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# Charge Ordering Fluctuation and Optical Pseudogap in La1-xCaxMnO3

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## Abstract

Optical spectroscopy was used to investigate the optical gap (2$`\mathrm{\Delta }`$) due to charge ordering (CO) and related pseudogap developments with x and temperature (T) in La1-xCaxMnO3 (0.48 $`x`$ 0.67). Surprisingly, we found 2$`\mathrm{\Delta }`$/k$`_\text{B}`$T$`_{\text{CO}}`$ is as large as 30 for x$``$0.5, and decreases rapidly with increasing x. Simultaneously, the optical pseudogap, possibly starting from $`T`$* far above T$`_{\text{CO}}`$ becomes drastically enhanced near x=0.5, producing non-BCS T-dependence of 2$`\mathrm{\Delta }`$ with the large magnitude far above T$`_{\text{CO}}`$, and systematic increase of $`T`$* for x$``$0.5. These results unequivocally indicate systematically-enhanced CO correlation when x approaches 0.5 even though T$`_{\text{CO}}`$ decreases.

\]

It is one of key problems of current condensed matter physics to understand mysterious nature of charge/spin stripes in strongly correlated materials . Some exotic, but complex physical phenomena such as high $`T_c`$ superconductivity in cuprates and colossal magnetoresistance (CMR) in manganites can be intimately linked to the striped charge/spin correlations. However, in the cuprates it is still under debate how dynamic and/or short-range charge/spin stripes are related to the pseudogap phenomena at high temperatures . In the manganites , it has been recently recognized that dynamic or spatially fluctuating correlations of charge/spin/orbital can play an important role in the CMR phenomena . In particular, neutron scattering experiments showed that short-range correlation of the so-called CE-type charge ordering (CO) exists in ferromagnetic (FM) manganites, La$`_{\text{1-}x}`$CaxMnO$`_\text{3}`$ for $`x`$0.30, above the Curie temperature T$`_\text{C}`$, explaining its large resistivity and magnetoresistance near T$`_\text{C}`$ . Therefore, it is fundamentally important to better understand the roles of dynamic or short-range charge/spin stripes, in relation to the physical properties of those correlated materials.

Historically, the ‘CE-type’ CO in manganites was named for representing the special CO pattern observed in La$`_{\text{0.5}}`$Ca$`_{\text{0.5}}`$MnO$`_\text{3}`$ below $`T_{\text{CO}}`$180 K . A recent transport and structural study indicated that the short range CE-type CO correlation can be robust even to very high temperature (T) regions above $`T_{\text{CO}}`$ in La$`_{\text{1-}x}`$CaxMnO$`_\text{3}`$ for $`x`$0.50. However, an origin of the strong CE-type correlation and its presence over the other doping ranges are still enigmatic, partly due to intrinsic experimental difficulties in measuring fluctuating and short-ranged physical objects.

Optical spectroscopy has been powerful to probe fluctuating order parameters of solids because the frequency of the electromagnetic wave can be much higher than that of the fluctuating sources. Thus, it has successfully probed a phase-correlation time of superconducting order parameter of Bi$`_\text{2}`$Sr$`_\text{2}`$CaCu$`_\text{2}`$O$`_{\text{8+}\delta }`$ , an optical pseudogap in Nd2-xCexCuO4 in the normal states , and fluctuating charge-density-wave order parameters of K$`_{\text{0.3}}`$MoO$`_\text{3}`$ and (TaSe$`_\text{4}`$)$`_\text{2}`$I at high temperatures . However, there are few optical conductivity studies probing short-range CO fluctuation in strongly correlated materials.

In this Letter, we present systematic optical conductivity spectra $`\sigma `$($`\omega `$) of La$`_{\text{1-}x}`$CaxMnO$`_\text{3}`$ (0.48 $``$ x $``$ 0.67) revealing evidence of the short-range CO fluctuation at high temperatures. We find optical pseudogaps in La$`_{\text{1-}x}`$CaxMnO$`_\text{3}`$ (0.50 $``$x$``$ 0.67) due to the spatially fluctuating CO correlation, which presumably starts at a characteristic temperature $`T`$* far above $`T_{\text{CO}}`$. This optical pseudogap is greatly enhanced near x=0.50 and systematically diminishes as x increases. Furthermore, the systematic pseudogap evolution with x is well correlated with T-dependence of charge gap evolution with x, which deviates from the conventional BCS functional form for x$``$0.50 and recovers the form for x$``$0.67. These results are in contrast with a previous optical transmission study with powdered samples in a limited photon energy range (0.05 - 0.19 eV) , interpreting the BCS functional form for the charge gap behavior of $`x`$=0.50.

Single crystals of La$`_{\text{1-}x}`$CaxMnO$`_\text{3}`$ with high Ca concentration are difficult to grow. And, thus, high density polycrystalline specimens of La$`_{\text{1-}x}`$CaxMnO$`_\text{3}`$ (x=0.48, 0.50, 0.52, 0.60, and 0.67) were prepared with the standard solid state reaction method. $`T_{\text{CO}}`$ and/or $`T_\text{C}`$ of the samples were determined from magnetization (M) studies. For $`x`$=0.48, a FM metallic state is dominant below $`T_\text{C}`$220 K, possibly with a small CO phase emergent below 180 K (the inset of Fig. 1 (a)). However, the antiferromagnetic long-range CO becomes a dominant phase at low T for $`x`$0.50 so that $`T_{\text{CO}}`$ values of x=0.50, 0.52, 0.60, and 0.67 were 180, 190, 250, and 257 K, respectively. Because the x$`=`$0.50 sample is located at the phase boundary between FM metallic and CO insulating states, it shows also $`T_\text{C}`$220 K. All of the ordering temperatures were quite consistent with the established phase diagram of La$`_{\text{1-}x}`$CaxMnO$`_\text{3}`$ . Near normal incident reflectivity spectra $`R(\omega )`$ of those samples were measured from 6 meV to 30 eV in a T range between 10 and 300 K during a heating cycle. To subtract surface scattering effects from $`R(\omega )`$, after measuring reflectivity of the sample surface, a $`1000`$ Å thin layer of gold is evaporated onto the sample and the reflectivity is measured again and used for normalizing $`R(\omega )`$ of the samples . From the normalized $`R(\omega )`$, $`\sigma `$($`\omega `$) were calculated by the Kramers-Kronig transformation. The resultant $`\sigma `$($`\omega `$) matched well the $`\sigma `$($`\omega `$) from the spectroscopic ellipsometry between 1.5 and 4.5 eV. High $`T`$-resistivity measurements were performed in a flowing inert gas condition up to $``$1000 K.

Figure 1 (a) shows $`\sigma `$($`\omega `$) of the $`x`$=0.48, 0.50, and 0.52 samples at 10 K. $`\sigma `$($`\omega `$) of $`x`$=0.48 have a large absorption band centered at $``$0.5 eV, which can be related to incoherent hopping motion of polarons from Mn3+ to Mn4+ sites in the metallic state . On the other hand, an optical gap due to the long-range CO, namely, a charge gap is clearly observed in $`\sigma `$($`\omega `$) of $`x`$=0.50 and 0.52 at 10 K. We define a charge gap, 2$`\mathrm{\Delta }`$, as an onset energy of the steeply rising part of $`\sigma `$($`\omega `$), which can be determined from a crossing point between x-abscissa and a linear extrapolation line drawn at the inflection point of $`\sigma `$($`\omega `$). This procedure has been a common practice to evaluate 2$`\mathrm{\Delta }`$ of various CO materials , resulting in 2$`\mathrm{\Delta }`$(10 K)$``$0.45 eV for both $`x`$=0.50 and 0.52 samples. The charge gap energy at the ground state, 2$`\mathrm{\Delta }`$(0)$``$0.45 eV is the largest among numerous CDW systems  and charge-ordered oxides . This large 2$`\mathrm{\Delta }`$(0) can be a peculiar characteristic of the CE-type CO, indicating unusual stability of the special CO pattern .

On the other hand, $`\sigma `$($`\omega `$) of $`x`$=0.50 at 10 K show significant in-gap absorption below 0.5 eV, while in-gap absorption of $`x`$=0.52 is negligible at 10 K. One key finding from our experiments is that the spectral weight of the in-gap absorption is proportional to the amount of FM phase inside the samples. For example, decrease of M/H values at 10 K from $`x`$=0.48 to 0.52 (the inset of Fig. 1 (a)) is well correlated with decrease of spectral weight of $`\sigma `$($`\omega `$) below 0.5 eV at 10 K. In addition, the larger M/H values of x=0.50 than $`x`$=0.52 are consistent with the increased FM regions in x=0.50, located near the CO/FM phase boundary . Therefore, the in-gap absorption of x=0.50 is attributed to a FM phase coexisting with a CO phase at low $`T`$.

In Fig. 1 (b), $`\sigma `$($`\omega `$) of $`x`$=0.50 at 300 K reveal anomalous spectral features; $`\sigma `$($`\omega `$) below 1.0 eV are smaller than those of neighboring compounds. Furthermore, $`\sigma `$($`\omega `$) increase steeply with $`\omega `$, showing a positive curvature at low photon energy, which is very similar to the gap-feature observed at 10 K. It is noted that this spectral response is not compatible with a single polaron absorption model . Instead, the gap feature at 300 K suggests the presence of short-range CO or correlated multipolarons even far above $`T_{\text{CO}}`$. We note that it is not yet known if a theory for correlated multipolaron absorption could account for the peculiar $`\sigma `$($`\omega `$) of $`x`$=0.50 above $`T_{\text{CO}}`$.

To understand further the anomalous $`\sigma `$($`\omega `$) of $`x`$=0.50, we systematically investigated $`\sigma `$($`\omega `$) of La$`_{\text{1-}x}`$CaxMnO$`_\text{3}`$ with $`x`$=0.50, 0.52, 0.60, and 0.67 (Fig. 2). It is noted that T-dependence of the charge gap for $`x`$=0.50 is also peculiar; at 10 K$``$T$``$180 K, large 2$`\mathrm{\Delta }`$ values are observed in $`\sigma `$($`\omega `$) of x=0.50. In particular, 2$`\mathrm{\Delta }`$ values at T=250 and 300 K still remain finite, remarkably having almost the same magnitude with 2$`\mathrm{\Delta }`$ at 200 K. The $`\sigma `$($`\omega `$) of $`x`$=0.52 with $`T_{\text{CO}}`$190 K also show that 2$`\mathrm{\Delta }`$ remains nonzero up to T$``$240 K. These observations strongly suggest that the strong fluctuations of short-range CO (or correlated multipolaron) can be responsible for the finite charge gap far above $`T_{\text{CO}}`$ in the x$`=`$0.50 and 0.52 samples.

Even at high $`T>`$ 240 K, where 2$`\mathrm{\Delta }`$ is no longer finite, there exists significant suppression of spectral weight below an energy of maximum $`\sigma `$($`\omega `$), $`\omega _\text{m}`$. (arrows in Fig. 2). This suppression of spectral weight is accompanied by a pseudogap in $`\sigma `$($`\omega `$), i. e., decreasing $`\sigma `$($`\omega `$) below $`\omega _\text{m}`$ at each $`T`$. This pseudogap is also observed in the $`\sigma `$($`\omega `$) of x=0.60 and 0.67 at temperatures up to at least 300 K, even if 2$`\mathrm{\Delta }`$ of $`x`$=0.60 and 0.67 becomes zero just above $`T_{\text{CO}}`$. Surprisingly, it is found that the pseudogap feature shows systematic doping dependence. First, $`\omega _\text{m}`$ at 300 K systematically increases as x$``$0.50 from above (See Fig. 2). Second, the suppression of spectral weight below $`\omega _\text{m}`$ at 300 K becomes more evident as $`x`$ approaches 0.50, which finally produces a nonzero 2$`\mathrm{\Delta }`$ even at 300 K. This systematic enhancement of the pseudogap feature and its proximity to the finite 2$`\mathrm{\Delta }`$ far above $`T_{\text{CO}}`$ near $`x`$=0.50 consistently suggest that the optical pseudogap can be attributed to the spatially fluctuating CO correlation of La$`_{\text{1-}x}`$CaxMnO$`_\text{3}`$ (x$``$0.50) at high $`T`$ region.

To investigate the charge gap and its pseudogap developments quantitatively, we determined $`T`$-dependent suppressed spectral weight, $`\mathrm{\Delta }\sigma `$($`T`$)$`\sigma (\omega _\text{m})\omega _\text{m}`$-$`_0^{\omega _\text{m}}\sigma (\omega )𝑑\omega `$ and 2$`\mathrm{\Delta }`$($`T`$) for each x, as shown in figure 3 (a) and (b), respectively. Below $`T_{\text{CO}}`$, the $`\mathrm{\Delta }\sigma `$($`T`$) values of $`x`$=0.50 are smaller than those of $`x`$=0.52. The proximity to FM phase boundary at $`x`$=0.50 may be responsible for the reduction of $`\mathrm{\Delta }\sigma `$($`T`$) of $`x`$=0.50 at low $`T`$. It is noted that high-$`T`$ $`\mathrm{\Delta }\sigma `$($`T`$) values of all the samples are clearly nonzero up to at least 300 K. In particular, $`\mathrm{\Delta }\sigma `$($`T`$) values at 300 K increase systematically as x$``$0.50. At the same time, 2$`\mathrm{\Delta }`$($`0`$) values in Fig. 3 (b) increase as x$``$0.50; 2$`\mathrm{\Delta }`$($`0`$)$``$ 0.2, 0.26, 0.45, and 0.45 eV for x= 0.67, 0.60, 0.52 and 0.50, respectively . This increase of the 2$`\mathrm{\Delta }`$($`0`$) is well correlated with the increase of $`\mathrm{\Delta }\sigma `$($`T`$) at 300 K as x approaches 0.50. These findings indicate that the strength of CO stability is clearly maximized for x$``$0.50, being responsible for the enhanced CO fluctuation at high temperature. On the other hand, $`T_{\text{CO}}`$ of these compounds decreases as x approaches 0.50. Therefore, 2$`\mathrm{\Delta }`$($`0`$)/k$`{}_{\text{B}}{}^{}T_{\text{CO}}^{}`$ values systematically increase: 2$`\mathrm{\Delta }`$($`0`$)/k$`{}_{\text{B}}{}^{}T_{\text{CO}}^{}`$9, 12, 28, and 30 for x=0.67, 0.60, 0.52 and 0.50, respectively. This 2$`\mathrm{\Delta }`$($`0`$)/k$`{}_{B}{}^{}T_{\text{CO}}^{}`$ increase up to 30, an unusually large value among many charge-ordered oxides, indicates strongly-enhanced electron correlation near x$`=`$0.50 .

Related with the enhanced pseudogap feature and large 2$`\mathrm{\Delta }`$($`0`$)/k$`{}_{B}{}^{}T_{\text{CO}}^{}`$ value for x$``$0.50, 2$`\mathrm{\Delta }`$($`T`$)/2$`\mathrm{\Delta }`$($`0`$) vs T/$`T_{\text{CO}}`$ curves of $`x`$=0.50 and 0.52 clearly deviate from the BCS functional form ( the inset of Fig. 3 (b)). For example, 2$`\mathrm{\Delta }`$($`T`$)/2$`\mathrm{\Delta }`$($`0`$) values of $`x`$=0.50 are still about 0.25 at T/T$`{}_{\text{CO}}{}^{}`$1.7 (T=300 K) and those values of $`x`$=0.52 are nonzero up to at least T/T$`{}_{\text{CO}}{}^{}`$1.2 (T$``$ 240 K). These unique 2$`\mathrm{\Delta }`$($`T`$)/2$`\mathrm{\Delta }`$($`0`$) curves of non-BCS-type are quite consistent with the greatly enhanced spatial and/or temporal CO fluctuation near x=0.50 at high temperature regions. However, as $`x`$ is increased, 2$`\mathrm{\Delta }`$($`T`$)/2$`\mathrm{\Delta }`$($`0`$) curves recover the BCS form for $`x`$=0.60 and 0.67, as observed in most of CO materials .

To gain insights on how high temperatures this CO fluctuation survives, we studied high-$`T`$ resistivity of La$`_{\text{1-}x}`$CaxMnO$`_\text{3}`$ with x$``$0.50, as shown in Fig. 4 (a). The $`x`$=0.50 sample shows insulating behavior up to above $``$850 K, where orthorhombic (low $`T`$) to rhombohedral (high $`T`$) structural transition occurs. Surprisingly, for x$``$0.52, there exists a crossover from metallic to insulating states as $`T`$ decreases. Moreover, the crossover temperature defined as, $`T`$\*, decreases systematically as $`x`$ increases from 0.50. This $`T`$* evolution with $`x`$ is well correlated to 2$`\mathrm{\Delta }`$($`0`$) and $`\mathrm{\Delta }\sigma `$(300 K) behaviors for 0.50$``$x$``$0.67. Furthermore, in Fig. 4 (b), $`T`$* decreases as $`T_{\text{CO}}`$ does above $`x`$ $`=`$0.67. Our previous study of x=0.80 showed 2$`\mathrm{\Delta }`$($`0`$)$``$0.08 eV, indicating that both $`T_{\text{CO}}`$ and 2$`\mathrm{\Delta }`$($`0`$) decrease together above $`x=`$0.67 . Therefore, $`T`$* of charge-ordered La$`_{\text{1-}x}`$CaxMnO$`_{\text{}}`$is clearly linked to 2$`\mathrm{\Delta }`$($`0`$). This observation supports that $`T`$* can be the temperature where high $`T`$-CO correlation starts and thus optical pseudogap appears.

One convincing explanation for the enhanced CO fluctuation for x$``$0.50, can be a competition of order parameters in La$`_{\text{1-}x}`$CaxMnO$`_\text{3}`$ (x=0.50). Obviously, the commensurate 1:1 ratio of Mn3+ and Mn4+ ions is compatible with the strong CO tendency at x=0.50. At the same time, the double exchange mechanism predicts that the strength of the FM correlation in La$`_{\text{1-}x}`$CaxMnO$`_\text{3}`$ should be varied as x(1-x) and optimized at x=0.50 . Indeed, La1-xCaxMnO$`_{3\text{ }}`$($`x`$=0.50) has a thermodynamic bicritical point, where the FM metallic and the CO insulting states meet with the paramagnetic insulating state. Therefore, near the critical point, competing order parameters can lead to the suppression of ordering temperatures as well as increased spatial/temporal fluctuation among those phases. This scenario is further supported by a recent computational study, predicting that large charge fluctuations could be a generic feature of the mixed-phase systems at or near the regimes where a phase separation occurs as T$``$0 .

In conclusion, using systematic optical conductivity and transport studies, we determined doping dependent evolutions of charge ordering gap and its pseudogap in La1-xCaxMnO3 (0.50$``$x$``$0.67). With decreasing x from 0.67 to 0.50, the low temperature charge gap systematically increased while charge ordering temperature decreased. Simultaneously, the optical pseudogap, indicating charge ordering fluctuation at high temperatures, is greatly enhanced as x approaches 0.50. This $`\sigma `$($`\omega `$) study provided a convincing evidence that short-range charge ordering fluctuation is anomalously strong in manganites.

This work was financially supported by Ministry of Science and Technology through the Creative Research Initiative Program. KHK is supported by the BK-21 Project of the Ministry of Education. SWC is supported by the NSF-DMR-0080008. We thank M. G. Cho, Y. S. Lee, M. Jaime, and G. S. Boebinger for discussions.


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# An Analytical Formulation of CPMAS

## I Introduction

The most frequently used technique to improve the sensitivity of nuclei with low gyromagnetic ratios and/or low isotopic abundances in solid-state NMR is the Hartmann-Hahn cross polarization (CP) in the rotating frame Pines . With this technique, polarization can be transferred from sensitive and often abundant nuclear spins $`I`$ (e.g., protons) to the insensitive nuclear spins $`S`$ (e.g., 13C, 15N). It is driven by the flip-flop transitions where both dipolar coupled spins $`I`$ and $`S`$ change their magnetic quantum number in an energy conserving process. Since this transfer of polarization takes time to develop, CP can be observed only if the whole spin system has reasonably long relaxation times. The CP spin dynamics has already been discussed more then 25 years ago and since then has been the subject of a variety of additional studies. The polarization of the abundant $`I`$ spins (usually with a high gyromagnetic ratio) is spin-locked in the rotating frame by a radiofrequency (rf) field. When a second rf field of appropriate magnitude is then simultaneously applied to the dipolar coupled rare $`S`$ spins (usually with a low gyromagnetic ratio), flip-flop processes become energy conserving and thus allow the transfer of polarization from the $`I`$ spins to the unpolarized $`S`$ spins. An overview of the Cross Polarization under Magic Angle Spinning (CPMAS) can be found in a number of places, a partial list of which is Refs. Fyfe, ; Mehring, ; Encyc, ; Meier94, . The emphasis in this paper is on an exact theoretical formulation of CPMAS and no attempt is made to review the experimental methods and/or results that have been achieved using them.

Several theoretical approaches have been presented for the description of CPMAS. One such approach is based on there being a spin temperature, which assumes the spins are in thermal equilibrium in an appropriate rotating frame, the recent paper by Meier Meier92  exemplifies how this approach can be used. Another method, due to Müller et al Muller , resulted in an empirical fitting formula which has been extensively used by many workers. A third type of approach is based on the use of floquet theory Ernst ; Marks  and a comprehensive program GAMMA has been written GAMMA  which can be used for treating spin dynamics and numerically solving the quantum Liouville equation. A method of describing the spin dynamics in terms of rotations by parts of the hamiltonian has been used by Levitt Levitt91  and Zhang et al Zhang . Finally, there are methods that use the Mori Mori  approach to nonequilibrium statistical mechanics. One method is based on projecting onto selected parts of the hamiltonian Demco  whereas another Engelke  uses standard approximation methods for estimating the memory kernel. In contrast to this variety of methods, the approach presented here utilizes the special nature of the hamiltonian in the doubly rotating frame, and the specific properties of spin-1/2 systems to obtain an exact integrodifferential equation (correctly a pair of such equations) for the cross polarization. A solution of these equations is complicated by any time dependence of the dipolar coupling, while an exact solution is immediately available for a time independent and orientation fixed coupling constant. The powder average of the resulting solution can be done numerically.

While the spin temperature approach is very appealing in that it provides a relatively simple explanation for the qualitative behaviour of cross polarization, it has a number of weaknesses. First of all, it is noticed that the spin system suffers no (or at most negligible) relaxation during a cross polarization experiment. Thus there is no basis for an equilibrium to be obtained and thus no basis for assuming a thermal distribution. An argument might be made for ergodic behaviour but we do not find that appealing. Second, the thermal equilibrium is to be in the doubly rotating frame, in which the hamiltonian must still be time dependent if magic angle spinning is performed. Thus a selection has to be made in some way to extract a time independent hamiltonian in order to have a thermal distribution. Exactly how this is done is arbitrary. Thirdly, only one Hartmann-Hahn matching condition can be described at a time, after selecting out the right time independent hamiltonian. The theory presented here is a purely dynamical theory (no relaxation is involved), is capable of treating the magic angle spinning exactly (approximations simplifying the calculation are made, but all time dependence could be included), and all four peaks of the CPMAS matching profile are obtained from the same calculation.

The paper starts by reviewing some relevant properties of spin-1/2 systems together with their rotational properties. These are used in Sec. III to examine the specific nature of the spin hamiltonian in the doubly rotating frame and thus show that the relevant operator space for describing cross polarization is only 6 dimensional. Section IV then derives a formal expression for cross polarization, described in terms of two integrodifferential equations. Section V gives an exact expression for the static (no spinning) case and exemplifies the purely oscillatory time dependence for a constant dipolar coupling strength (fixed direction of the vector joining the particles containing the spins), and also the destructive interference effects that occur in a powder sample. Sec. VI describes the effect of magic angle spinning and a short discussion ends the paper. Figures illustrating a variety of different behaviors are presented.

## II A system of two Spin-1/2 Particles

The spin operators for the two particles are labelled as $`S_x,S_y,S_z`$ and $`I_x,I_y,I_z`$. There are also the identities $`1_S`$ and $`1_I`$ for the respective spin spaces. As spin-1/2 particles, these operators satisfy the product conditions

$$S_xS_y=\frac{i}{2}S_z,I_xI_y=\frac{i}{2}I_z,$$
(1)
$$S_xS_x=\frac{1}{4}1_S,I_xI_x=\frac{1}{4}1_I,$$
(2)
and their cyclic permutations. The first set of product conditions are of course just part of the commutation relations

$$[S_x,S_y]_{}=iS_z[I_x,I_y]_{}=iI_z,$$
(3)
and their cyclic permutations. \[Throughout this work, $`\mathrm{}`$ is set equal to 1.\] The four operators for each spin (including the identity) implies a total operator space of 16 dimensions, which exactly coincides with the dimension of a matrix representation of a system of two spin-1/2 particles. Thus any operator can be expressed in terms of the sum of products of $`S`$ and $`I`$ spin operators. For simplicity of presentation, the identity operators are usually not written explicitly. Thus the operator $`S_z`$ is understood to stand for the product $`S_z1_I`$, etc.

Another important property of spin operators (not just of spin-1/2) is that the commutator of a spin operator generates a rotation. Setting the commutator superoperator

$$𝒮_zA[S_z,A]_{},$$
(4)
the exponential superoperator

$$e^{i\theta 𝒮_z}S_x=e^{i\theta S_z}S_xe^{i\theta S_z}=S_x\mathrm{cos}\theta +S_y\mathrm{sin}\theta $$
(5)
rotates the $`S`$-spin operator on which it acts (here $`S_x`$) about the $`\widehat{z}`$ axis. $`_z`$ is used to denote the corresponding commutator superator for $`I_z`$. Analogous commutator superoperators for the other spin directions can be defined but are not needed in this work.

## III Natural Partitioning of the Operator space in the Doubly-Rotating Tilted Frame

This is phrased in the tilted frame, namely the rf fields are labelled as being in the $`\widehat{z}`$ direction and the spin operators of the truncated (often referred to as the secular part of the) dipolar hamiltonian lying along the $`\widehat{x}`$ direction. Thus the hamiltonian is Levitt86

$$H(t)=\omega _{1I}I_z+\omega _{1S}S_z+2b(t)I_xS_x.$$
(6)
The angular velocities $`\omega _{1I}=|\gamma _IB_{1I}|`$ and $`\omega _{1S}=|\gamma _SB_{1S}|`$ are proportional to the radio frequency field amplitudes $`B_{1I}`$ and $`B_{1S}`$. In the laboratory frame, these rf fields are oscillating at the respective resonance Zeeman frequencies determined by a large static magnetic field in the $`\widehat{x}`$ direction. $`b(t)`$ is the (possibly) time dependent heteronuclear dipolar coupling strength. Fundamentally this coupling strength depends on the angle $`\theta `$ between the vector $`𝐫`$ pointing from the nucleus having its spin labelled $`I`$ to the nucleus whose spin is labelled $`S`$ relative to the Zeeman field direction $`\widehat{x}`$, being explicitly given by

$$b(\theta )=b_0(\mathrm{cos}^2\theta 1/3),$$
(7)
where $`b_0=3\mu _0\gamma _I\gamma _S\mathrm{}/(8\pi r^3)`$ is the dipolar coupling constant. Ignoring any internal (rotational or vibrational) motion of the molecules in the chemical system, a time dependence arises only through the physical spinning of the sample about an axis at the magic angle \[$`\mathrm{arccos}(1/\sqrt{3})`$\] to the Zeeman field ($`\widehat{x}`$ direction). Thus $`\theta `$ becomes time dependent and $`b(t)`$ is written as a shorthand for $`b(\theta (t))`$. There is inherently a remaining orientation dependence of $`b(t)`$, associated with the original orientation $`\theta (0)`$ of $`𝐫`$. In a powder sample there is a random distribution of such angles so an average over $`\theta (0)`$ needs to be made for such samples. But for the analysis of the spin dynamics, only the possible time dependence of $`b(t)`$ is important, so only this time dependence is explicitly displayed. Later on, when a powder sample is considered, the extra averaging over initial orientations (or its equivalent) is made.

It is also noted that, if $`b`$ is time independent (and has a fixed interspin orientation, $`\theta `$), the energy eigenvalues of this hamiltonian are $`\pm (1/2)\sqrt{b^2+(\omega _I\pm \omega _S)^2}`$. These eigenvalues have been noted (at least) by Levitt, et al Levitt86 , but their method of solving the spin dynamics, as do some other treatments, for example Levitt91 ; Zhang ; Wu , is based on a separation of the hamiltonian, Eq. (6), into two commuting parts. Neither the eigenvalues, nor their respective eigenvectors, seem to be standardly quoted in the literature. They are listed for reference in Appendix A. The method used in this paper does not explicitly use these eigenvalue properties nor the above noted separation of the hamiltonian into commuting parts.

The purpose of this section is to catalog how the 16 spin operators behave under the action of the commutator superoperator $`(t)`$ for the hamiltonian,

$$(t)A[H(t),A]_{}=_{\mathrm{rf}}A+_\mathrm{d}(t)A.$$
(8)
This is listed as a sum of radio frequency and dipolar parts. It is to be shown that this set of operators is partitioned into four dynamically separate sets of operators. Crucial to this partitioning is the vanishing of commutators of the form

$`[S_xI_x,S_yI_y]_{}`$ $`=`$ $`S_x[I_x,S_yI_y]_{}+[S_x,S_yI_y]_{}I_x`$ (9)
$`=`$ $`S_xS_y(iI_z)+iS_zI_yI_x`$
$`=`$ $`(i/2)S_z(iI_z)+iS_z(i/2)I_z=0.`$
This relation is special to spin-1/2 systems since it depends on the special product conditions, Eq. (1), of the spin-1/2 operators.

Starting with the operator $`I_z`$, the action of $`(t)`$ on successively appearing operators is

$`I_z`$ $`=`$ $`2ibS_xI_y,`$
$`S_xI_y`$ $`=`$ $`i\omega _{1S}S_yI_yi\omega _{1I}S_xI_x+{\displaystyle \frac{i}{2}}bI_z`$
$`S_yI_y`$ $`=`$ $`i\omega _{1S}S_xI_yi\omega _{1I}S_yI_x`$
$`S_xI_x`$ $`=`$ $`i\omega _{1S}S_yI_x+i\omega _{1I}S_xI_y`$
$`S_yI_x`$ $`=`$ $`i\omega _{1S}S_xI_x+i\omega _{1I}S_yI_y+{\displaystyle \frac{i}{2}}bS_z`$
$`S_z`$ $`=`$ $`2ibS_yI_x.`$ (10)
The possible time dependence of $``$ and $`b`$ has not been indicated in these equations. This gives a closed set of 6 operators, namely $`I_z,S_z,S_xI_x,S_xI_y,S_yI_x`$ and $`S_yI_y`$. It is this set of operators that govern the behaviour of a CPMAS experiment. The set of commutators (III) have some special properties which are useful for the subsequent analysis. Specifically it is noticed that the dipolar hamiltonian acts only to couple the single 1-spin operators $`S_z`$ and $`I_z`$ to the product spin operators, whereas the rf operators act only on the product spin operators.

Another closed set consists of the identity $`1_S1_I`$ as its sole member, since this operator is unchanged by $``$. So it is a set all by its own. The same is true for the product operator $`S_zI_z`$ since it commutes with both rf operators and, because of the commutator type of Eq. (9), it also commutes with the truncated dipolar operator. Finally there are the remaining 8 operators, which can easily be shown to be all dynamically coupled, so there is no further partitioning of the spin space.

Since the 16 operators span the operator space, any operator, and in particular the density operator $`\rho `$, can be expressed as a linear combination of these operators Fano . For the CPMAS set of operators, the relevant space consists only of 6 operators plus the identity, the latter being retained in order that the density operator be normalized, namely that the trace over both spins (a total of four Dirac states) is consistent with $`\mathrm{Tr}\rho =1`$. Of these operators, only the identity has a finite trace, so $`\rho `$ must have $`(1/4)1_S1_I`$ as one of its terms. Recognizing the expansion coefficients as proportional to the corresponding expectation values, the CPMAS density operator can thus be expressed as

$`\rho `$ $`=`$ $`(1/4)1_S1_I+S_zS_z+I_zI_z+4S_xI_xS_xI_x`$ (11)
$`+4S_xI_yS_xI_y+4S_yI_xS_yI_x+4S_yI_yS_yI_y.`$
Thus the study of the evolution of the density operator is equivalent to the study of the evolution of the expectation values of these observables.

It is appropriate to subdivide this set of operators further, namely into the set of 1-spin operators $`S_z`$ and $`I_z`$, plus the identity to preserve normalization, and the remaining set of 2-spin operators. Appropriate for this subdivision, a projection superoperator $`𝒫`$ is defined that selects out the 1-spin part of the operator space, thus

$$𝒫=(1/4)1_S1_I\mathrm{Tr}+S_z\mathrm{Tr}S_z+I_z\mathrm{Tr}I_z,$$
(12)
where the trace is to be taken over both spin spaces. Necessarily, this superoperator is idempotent $`𝒫𝒫=𝒫`$, which determines the numerical factors. $`1𝒫`$ is written for the projector onto the remaining (2-spin) operators. Because of the commutation relations, it is noticed that

$`𝒫𝒫`$ $`=`$ $`0,`$
$`(1𝒫)(1𝒫)`$ $`=`$ $`_{\mathrm{rf}}=\omega _{1S}𝒮+\omega _{1I},`$
$`𝒫(1𝒫)`$ $`=`$ $`𝒫_\mathrm{d},`$
$`(1𝒫)𝒫`$ $`=`$ $`_\mathrm{d}𝒫`$ (13)
separates the action of $``$ within the $`𝒫`$ and $`1𝒫`$ spaces to be entirely due to the rf fields (vanishing for the $`𝒫`$ space), while the coupling between these two subspaces is due solely to the dipolar hamiltonian. The retention of one projector in each of the subspace coupling cases serves to select which space is to be acted upon and which is to be mapped into. Again it is emphasized that any time dependence of the dipolar coupling strength has no effect on this separation of the different parts of $``$.

## IV The spin operator dynamics for Cross Polarization

After a 90 pulse to align the $`I`$-spin along the $`\widehat{z}`$ axis (doubly rotating tilted frame), the time evolution of the expectation value $`S_z`$ of the $`S`$-spin is monitored experimentally. Thus the calculation is to use the value of $`I_z(0)`$ as the only nonzero spin expectation value as the initial condition and to calculate the consequent time dependence of $`S_z(t)`$. Since it is the expectation values of $`S_z`$ and $`I_z`$ that are of importance, it is the partition consisting of these two operators that is relevant for the analysis of these experiments. The projection superoperator $`𝒫`$ defined above carries out this selection.

The density operator $`\rho `$ for the spin system satisfies the quantum Liouville equation (von Neumann equation)

$$i\frac{\rho }{t}=\rho =[H,\rho ]_{}.$$
(14)
Again $`\mathrm{}`$ is set to 1. The expectation value for any observable $`A`$ is calculated as the trace $`A=\mathrm{Tr}A\rho `$ whose time dependence can be calculated according to

$$\frac{A}{t}=\mathrm{Tr}A\frac{\rho }{t}=i\mathrm{Tr}A\rho =i\mathrm{Tr}(A)\rho ,$$
(15)
in the Schrödinger picture (first form) or Heisenberg picture (last form). From the commutation relations (III), it is a set of 6 coupled equations that must be solved in order to predict the time evolution of $`S_z(t)`$. Since only the $`S_z`$ and $`I_z`$ part of the operator space reflects the experimentally observed quantities, a separation of the dynamics to emphasize these can be useful. The generalized master equation Zwanzig  approach does this in a natural way. This method is summarized in the following subsection.

### IV.1 Derivation of the generalized master equation

The derivation of the generalized master equation is reviewed in its generality since there is no immediate simplification of the derivation by specializing the superoperators to the present case. Note that a time dependence of $`(t)`$ is allowed for here, which is standardly not considered.

Define the relevant part of the density operator as $`\rho _1𝒫\rho `$ and the irrelevant part as the remainder $`\rho _2(1𝒫)\rho `$. Then these parts evolve according to

$`i{\displaystyle \frac{\rho _1(t)}{t}}`$ $`=`$ $`𝒫(t)\rho (t)=𝒫𝒫\rho _1(t)+𝒫(t)(1𝒫)\rho _2(t),`$
$`i{\displaystyle \frac{\rho _2(t)}{t}}`$ $`=`$ $`(1𝒫)(t)\rho (t)=(1𝒫)(1𝒫)\rho _2(t)`$ (16)
$`+(1𝒫)(t)𝒫\rho _1(t).`$
Here the possible time dependence of the coupling superoperators $`𝒫(t)(1𝒫)`$ and $`(1𝒫)(t)𝒫`$ are explicitly displayed. Solve formally for $`\rho _2(t)`$,

$`\rho _2(t)`$ $`=`$ $`e^{i(1𝒫)(1𝒫)t}\rho _2(0)`$ (17)
$`i{\displaystyle _0^t}e^{i(1𝒫)(1𝒫)(tt^{})}(1𝒫)(t^{})𝒫\rho _1(t^{})𝑑t^{}.`$
Note that it is assumed that there is no time dependence of $`(1𝒫)(1𝒫)`$, so the exponential evolution superoperator is correct as written. This is the case for the present problem. Substitute this equation for $`\rho _2(t)`$ back into the differential equation for $`\rho _1(t)`$,

$`i{\displaystyle \frac{\rho _1}{t}}`$ $`=`$ $`𝒫\rho =𝒫𝒫\rho _1`$ (18)
$`+𝒫(1𝒫)(t)e^{i(1𝒫)(1𝒫)t}\rho _2(0)`$
$`i{\displaystyle _0^t}𝒫(t)(1𝒫)e^{i(1𝒫)(1𝒫)(tt^{})}`$
$`\times (1𝒫)(t^{})𝒫\rho _1(t^{})dt^{}.`$
This is the generalized master equation of Zwanzig Zwanzig , with an additional time dependence of the coupling superoperators. It describes the exact evolution of the relevant observables while taking into account the role of the irrelevant observables in this evolution by means of an integral over the time history (memory) of the relevant observables.

### IV.2 Application of the generalized master equation

For a cross polarization experiment involving spin-1/2 particles, the special properties, (III), of the Liouville superoperator allows all projection superoperators to be dropped in the generalized master equation for $`\rho _1(t)`$. Moreover, the initial condition on the density operator

$$\rho (0)=\rho _1(0)=(1/4)1_S1_I+I_zI_z(0)$$
(19)
lies entirely in the relevant space, so the generalized master equation reduces to

$$\frac{\rho _1(t)}{t}=_0^t_\mathrm{d}(t)e^{i_{\mathrm{rf}}(tt^{})}_\mathrm{d}(t^{})\rho _1(t^{})𝑑t^{}.$$
(20)
This is exact for this system!

On taking the trace of this equation with $`S_z`$ and using the expansion

$$\rho _1(t)=𝒫\rho (t)=(1/4)1_S1_I+S_zS_z(t)+I_zI_z(t)$$
(21)
for $`\rho _1(t)`$, the equation of change for the expectation value $`S_z(t)`$ is calculated to be

$`{\displaystyle \frac{S_z(t)}{t}}`$ $`=`$ $`{\displaystyle _0^t}b(t)[K_{SS}(tt^{})S_z(t^{})`$ (22)
$`+K_{SI}(tt^{})I_z(t^{})]b(t^{})dt^{}.`$
Here the (possibly time dependent) dipolar coupling strengths are written out explicitly and it should be noted how they depend on different times. The memory kernel $`K_{SS}(s)`$ is defined as

$`K_{SS}(s)`$ $`=`$ $`4\mathrm{T}\mathrm{r}[S_z,S_xI_x]_{}e^{i(\omega _{1S}𝒮_z+\omega _{1I}_z)s}[S_xI_x,S_z]_{}`$ (23)
$`=`$ $`4\mathrm{T}\mathrm{r}(i)S_yI_xe^{i(\omega _{1S}𝒮_z+\omega _{1I}_z)s}(i)S_yI_x`$
$`=`$ $`4\mathrm{T}\mathrm{r}S_yI_x\left[S_y\mathrm{cos}(\omega _{1S}s)S_x\mathrm{sin}(\omega _{1S}s)\right]`$
$`\times \left[I_x\mathrm{cos}(\omega _{1I}s)+I_y\mathrm{sin}(\omega _{1I}s)\right]`$
$`=`$ $`\mathrm{cos}(\omega _{1S}s)\mathrm{cos}(\omega _{1I}s)`$
$`=`$ $`{\displaystyle \frac{1}{2}}\left[\mathrm{cos}((\omega _{1S}+\omega _{1I})s)+\mathrm{cos}((\omega _{1S}\omega _{1I})s)\right].`$
In the first term the commutator $`[S_z,S_xI_x]_{}`$ arises by using the invariance of the trace to interchange the order of commutation arising from $`\mathrm{Tr}S_z_\mathrm{d}\mathrm{}`$. The memory kernel $`K_{SI}(s)`$ is calculated in a similar manner to give

$$K_{SI}(s)=(1/2)\left[\mathrm{cos}((\omega _{1S}+\omega _{1I})s)\mathrm{cos}((\omega _{1S}\omega _{1I})s)\right].$$
(24)
The corresponding equation for $`I_z(t)`$ is obtained by interchanging $`S`$ and $`I`$ labels on the various terms. Specifically this gives

$`{\displaystyle \frac{I_z(t)}{t}}`$ $`=`$ $`{\displaystyle _0^t}b(t)[K_{IS}(tt^{})S_z(t^{})`$ (25)
$`+K_{II}(tt^{})I_z(t^{})]b(t^{})dt^{}.`$
The memory kernels

$`K_{II}(s)`$ $`=`$ $`1/2\left[\mathrm{cos}((\omega _{1S}+\omega _{1I})s)+\mathrm{cos}((\omega _{1S}\omega _{1I})s)\right],`$
$`K_{IS}(s)`$ $`=`$ $`1/2\left[\mathrm{cos}((\omega _{1S}+\omega _{1I})s)\mathrm{cos}((\omega _{1S}\omega _{1I})s)\right],`$
are of the same form as the previous pair. As a consequence, the equations for $`S_z`$ and $`I_z`$ can be simplified when rewritten in terms of the sum and difference expectation values, namely

$$\frac{S_zI_z(t)}{t}=_0^tb(t)b(t^{})\mathrm{cos}(\mathrm{\Delta }(tt^{}))S_zI_z(t^{})𝑑t^{}$$
(27)
and

$$\frac{S_z+I_z(t)}{t}=_0^tb(t)b(t^{})\mathrm{cos}(\mathrm{\Sigma }(tt^{}))S_z+I_z(t^{})𝑑t^{},$$
(28)
involving the difference $`\mathrm{\Delta }\omega _{1S}\omega _{1I}`$ and sum $`\mathrm{\Sigma }\omega _{1S}+\omega _{1I}`$ frequencies.

It is thus shown that the calculation of the cross polarization separates into two independent parts. This completes the part of the calculation which involves the spin operators, the remaining part of the calculation requires solving the two integrodifferential equations. In order to carry this out, it is necessary to specify the detailed time dependence of the dipolar coupling strength $`b(t)`$. The static \[$`b(t)`$ time independent\] and magic angle spinning cases are discussed in turn.

## V Static Cross Polarization

In the static case, the dipolar coupling strength $`b`$ is time independent, but still depends on the angle $`\theta `$ of the vector $`𝐫`$ separating the $`S`$ and $`I`$ spin particles and the direction ($`\widehat{x}`$) of the static magnetic field. In a powder sample there is a random arrangement of this direction so an ensemble average of $`S_z(t)`$ over $`\theta `$ needs to be taken. But this is to be done after $`S_z`$ has been calculated for each fixed direction.

### V.1 Fixed orientation of the dipolar coupling strength

The expectation of the difference of the spins $`D(t)S_zI_z(t)`$ is considered first. According to Eq. (27), this satisfies the integrodifferential equation

$$\frac{D(t)}{t}=b^2_0^t\mathrm{cos}(\mathrm{\Delta }(tt^{}))D(t^{})𝑑t^{}.$$
(29)
Differentiating this equation gives

$$\frac{^2D(t)}{t^2}=b^2D(t)+b^2\mathrm{\Delta }_0^t\mathrm{sin}(\mathrm{\Delta }(tt^{}))D(t^{})𝑑t^{},$$
(30)
and differentiating again

$`{\displaystyle \frac{^3D(t)}{t^3}}`$ $`=`$ $`b^2{\displaystyle \frac{D(t)}{t}}+b^2\mathrm{\Delta }^2{\displaystyle _0^t}\mathrm{cos}(\mathrm{\Delta }(tt^{}))D(t^{})𝑑t^{}`$ (31)
$`=`$ $`(b^2+\mathrm{\Delta }^2){\displaystyle \frac{D(t)}{t}}.`$
As a consequence, the time derivative of $`D(t)`$ must satisfy

$$\frac{D(t)}{t}=A\mathrm{cos}(ft)+B\mathrm{sin}(ft)$$
(32)
where

$$f=\sqrt{b^2+\mathrm{\Delta }^2}$$
(33)
is the natural oscillation frequency for $`D(t)`$. From the fact that $`D(t)/t`$ vanishes at $`t=0`$, as follows from Eq. (29), the coefficient $`A`$ vanishes. At $`t=0`$ the second derivative of $`D(t)`$ equals $`b^2D(0)`$, so $`B`$ is given by $`b^2D(0)/f`$. Consequently the derivative of $`D(t)`$ is given by

$$\frac{D(t)}{t}=\frac{b^2}{f}D(0)\mathrm{sin}(ft).$$
(34)
Integrating this result and choosing the integration constant so as to satisfy the initial condition, $`D(t)`$ is determined to be

$$D(t)=\frac{\mathrm{\Delta }^2+b^2\mathrm{cos}(ft)}{b^2+\mathrm{\Delta }^2}D(0)$$
(35)
Expressed in terms of the spin expectation values, note that $`D(0)=I_z(0)`$, this is

$$S_zI_z(t)=\left[\frac{b^2(1\mathrm{cos}(ft))}{b^2+\mathrm{\Delta }^2}1\right]I_z(0).$$
(36)
An analogous calculation of the sum of the spin expectation values implies

$$S_z+I_z(t)=\left[1\frac{b^2(1\mathrm{cos}(Ft))}{b^2+\mathrm{\Sigma }^2}\right]I_z(0),$$
(37)
where the frequency $`F=\sqrt{b^2+\mathrm{\Sigma }^2}`$ is natural for the sum of the spin expectation values. Finally, the sum of these results determines the time dependence of the $`S_z`$ expectation value, experimentally referred to as the “buildup curve”, namely

$$S_z(t)=\frac{1}{2}b^2\left[\frac{1\mathrm{cos}(ft)}{b^2+\mathrm{\Delta }^2}\frac{1\mathrm{cos}(Ft)}{b^2+\mathrm{\Sigma }^2}\right]I_z(0).$$
(38)
Thus it is seen that, for a constant $`b`$ (specific orientation of the vector connecting the $`S`$ and $`I`$ spin particles), the time dependence of $`S_z(t)`$ is governed by a difference between oscillating terms. Actually, since $`\omega _{1S}`$ and $`\omega _{1I}`$ are both positive (they are the amplitudes of the radio frequency fields), the sum frequency $`\mathrm{\Sigma }`$ is larger than the magnitude of the difference frequency $`|\omega _{1S}\omega _{1I}|`$. As a consequence, the amplitude $`b^2/(b^2+\mathrm{\Sigma }^2)`$ of the sum frequency contribution is smaller than the amplitude of the difference frequency contribution, implying that the rapid oscillations of the sum frequency are likely lost as noise on top of the slower oscillations of the difference frequency.

Equation (38) has been obtained by Levitt Levitt91  and Zhang et al Zhang  by using a sequence of rotations using effective spin operators based on a decomposition of the hamiltonian into two commuting parts.

Experimentally, the matching profile is obtained by scanning the rf amplitude of the $`S`$-spin channel and the (relatively) longtime average of $`S_z(t)`$ measured. This should be compared with

$$\overline{S_z(t)}_{\mathrm{time}}=\frac{1}{2}\left[\frac{b^2}{b^2+\mathrm{\Delta }^2}\frac{b^2}{b^2+\mathrm{\Sigma }^2}\right]I_z(0).$$
(39)
This time average is dominated by the difference frequency term which, if the dominance is sufficient, implies that the experimental plot of $`\overline{S_z}_{\mathrm{time}}`$ versus $`\omega _{1S}`$ is Lorentzian.

### V.2 Powder average

In a powder all orientations must be averaged over, so the cross polarization time dependence is

$`\overline{S_z(t)}_{\mathrm{powder}}`$ $`=`$ $`{\displaystyle \frac{1}{4}}{\displaystyle _0^\pi }b^2(\theta )[{\displaystyle \frac{1\mathrm{cos}(f(\theta )t)}{b^2(\theta )+\mathrm{\Delta }^2}}`$ (40)
$`{\displaystyle \frac{1\mathrm{cos}(F(\theta )t)}{b(\theta )^2+\mathrm{\Sigma }^2}}]\mathrm{sin}\theta d\theta I_z(0),`$
with an analogous expression for the time average. Note that since there is no $`\varphi `$ dependence in $`b`$, the average over $`\varphi `$ is unnecessary while the frequencies $`f`$ and $`F`$ are $`\theta `$ dependent through their dependence on $`b(\theta )`$. Figure 1 shows the effects of the angle averaging on the time dependence of $`S_z(t)`$, two of the rapidly oscillating contributions to this powder average are also shown. Compare the corresponding depolarization curves in Ref. Meier94, . The corresponding matching profile, namely a scan of the time and powder average $`\overline{S_z}_{\mathrm{time},\mathrm{powder}}`$ for different $`\omega _{1S}`$, is given in Fig. 2. A Lorentzian, picked to have the same height and width at half height, is also plotted. This shows that the powder CP line shape is close to Lorentzian, but not quite.

## VI Cross Polarization with magic angle spinning

The orientation of the vector $`𝐫`$ connecting the positions of the two spins is made time dependent by rotation about an axis $`\widehat{n}`$ at a frequency of $`\omega _r`$. For magic angle spinning, the angle between the rotation axis $`\widehat{n}`$ and the direction $`\widehat{x}`$ of the static magnetic (Zeeman) field is $`\mathrm{arccos}(1/\sqrt{3})`$. At that angle the dipolar angle dependence is split into four time dependent parts, rather than the five parts for a general splitting of the order 2 spherical harmonics. Explicitly this time dependence is given by

$$b(t)=b_2^{}e^{2i\omega _rt}+b_1^{}e^{i\omega _rt}+b_1e^{i\omega _rt}+b_2e^{2i\omega _rt},$$
(41)
where

$$b_1=\frac{\sqrt{2}}{3}b_0\mathrm{cos}\theta _r\mathrm{sin}\theta _re^{i\varphi _r}$$
(42)
and

$$b_2=\frac{1}{6}b_0\mathrm{sin}^2\theta _re^{2i\varphi _r}$$
(43)
are proportional to the spherical harmonics $`Y_{21}(\theta _r,\varphi _r)`$ and $`Y_{22}(\theta _r,\varphi _r)`$, expressed in terms of the angles $`\theta _r,\varphi _r`$ defining the direction between the particles containing the spins with respect to the axis of rotation $`\widehat{n}`$. A short discussion of how this splitting arises is given in Appendix B.

### VI.1 General formulation for magic angle spinning

The dipolar coupling strength $`b(t)`$ enters into the integrodifferential equations (27-28) for the cross polarization in the form of the product $`b(t)b(t^{})`$. From the explicit time dependence given by Eq. (41), the product has a total of 16 different terms. Four of these are naturally combined into two simple forms involving the time difference $`tt^{}`$, while the remainder have a variety of time dependences. In detail, the combination of time dependences is

$`b(t)b(t^{})`$ $`=`$ $`2|b_1|^2\mathrm{cos}(\omega _r(tt^{}))+2|b_2|^2\mathrm{cos}(2\omega _r(tt^{}))`$ (44)
$`+b_2^2e^{2i\omega _r(t+t^{})}+b_1^2e^{i\omega _r(t+t^{})}+(b_1^{})^2e^{i\omega _r(t+t^{})}+(b_2^{})^2e^{2i\omega _r(t+t^{})}`$
$`+b_1b_2\left[e^{i\omega _r(2t+t^{})}+e^{i\omega _r(t+2t^{})}\right]+b_1^{}b_2^{}\left[e^{i\omega _r(2t+t^{})}+e^{i\omega _r(t+2t^{})}\right]`$
$`+b_1b_2^{}\left[e^{i\omega _r(2t+t^{})}+e^{i\omega _r(t2t^{})}\right]+b_1^{}b_2\left[e^{i\omega _r(2tt^{})}+e^{i\omega _r(t+2t^{})}\right].`$
In the following it is assumed that only the terms involving the time difference $`tt^{}`$ are important, and the remainder act to produce a variety of interference effects. Retaining only these two terms, the frequency difference formula (27) is approximated by

$`{\displaystyle \frac{D(t)}{t}}`$ $`=`$ $`2{\displaystyle _0^t}\left[|b_1|^2\mathrm{cos}(\omega _r(tt^{}))+|b_2|^2\mathrm{cos}(2\omega _r(tt^{}))\right]\mathrm{cos}(\mathrm{\Delta }(tt^{}))D(t^{})𝑑t^{}`$ (45)
$`=`$ $`N_2(t)N_1(t)N_1(t)N_2(t),`$
where $`D(t)`$ is again used as an abbreviation for $`S_zI_z(t)`$. The integral in this equation is naturally divided up into four terms, whose generic definition is

$$N_n(t)|b_n|^2_0^t\mathrm{cos}((\mathrm{\Delta }+n\omega _r)(tt^{}))D(t^{})𝑑t^{},$$
(46)
with the obvious definition $`|b_n|^2=|b_n|^2`$. A solution of Eq. (45) is required. This can be accomplished as in the static CP situation by using successive derivatives of Eq. (45), see Sec. V. But it is necessary to go up to the ninth derivative of $`D(t)`$ before a sufficient number of terms are obtained in order to eliminate the $`N_n(t)`$’s. This calculation is described in Appendix C while an approximation is made in the following subsection that provides a simple analytical estimation of the cross polarization with magic angle spinning.

### VI.2 Independent Sideband Approximation

The idea here is that, near a Hartmann-Hahn matching condition, only one of the $`N_n(t)`$’s is of importance, that is, of appreciable magnitude. As a consequence, $`D(t)`$ can be considered as a sum of four terms, each of which is determined by a separate equation. With a similar approximation for the $`\mathrm{\Sigma }`$ based $`G(t)S_z+I_z(t)`$, the total cross polarization is described as a sum of eight terms.

To implement this idea, $`D(t)`$ is written as the sum

$$D(t)=D_2(t)+D_1(t)+D_1(t)+D_2(t),$$
(47)
each term of which is to be approximated as the solution of

$$\frac{D_n(t)}{t}=|b_n|^2_0^t\mathrm{cos}((\mathrm{\Delta }+n\omega _r)(tt^{}))D_n(t^{})𝑑t^{}.$$
(48)
A decoupling of Eq. (45) has thus been accomplished. Since the equation for $`D_n(t)`$ has the same structure as that of Eq. (29), so its solution is, according to Eq. (35),

$$D_n(t)=\frac{(\mathrm{\Delta }+n\omega _r)^2+|b_n|^2\mathrm{cos}(f_nt)}{|b_n|^2+(\mathrm{\Delta }+n\omega _r)^2}D(0),$$
(49)
with an effective frequency given by

$$f_n=\sqrt{|b_n|^2+(\mathrm{\Delta }+n\omega _r)^2}.$$
(50)
On the basis that only one $`D_n(t)`$ has a significant contribution when near a matching condition, it has been assumed that $`D_n(0)`$ is well estimated by $`D(0)`$. Adding in the corresponding approximation for $`S_z+I_z(t)`$ and doing some minor algebra, the complete time dependence of $`S_z(t)`$ is estimated by the sum of eight terms

$`S_z`$ $`=`$ $`{\displaystyle \frac{1}{2}}{\displaystyle \underset{n=2,1,1,2}{}}|b_n|^2[{\displaystyle \frac{1\mathrm{cos}(f_nt)}{|b_n|^2+(\mathrm{\Delta }+n\omega _r)^2}}`$ (51)
$`{\displaystyle \frac{1\mathrm{cos}(F_nt)}{|b_n|^2+(\mathrm{\Sigma }+n\omega _r)^2}}]I_z(0).`$
Here the frequencies for the sum terms are given by

$$F_n=\sqrt{|b_n|^2+(\mathrm{\Sigma }+n\omega _r)^2}.$$
(52)
A powder average of this result is easily calculated since the $`|b_n|^2`$’s depend only on the single angle $`\theta _r`$. The time average of Eq. (51) is obtained by merely dropping the cosine terms, to give an estimation of the CPMAS matching profile.

Figures 3 and 4 illustrate the typical matching profiles that can be attained. Figure 3 exemplifies what is standardly observed in an experiment, namely four peaks at the shifted Hartmann-Hahn matching conditions $`\omega _{1S}=\omega _{1I}+n\omega _r`$ for $`n`$=-2,-1,1 and 2. These are due to the set of first terms in the sum of Eq. (51) \[with the cosine term dropped to reflect the time average\], associated with the conditions $`\mathrm{\Delta }+n\omega _r=0`$. In such a situation the second set of terms is small because $`\mathrm{\Sigma }+n\omega _r\mathrm{\Delta }+n\omega _r`$. But if $`2\omega _r>\omega _{1I}`$ then $`\omega _{1I}2\omega _r<0`$ and the matching condition $`\mathrm{\Delta }+2\omega _r`$ requires a negative $`\omega _{1S}`$. This is not experimentally possible ($`\omega _{1S}`$ measures the strength of an rf field) so this matching condition cannot be attained and the peak in the matching profile is absent. However, in this case, one of the second set of terms in Eq. (51) can have a small denominator, so a peak in the matching profile arises from that term. This gives a negative $`S_z(t)`$ so the peak is negative. Figure 4 illustrates this case. The structure is emphasized by choosing a small $`\omega _{1I}`$ while a large $`\omega _r`$ is needed to allow the matching condition $`\omega _{1S}=2\omega _r\omega _{1I}`$ to be attained for positive $`\omega _{1S}`$. Meier Meier92  has a figure of experimental data illustrating this kind of behavior, but for the 3-spin system CH2. An even more interesting profile, which does not seem to have yet been observed experimentally, is when $`\omega _{1I}`$ is even smaller, so that two matching conditions are from the second term, namely $`\mathrm{\Sigma }2\omega _r=0`$ and $`\mathrm{\Sigma }\omega _r=0`$, while the other two matching conditions are $`\mathrm{\Delta }\omega _r=0`$ and $`\mathrm{\Delta }2\omega _r`$. The result is a matching profile with two negative and two positive peaks. This is illustrated by the second profile shown in Fig. 4. It is clear that there can be at most only two negative peaks in a matching profile.

## VII Discussion

The special properties of spin-1/2 systems and the special nature of the hamiltonian, Eq. (6), have been used to give a formally exact method of calculating the cross polarization buildup curves and matching profiles for an isolated pair of spins. For the static case (no sample spinning), this can be expressed in closed form, Eq. (38), if the interspin direction is fixed, while a powder average can be easily calculated numerically, Eq. (40). These results have also been obtained by Levitt Levitt91  and Zhang et al Zhang  using a sequence of rotations based on a particular division of the hamiltonian into commuting parts. It is of note that the time dependence of the cross polarization is purely oscillatory if a single orientation of the dipolar coupling strength is involved. It is the sensitive dependence of the frequency of this oscillation on the orientation, which causes an enormous destructive interference in a powder sample. The decay-like nature of the envelope of the oscillations in a powder sample, see Fig. 1, arises from this destructive interference rather than from any spin relaxation (or spin diffusion), which of course is not included in the hamiltonian dynamics of an isolated system.

Magic angle spinning is formally easy to include, it is just a case of recognizing the correct time dependence of the dipolar coupling strengths in the integrodifferential equations (27) and (28). But how to obtain a general solution of these equations is not clear. Two simplifying approximations have been made. First, only those terms in the product of the dipolar coupling strengths, Eq. (44), are kept that depend on the time difference. It is assumed that the other time dependences lead to minor interference effects but that has not been explored. A method of solving the equations with the above single approximation is given in Appendix C, and been explored with some calculations. The results found, which are not presented here, indicate that the solutions are qualitatively in agreement with those using the further approximation of Sec. VI.2. This second approximation assumes that only one term in Eq. (45) is of importance in a range of $`\omega _{1S}`$ values. An analytic expression, Eq. (51), for the cross polarization is then obtained for fixed interspin orientation, and it is in a form in which a powder average can easily be carried out numerically. Its form is very simple and it is immediately seen how the cross polarization is significant when the standard matching conditions $`\mathrm{\Delta }+n\omega _r=0`$ are met. It is also seen that there is another set of matching conditions, $`\mathrm{\Sigma }+n\omega _r=0`$ which can lead to an enhancement of the cross polarization, but now with $`S_z`$ and $`I_z(0)`$ having opposite signs. There can be at most two negative peaks in the matching profile, but there are always four physically possible matching conditions for a given $`\omega _{1I}`$ and $`\omega _r`$.

The method presented here, with the approximations, has the advantage that the qualitative behavior of experimental buildup curves and matching profiles can be given simple explanations. The quantitative connection between the dipolar coupling strength and the size and width of the matching profiles, and the oscillatory nature of the buildup curves is formally available. How well that can be done experimentally can also depend on the real physical system. The spin pair is never truly isolated, so small interactions can cause some more interference effects, and the surroundings afford relaxation. Such effects can surely influence the shape of the buildup curves, contributing to a more rapid closure of the envelope of the oscillations as time progresses. It would also affect the height of the matching profile peaks, but hopefully not perturb too much the position of the peaks.

It is interesting that the thermodynamic method can give the same formulas for the $`\mathrm{\Delta }`$-based peaks in the matching profile as the independent sideband approximation, provided an $`\omega _r`$-dependent transformation is used to get a time independent rotating frame hamiltonian. However, this must be done one peak at a time whereas the present method gives all four peaks predicted by the same formalism and there is no question about any further frame transformation.

Of the previously introduced methods that we are aware of for interpreting cross polarization, the one used by Levitt Levitt91  and Zhang et al Zhang  seems the closest to being fundamentally based. But it does not seem to have been extended to include the magic angle spinning case. It is also not clear to us how that might be incorporated into their formalism. We see the formula introduced by Müller Muller , and extensively used for fitting experimental buildup curves, as a very useful fitting tool. But since it inherently has exponential decays built into it, care should be taken when interpreting the parameters found in terms of physical quantities, since no relaxation is fundamental to the explanation of the buildup curves. We hasten to add that, as we indicated above, in a real system the spins are not truly isolated so relaxation effects are present and these can influence the detailed shapes of the experimental curves, but not their fundamental behavior.

###### Acknowledgements.

This work was supported in part by the Natural Sciences and Engineering Research Council of Canada. The authors thank Professor C. A. Fyfe and Dr. A. Lewis for pointing out a number of references and for their support in trying to put this work into perspective. One of the authors (F. M., on leave from the University of Bucharest, Romania) would like to thank the Natural Sciences and Engineering Research Council of Canada for the award of a NATO Science Postdoctoral Fellowship held during the course of this work.

## Appendix A Eigenvalues and eigenvectors of $`H`$

This lists the eigenvectors and eigenvalues of the hamiltonian defined in Eq. (6) for time independent $`b`$ and for fixed orientation. The basis $`|mn`$, $`m,n=\pm 1/2`$ used for this calculation is that of the simultaneous eigenvectors of $`S_z`$ and $`I_z`$, namely

$$S_z|mn=m|mn;I_z|mn=n|mn.$$
(53)
As a notation similar to Zhang’s Zhang , the quantities

$$\omega ^\mathrm{\Delta }\sqrt{b^2+\mathrm{\Delta }^2};\omega ^\mathrm{\Sigma }\sqrt{b^2+\mathrm{\Sigma }^2}$$
(54)
are introduced. Then the eigenvectors, labelled with their respective energy eigenvalues are:

$`|\psi _{(1/2)\omega ^\mathrm{\Delta }}`$ $`=`$ $`{\displaystyle \frac{b|1/2,1/2+(\omega ^\mathrm{\Delta }\mathrm{\Delta })|1/2,1/2}{\sqrt{b^2+(\omega ^\mathrm{\Delta }\mathrm{\Delta })^2}}}`$
$`|\psi _{(1/2)\omega ^\mathrm{\Delta }}`$ $`=`$ $`{\displaystyle \frac{b|1/2,1/2(\omega ^\mathrm{\Delta }\mathrm{\Delta })|1/2,1/2}{\sqrt{b^2+(\omega ^\mathrm{\Delta }\mathrm{\Delta })^2}}}`$
$`|\psi _{(1/2)\omega ^\mathrm{\Sigma }}`$ $`=`$ $`{\displaystyle \frac{b|1/2,1/2+(\omega ^\mathrm{\Sigma }\mathrm{\Sigma })|1/2,1/2}{\sqrt{b^2+(\omega ^\mathrm{\Sigma }\mathrm{\Sigma })^2}}}`$
$`|\psi _{(1/2)\omega ^\mathrm{\Sigma }}`$ $`=`$ $`{\displaystyle \frac{b|1/2,1/2(\omega ^\mathrm{\Sigma }\mathrm{\Sigma })|1/2,1/2}{\sqrt{b^2+(\omega ^\mathrm{\Sigma }\mathrm{\Sigma })^2}}}.`$
It is be noted that these are NOT the same as the eigenvalues and eigenvectors of Zhang’s $`H^\mathrm{\Delta }`$ and/or $`H^\mathrm{\Sigma }`$, arising from his decomposition of the hamiltonian of Eq. (6), even taking into account the difference in the labelling of the coordinate axes.

The limits of these eigenvectors when $`b0`$ and $`\mathrm{\Delta }0`$ or $`\mathrm{\Sigma }0`$ give respectively the eigenvectors of the rf hamiltonian and of the truncated dipolar hamiltonian. In particular, as $`b0`$ with $`\mathrm{\Delta }>0`$, the expansion of $`\omega ^\mathrm{\Delta }`$ is

$$\omega ^\mathrm{\Delta }=\mathrm{\Delta }\sqrt{1+\frac{b^2}{\mathrm{\Delta }^2}}=\mathrm{\Delta }+\frac{b^2}{2\mathrm{\Delta }}+\mathrm{},$$
(55)
while $`\omega ^\mathrm{\Delta }b`$ as $`\mathrm{\Delta }0`$. As a consequence, the first listed eigenvector has the limits

$$|\psi _{1/2\omega ^\mathrm{\Delta }}\{\begin{array}{cc}|1/2,1/2\hfill & \text{as }b0\text{ for }\mathrm{\Delta }>0\hfill \\ |1/2,1/2\hfill & \text{as }b0\text{ for }\mathrm{\Delta }<0\hfill \\ (1/\sqrt{2})\left[|1/2,1/2+|1/2,1/2\right]\hfill & \text{as }\mathrm{\Delta }0\text{.}\hfill \end{array}$$
(56)
The limits of the other eigenvectors are obtained in an analogous manner.

## Appendix B Magic Angle Spinning

A vector based derivation is given for the effect of spinning the orientation dependent dipolar coupling strength.

The rotation of any unit vector $`\widehat{r}`$ about an axis $`\widehat{n}`$ by an angle $`\chi `$ produces the rotated vector

$$\widehat{r}^{}=\widehat{n}\widehat{n}\mathbf{}\widehat{r}+(\widehat{r}\widehat{n}\widehat{n}\mathbf{}\widehat{r})\mathrm{cos}\chi +\widehat{n}\mathbf{\times }\widehat{r}\mathrm{sin}\chi .$$
(57)
The component of the rotated vector along the Zeeman field direction $`\widehat{x}`$ is then

$$\mathrm{cos}\theta =\widehat{x}\mathbf{}\widehat{r}^{}=\widehat{x}\mathbf{}\widehat{n}\widehat{n}\mathbf{}\widehat{r}+(\widehat{x}\mathbf{}\widehat{r}\widehat{x}\mathbf{}\widehat{n}\widehat{n}\mathbf{}\widehat{r})\mathrm{cos}\chi +\widehat{x}\mathbf{\times }\widehat{n}\mathbf{}\widehat{r}\mathrm{sin}\chi .$$
(58)
If the unit vector $`\widehat{r}`$ is expressed in a right handed coordinate frame based on the rotation axis $`\widehat{n}`$ and the $`\widehat{x}\widehat{n}`$ plane,

$$\widehat{r}=\widehat{n}\mathrm{cos}\theta _r+\frac{\widehat{x}\widehat{n}\widehat{n}\mathbf{}\widehat{x}}{\sqrt{1(\widehat{n}\mathbf{}\widehat{x})^2}}\mathrm{sin}\theta _r\mathrm{cos}\varphi _r+\frac{\widehat{n}\mathbf{\times }\widehat{x}}{\sqrt{1(\widehat{n}\mathbf{}\widehat{x})^2}}\mathrm{sin}\theta _r\mathrm{sin}\varphi _r,$$
(59)
then

$$\mathrm{cos}\theta =\widehat{x}\mathbf{}\widehat{n}\mathrm{cos}\theta _r+\sqrt{1(\widehat{n}\mathbf{}\widehat{x})^2}\mathrm{sin}\theta _r\mathrm{cos}(\varphi _r+\chi ).$$
(60)
The angle dependence of the rotated dipolar coupling strength is then expressed by

$`\mathrm{cos}^2\theta 1/3`$ $`=`$ $`(\widehat{n}\mathbf{}\widehat{x})^2\mathrm{cos}^2\theta _r1/3+[1(\widehat{n}\mathbf{}\widehat{x})^2]\mathrm{sin}^2\theta _r\mathrm{cos}^2(\varphi _r+\chi )`$ (61)
$`+2\widehat{n}\mathbf{}\widehat{x}\sqrt{1(\widehat{n}\mathbf{}\widehat{x})^2}\mathrm{cos}\theta _r\mathrm{sin}\theta _r\mathrm{cos}(\varphi _r+\chi ).`$
The trigonometric identity

$$\mathrm{cos}^2(\varphi _r+\chi )=\frac{1}{2}[\mathrm{cos}2(\varphi _r+\chi )+1]$$
(62)
simplifies this expression. Finally, if $`\widehat{n}\mathbf{}\widehat{x}`$ is chosen as $`1/\sqrt{3}`$ and the angle $`\chi `$ is set equal to the $`\omega _rt`$, the time dependence of the dipolar coupling strength is

$`b_0\left(\mathrm{cos}^2\theta {\displaystyle \frac{1}{3}}\right)`$ $`=`$ $`b_0{\displaystyle \frac{1}{3}}\mathrm{sin}^2\theta _r\mathrm{cos}[2(\varphi _r+\omega _rt)]+b_0{\displaystyle \frac{2\sqrt{2}}{3}}\mathrm{cos}\theta _r\mathrm{sin}\theta _r\mathrm{cos}(\varphi _r+\omega _rt)`$ (63)
$`=`$ $`b_2^{}e^{2i\omega _rt}+b_1^{}e^{i\omega _rt}+b_1e^{i\omega _rt}+b_2e^{2i\omega _rt},`$
where $`b_1`$ and $`b_2`$ are given explicitly in Eqs. (42) and (43).

It is noted that the sum of the squares of the magnitudes of these parts of the coupling strengths, when averaged over all angles, preserves the total square of the coupling strength, namely

$`{\displaystyle b_0^2(\mathrm{cos}^2\theta \frac{1}{3})^2\mathrm{sin}\theta d\theta d\varphi }`$ $`=`$ $`{\displaystyle 2|b_1|^2}+2|b_2|^2\mathrm{sin}\theta _rd\theta _rd\varphi _r`$
$`={\displaystyle \frac{8\pi }{45}}b_0^2`$ $`=`$ $`{\displaystyle \frac{16\pi }{135}}b_0^2+{\displaystyle \frac{8\pi }{135}}b_0^2.`$ (64)
Thus the contributions of the $`b_1`$ terms are twice those of the $`b_2`$ terms.

## Appendix C Complete Sideband Calculation

This appendix gives a method for carrying out the exact calculation of $`D(t)`$ from Eq. (45). For this purpose, the second derivative of $`N_n(t)`$ is

$$\frac{^2N_n(t)}{t^2}=|b_n|^2\frac{D(t)}{t}(\mathrm{\Delta }+n\omega _n)^2N_n(t).$$
(65)
Then the third derivative of $`D(t)`$ can be expressed in terms of the first derivative and the $`N_n(t)`$’s, that is

$$\frac{^3D(t)}{t^3}=\underset{n}{}|b_n|^2\frac{D(t)}{t}+\underset{n}{}(\mathrm{\Delta }+n\omega _n)^2N_n(t).$$
(66)
Continuing in this way, the higher odd-ordered derivatives of $`D(t)`$ can be calculated in terms of lower ordered derivatives and the $`N_n(t)`$’s. The first 4 equations obtained in this way (up to the 7th order derivative) can be used to solve for the $`N_n(t)`$’s in terms of the derivatives of $`D(t)`$. Substituting these into the equation for the 9th order derivative produces a differential equation for $`D(t)`$ of 9th order, but with constant coefficients. Such an equation has 9 solutions of the form $`D(t)=e^{\lambda t}`$, whose proper combination gives the time dependence of $`D(t)`$.

To simplify this calculation, it is convenient to introduce the notation $`D^{(m)}(t)`$ for the $`m`$th derivative of $`D(t)`$, and the sums

$$SS_m\underset{n}{}(\mathrm{\Delta }+n\omega _r)^m|b_n|^2.$$
(67)
Then the needed equations for the higher odd-ordered derivatives of $`D(t)`$ are

$`D^{(5)}(t)`$ $`=`$ $`SS_0D^{(3)}+SS_2D^{(1)}{\displaystyle \underset{n}{}}(\mathrm{\Delta }+n\omega )^4N_n(t)`$
$`D^{(7)}(t)`$ $`=`$ $`SS_0D^{(5)}+SS_2D^{(3)}SS_4D^{(1)}`$
$`+{\displaystyle \underset{n}{}}(\mathrm{\Delta }+n\omega )^6N_n(t)`$
$`D^{(9)}(t)`$ $`=`$ $`SS_0D^{(7)}+SS_2D^{(5)}SS_4D^{(3)}`$ (68)
$`+SS_6D^{(1)}{\displaystyle \underset{n}{}}(\mathrm{\Delta }+n\omega )^8N_n(t).`$
A formal inversion of the matrix of frequency powers multiplying the $`N_n(t)`$’s from the 4 odd-ordered derivatives $`D^{(1)}(t)`$ to $`D^{(7)}(t)`$ allows the $`N_n(t)`$’s to be expressed in terms of the $`D^{(m)}(t)`$’s. Substitution into the $`D^{(9)}(t)`$ equation gives the desired differential equation for $`D(t)`$. This involves only odd-ordered derivatives of $`D(t)`$. If $`e^{\lambda t}`$ is substituted in for $`D(t)`$, this gives a fourth order polynomial in $`\lambda ^2`$ times a factor of $`\lambda `$. The polynomial has 4 roots which must be negative since the spin dynamics is governed by the quantum Liouville equation (and thus the spin system must oscillate without any relaxation), and there is also the zero root from the multiplicative factor of $`\lambda `$. The 4 eigenfrequencies $`\mathrm{\Omega }_m`$ (square roots of minus the polynomial roots) and the zero frequency determine the time dependence of $`D(t)`$. A further simplification arises from noticing that $`N_n(0)=0`$, which implies that all odd derivatives of $`D(t)`$ vanish at $`t=0`$. Thus $`D(t)`$ must be an even function of $`t`$ and can be expressed as the sum

$$D(t)=A_0+\underset{m=1}{\overset{4}{}}A_m\mathrm{cos}(\mathrm{\Omega }_mt).$$
(69)
The expansion coefficients $`A_m`$ ($`m=0\mathrm{}4`$) still need to be determined.

The coefficients $`A_m`$ are determined from the even-ordered derivatives $`D^{(2\mathrm{})}(t)`$ evaluated at $`t=0`$. These can be found directly by differentiating Eqs. (45), (66) and (C), and evaluating them at $`t=0`$. Specifically, the 5 required relations are

$`A_0+{\displaystyle \underset{m}{}}A_m`$ $`=`$ $`D(0)`$
$`{\displaystyle \underset{m}{}}\mathrm{\Omega }_m^2A_m`$ $`=`$ $`D^{(2)}(0)=SS_0D(0)`$
$`{\displaystyle \underset{m}{}}\mathrm{\Omega }_m^4A_m`$ $`=`$ $`D^{(4)}(0)=(SS_0^2+SS_2)D(0)`$
$`{\displaystyle \underset{m}{}}\mathrm{\Omega }_m^6A_m`$ $`=`$ $`D^{(6)}(0)=[SS_0(SS_0^2+2SS_2)`$
$`+SS_4]D(0)`$
$`{\displaystyle \underset{m}{}}\mathrm{\Omega }_m^8A_m`$ $`=`$ $`D^{(8)}(0)=[SS_0^2(SS_0^2+3SS_2)`$ (70)
$`+2SS_0SS_4+SS_2^2+SS_6]D(0).`$
These equations are to be solved for the expansion coefficients.

This determines the difference $`S_zI_z(t)=D(t)`$ of the expectation values of the two spin operators. A calculation of the sum $`S_z+I_z(t)=G(t)`$ involves the same treatment, but with the sum frequency $`\mathrm{\Sigma }`$ replacing the difference frequency $`\mathrm{\Delta }`$ in all the above formulas. The cross polarization is given by one half the sum of these two quantities

$$S_z(t)=\frac{1}{2}[D(t)+G(t)].$$
(71)
Note that $`G(0)=D(0)=I_z(0)`$. To calculate the powder average CPMAS, the above computations need to be carried out for every possible orientation of the vector pointing from one spin to the other. A bonus of the approximation of retaining only the terms $`|b_1|^2`$ and $`|b_2|^2`$ in the product of the time dependent coupling strengths, Eq. (44), is that these quantities are independent of the angle $`\varphi _r`$ in the description of this orientation, so only the $`\theta _r`$ average needs to be done. Thus the powder CPMAS is given by

$$\overline{S_z}_{\mathrm{powder}}(t)=\frac{1}{4}_1^1[D(t)+G(t)]d\mathrm{cos}\theta _r.$$
(72)