# Orbital Dynamics: The Origin of Anomalous Magnon Softening in Ferromagnetic Manganites

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## Abstract

We study the renormalization of magnons by charge and coupled orbital-lattice fluctuations in colossal magnetoresistance compounds. The model considered is an orbitally degenerate double-exchange system coupled to Jahn-Teller active phonons. The modulation of ferromagnetic bonds by low-energy orbital fluctuations is identified as the main origin of the unusual softening of the zone-boundary magnons observed experimentally in manganites.

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Recently, distinct new features in the spin dynamics of the ferromagnetic manganese oxide compound Pr<sub>0.63</sub>Sr<sub>0.37</sub>MnO<sub>3</sub> have been reported . Striking deviations from the predictions of the canonical double-exchange (DE) theory  were observed. In particular, an anomalous softening of magnons at the zone boundary was found even well below the Curie temperature $`T_C`$. It is noted that these anomalies are closely related to the reduced values of $`T_C`$: For higher-$`T_C`$ compounds no considerable deviations from a simple cosine dispersion is observed .

These experimental findings seem to be of high importance. They in fact indicate that some very specific features of magnetism in colossal magnetoresistance manganites have still to be identified. In this paper we propose a mechanism which might explain the above experimental observations. Our basic idea is the following: The strength of ferromagnetic interaction in a given bond strongly depends on which orbital is occupied by an $`e_g`$ electron (Fig. 1). Suppose that orbitals and Jahn-Teller (JT) distortions are disordered in the ferromagnetic phase. It is then evident that temporal fluctuations of orbitals affect the short-wavelength magnons through a strong modulation of exchange bonds. Quantitatively, the effect is expected to be controlled by the characteristic time scale of orbital fluctuations: A slowing-down of the dynamics of the coupled system of orbitals and JT phonons should lead to a stronger magnon renormalization. In other words, the observed zone-boundary magnon softening is interpreted in this picture as a precursor effect in the proximity of static orbital-lattice ordering.

More specifically, we calculate the dispersion of one-magnon excitation at zero temperature. First, we map the ferromagnetic Kondo-lattice model onto a Hamiltonian of interacting magnons and spinless fermions. Yet the fermions carry orbital quantum number, the fluctuations of which the magnon can scatter on. Second, we show that as the orbitals are strongly coupled to the lattice there is an indirect coupling of magnons to JT phonons via the orbital sector. Put another way, the orbital-lattice coupling produces a low-energy component in the orbital fluctuation spectrum at phonon frequencies. We then calculate the self-energy corrections to the magnon dispersion perturbatively (employing a $`1/S`$ expansion). Charge fluctuations are found to produce a moderate softening of magnons throughout the Brillouin zone. The effect of orbital and lattice fluctuations on the magnon dispersion is more pronounced and becomes dramatic as static order in the orbital-lattice sector is approached.

We start with a model describing the ferromagnetic coupling of double-degenerate $`e_g`$-band electrons to an otherwise noninteracting system of localized spins $`𝑺_t`$ on a cubic lattice:

$`H`$ $`=`$ $`{\displaystyle \underset{ij_\gamma }{}}t_\gamma ^{\alpha \beta }\left(e_{i\sigma \alpha }^{}e_{j\sigma \beta }+\text{H.c.}\right)J_H𝑺_{it}𝒔_{ie}`$ (2)   
$`+{\displaystyle \underset{\alpha }{}}Un_{i\alpha }n_{i\alpha }+{\displaystyle \underset{\alpha \beta }{}^{}}\left(U^{}J_H\widehat{P}\right)n_{i\alpha }n_{i\beta }`$   
with $`\gamma \{x,y,z\}`$ and $`\widehat{P}=(𝒔_{i\alpha }𝒔_{i\beta }+\frac{3}{4})`$. Hereafter, the indices $`\alpha /\beta `$ and $`\sigma `$ stand for orbital and spin quantum numbers of $`e_g`$ electrons, respectively; summation over repeated indices is implied and double counting is excluded from the primed sum. The spin operator $`𝒔_{i\alpha }`$ acts on orbital $`\alpha `$ and $`𝒔_{ie}=_\alpha 𝒔_{i\alpha }`$. The last two terms in Eq. (2) describe intra- (inter-) orbital Coulomb interaction $`U`$ ($`U^{}`$) and Hund’s coupling between $`e_g`$ electrons in doubly occupied states. Correlations are assumed to be strong: $`U,U^{},(U^{}J_H)t`$. The important point is the peculiar orbital and bond dependencies of the electron hopping matrix elements. In orbital basis $`\alpha \{|3z^2r^2,|x^2y^2\}`$ (see Fig. 1) one has :

$`t_{x/y}^{\alpha \beta }=t\left(\begin{array}{cc}1/4& \sqrt{3}/4\\ \sqrt{3}/4& 3/4\end{array}\right),t_z^{\alpha \beta }=t\left(\begin{array}{cc}1& 0\\ 0& 0\end{array}\right).`$

We work in the limit $`J_H\mathrm{}`$. Then the combined action of the on-site Hund’s “ferromagnetism” and the spin-diagonal nature of electron hopping results in a global ferromagnetic ground state. Two different contributions to the spin stiffness should be noticed: Conventional double exchange due to metallic charge motion and superexchange which accounts for the kinetic energy gain by virtual hoppings of $`e_g`$ electrons. We now derive the effective Hamiltonian describing the spin excitations at $`TT_C`$.

Double exchange.— At $`J_H\mathrm{}`$, $`𝑺_t`$ and the $`e_g`$ spin $`𝒔_e`$ are not independent anymore: $`𝒔_{ie}=n_{ie}𝑺_t/2S_t`$. They form a total on-site spin $`𝑺_i`$ with spin value $`S_t+\frac{1}{2}`$ if an $`e_g`$ electron is present, $`n_{ie}=1`$, or simply $`S_t`$ otherwise. The unification of band and local spin subspaces implies spin-charge separation. That is, the spin component $`b_{i\sigma }`$ of the $`e_g`$ electron $`e_{i\sigma \alpha }=b_{i\sigma }c_{i\alpha }`$ is decoupled and “absorbed” by the total spin, and we are left with a charged fermion $`c_{i\alpha }`$ carrying the orbital index. At $`TT_C`$, the Schwinger boson $`b_i`$ simply becomes a part of the magnon operator $`b_i`$, namely $`b_i=b_i/(2S)^{1/2}`$, while $`b_i`$ is almost condensed, $`b_i=(n_{ie}n_i)^{1/2}1b_i^{}b_i/4S`$. Hereafter, $`S=S_t+\frac{1}{2}`$. Further, we keep the relevant leading $`1/S`$ terms only and assume small doping $`x`$. The kinetic energy then reads

$`H_{\text{kin}}`$ $`=`$ $`{\displaystyle \underset{ij_\gamma }{}}t_\gamma ^{\alpha \beta }c_{i\alpha }^{}c_{j\beta }+{\displaystyle \frac{1}{2S}}{\displaystyle \underset{ij_\gamma }{}}t_\gamma ^{\alpha \beta }`$ (4)   
$`\times c_{i\alpha }^{}c_{j\beta }\left({\displaystyle \frac{1}{2}}b_i^{}b_i+{\displaystyle \frac{1}{2}}b_j^{}b_jb_i^{}b_j\right)+\text{H.c.}`$   
The first term here describes the fermionic motion in a ferromagnetic background (yet this motion is strongly correlated in the presence of orbital disorder ), while the second term controls the spin dynamics and spin-fermion interaction. The latter term would come out from a spin-wave expansion of an effective Heisenberg model $`J_{\text{DE}}(𝑺_i𝑺_j)`$ with $`J_{\text{DE}}=(2S^2)^1t_\gamma ^{\alpha \beta }c_{i\alpha }^{}c_{j\beta }`$ if one considers the fermionic sector on average as in mean-field treatments of the DE model. However, the bond variable $`c_{i\alpha }^{}c_{j\beta }`$ is a fluctuating complex quantity and the spin structure of Eq. (4) is therefore not of Heisenberg form. Explicitly ($`TT_C`$):

$`H_{\text{kin}}`$ $`=`$ $`{\displaystyle \underset{ij_\gamma }{}}t_\gamma ^{\alpha \beta }c_{i\alpha }^{}c_{j\beta }`$ (6)   
$`\times \left[{\displaystyle \frac{3}{4}}+{\displaystyle \frac{1}{4S^2}}\left(S_i^zS_j^z+S_i^{}S_j^+\right)\right]+\text{H.c.}`$   
In the classical limit for spins, one recovers from Eq. (6) the effective fermionic model with phase-dependent hopping . In addition to the above peculiarities, the band/local duality of spin in the DE system further results in the following important point: Going to momentum representation in Eq. (4) one immediately realizes that the magnon-fermion interaction vertex does not vanish at zero-momentum transfer. What is wrong? The boson $`b_i`$ should not be regarded as a physical magnon. The true Goldstone particle of the DE model is the following object with both local spin and itinerant features:

$`B_i`$ $`=`$ $`b_i\left[n_{ic}+\sqrt{{\displaystyle \frac{2S1}{2S}}}\left(1n_{ic}\right)\right]`$ (7)   
$``$ $`b_i{\displaystyle \frac{1}{4S}}\left(1n_{ic}\right)b_i.`$ (8)   
The composite character of the physical magnon $`B_i`$ is the price one has to pay for spin-charge separation and for the rearrangement of the original Hilbert space. The itinerant component of $`B_i`$ is of order $`1/S`$ only. However, the spin stiffness is itself of the same order, and the $`1/S`$ correction in Eq. (8) is of crucial importance to ensure spin dynamics consistent with the Goldstone theorem. Now, commuting Eq. (8) with Eq. (4) one finds the mean-field magnon dispersion $`\omega _𝒑`$ and the correct momentum structure of the magnon-fermion scattering vertex:

$`[B_𝒑,H]`$ $`=`$ $`\omega _𝒑B_𝒑+{\displaystyle \frac{t}{2S}}{\displaystyle \underset{𝒒}{}}A_𝒑^{\alpha \beta }(𝒌)c_{𝒌\alpha }^{}c_{𝒌𝒒,\beta }B_{𝒑+𝒒},`$ (10)   
$`A_𝒑^{\alpha \beta }(𝒌)=\gamma _𝒌^{\alpha \beta }\gamma _{𝒌+𝒑}^{\alpha \beta }.`$   
Here, $`\omega _𝒑=zD_s\left(1\gamma _𝒑\right)`$, $`D_s=J_{\text{DE}}S`$, $`J_{\text{DE}}`$ is defined above, $`z=6`$, and the form factors $`\gamma _𝒌=z^1_𝜹\mathrm{exp}(i𝒌𝜹)`$, $`\gamma _𝒌^{\alpha \beta }=(zt)^1_𝜹t_\delta ^{\alpha \beta }\mathrm{exp}(i𝒌𝜹)`$. The physics behind the second term in Eq. (10) is the temporal fluctuations of the “exchange constant” due to the charge and orbital dynamics. From now on, the conventional diagrammatic method with bare magnon-fermion vertex given in Eq. (10) can be used.

Now we turn to the correlations in the fermionic band. We separate the charge and orbital degrees of freedom by the parameterization $`c_{i\alpha }=h_i^{}f_{i\alpha }`$, where the slave boson $`h_i`$ and the fermion $`f_{i\alpha }`$ represent the density and orbital fluctuations, respectively . Further, approximating $`\delta (c_{i\alpha }^{}c_{j\beta })=h_j^{}h_if_{i\alpha }^{}f_{j\beta }+f_{i\alpha }^{}f_{j\beta }h_j^{}h_i`$, one finds from Eq. (10) two different contributions to the magnon self energy.

Superexchange.— At low dopings, the virtual charge transfer across the Hubbard gap becomes of importance. In limit of large $`J_H`$, transitions to the high-spin intermediate state with energy $`U_1=(U^{}J_H)U^{},U`$ dominate. The corresponding superexchange Hamiltonian is then obtained to be:

$$H_{\text{SE}}=J_{\text{SE}}\underset{ij_\gamma }{}\left[𝑺_i𝑺_j+S(S+1)\right]\left(1\tau _i^\gamma \tau _j^\gamma \right).$$
(11)   
Here, $`J_{\text{SE}}=(t^2/U_1)[2S(2S+1)]^1`$ and $`\tau ^{x/y}=\left(\sigma ^z\pm \sqrt{3}\sigma ^x\right)/2`$, $`\tau ^z=\sigma ^z`$ with Pauli matrices $`\sigma ^{x/z}`$ acting on orbital subspace $`f_\alpha `$. Eq. (11) is the generalization of orbitally degenerate superexchange models  for arbitrary values of spin. Superexchange is of ferromagnetic nature because the $`J_H\mathrm{}`$ limit is assumed, and the exchange strength depends on orbital orientations . In an orbitally disordered state one can represent the orbital part of Eq. (11) in terms of fluctuating bond operators $`f_{i\alpha }^{}f_{j\beta }`$ . Then the effect of superexchange is simply to add a new term

$$A_𝒑^{\alpha \beta }(𝒌,𝒒)=x_0\left(\gamma _𝒌^{\alpha \beta }+\gamma _{𝒌𝒒}^{\alpha \beta }\gamma _{𝒌+𝒑}^{\alpha \beta }\gamma _{𝒌𝒒𝒑}^{\alpha \beta }\right)$$
(12)   
to the scattering amplitude in Eq. (10) and to renormalize $`D_s(J_{\text{DE}}+J_{\text{SE}})S=t\chi _0(x+x_0)/2S`$. Here the constant $`x_0=2\chi _0t/U_1`$ with mean-field parameter $`\chi _0=f_{i+c}^{}f_i\frac{1}{2}(1x)`$ defines the effective doping level below which the superexchange contribution becomes of importance.

To summarize up to now: We have developed a quantum theory of the double-exchange model at $`T<T_C`$ which also includes the correlation effects present in transition metal oxides. The obvious advantage of this approach over earlier treatments  is that the theory has a transparent structure adjusted to describe the low-energy spin dynamics, and the large atomic scale $`J_H`$ does not appear in the calculations, either. Yet the corrections $`t/J_H`$ can be accounted for perturbatively, if necessary.

Indirect magnon-phonon coupling via orbital sector.— An important piece of physics relevant to the experiment  is still missed in model (2), that is the Jahn-Teller orbital-lattice coupling . This can be written as:

$$H_{\text{JT}}=g_0\left(Q_{2i}\sigma _i^x+Q_{3i}\sigma _i^z\right),$$
(13)   
where $`Q_2`$ and $`Q_3`$ are the distortions of appropriate symmetry . The deformation energy including intersite correlations is given by

$$H_{\text{ph}}=\frac{1}{2}K\underset{i}{}𝑸_i^2+K_1\underset{ij_\gamma }{}\stackrel{~}{Q}_{3i}^\gamma \stackrel{~}{Q}_{3j}^\gamma ,$$
(14)   
with $`\stackrel{~}{Q}_3^{x/y}=(Q_3\pm \sqrt{3}Q_2)/2`$, $`\stackrel{~}{Q}_3^z=Q_3`$, and $`𝑸=(Q_2,Q_3)`$. In general, the JT interaction strongly mixes the orbital and lattice dynamics, leading to a fluctuation of exchange bonds at low (phonon) frequencies. Here, we treat this problem only perturbatively as shown in Fig. 2.

We arrive at the following effective spin-phonon Hamiltonian:

$$H_{\text{s-ph}}=\underset{𝒑𝒒}{}\left(𝒈_{𝒑𝒒}𝑸_𝒒\right)B_𝒑^{}B_{𝒑+𝒒}.$$
(15)   
The coupling constants $`g_{𝒑𝒒}^{(\alpha )}=g_0a_0(\eta _𝒒^{(\alpha )}\eta _𝒑^{(\alpha )}\eta _{𝒑+𝒒}^{(\alpha )})/S`$, where $`\eta _𝒒^{(2)}=\sqrt{3}(c_xc_y)/2`$, $`\eta _𝒒^{(3)}=c_z\frac{1}{2}c_x\frac{1}{2}c_y`$, $`c_\alpha \mathrm{cos}q_\alpha `$, and the parameter $`a_0=t(x+x_0)(f_{i+c}^{}f_i)(\sigma _i^z)_{\omega =0}`$.

Magnon self energies— We are now in the position to calculate the renormalization of the magnon dispersion. The leading $`1/S^2`$ corrections are shown in Fig. 3.

Charge and orbital susceptibilities in Figs. 3(a) and 3(b), respectively, are calculated using mean-field Green’s functions in slave boson $`h`$ and fermion $`f`$ subspaces. For the spectral density of JT phonons in Fig. 3(c) we use

$$\rho _\pm ^{\text{ph}}(\omega ,𝒒)=\frac{1}{\pi }\frac{\omega }{\omega _𝒒^\pm }\frac{\mathrm{\Gamma }}{(\omega \omega _𝒒^\pm )^2+\mathrm{\Gamma }^2}$$
(16)   
accounting phenomenologically for the damping $`\mathrm{\Gamma }`$ due to coupling to orbital fluctuations. The phonon dispersions $`\omega _𝒒^\pm =\omega _0^{\text{ph}}[\kappa _{1𝒒}\pm (\kappa _{2𝒒}^2+\kappa _{3𝒒}^2)^{1/2}]^{1/2}`$ with $`\omega _0^{\text{ph}}=(K/M)^{1/2}`$ follow from Eq. (14). Here, $`\kappa _{1𝒒}=1+k_1(c_x+c_y+c_z)`$, $`\kappa _{2𝒒}=k_1\eta _𝒒^{(2)}`$, $`\kappa _{3𝒒}=k_1\eta _𝒒^{(3)}`$, and $`k_1=K_1/K`$. The expressions obtained from the diagrams in Fig. 3 contain summations over momentum space which we perform numerically. We find the effect of charge fluctuations on the magnon spectrum to be quite featureless and moderate (see Fig. 4),

which is due to the fact that the spectral density of charge fluctuations lies well above the magnon band. On contrary, the relatively low-energy fluctuations of the orbital and lattice degrees of freedom are found to affect the spin-wave dispersion in a peculiar way, particularly in $`(0,0,q)`$ and $`(0,q,q)`$ directions. Fig. 4 shows the magnon dispersion. The hopping amplitude $`t=0.4`$ eV is chosen to fit the spin stiffness in Pr<sub>0.63</sub>Sr<sub>0.37</sub>MnO<sub>3</sub>; further we use $`U_1=4`$ eV . The phonon contribution depends on the quantity $`(g_0a_0)^2/2KE_{\text{JT}}a_0^2`$. We set $`E_{\text{JT}}a_0^2=0.004`$ eV , $`\omega _0^{\text{ph}}=0.08`$ eV , $`\mathrm{\Gamma }=0.04`$ eV. Our key observation is the crucial effect of intersite correlations of JT distortions, controlled by $`k_1`$, on the magnon dispersion (see Fig. 5). To explain the experimental data  we are forced to assume ferro-type correlations ($`k_1<0`$). We interpret this surprising result in the following way: Conventionally $`k_1>0`$ corresponding to AF order of JT distortions and orbitals is expected in undoped compounds . However, in the doped case charge mobility prefers a ferro-type local orientation of orbitals which minimizes the kinetic energy. This competition between JT and kinetic energies can be simulated by tuning $`k_1`$. At large enough doping, ferro-type orbital correlations are expected to prevail, hence effectively $`k_1<0`$. In fact, a ferro-type ordering of orbitals leading to a layered AFM spin structure is experimentally observed  at dopings about $`x=0.5`$. As this instability is approached, low-energy, quasi static fluctuations of exchange bonds develop, yielding a magnon evolution as shown in Fig. 5. Remarkably, the small $`q`$ spin stiffness is not affected by this physics, while a strong reduction of $`T_C`$ by soft magnons at the zone boundary is predicted. This explains the origin of the anomalous enhancement of the $`D_s/T_C`$ ratio in low-$`T_C`$ manganites .

In summary, we have presented a theory of spin dynamics in a model relevant to manganites, emphasizing particularly the interplay between double-exchange physics and orbital-lattice dynamics. The unusual magnon dispersion in lower-$`T_C`$ compounds is explained as due to the proximity to orbital-lattice ordering. Apparently, strongly correlated orbital fluctuations play a crucial role in the physics of manganites.

We would like to thank H. Y. Hwang for stimulating discussions.