apparently not known whether the non-Fermi-liquid behavior of the impurity problem survives in the lattice. Although Yatskar et al. observed an uncharacteristic temperature dependence of the low-temperature electrical resistivity in PrInAg<sub>2</sub>, they found a substantially temperature-independent $`\gamma (T)`$ below $``$0.2 K and no evidence for residual entropy. Thus it is unclear whether or not PrInAg<sub>2</sub> is a Fermi liquid.

### B Zero- and low-field muon spin relaxation

$`\mu `$SR is a sensitive local probe of static and dynamic magnetism in solids. Spin-polarized positive muons ($`\mu ^+`$) are implanted into the sample, and the subsequent decay of the $`\mu ^+`$ spin polarization is monitored in time by measuring the asymmetry in the numbers of muon decay positrons emitted parallel and antiparallel to the $`\mu ^+`$ spin direction. The resulting relaxation function $`G(t)`$ is analogous to the free induction signal in a pulsed nuclear magnetic resonance (NMR) experiment. It is straightforward to carry out $`\mu `$SR experiments in zero or weak applied magnetic fields, which is not the case for NMR.

The shape and duration of $`G(t)`$ is controlled by the local magnetic fields at the $`\mu ^+`$ sites due to their magnetic environments. There are two kinds of effects. Relaxation by static local fields reflects a spatial distribution of $`\mu ^+`$ Larmor precession frequencies and hence of the local fields. The decay of $`G(t)`$ is then due to loss of phase coherence between precessing $`\mu ^+`$ spins, and the relaxation time is of the order of the inverse of the spread in Larmor frequencies. If the $`\mu ^+`$ local field distribution is due to randomly-oriented neighboring magnetic dipole moments (nuclear or electronic), the Central Limit Theorem suggests a Gaussian field distribution if more than a few moments contribute, in which case $`G(t)`$ is also Gaussian. Fields due to randomly-oriented nuclear dipolar moments, which usually do not reorient on the time scale of $`\mu `$SR experiments, often give rise to static relaxation. $`\mu `$SR is also a very good test for static magnetism, with or without long-range order, with a sensitivity $`10^3\mu _B`$, since dipolar fields from such small moments produce observable static relaxation. Dynamic (fluctuating) $`\mu ^+`$ local fields lead to spin-lattice relaxation, as in NMR, which is a measure of the spectral density of the fluctuations at low frequencies. For dynamic relaxation $`G(t)`$ is often but not always exponential.

Static and dynamic relaxation mechanisms can be distinguished by $`\mu `$SR experiments in a longitudinal field $`𝐇_L`$ (i.e., a field parallel to the $`\mu ^+`$ spin direction) much larger in magnitude than a typical local field $`𝐇_{\mathrm{loc}}`$. This produces a resultant field $`𝐇_L+𝐇_{\mathrm{loc}}`$ essentially in the direction of the applied field and hence of the $`\mu ^+`$ spin. Then the muons do not precess substantially, and if $`𝐇_{\mathrm{loc}}`$ is static their spin polarization is maintained indefinitely. This procedure is known as “decoupling” of the $`\mu ^+`$ spin from the static local fields. If on the other hand the relaxation is dynamic, then it is usually much less affected by the relatively weak applied field (typically $`H_L100`$ Oe). The expected field for decoupling is a few times the spread $`\mathrm{\Delta }H_{\mathrm{loc}}`$ in local fields, which can be estimated self-consistently by assuming that the relaxation is static. In this case the observed relaxation rate gives the spread $`\sigma `$ of $`\mu ^+`$ precession frequencies, so that

$$\mathrm{\Delta }H_{\mathrm{loc}}=\sigma /\gamma _\mu ,$$
(1)   
where $`\gamma _\mu `$ is the $`\mu ^+`$ gyromagnetic ratio.

Zero-field and low-field $`\mu `$SR (ZF- and LF-$`\mu `$SR) relaxation data are often analyzed using the Kubo-Toyabe (K-T) model, in which the shape of the relaxation function and its rate of decay are functions of the parameters which characterize the local field distribution and dynamics (i.e., $`\sigma `$ and the fluctuation rate $`\nu `$ of the local field), and also the conditions of measurement (i.e., the value of the applied field and its orientation relative to the $`\mu ^+`$ spin direction).

### C Hyperfine-enhanced nuclear magnetism

The best-known hyperfine-enhancement effect is the enhancement of the applied field at the nuclear site by a factor $`1+K`$ (Ref. ), with

$$K=a_{\mathrm{hf}}\chi _{\mathrm{VV}}.$$
(2)   
Here $`a_{\mathrm{hf}}`$ is the $`f`$ atomic hyperfine coupling constant, expressed in units of mole emu<sup>-1</sup>, and $`\chi _{\mathrm{VV}}`$ is the (molar) Van Vleck susceptibility of the $`f`$ ions. The factor $`K`$ is the usual paramagnetic NMR frequency shift (Knight shift in metals), due in this case to $`\chi _{\mathrm{VV}}`$. The latter is given approximately by

$$\chi _{\mathrm{VV}}\frac{𝒞}{(\mathrm{\Delta }_{\mathrm{CEF}}/k_B)},$$
(3)   
where $`𝒞`$ is the $`f`$-ion Curie constant and $`\mathrm{\Delta }_{\mathrm{CEF}}`$ is the excitation energy of the lowest CEF magnetic excited state. For typical Pr<sup>3+</sup> splittings $`\mathrm{\Delta }_{\mathrm{CEF}}=10`$–100 K, so that $`\chi _{\mathrm{VV}}=0.01`$–0.1 emu mole<sup>-1</sup>. With $`a_{\mathrm{hf}}(\mathrm{Pr}^{3+})=187.7`$ mole emu<sup>-1</sup> (Ref. ), one finds $`K=2`$–20. These considerable field increases are exploited in hyperfine-enhanced nuclear cooling.

Other effects of hyperfine enhancement include the following:

* The $`f`$ electrons are polarized by the nuclear magnetic dipole moment via a Van Vleck-like response, leading to an enhanced effective nuclear moment $`\mu _{\mathrm{nuc}}^{(\mathrm{enh})}=(1+K)\mu _{\mathrm{nuc}}^{(\mathrm{bare})}`$. The nuclear moment itself is of course unchanged; the term “hyperfine enhancement”, used here in much the same sense as “many-body enhancement of the electron mass” in heavy-fermion systems, refers to the interaction of the effective (nuclear + $`f`$-electron) moment with its magnetic environment.
* The electronic exchange coupling between neighboring $`f`$ ions mediates an indirect exchange interaction between nuclear spins, with exchange constant $`𝒥_{\mathrm{nuc}}`$ given by

$$𝒥_{\mathrm{nuc}}=\left(\frac{\gamma _{\mathrm{nuc}}\mathrm{}}{g_J\mu _B}\right)^2K^2𝒥_{\mathrm{el}};$$
(4)   
here $`\gamma _{\mathrm{nuc}}`$ is the nuclear gyromagnetic moment and $`𝒥_{\mathrm{el}}`$ is the electronic exchange constant.

As Bleaney puts it, “…we are dealing with nuclear lambs in electronic wolves’ clothing.”

Hyperfine enhancement phenomena were first observed in singlet ground-state $`f`$-ion compounds, but are also expected for $`f`$ ions with nonmagnetic multiplet ground states. Such effects do not occur at temperatures $`\mathrm{\Delta }_{\mathrm{CEF}}/k_B`$ (Ref. ) or if the ground state of the $`f`$ ion is magnetic. In both of these circumstances the $`f`$-electron polarization induced by the nucleus is lost in the much larger electronic magnetic moment of the $`f`$ ion, and hyperfine-enhancement phenomena are obliterated.

## II Experimental results

The sample of PrInAg<sub>2</sub> was prepared as described previously.$`\mu `$SR experiments were carried out at the $`\pi `$M3 beam line of the Paul Scherrer Institute (PSI), Villigen, Switzerland, using the General Purpose Spectrometer (GPS) and Low Temperature Facility (LTF), and at the M20 beam line at TRIUMF, Vancouver, Canada. ZF-$`\mu `$SR data were obtained over the temperature range 0.1–100 K, and the dependence of the relaxation function on longitudinal field was studied at a temperature of 0.7 K. We describe these results below, and discuss their implications in Sect. III.

### A ZF muon relaxation between 0.1 K and 100 K

As a preliminary characterization of the ZF relaxation function we fit the relaxation data to a “power exponential” function

$`G(t)=\mathrm{exp}\left[(\mathrm{\Lambda }t)^\beta \right],`$

where $`\mathrm{\Lambda }`$ is a generalized relaxation rate and the exponent $`\beta `$ interpolates between exponential ($`\beta =1`$) and Gaussian ($`\beta =2`$) limits. This fit function and parameters give a rough indication of the behavior of the relaxation, i.e., whether as discussed in Sect. I B it is dynamic (exponential), static (Gaussian), or an intermediate case.

The temperature dependence of $`\mathrm{\Lambda }`$ and $`\beta `$ is given in Fig. 1.

Both parameters are essentially independent of temperature from 0.1 K to $``$10 K. At low temperatures $`\mathrm{\Lambda }0.8\mu \mathrm{s}^1`$; we shall see that this is much larger than expected from <sup>115</sup>In and “bare” <sup>141</sup>Pr nuclear dipole fields. The low-temperature value $`\beta 1.2`$ indicates that the relaxation is nearly but not quite exponential.

Above 10 K both $`\mathrm{\Lambda }`$ and $`\beta `$ vary with temperature. A decrease of $`\mathrm{\Lambda }`$ to $`0.18\pm 0.02\mu \mathrm{s}^1`$ occurs between $``$10 K and $``$50 K, and above 50 K $`\beta `$ increases to $`2`$ at 80 K. This suggests a crossover to static relaxation at high temperatures. Although LF decoupling experiments have not been carried out above 0.7 K, the Gaussian shape and slow rate of the high-temperature muon relaxation function are consistent with nuclear dipolar relaxation in the static limit.

### B ZF and LF muon relaxation at 0.7 K

Figure 2 shows the experimental $`\mu ^+`$ relaxation functions $`G(t)`$ for $`T=0.7`$ K in zero field and in a longitudinal applied field $`H_L=100`$ Oe.

If the relaxation were due to a distribution of static $`\mu ^+`$ local fields, the observed ZF relaxation rate leads to an estimate of $``$10 Oe for the spread of these local fields. Then a longitudinal field of 100 Oe should completely decouple the local fields and there should be no relaxation. But it can be seen from Fig. 2 that although the relaxation rate is reduced for $`H_L=100`$ Oe it remains appreciable ($`0.07\mu \mathrm{s}^1`$). This strongly suggests that dynamic relaxation is involved. The curves in Fig. 2 are fits to the dynamic K-T model as described below in Sect. III B.

## III Discussion

In this section we first consider the implications of the temperature-independent ZF relaxation between 0.1 K and 10 K, using the rough “power exponential” analysis of Sect. II A and the data of Fig. 1. We then carry out a K-T analysis of the data of Fig. 2 and obtain the rms width and fluctuation rate of the local field at 0.7 K. Finally, we show that (a) the rms widths at 0.7 K and 100 K are quantitatively explained by nuclear magnetism (including <sup>141</sup>Pr hyperfine enhancement at low temperatures) alone, so that no Pr<sup>3+</sup> electronic magnetic moment need be invoked, and (b) the <sup>141</sup>Pr fluctuation rate at 0.7 K is consistent with the indirect nuclear exchange mechanism described above in Sect. I C.

### A Zero-field muon relaxation rate at low temperatures

The data of Fig. 1 put an upper bound of $`0.05\mu \mathrm{s}^1`$ on any change of $`\mathrm{\Lambda }`$ between 0.1 K and 10 K. This result has important implications for the two possible explanations of the low-temperature anomalies of Yatskar et al. which involve hypothetical Pr<sup>3+</sup> magnetic moments: (a) weak-moment static magnetism, and (b) “conventional” Kondo spin fluctuations.

#### a Weak-moment static magnetism due to spin freezing.

We show below in Sect. III C that in the absence of hyperfine-enhancement effects the (quasistatic) nuclear contribution to the ZF muon relaxation rate is considerably less than $`0.8\mu \mathrm{s}^1`$. Thus the persistence of such rapid relaxation to 10 K and above is already an indication that its cause is not related to the onset of static magnetism below 0.5–1 K, which would be required to explain the specific heat anomaly by such spin freezing. We nevertheless take the observed relaxation rate $`\mathrm{\Lambda }(T)`$ to be due to a temperature-independent component $`\mathrm{\Lambda }_0`$ and static relaxation and a temperature-dependent component $`\lambda (T)`$ due to the spin freezing; the latter presumably exhibits an anomaly in the neighborhood of the freezing temperature. Assuming conservatively that these components add in quadrature we have

$`\mathrm{\Lambda }(T)=\left[\mathrm{\Lambda }_0^2+\lambda (T)^2\right]^{1/2}.`$

With $`\mathrm{\Lambda }_00.8\mu \mathrm{s}^1`$ and $`\mathrm{\Lambda }(T)\mathrm{\Lambda }_00.05\mu \mathrm{s}^1`$ we obtain

$`\lambda (T)0.29\mu \mathrm{s}^1,`$

which yields an upper bound on the frozen Pr<sup>3+</sup> magnetic moment of order

$`\mu (\mathrm{Pr}^{3+})3\times 10^3\mu _B.`$

Static magnetism is therefore ruled out at this level. If $`\mathrm{\Lambda }_0`$ and $`\lambda (T)`$ were assumed to add linearly the upper limit on $`\lambda (T)`$ would be much smaller: $`\lambda (T)0.05\mu \mathrm{s}^1`$. Thus Pr<sup>3+</sup> spin freezing fails to account for our results, and in addition leaves unexplained the fast and temperature-independent $`\mu ^+`$ relaxation above $``$1 K.

#### b Conventional (spin) Kondo physics.

For temperatures $`T_K`$ a Kondo spin fluctuates at a rate $`\nu k_BT_K/\mathrm{}`$, which is $`10^{11}\mathrm{s}^1`$ for $`T_K1`$ K. In the neighborhood of $`T_K`$ the $`\mu ^+`$ relaxation rate $`T_1^1`$ is a maximum given by

$`(T_1^1)_{\mathrm{max}}2\sigma ^2/\nu ,`$

where $`\sigma `$ is the spread of $`\mu ^+`$ frequencies due to Pr<sup>3+</sup> dipole moments. We estimate $`\sigma `$ using Eq. (1), with the value $`\mathrm{\Delta }H_{\mathrm{loc}}=1.10\mathrm{kOe}/\mu _B`$ calculated via a lattice sum over Pr sites assuming uncorrelated Pr-moment fluctuations. This gives

$`(T_1^1)_{\mathrm{max}}0.2\mu \mathrm{s}^1`$

for a Pr<sup>3+</sup> moment of the order of 1 $`\mu _B`$. We expect this rate for $`TT_K`$, with a crossover to a Korringa law

$$T_1^1(T_1^1)_{\mathrm{max}}\left(\frac{T}{T_K}\right)$$
(5)   
(i.e., a considerable decrease of $`T_1^1`$) for $`T<T_K`$.

As discussed above in connection with the possibility of static magnetism, a change of this order of magnitude is in fact not seen: the observed rate $`\mathrm{\Lambda }0.8\mu \mathrm{s}^1`$ is constant down to $``$0.1 K (Fig. 1), whereas from Eq. (5) and $`T_K1`$ K (Ref. ) one expects a decrease of $`T_1^1`$ at 0.1 K to $``$10% of its value at 1 K. It might be argued that the Korringa rate is masked by a temperature-independent rate $`\mathrm{\Lambda }_0`$, as in the above discussion of spin freezing, in which case the minimum observable change of $`0.29\mu \mathrm{s}^1`$ derived above would apply and a Korringa-like change of $`0.2\mu \mathrm{s}^1`$ could not be ruled out by the data. But in the “conventional Kondo” scenario, as in the spin-freezing picture, there is no mechanism for a temperature-independent rate as large as $`\mathrm{\Lambda }_0`$. We therefore conclude that the experimental results are not consistent with conventional Kondo behavior.

### B ZF and LF muon relaxation at 0.7 K

We compare the relaxation functions at $`T=0.7`$ K (Fig. 2) with the K-T model in the “strong-collision” approximation of Hayano et al. This approximation takes the fluctuation to be of the form of uncorrelated sudden jumps of the local field. We make it as a matter of convenience, since it is easier to treat numerically than the Gaussian-Markovian process originally described by Kubo and Toyabe and the quantitative differences are small.

The model assumes that the $`\mu ^+`$ local field $`𝐇_{\mathrm{loc}}`$ is distributed in magnitude and direction, with each Cartesian component distributed around zero with rms value $`\sigma /\gamma _\mu `$, and that $`𝐇_{\mathrm{loc}}`$ fluctuates randomly in time with fluctuation rate $`\nu `$. In the following we refer to $`\sigma `$ as the static relaxation rate. In zero field a crossover occurs with increasing fluctuation rate from the “quasistatic” regime ($`\nu \sigma `$) to the “motionally-narrowed” regime ($`\nu \sigma `$). For $`\nu \sigma `$ the main dependence of the ZF relaxation function is on the combination $`\sigma ^2/\nu `$; the dependence on $`\sigma `$ and $`\nu `$ separately is weaker (and vanishes in the extreme narrowing limit $`\nu \sigma `$). Thus the ZF data alone do not suffice to determine both parameters, and the added constraint provided by the applied field is essential. This circumstance also prohibits a meaningful comparison of the ZF muon relaxation at other temperatures with the K-T model.

The best agreement with both ZF and LF relaxation data, given by the curves in Fig. 2, is obtained for $`\sigma =1.15\pm 0.05\mu \mathrm{s}^1`$, $`\nu =2.2\pm 0.1\mu \mathrm{s}^1`$. The relaxation is therefore in the regime of moderate motional narrowing.

### C Nuclear magnetism and muon relaxation

In this section we argue that the results of Sect. III B, together with the temperature dependence of the ZF relaxation rate $`\mathrm{\Lambda }(T)`$ (Fig. 1), can be understood by assuming that nuclear magnetism is the principal source of the $`\mu ^+`$ local field $`𝐇_{\mathrm{loc}}`$, and that furthermore the <sup>141</sup>Pr nuclear magnetism is hyperfine enhanced at low temperatures. In other words there is no sign of a Pr<sup>3+</sup> electronic magnetic moment, consistent with the hypothesis of a nonmagnetic CEF ground state.

The decrease of $`\mathrm{\Lambda }(T)`$ above $``$10 K is qualitatively consistent with the onset of <sup>141</sup>Pr nuclear spin-lattice relaxation by thermally-populated magnetic Pr<sup>3+</sup> CEF excited states; the corresponding increase of $`\nu `$ motionally narrows the muon relaxation. At sufficiently high temperatures (above 50 K, cf. Fig. 1) the exponent $`\beta `$ tends to the value $`\beta =2`$ characteristic of a Gaussian distribution of static fields. There are two possible explanations of this behavior. Either the <sup>141</sup>Pr relaxation remains so rapid that it is motionally narrowed and only the <sup>115</sup>In nuclei contribute to the (quasistatic) muon local field, or the Pr<sup>3+</sup> fluctuations become fast enough so that their contribution to the <sup>141</sup>Pr relaxation itself becomes motionally narrowed and negligible. Then the <sup>141</sup>Pr nuclei relax slowly under the influence of (unenhanced) nuclear dipolar fields. In either case the $`\mu ^+`$ relaxation is describable by the K-T model in the quasistatic limit, and one would observe essentially static nuclear dipolar fields at the muon sites. We shall see that the accuracy of our experiments does not allow us to distinguish between these two possibilities.

\[It should be noted that the absence of muon relaxation by fluctating fields due directly to Pr<sup>3+</sup> CEF excitations at high temperatures is not surprising. These fluctuations would be expected to be rapid, at least of the order of $`\mathrm{\Delta }_{\mathrm{CEF}}/\mathrm{}`$, in which case arguments similar to those of Sect. III A show that the muon relaxation rate is unobservably small ($`0.004\mu \mathrm{s}^1`$).\]

The above picture can be put on a more quantitative footing by comparing the data with the expected relaxation behavior at low and high temperatures, i.e., with and without hyperfine enhancement, respectively. We start by calculating the expected relaxation at high temperatures, where according to the above picture the nuclear contributions to the $`\mu ^+`$ relaxation can be calculated using the usual Van Vleck method of moments. Then one has static dipolar broadening from <sup>115</sup>In nuclei, together with a contribution from (unenhanced) <sup>141</sup>Pr nuclei if this contribution is not motionally narrowed.

The $`\mu ^+`$ electric charge produces an electric field gradient at the <sup>141</sup>Pr ($`I=5/2`$) and <sup>115</sup>In ($`I=9/2`$) sites. This produces a quadrupole splitting for both nuclides, which are not split in the unperturbed crystal because both sites possess cubic point symmetry. The quadrupole splitting in turn modifies the secular terms in the dipolar interaction, which must be taken into account in calculating the $`\mu ^+`$ relaxation in zero field. The $`\mu ^+`$ stopping site is unknown in PrInAg<sub>2</sub>. Calculated values of $`\sigma `$ for several candidate $`\mu ^+`$ sites are shown in Table I, which gives individual contributions $`{}_{}{}^{141}\sigma _{\mathrm{ZF}}^{}`$ and $`{}_{}{}^{115}\sigma _{\mathrm{ZF}}^{}`$ from <sup>141</sup>Pr and <sup>115</sup>In nuclei, respectively, together with the total rate $`\sigma _{\mathrm{ZF}}^{\mathrm{tot}}=\left({}_{}{}^{141}\sigma _{\mathrm{ZF}}^{2}+{}_{}{}^{115}\sigma _{\mathrm{ZF}}^{2}\right)^{1/2}`$.

Best agreement with the observed high-temperature static rate of $`0.18\pm 0.02\mu \mathrm{s}^1`$ is found for the $`(\frac{1}{4},\frac{1}{4},0)`$ $`d`$ site (Wyckoff notation) with or without an (unenhanced) <sup>141</sup>Pr contribution to $`\sigma _{\mathrm{ZF}}^{\mathrm{tot}}`$.

The muon may distort the lattice locally, thereby modifying the near-neighbor dipolar interactions primarily responsible for the relaxation. These dipolar interactions vary as the cube of the near-neighbor distances, the change of which can therefore be estimated from a comparison of calculated and measured $`\mu ^+`$ static relaxation rates. This calculation yields a local dilatation of $`5\pm 4`$%, assuming the muon occupies the $`d`$ site and that the <sup>141</sup>Pr contribution is present. This is comparable to the values 2–5% found in copper under similar circumstances by Camani et al. and Luke et al., but the high-temperature data are equally consistent with no <sup>141</sup>Pr contribution and/or little if any dilatation.

At 0.7 K the <sup>141</sup>Pr contribution to the $`\mu ^+`$ static relaxation rate will be increased by the factor $`1+K`$ if the <sup>141</sup>Pr dipole moment is hyperfine enhanced (Sect. I C). Using $`a_{\mathrm{hf}}=187.7\text{mole\hspace{0.17em}emu}^1`$ (Ref. ) and the extrapolated low-temperature value of the Van Vleck susceptibility $`\chi _{\mathrm{VV}}0.04\text{emu\hspace{0.17em}mole}^1`$ (Ref. ), we obtain $`K7.5`$ from Eq. (2), in agreement with the value obtained from the nuclear Schottky anomaly in the low-temperature specific heat. This gives an expected low-temperature rate

$`\sigma (\text{low }T)`$ $`=`$ $`\left[{}_{}{}^{141}\sigma _{\mathrm{ZF}}^{2}(1+K)^2+{}_{}{}^{115}\sigma _{\mathrm{ZF}}^{2}\right]^{1/2}`$   
$`=`$ $`1.1419\mu \mathrm{s}^1`$   
for the $`d`$ site, in excellent agreement with the observed low-temperature value of $`1.15\pm 0.05\mu \mathrm{s}^1`$ quoted above.

We now turn to the observed value $`\nu =2.2\mu \mathrm{s}^1`$ of the low-temperature fluctuation rate (Sect. III B). The magnitude and temperature independence of this rate below 10 K lead us to interpret it as due to the like-spin coupling between (hyperfine-enhanced) <sup>141</sup>Pr nuclear moments. Using the Van Vleck method of moments, the calculated <sup>141</sup>Pr zero-field rms relaxation rate (neglecting quadrupolar splitting) is $`{}_{}{}^{141}\sigma _{\mathrm{ZF}}^{}=0.7490\mu \mathrm{s}^1`$. This is smaller by a factor of $``$3 than the observed fluctuation rate.

We first attempt to resolve this discrepancy by noting that the electric field gradient due to the $`\mu ^+`$ charge will induce quadrupole splitting of the neighboring <sup>141</sup>Pr nuclei. The effect of this splitting on the muon dynamics has been taken into account, but it also has an effect on the <sup>141</sup>Pr relaxation. In the presence of such quadrupole splitting the like-spin zero-field linewidth has only been calculated for $`I=1`$ and 3/2 (Ref. ), where it is found that $`\sigma _{\mathrm{ZF}}`$ is increased by factors of 1.19 and 1.26 respectively. These are not enough to explain the shortfall. It is likely that the corresponding factor for $`I=5/2`$ is larger than 1.26, but the trend does not seem to allow explanation of a factor of 3 by this mechanism.

We next consider the indirect exchange interaction between <sup>141</sup>Pr nuclei described in Sect. I C, which is mediated by the electronic exchange between neighboring Pr<sup>3+</sup> ions. We take the observed fluctuation rate $`\nu `$ as a measure of the nuclear exchange constant $`𝒥_{\mathrm{nuc}}/\mathrm{}`$, and use $`K=7.5`$ and Eq. (4) to obtain the estimate

$`𝒥_{\mathrm{el}}/k_B0.19\mathrm{K}`$

for the electronic exchange constant $`𝒥_{\mathrm{el}}`$. This value is reasonable when compared with results in other nonmagnetic-ground-state Pr-based compounds: $`𝒥_{\mathrm{el}}/k_B=0.61\mathrm{K}`$ in PrP (Ref. ) and 0.39 K in PrNi<sub>5</sub>. In PrInAg<sub>2</sub> $`𝒥_{\mathrm{el}}`$ is comparable to the Kondo energy scale of 0.5–1 K, and should therefore be taken into account in the theory of the nonmagnetic Kondo effect in this system.

### D Effect of muon charge on Pr<sup>3+</sup> ions

In addition to contributing an electric field gradient at near-neighbor nuclear sites, the $`\mu ^+`$ charge produces an electric field which perturbs the CEF splitting of Pr<sup>3+</sup> near neighbors. The symmetry of these Pr<sup>3+</sup> sites is lowered and some degeneracies, including that of the $`\mathrm{\Gamma }_3`$ ground-state doublet, are lifted. The corresponding modification of the Van Vleck susceptibility has been observed by transverse-field $`\mu `$SR (TF-$`\mu `$SR) in a number of Pr-based intermetallics. The ground state singlet is, however, still nonmagnetic, and Van Vleck paramagnetism and the corresponding nuclear hyperfine enhancement will remain features of the perturbed system.

If the Pr<sup>3+</sup> ground state were magnetic ($`\mathrm{\Gamma }_4`$, $`\mathrm{\Gamma }_5`$), no qualitative effect of the $`\mu ^+`$ charge would expected except under extreme conditions. If it were argued that in PrInAg<sub>2</sub> the $`\mu ^+`$ electric field splits a magnetic Pr<sup>3+</sup> ground state so that the perturbed ground state is nonmagnetic, then this perturbation must split the degeneracy by an amount of the order of the unperturbed excitation energy ($`\mathrm{\Delta }_{\mathrm{CEF}}/k_B60`$ K) to explain the absence of temperature dependence of the ZF relaxation rate below 10 K (Fig. 1). This would be an improbable coincidence, and furthermore the perturbation would have to be considerably larger than observed previously (see the following section).

### E Comparison with $`𝝁`$SR and NMR in other Pr-based compounds

We review some earlier results in nonmagnetic ground state Pr-based compounds for comparison with the present work.

#### a PrNi<sub>5</sub>.

The ground state in this compound is a $`\mathrm{\Gamma }_1`$ singlet, and the smallest CEF splitting is $`k_B\times 23`$ K. ZF- and TF-$`\mu `$SR studies suggest considerable perturbation of the Pr<sup>3+</sup> CEF levels by the $`\mu ^+`$ electric field, since the TF-$`\mu `$SR frequency shift does not track the bulk susceptibility. A reduction of the CEF splitting by $`k_B\times 10`$ K (i.e., $``$100%) is needed to account for the modified susceptibility.

<sup>141</sup>Pr NMR has also been reported in PrNi<sub>5</sub>. Estimates of the hyperfine enhancement parameters $`𝒥_{\mathrm{el}}0.02`$ eV and $`K12`$ have been obtained from the data. We use these to calculate $`𝒥_{\mathrm{nuc}}/\mathrm{}5.5\times 10^6\mathrm{s}^1`$ from Eq. (4), which is roughly consistent with an independent estimate of the “zero-field splitting” $`10^6\mathrm{s}^1`$ from the low-temperature NMR data.

#### b PrIn<sub>3</sub>.

In this singlet-ground-state compound the Pr<sup>3+</sup> ions have considerably larger CEF splittings ($`\mathrm{\Delta }_{\mathrm{CEF}}/k_B=101`$ K; cf. Ref. ) than in PrNi<sub>5</sub>. As in the latter compound the TF-$`\mu `$SR frequency shift does not track the bulk susceptibility, but the discrepancy is much smaller in PrIn<sub>3</sub>. The change in $`\mathrm{\Delta }_{\mathrm{CEF}}/k_B`$ was found to be of the same order of magnitude ($``$10 K) as in PrNi<sub>5</sub>, so that the smaller effect on the susceptibility is related to the inverse relation between $`\mathrm{\Delta }_{\mathrm{CEF}}`$ and $`\chi _{\mathrm{VV}}`$ \[Eq. (3)\]: a given absolute change of $`\mathrm{\Delta }_{\mathrm{CEF}}`$ has a smaller effect on $`\chi _{\mathrm{VV}}`$ when $`\mathrm{\Delta }_{\mathrm{CEF}}`$ is large. Neither ZF- nor LF-$`\mu `$SR has been reported to date in PrIn<sub>3</sub>.

<sup>141</sup>Pr NMR in PrIn<sub>3</sub> (Ref. ) yields $`2.3\pm 0.3\mu \mathrm{s}^1`$ for the spin-spin relaxation rate $`1/T_2`$, which is comparable to the value of $`\nu `$ found in PrInAg<sub>2</sub> as described above. But $`1/T_2`$ increases with increasing temperature below 4.2 K, whereas $`\mu ^+`$ motional narrowing is observed only above $``$10 K. This discrepancy is not understood.

## IV Conclusions

Two features of the ZF- and LF-$`\mu `$SR results in PrInAg<sub>2</sub> corroborate the conclusion of Yatskar et al. that the Kondo behavior of the low-temperature specific heat in this compound originates from an unconventional Kondo effect associated with a nonmagnetic Pr<sup>3+</sup> $`\mathrm{\Gamma }_3`$ CEF ground state. First, the fact that the data show no magnetic anomaly between 100 mK and 10 K rules out both static magnetism and Kondo spin fluctuations associated with the degenerate Pr<sup>3+</sup> CEF ground state, so that neither of these mechanisms can be responsible for the low-temperature specific heat anomaly.

Second, the low-temperature muon-spin dynamics can be quantitatively understood in terms of nuclear magnetism only; there is no sign of a Pr<sup>3+</sup> electronic magnetic moment. Furthermore, quantitative agreement is obtained only if the <sup>141</sup>Pr nuclear magnetism is hyperfine-enhanced, which can occur only if the Pr<sup>3+</sup> CEF ground state is nonmagnetic. The experimental value of the $`\mu ^+`$<sup>141</sup>Pr dipolar coupling is in good agreement with that calculated assuming hyperfine enhancement of the <sup>141</sup>Pr nuclear dipole moment. In addition, the experimental estimate of the coupling between <sup>141</sup>Pr nuclei is about 3 times larger than the value calculated neglecting the indirect nuclear coupling which arises from hyperfine enhancement. This strongly suggests the existence of such an indirect mechanism; the required value of the electronic exchange interaction between Pr<sup>3+</sup> ions ($`𝒥_{\mathrm{el}}/k_B0.19`$ K) is less than but comparable to that in similar Pr-based compounds with nonmagnetic CEF ground states. Both these results depend crucially on hyperfine enhancement, and thus are evidence for the absence of a Pr<sup>3+</sup> ground-state magnetic moment. We emphasize that this electronic exchange should be taken into account in a complete theory of a nonmagnetic Kondo effect in PrInAg<sub>2</sub>.

We are grateful to W. P. Beyermann and R. Movshovich for discussing their research with us. One of us (D.E.M.) wishes to thank the staff of the MST-10 group, Los Alamos National Laboratory, for their hospitality during his stay at Los Alamos. This work was supported in part by the U.S. National Science Foundation, Grant Nos. DMR-9418991 (Riverside) and DMR-9510454 (Columbia), and in part by the U.C. Riverside Academic Senate Committee on Research, the Director for Energy Research, Office of Basic Energy Sciences, U.S. Department of Energy (DOE) (Ames), the Japanese agency NEDO (Columbia), and the Netherlands agencies FOM and NWO (Leiden); and was carried out in part under the auspices of the U.S. DOE (Los Alamos). Ames Laboratory is operated for the U.S. DOE by Iowa State University under Contract No. W-7405-Eng-82.