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# 1 C/T vs T for Ce(1-x)La(x)RhIn(5)

Specific Heat of Ce1-xLaxRhIn5 in Zero and Applied Magnetic Field: A Very Rich Phase Diagram

J. S. Kim, J. Alwood, D. Mixson, P. Watts, and G. R. Stewart

Department of Physics, University of Florida, Gainesville, Fl. 32611-8440

Abstract: Specific heat and magnetization results as a function of field on single- and poly-crystalline samples of Ce1-xLaxRhIn5 show 1.) a specific heat $`\gamma `$ of about 100 mJ/moleK2 (in agreement with recent dHvA results of Alvers et al.); 2.) upturns at low temperatures in C/T and $`\chi `$ that fit a power law behavior ($`<`$=$`>`$ Griffiths phase non-Fermi liquid behavior); 3.) a field induced anomaly in C/T as well as M vs H behavior in good agreement with the recent Griffiths phase theory of Castro Neto and Jones, where M~H at low field, M~Hλ above a crossover field, C/T~T-1+λ at low field, and C/T~(H2+λ/2/T3-λ/2)\*exp(-$`\mu _{eff}`$H/T) above the same crossover field as determined in the magnetization and where $`\lambda `$ is independently determined from the temperature dependence of $`\chi `$ at low temperatures, $`\chi `$~T-1+λ and low fields.

I Introduction

Recently, a new family of heavy-fermion compounds has been discovered that crystallize in a layered, tetragonal structure with chemical composition CeMIn5, where M= Ir, Co, and Rh. Characteristic of heavy-fermion systems, each member exhibits a large Sommerfeld coefficient $`\gamma `$ ($``$C/T as T$``$0) in the specific heat C. CeIrIn5 and CeCoIn5 are bulk superconductors1-2 with transition temperatures at Tc = 0.4 K and 2.3 K and normal-state values of $`\gamma `$ 750 mJ/molK2 and 1200 mJ/molK2, respectively. CeRhIn5 displays heavy-fermion antiferromagnetism with3 TN = 3.8 K. A precise value of $`\gamma `$ is difficult to establish unambiguously because of the Néel order; a lower limit of approximately 400 mJ/molK2 has been quoted4-5.

In our high field specific heat measurements6 on the CeMIn5 compounds, we found that the large upturn for M=Rh in C/T above TN (C/T is already 1000 mJ/molK2 at TN) as temperature is lowered appeared to be primarily due to magnetic interactions above the antiferromagnetic transition since the specific heat data at a given temperature for T$`>`$TN in different fields up to 32 T all coincide with one another when the temperature axis was scaled to T/TN. Recently Alver, et al. have performed7 dHvA measurements on twelve single crystal samples spanning the whole composition range of Ce1-xLaxRhIn5 and find rather low (i. e. inconsistent by approximately an order of magnitude with a $`\gamma `$ of 400 mJ/molK$`{}_{}{}^{2})`$ effective masses from the dilute Ce, large x end of the phase diagram up to x=0.1. At this Ce-rich end of the composition range they find an increase in the effective masses (which still remain $``$ 10 me) which they ascribe to spin fluctuation effects. Alver, et al. conclude that the Ce f-electrons remain localized in Ce1-xLaxRhIn5 for all x, with the (modest) observed mass enhancement near pure CeRhIn5 due to spin fluctuation effects. Although comparisons between specific heat and dHvA data have inherent problems (not the least of which is the possibility of unseen, heavier mass orbits in the dHvA measurements), an effective mass enhancement of approximately ten normally corresponds to a specific heat $`\gamma `$ of only ~50 mJ/molK2. This is a wide discrepancy from the estimate of 400 mJ/molK2 in4-5 the literature; this discrepancy would be consistent with our high field specific heat result6 that the upturn above TN in C/T in pure CeRhIn5 is primarily caused by magnetic interactions, which would not cause a mass enhancement observable, e.g., in dHvA measurements.

In order to help resolve this seeming disagreement, to determine the specific heat $`\gamma `$ (also proportional to the effective mass) in a region of the phase diagram away from the antiferromagnetic anomaly, and to look for possible new behavior in the dilute limit we report here on a specific heat study of both single and polycrystalline samples of Ce1-xLaxRhIn5, 0$``$x$``$0.95. Certainly, doping studies8-10 on other heavy Fermion systems, e.g. Ce1-xLaxCu2Si2, Ce1-xThxCu2Si2, and U1-xThxBe13, have revealed interesting new information - both about the respective parent compound as well as new physics in the dilute limit. Polycrystalline samples were originally chosen for the study as being more easily and rapidly prepared. However, specific heat results for polycrystalline Ce1-xLaxRhIn5, x=0.5 and 0.8 were determined to disagree with specific heat results for single crystal samples, while results agreed for x=0.15 and 0.95. This disagreement appears due to the presence of a second phase which we were able to eliminate through long term annealing of the polycrystalline samples at a relatively low temperature.

II Experimental

Single crystal samples of Ce1-xLaxRhIn5 were prepared using the procedure described in ref. 6, which was similar to that used in refs. 4 and 7. Excess In was removed from the resulting flat platelet crystals using an H2O:HF:H2O2 4:1:1 etch which was different than the centrifugal method (H2O:HCl 4:1 etch) used in ref. 4 (7); however the present work’s specific heat results (which are a measure of bulk properties) should be relatively independent of such surface treatments. The polycrystalline samples in the present work (previous work in the literature has been almost uniformly on single crystal samples) were prepared by melting together stoichiometric amounts of the appropriate high purity starting elements (using Ames Laboratory Ce and La, 99.95% pure Rh from Johnson Mathey Aesar, and 99.9999% In from Johnson Matthey Aesar - the same starting materials as used for the single crystals) under a purified inert Ar atmosphere. Weight losses after four melts, with a flipping of the arc-melted button between melts to improve homogeneity, were in the range of 1%, primarily due to In loss. Additional In was added in the beginning to correct for this, such that the In concentrations after the last melt were within $`\pm `$0.2% of the stoichiometric amount.

Specific heat in fields to 13 T were measured using established techniques11, while magnetic susceptibility data were measured in a SQUID magnetometer from Quantum Design.

III Results and Discussion

Figure 1 shows the specific heat divided by temperature vs temperature for single crystal Ce1-xLaxRhIn5, x=0, 0.15, 0.5, 0.8, and 0.95 and polycrystal Ce1-xLaxRhIn5, x=0.32. All samples were single phase. Results for unannealed polycrystalline Ce1-xLaxRhIn5, x=0.15 and 0.95, and annealed (35 days at 720 oC) polycrystalline Ce1-xLaxRhIn5, x=0.5 and 0.8, were comparable to the single crystal results (see inset of Fig. 1 for an example); however, unannealed polycrystalline samples for x=0.5 and 0.8 contained a second phase that ordered antiferromagnetically below 1 K. This was taken as a sign of an incipient miscibility gap which - due to previous work being focussed on single crystal samples - was heretofore unknown.

From the data shown in Fig. 1, one can follow the suppression of the antiferromagnetic transition with increasing La doping; there is a clear, although reduced in magnitude, transition at 2 K for 15% La doping that is absent by x=0.32. Although one might expect12 non-Fermi liquid (’nFl’) behavior when

TN is suppressed to T=0, the temperature dependence of the C/T data for x=0.32 - although the

data show an upturn - is only measured for ~0.5 K below the hump. This is too restricted a temperature range to allow conclusions about the temperature dependence.

Before we discuss the behavior of $`\gamma `$ as a function of x in Ce1-xLaxRhIn5, we will first focus on the upturn at low temperatures for x$``$0.5.

A Upturn in C/T for x$``$0.5

The upturn in C/T for x$``$0.5 in Ce1-xLaxRhIn5 shown in Figs. 1 is fit in Figs. 2 and 3 for single crystalline, as well as single phase polycrystalline, material. Note in Fig. 2 that the data for the three different samples agree rather well. There is certainly no sign in the dHvA results of Alver, et al. for a strong, heavy fermion upturn in C/T that would cause large effective masses. Thus, this upturn at low temperatures in C/T likely has a magnetic interaction explanation (see section C below for the field dependence). The temperature dependence of the upturns in C/T (see Figs. 2 and 3) for single crystal Ce1-xLaxRhIn5, x=0.5, 0.8, and 0.95, is not at all like the high temperature side of a Schottky peak (C ~1/T2) but rather appears (in the somewhat limited temperature range that we have data) to follow C/T ~T-1+λ,$`\lambda _{\text{C/T}}`$=0.63 $`\pm `$ 0.1, 0.37 $`\pm `$ 0.1, and ~0 respectively. This is the temperature dependence predicted for non-Fermi liquid behavior caused by disorder-induced spin clusters, the so-called Griffiths phase12-13. (Note that the fits of $`\chi `$ to T-1+λ below 1.2 K are much better than fits to either log T or T0.5.) In this theory, the magnetic susceptibility

at low temperature should have the same power law dependence as C/T. The susceptibility at low temperatures for these same compositions of single crystal Ce1-xLaxRhIn5, see Fig. 4, does indeed fit this T-1+λ temperature dependence, with $`\lambda _\chi `$ ={0.73,0.90}, {0.50,0.70}, {0.14,0.30} respectively for H {$``$,$``$} the c-axis, where the absolute error bar for each value is $`\pm `$ 0.1 (with, however, somewhat better precision, useful for intercomparison between values derived from a given measurement technique. For example, 0.14 derived from $`\chi `$ for x=0.95 is certainly less than 0.30 derived for the other field direction, but is comparable to the value of ~0 derived for the same composition from the specific heat.) (Note that other standard non-Fermi liquid temperature dependences, such as $`\chi `$ ~log T or T0.5, do not fit the $`\chi `$ data at all well.) Although for a given composition the respective exponents for C/T and $`\chi `$ agree within experiment accuracy only for $`\chi `$(H $``$ c), the recent theory14 of Castro Neto and Jones actually predicts that $`\chi `$ and C/T may diverge differently at low temperature, relaxing the requirement of the early theory12-13 that $`\lambda _\chi `$=$`\lambda _{\text{C/T}}`$. It is clear that the disorder requirement for uncompensated spins (which requires that M vs H is shows saturation behavior) is fulfilled for all these compositions (see discussion and accompanying figures in section C below.) In addition, the agreement in $`\lambda _{C/T}`$ and $`\lambda _\chi `$found for the upturn in C/T and $`\chi `$ in the present work is comparable to that found by, e. g., deAndrade et al.15 in their study of Th1-xUxPd2Al3 \- even though they measured $`\chi `$ down to 0.5 K, i. e. in a temperature range comparable to that for their specific heat measurements. The anisotropy of the susceptibility-determined $`\lambda `$ values is thought to be real, and not related to the discrepancy between $`\lambda _{C/T\text{ }}`$and $`\lambda _\chi `$.

As one possible check for a tendency towards magnetic behavior, the Wilson ratio (R $``$ $`\chi `$/$`\gamma \mu _{eff}^2`$) - which is used16 in the study of heavy Fermion systems to track the tendency towards magnetism, with R $``$ 0.8 indicating16 magnetic behavior - for these Ce1-xLaxRhIn5 alloys is in the range of 1.0 to 1.8, i. e. they definitely show magnetic character. As a further check for evidence for spin clusters, we investigated these compositions for spin glass behavior and - to within the limits ($`\pm `$2 %) of the accuracy of the measurements - found no difference between field cooled and zero field cooled data down to 1.8 K. This lack of observable spin glass behavior in the dc magnetic susceptibility in these samples does not rule out a Griffiths phase interpretation17.

B Specific Heat $`\gamma `$ as a Function of x

The original goal of this work, besides the hope for new physics of interest in the dilute range (already partially fulfilled by the results discussed above for the low temperature upturn in C/T and $`\chi )`$ was to investigate the specific heat $`\gamma `$ (defined as C/T as T$``$0) away from the region of the phase diagram where antiferromagnetism obscures C/T as T$``$0 in CeRhIn5 diluted with La. As discussed above, after the antiferromagnetism is suppressed (x$`>`$0.15), a low temperature upturn in the C/T data (Fig. 1) occurs that, normalized per Ce-mole, becomes more pronounced with increasing dilution of the Ce. This upturn appears not to be related to the effective masses measured by the dHvA measurements.

A further complication to determining the specific heat $`\gamma `$ is the rounded feature in C/T centered at ~3 K visible already for x=0.15 above TN. As may be seen from Fig. 5, the C/T data for x$`=`$0.5 (triangles) and 0.8 (circles) in Ce1-xLaxRhIn5 above the low temperature upturn show a tendency to curve or bend downwards down to about 1.5 K, at which point the upturn discussed in the section above begins. This ’hump’ in C/T centered at ~3 K makes extrapolating C/T to T=0 to determine $`\gamma `$ a somewhat imprecise procedure. It should be stressed that this rounded feature, or hump, in C/T has its provenance in the f-electron sublattice: such a feature is not present in C/T data for pure LaRhIn$`{}_{}{}^{18}{}_{5}{}^{}`$. One possibility for correcting for this feature in order to determine $`\gamma `$ is to subtract off both the low temperature upturn (see Fig. 3 for the fits to the upturns) and a fit18 to pure LaRhIn5 and examine the remainder. As shown in the inset to Fig. 5 for x=0.5, this very rough approximation (the apparent negative value below about 1 K is, see Fig. 3, merely a sign that the fit to the upturn - which goes up to over 1000 mJ/Ce-moleK2 at 0.3 K - is in error as T$``$1 K) allows us to assign an approximate19 $`\gamma `$ value per Ce mole of $``$100 mJ/CemolK2 for x$``$0.5. This agrees much better with Alver, et al.’s dHvA results than the estimates of 400 mJ/CemolK2 estimated4-5 in the literature. However, as the La dilution is removed, for x$``$0.1, Alver, et al. report approximately a factor of two increase in effective mass due to spin fluctuation effects, with an effective mass for pure CeRhIn5 that would correspond to a $`\gamma `$ of approximately 50 mJ/CemolK2. In the dilute limit, Alver et al.’s effective measured effective mass corresponds to a $`\gamma `$ of only 25 mJ/CemolK2. However, as may be seen in Fig. 5, our C/T data at low temperature are much too obscured by the unexpected upturn as well as by the rounded maximum to supply any sort of accurate estimate for $`\gamma `$ beyond the dilute, x$``$0.5, range of $``$100 mJ/CemolK2 already quoted above.

C Field Induced Anomaly for x$``$0.5

As a final aspect of new, unexpected behavior for CeRhIn5 diluted with La, when we were investigating the field dependence of the upturn in the specific heat divided by temperature using magnetic field as a probe, we discovered that applied field suppresses the low temperature upturn in C/T at rather low field and induces an peak in C/T that, with increasing field, moves up in temperature and becomes broader and less pronounced. This rounded anomaly, shown in Fig. 6 for x=0.95 (these data are typical of the results for all x$``$0.5) with field in the basal plane (data in the perpendicular direction are within 15 percent of these), is not that of either a spin glass (where C~1/T above the peak) or a Schottky anomaly (C~1/T2 above the peak) but rather seems to be a field-induced anomaly. (The upturns in C/T for H $``$ 6 T are caused by the applied field splitting the nuclear magnetic moment energy levels and creating a Schottky peak in the specific heat.)

Castro Neto and Jones have recently published14 a theory of how the specific heat and magnetization of materials with non-Fermi liquid behavior caused by disorder-induced Griffiths phase spin clusters should scale with magnetic field. In general, both the magnetization and specific heat are predicted to exhibit low field behaviors (M ~H and C/T ~T-1+λ) which crossover over to the respective high field behaviors (M ~Hλ and C/T ~(H2+λ/2/T3-λ/2)e$`^{\mu _{eff}H/T}`$) at the same magnetic field. The prediction for the field and temperature dependence for the high field specific heat leads to a peak in C/T (or a shoulder in C) as a function of increasing temperature - thus qualitatively consistent with the data shown in Fig. 6.

Although the specific heat data in field was taken in fairly widely spaced fields, the fact that a peak occurs already in C/T in H=3 T offers a prediction (the equality of the crossover field requires that the crossover field for the magnetization data be perforce below 3 T) that can be checked by examining the M vs H data, where a much more finely spaced sequence of fields was used. In addition, the high field prediction that M ~Hλ can be checked up to 5.5 T, and this field-dependence determination of $`\lambda `$ can then be compared with that independently determined from the temperature dependence of $`\chi `$ in Figure 4. Thus, magnetization data for both field directions for single crystal Ce0.05La0.95RhIn5 are shown fitted to these Griffiths phase low and high field predictions in Figures 7 and 8, H $``$,$``$ basal plane respectively. As may be seen, using the values for $`\lambda _\chi `$ determined from Fig. 4 (0.14 and 0.41 for H($``$,$``$) basal plane respectively) gives rather good20 agreement between the predicted, M ~Hλ dependence and the high field magnetization data. (The fit to the higher field data with the lowest standard deviation actually gives $`\lambda `$=0.67; however, the standard deviations are within 8% of one another.) Further, the deviation from linear behavior at low fields occurs (see Figs. 7 and 8) above 0.8 T and the deviation from the M ~Hλ power law occurs below 1.2 T. These estimates for the crossover field are not inconsistent with the peak in C/T (where a peak is characteristic of the high field regime) occuring in 3 T, Fig. 6. (Work under way21 to more thoroughly characterize the low and high field behavior for M and C/T for x=0.95 has found that a peak in C/T field data taken in 0.5 T increments down to 0.3 K first appears at 1.5 T.)

Another prediction14 of the Griffiths phase theory of Castro Neto and Jones, the field and temperature dependence of C/T in the high field limit, is compared22 to the 3T Ce0.05La0.95RhIn5 data (with the fit18 to pure LaRhIn5 and the small, $`<`$10% at the lowest temperature, contribution due to the field splitting of the nuclear moments, subtracted off), H $``$ basal plane, in Fig. 9. Using only two fit parameters (the amplitude and the effective moment, $`\mu _{eff}`$) and fixing $`\lambda `$ = 0.14 (based on $`\lambda _\chi `$) gives the fit (dashed line in Fig. 9) as shown, with the reasonable14,23 fitted value for $`\mu _{eff}`$ (which corresponds to the average moment in the Griffiths phase spin cluster) of 1.25 $`\mu _B`$. Clearly, fitting C/T to (H2+λ/2/T3-λ/2)e$`^{\mu _{eff}H/T}`$ is a fairly good representation of the data. (To give an idea how the fit depends on the effective moment, a fit to these 3 T data with $`\mu _{eff}`$ constrained to be 1.0 $`\mu _B`$ is shifted by to lower temperatures by ~0.2 K from the present fit.)

IV Conclusions

Despite the difficulty of precisely compensating for the broad peak in C/T in Ce1-xLaxRhIn5 centered at about 3 K, the apparent $`\gamma `$ per Ce mole for x$``$0.5, away from the antiferromagnetic transition in the phase diagram, appears to be less than 100 mJ/Ce-moleK2 \- in disagreement with estimates for $`\gamma `$ in the literature4-5 but not inconsistent with the dHvA results of Alvers et al.7 There is a strong upturn in C/T below 1 K for x$``$0.5 that, when compared to the temperature dependence of the susceptibility and the non-linear M vs H data, is consistent with non-Fermi liquid behavior due to disordered spin clusters (’Griffiths phases.’) Applied magnetic field suppresses this upturn in C/T already by 3 T; above 3 T the C/T results show a broad anomaly that further broadens and moves to higher temperatures as field is increased. This field induced anomaly, together with the field dependence of the magnetization, compares well with the predictions of the Griffiths phase theory14,24 of Castro Neto and Jones, particularly in the magnetization data as a function of field and the agreement of these data with the predicted $`\lambda _\chi `$ exponent from the temperature dependence of the susceptibility. In summary, the breadth of behavior observed in Ce1-xLaxRhIn5 in zero and applied field is indicative of a phase diagram of unusual richness and variety.

Acknowledgements: The authors wish to thank Antonio Castro Neto for quite fruitful discussions. Work at the University of Florida by performed under the auspices of the United States Department of Energy, contract no. DE-FG05-86ER45268. Partial summer support for J. Alwood and P. Watts from the NHMFL and University of Florida NSF REU programs respectively is gratefully acknowledged.

References

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2. C. Petrovic, P. G. Pagliuso, M. F. Hundley, R. Movshovich, J. L. Sarrao, J. D. Thompson, and Z. Fisk, J. Condens. Mat. Phys. 13, L337 (2001).

3. N. J. Curro, P. C. Hammel, P. G. Pagliuso, J. L. Sarrao, J. D. Thompson, and Z. Fisk, Phys. Rev. B 62, 6100 (2000); W. Bao, P. G. Pagliuso, J. L. Sarrao, J. D. Thompson, Z. Fisk, J. W. Lynn, and R. W. Irwin, Phys. Rev. B 62, 14621 (2000); W. Bao, P. G. Pagliuso, J. L. Sarrao, J. D. Thompson, Z. Fisk, J. W. Lynn, and R. W. Irwin, Phys. Rev. B 63, 219901(E) (2001).

4. H. Hegger, C. Petrovic, E. G. Moshopoulou, M. F. Hundley, J. L. Sarrao, Z. Fisk, and J. D. Thompson, Phys. Rev. Lett. 84, 4986 (2000).

5. A. L. Cornelius, P. G. Pagliuso, M. F. Hundley, and J. L. Sarrao, Phys. Rev. B 64, 144411 (2001).

6. J. S. Kim, J. Alwood, G. R. Stewart, J. L. Sarrao, and J. D. Thompson, Phys. Rev. B 64, 134524 (2001).

7. U. Alver, R. G. Goodrich, N. Harrison, D. W. Hall, E. C. Palm, T. P. Murphy, S. W. Tozer, P. G. Pagliuso, N. O. Moreno, J. L. Sarrao, and Z. Fisk, Phys. Rev. B 64, 180402R (2001).

8. B. Andraka, C.S. Jee, J.S. Kim, Hauli Li, M.W. Meisel, and G.R. Stewart, Physica B171, 384 (1991).

9. C.S. Jee, B. Andraka, J.S. Kim, Hauli Li, M.W. Meisel, and G.R. Stewart, Phys. Rev. B42, 8630 (1990); J. S. Kim, C. S. Jee, W. W. Kim, B. Andraka, P. Kumar, and G. R. Stewart, Phys. Rev. B44, 7473 (1991).

10. J. S. Kim, B. Andraka, and G. R. Stewart, Phys. Rev. B44, 6921 (1991).

11. G. R. Stewart, Rev. Sci. Instrum. 54, 1 (1983).

12. For a review of non-Fermi liquid behavior, see G. R. Stewart, Rev. Mod. Phys. 73, 797 (2001).

13. A. H. Castro Neto,G. Castilla, and B. A. Jones, Phys. Rev. Lett. 81, 3531 (1998).

14. A. H. Castro Neto and B. A. Jones, Phys. Rev. B 62, 14975 (2000).

15. M. C. DeAndrade, R. Chau, R. P. Dickey, N. R. Dilley, E. J. Freeman, D. A. Gajewski,

M. B. Maple, R. Movshovich, A. H. Castro Neto, G. Castilla, and B. A. Jones,

Phys. Rev. Lett. 81, 5620 (1998).

16. G. R. Stewart, Rev. Mod. Phys. 56, 755 (1984).

17. For a discussion of spin cluster, spin glass, and Griffiths phase behavior, see ref. 12.

18. Mike Hundley, private communication. See also ref. 4.

19. Note of course the unavoidable uncertainty is fitting the ’hump’ - which may very well involve entropy due to Ce-Ce interactions - to data from a more dilute composition and then applying this fit to more concentrated systems.

20. The ”best fit” value for the exponent $`\lambda `$ from the field dependence of the magnetization for H $``$ basal plane shown in Fig. 7 is within 0.1 of the value $`\lambda _\chi `$ = 0.14 determined from the temperature dependence of $`\chi `$ determined in Fig. 4, i. e. within the error bar. For H $``$ basal plane, the best fit to the magnetization data shown in Fig. 8 gives $`\lambda `$ = 0.67 instead of the value determined from the temperature dependence of $`\chi `$, where $`\lambda _\chi `$ = 0.41. However, the standard deviation for the fit (to 20 data points) using $`\lambda _\chi `$ = 0.41 is less than 8% higher than that for the ”best” fit.

21. J. S. Kim, J. Alwood, D. Mixson, and G. R. Stewart, to be published.

22. Fits to the 6 and 9 T data are similar, although the correction for the low temperature upturn in C/T caused by the nuclear hyperfine level splitting due to the applied field is larger and the size of the field-induced anomaly in C/T with increasing field is rapidly decreasing. Since the crossover field between low and high field dependences, as determined by the magnetization, is ~ 0.8 -1.2 T, the 3 T data should be well in the high field limit.

23. A. H. Castro Neto, private communication.

24. Although a recent paper (A. J. Millis, D. K. Morr, and J. Schmalian, Phys. Rev. Lett. 87, 167202 {2001}) has called the theory of Castro Neto and Jones into question based on dissipation arguments in the single impurity limit, an even more recent work by Castro Neto and Jones (cond-mat/0106176) argues that for concentrated systems the results of ref. 14 still hold.


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# Relativistic many-body calculations of transition rates from core-excited states in sodiumlike ions

## I Introduction

Transitions from $`2s^22p^53l3l^{}`$ and $`2s2p^63l3l^{}`$ states to the ground ($`2s^22p^63s`$) or singly-excited ($`2s^22p^63p`$ and $`2s^22p^63d`$) states form satellite lines to the bright electric-dipole (E1) lines created by transitions from $`2s^22p^53l`$ and $`2s2p^63l`$ states to the ground state ($`2s^22p^6`$) in Ne-like ions. These core-excited $`2s^22p^53l3l^{}`$ and $`2s2p^63l3l^{}`$ states (often called doubly-excited states) in sodiumlike ions have been studied extensively both experimentally and theoretically over the past 20-30 years.

Transition rates and oscillator strengths for Na-like ions have been calculated using multi-configuration Dirac-Fock (MCDF) Chen (1989); Nilsen (1989) and multi-configuration Hartree-Fock (MCHF) Zhang et al. (1989); Bruch et al. (1998a, b) methods. Recently, R-matrix calculations of electron-impact collision strengths for excitations from the inner $`L`$-shell into doubly excited states of Fe15+ was presented by Bautista (2000). Energies of $`2s^22p^63l`$ and $`2s^22p^53l3l^{}`$ states were calculated in that paper using the SUPERSTRUCTURE code Eissner et al. (1974). It was shown in Bautista (2000) that disagreement between calculated data and data recommended by Sugar and Corliss (1985) and Shirai et al. (1990) ranges from 0.5% to 5%.

Experimentally, the core-excited $`2s^22p^53l3l^{}`$ and $`2s2p^63l3l^{}`$ states were studied by the beam-foil technique Buchet et al. (1987); Jupén et al. (1988), photo-emission Burkhalter et al. (1979); Khakhalin et al. (1994); Akulinichev et al. (1994, 1995); Bollanti et al. (1995); Mingaleev et al. (1993); Beiersdorfer et al. (1986, 1995); Brown et al. (2001); Phillips et al. (1997), and Auger spectroscopy Schneider et al. (1989); Focke et al. (1989); Hutton et al. (1991); Schneider et al. (1995); Bliman et al. (1996). Strong line radiation involving $`n`$ = 3 to $`n`$ = 2 transitions in Ne-like ions together with satellite lines of Na-like ions were observed from laser-produced plasmas Burkhalter et al. (1979); Khakhalin et al. (1994); Akulinichev et al. (1994, 1995); Bollanti et al. (1995), X-pinch, Mingaleev et al. (1993), tokamaks Beiersdorfer et al. (1986, 1995), EBIT Brown et al. (2001), and solar flares Phillips et al. (1997). The identification of measured spectral lines was based on theoretical calculations carried out primarily using the MCDF method with Cowan’s code Cowan (1981).

In this paper, we present a comprehensive set of calculations for $`2s^22p^53l3l^{}`$ \- $`2s^22p^63l^{\prime \prime }`$ and $`2s2p^63l3l^{}`$ \- $`2s^22p^63l^{\prime \prime }`$ transitions to compare with previous calculations and experiments. Our aim is to provide benchmark values for the entire Na isoelectronic sequence. The large number of possible transitions have made experimental identification difficult. Experimental verifications should become simpler and more reliable using this more accurate set of calculations.

Relativistic many-body perturbation theory (RMBPT) is used here to determine matrix elements and transition rates for allowed and forbidden electric-dipole transitions between the odd-parity core-excited states ($`2s^22p^53s^2`$ \+ $`2s^22p^53p^2`$ \+ $`2s^22p^53d^2`$ \+ $`2s^22p^53s3d`$ \+ $`2s2p^63s3p`$ \+ $`2s2p^63p3d`$) and the ground state ($`2s^22p^63s`$) together with the two singly-excited states ($`2s^22p^63d`$) and the even-parity core-excited states ($`2s^22p^53s3p`$ \+ $`2s^22p^53p3d`$ \+ $`2s2p^63s^2`$ \+ $`2s2p^63p^2`$ \+ $`2s2p^63d^2`$ \+ $`2s2p^63s3d`$) and the two singly-excited states ($`2s^22p^63p`$) in Na-like ions with nuclear charges ranging from $`Z`$ = 14 to 100. Retarded E1 matrix elements are evaluated in both length and velocity forms. These calculations start from a Ne-like core Dirac-Fock (DF) potential. First-order perturbation theory is used to obtain intermediate coupling coefficients and second-order RMBPT is used to determine transition matrix elements. The energies used in the calculation of transition rates are obtained from second-order RMBPT.

## II Method

In this section, we discuss relativistic RMBPT for first- and second-order transition matrix elements for atomic systems with two valence electrons and one hole. Details of the RMBPT method for calculation of radiative transition rates for systems with one valence electron and one hole were presented for Ne-like and Ni-like ions in Safronova et al. (2000, 2001). Here, we follow the pattern of the corresponding calculation in Refs. Safronova et al. (2000, 2001) but limit our discussion to the model space and the first- and second-order particle-particle-hole diagram contributions in Na-like ions.

### II.1 Model space

For Na-like ions with two electrons above the Ne-like ($`1s^22s^22p_{1/2}^22p_{3/2}^4`$) core and one hole in the core, the model space is formed from particle-particle-hole states of the type $`a_v^{}a_w^{}a_a|0`$, where $`|0`$ is the core state function. Indices $`v`$ and $`w`$ designate valence electrons and $`a`$ designates a core electron. For our study of low-lying $`3l3l^{}2l^1`$ states of Na-like ions, the index $`a`$ ranges over $`2s`$, $`2p_{1/2}`$, and $`2p_{3/2}`$, while $`v`$ and $`w`$ range over $`3s`$, $`3p_{1/2}`$, $`3p_{3/2}`$, $`3d_{3/2}`$, and $`3d_{5/2}`$. To obtain orthonormal model states, we consider the coupled states $`(vwa)`$ defined by

$$\mathrm{\Psi }(QJM)=N(Q)vw|K_{12}K_{12}a|Ka_v^{}a_w^{}a_a|0,$$
(1)
where $`Q`$ describes a particle-particle-hole state with quantum numbers $`n_v\kappa _vn_w\kappa _w[J_{12}]n_a\kappa _a`$ and intermediate momentum $`J_{12}`$. We use the notation $`K_i=\{J_i,M_i\}`$ and $`v=\{j_v,m_v\}`$. The sum in Eq.(1) is over magnetic quantum numbers $`m_v`$, $`m_w`$, $`m_a`$, and $`M_{12}`$. The quantity $`K_1K_2|K_3`$ is a Clebsch-Gordan coefficient:

$$K_1K_2|K_3=(1)^{J_1J_2+M_3}\sqrt{[J_3]}\left(\begin{array}{ccc}J_1& J_2& J_3\\ M_1& M_2& M_3\end{array}\right),$$
(2)
where $`[J]=2J+1`$. Combining two $`n=3`$ particles with possible intermediate momenta and $`n=2`$ hole orbitals in sodium, we obtain 121 odd-parity states with $`J=1/2\mathrm{}\mathrm{\hspace{0.17em}11}/2`$ and 116 even-parity states with $`J=1/2\mathrm{}\mathrm{\hspace{0.17em}11}/2`$. The distribution of the 237 states in the model space is found in Table I of the accompanying EPAPS document EPA . Instead of using the $`3l^{}3l^{\prime \prime }[J_1]2l^1(J)`$ designations, we use simpler designations $`3l^{}3l^{\prime \prime }[J_1]2l(J)`$ in the tables and text below.

### II.2 Dipole matrix element

The first- and second-order reduced E1 matrix elements $`Z^{(1)}`$, and $`Z^{(2)}`$, and the second-order Breit correction to the reduced E1 matrix element $`B^{(2)}`$ for a transition between the uncoupled particle-particle-hole state $`\mathrm{\Psi }(QJM)`$ of Eq. (1) and the one-particle state $`a_x^{}|0`$ are given in Appendix.

The uncoupled reduced matrix elements are calculated in both length and velocity gauges. Differences between length and velocity forms are illustrated for the uncoupled \[$`3s3d_{5/2}[2]2p_{3/2}(1/2)`$ \- $`3s`$\] matrix element in panels (a) and (b) of Fig. 1. In the high-$`Z`$ limit, $`Z^{(1)}`$ is proportional to $`1/Z`$, $`Z^{(2)}`$ is proportional to $`1/Z^2`$, and $`B^{(2)}`$ is independent of $`Z`$ (see Safronova et al. (1999)). Taking into account this $`Z`$-dependence, we plot $`Z^{(1)}\times Z`$, $`Z^{(2)}\times Z^2`$, and $`B^{(2)}\times 10^4`$ in the figure. The contribution of the second-order matrix elements $`Z^{(2)}`$ is seen to be much larger in length form. Differences between results in length and velocity forms shown in Fig. 1 are precisely compensated by “derivative terms” $`P^{(\mathrm{derv})}`$, as shown later.

### II.3 Dipole matrix elements in Cu18+

In Table 1, we list values of uncoupled first- and second-order dipole matrix elements $`Z^{(1)}`$, $`Z^{(2)}`$, $`B^{(2)}`$, together with derivative terms $`P^{(\mathrm{derv})}`$ for Na-like copper, $`Z`$ = 29. For simplicity, we only list values for selected dipole transitions between odd-parity states with $`J`$ = 1/2 and the ground $`3s`$ and excited $`3d_{3/2}`$ states. Uncoupled matrix elements for other transitions in Na-like copper are given in Table II of the accompanying EPAPS document EPA . The derivative terms shown in Table 1 arise because transition amplitudes depend on energy, and the transition energy changes order-by-order in RMBPT calculations. Both length ($`L`$) and velocity ($`V`$) forms are given for the matrix elements. We find that the first-order matrix elements $`Z_L^{(1)}`$ and $`Z_V^{(1)}`$ differ by 10%; the $`L`$ \- $`V`$ differences between second-order matrix elements are much larger for some transitions. The term $`P^{(\mathrm{derv})}`$ in length form almost equals $`Z^{(1)}`$ in length form but $`P^{(\mathrm{derv})}`$ in velocity form is smaller than $`Z^{(1)}`$ in velocity form by three to four orders of magnitude.

Although we use an intermediate-coupling scheme, it is nevertheless convenient to label the physical states using the $`LS`$ scheme. Length and velocity forms of coupled matrix elements differ only in the fourth or fifth digits. These $`L`$ \- $`V`$ differences arise because we start our RMBPT calculations using a non-local Dirac-Fock potential. If we were to replace the DF potential by a local potential, the differences would disappear completely. Removing the second-order contribution increases $`L`$ \- $`V`$ differences by a factor of 10. Values of coupled reduced matrix elements in length and velocity forms are given in Table III of the accompanying EPAPS document EPA . Theoretical wavelengths $`\lambda `$ and transition probabilities $`A_r`$ for selected transitions in Na-like from $`Z`$ = 26 up to $`Z`$ = 30 are given in Table IV of EPA .

## III Results and comparison with other theory and experiment

Trends of the $`Z`$-dependence of transition rates for the transitions from core-excited even-parity states with $`J`$ = 1/2 to two possible singly-excited odd-parity states are presented in Fig. 2. Figures for transitions from other states are found in the accompanying EPAPS document EPA .

We find that transitions with smooth $`Z`$-dependence are rarer than transitions with sharp features. Smooth $`Z`$-dependence occurs for transitions from doublet and quartet core-excited states. Usually, singularities occur in the intermediate interval of $`Z`$ = 25 - 50 when neither $`LS`$ nor $`jj`$ coupling schemes describe the states of these ions properly. One general conclusion that can be derived from the figures is that the smooth $`Z`$-dependence occurs more frequently for transitions from low-lying core-excited states.

Singularities in the transition-rate curves have two distinct origins: avoided level crossings and zeros in dipole matrix elements. Avoided level crossings result in changes of the dominant configuration of a state at a particular value of $`Z`$ and lead to abrupt changes in the transition rate curves when the partial rates associated with the dominant configurations below and above the crossing point are significantly different. Zeros in transition matrix elements lead to cusp-like minima in the transition rate curves. Examples of each of these two singularity types can be seen in Fig. 2.

In Table 2, we present data for transitions from odd-parity states with $`J=1/2`$ in Fe+15 and Xe+43. We compare the present RMBPT values with those given by Nilsen (1989). More complete comparisons are given in the accompanying EPAPS document EPA . The calculations of Nilsen (1989) were based on a multiconfigurational relativistic bound-state and distorted-wave continuum code (YODA). Since $`jj`$ labeling was used in Nilsen (1989), we keep that labeling in Table 2. We find that the $`A_r`$-values from RMBPT and YODA differ by 10% in most cases. The differences are explained by the second-order corrections to dipole matrix elements included in RMBPT.

In Tables 3 \- 5, wavelengths and electric-dipole transition rates are presented for transitions in Na-like Fe, Co, Ni, Cu and Zn. We limit the tables to transitions given in Refs. Burkhalter et al. (1979); Akulinichev et al. (1994); Brown et al. (2001). Measurements for Fe15+ are presented in Tables 3 and 4 since two different ranges of spectra were investigated in Ref. Burkhalter et al. (1979) (16.8 - 17.8 Å) and Ref. Akulinichev et al. (1994) (15.1 - 15.5 Å). Three lines for Fe15+ were identified in region (15.1 - 15.26 Å) by Brown et al. in Ref. Brown et al. (2001). All possible $`3l_1j_13l_2j_2[J_1]2l_3j_3(J)`$ \- $`3l_j`$ transitions produce 393 spectrum lines. These lines in Fe15+ are covered by four spectral regions; 12.5 - 14.2 Å (114 lines), 15.1 \- 15.9 Å (174 lines), 16.8 - 17.9 Å (102 lines), and 19.3 - 19.7 Å (3 lines). The first 114 lines are from $`3dj_13dj_2[J_1]2s(J)`$ \- $`3l_j`$ and $`3pj_13dj_2[J_1]2s_{1/2}(J)`$ \- $`3l_j`$ transitions and the last three lines are from $`3s3s[0]2p_j(J)`$ \- $`3d_j`$ transitions. Our RMBPT data together with experimental measurements for Fe15+ in the region of 16.8 - 17.8 Å and 15.1 - 15.5 Å are presented in Tables 3 and 4, respectively. The agreement between our RMBPT wavelengths and the experimental values is 0.02 - 0.04% for both regions of the spectrum.

## IV Conclusion

We have presented a systematic second-order relativistic MBPT study of reduced matrix elements and transition rates for \[$`3l_1j_13l_2j_2[J_1]2l_3j_3(J)`$ \- $`3lj`$\] electric-dipole transitions in sodiumlike ions with the nuclear charges $`Z`$ ranging from 14 to 100. Our retarded $`E1`$ matrix elements include correlation corrections from Coulomb and Breit interactions. Both length and velocity forms of the matrix elements were evaluated and small differences (0.4% - 1%), caused by the non locality of the starting DF potential, were found between the two forms. Second-order RMBPT transition energies were used in our evaluation of transition rates. These calculations were compared with other calculations and with available experimental data. For $`Z20`$, we believe that the present theoretical data are more accurate than other theoretical or experimental data for transitions between the $`3l_1j_13l_2j_2[J_1]2l_3j_3(J)`$ core-excited states and the $`3lj`$ singly-excited states in Na-like ions. We hope that these results will be useful in analyzing older experiments and planning new ones. Additionally, these calculations provide basic theoretical input amplitudes for calculations of reduced matrix elements, oscillator strengths and transition rates for Cu-like satellites to transitions in Ni-like ions.

###### Acknowledgements.

The work of W.R.J. and M.S.S. was supported in part by National Science Foundation Grant No. PHY-0139928. U.I.S. acknowledges partial support by Grant No. B516165 from Lawrence Livermore National Laboratory. The work of J.R.A. was performed under the auspices of the U. S. Department of Energy by the University of California, Lawrence Livermore National Laboratory under contract No. W-7405-Eng-48.

*

## Appendix A The particle-particle-hole diagram contribution for dipole matrix element

The first-order reduced E1 matrix element $`Z^{(1)}`$ for a transition between the uncoupled particle-particle-hole state $`\mathrm{\Psi }(QJM)`$ of Eq. (1) and the one-particle state $`a_x^{}|0`$ is

$$Z^{(1)}(v^0w^0\left[J_{12}\right]aJ,xJ^{})=\underset{vw}{}\sqrt{[J_{12}][J]}P_{J_{12}}(v^0v,w^0w)\delta (J^{}x)\delta (vx)Z(va)\left\{\begin{array}{ccc}j_x\hfill & J\hfill & 1\hfill \\ j_a\hfill & j_w\hfill & J_{12}\hfill \end{array}\right\}(1)^{j_a+j_w},$$
(3)
where $`v`$, $`w`$ range over $`\{v^0,w^0\}`$. The quantity $`P_J(v^0v,w^0w)`$ is a symmetry coefficient defined by

$$P_J(v^0v,w^0w)=\eta _{v^0w^0}\left[\delta _{v^0v}\delta _{w^0w}+(1)^{j_v+j_w+J+1}\delta _{v^0w}\delta _{w^0v}\right],$$
(4)
where $`\eta _{vw}`$ is a normalization factor given by

$$\eta _{vw}=\{\begin{array}{cc}1\hfill & \text{for }wv\hfill \\ 1/\sqrt{2}\hfill & \text{for }w=v.\hfill \end{array}$$

The dipole matrix element $`Z(va)`$, which includes retardation, is given in velocity and length forms in Eqs.(3,4) of Ref. Safronova et al. (1999). The second-order reduced matrix element $`Z^{(2)}(v^0w^0\left[J_{12}\right]aJ,xJ^{})`$ consists of four contributions: $`Z^{(\mathrm{HF})}`$, $`Z^{(\mathrm{RPA})}`$, $`Z^{(\mathrm{corr})}`$, and $`Z^{(\mathrm{derv})}`$.

$`Z^{(\mathrm{HF})}(v^0w^0\left[J_{12}\right]aJ,xJ^{})={\displaystyle \underset{vw}{}}\sqrt{[J_{12}][J]}P_{J_{12}}(v^0v,w^0w)\delta (J^{}x)\delta (vx)(1)^{j_a+j_w}`$
$`\times \left\{\begin{array}{ccc}j_x\hfill & J\hfill & 1\hfill \\ j_a\hfill & j_w\hfill & J_{12}\hfill \end{array}\right\}{\displaystyle \underset{i}{}}\left[{\displaystyle \frac{\delta (j_wj_i)\mathrm{\Delta }(wi)Z(ia)}{ϵ(w)ϵ(i)}}+{\displaystyle \frac{\mathrm{\Delta }(ia)\delta (j_a,j_i)Z(wi)}{ϵ(a)ϵ(i)}}\right]`$ (7)
$`Z^{(\mathrm{RPA})}(v^0w^0\left[J_{12}\right]aJ,xJ^{})`$ $`=`$ $`{\displaystyle \frac{1}{3}}{\displaystyle \underset{vw}{}}\sqrt{[J_{12}][J]}P_{J_{12}}(v^0v,w^0w)\delta (J^{}x)\delta (vx)\left\{\begin{array}{ccc}j_x\hfill & J\hfill & 1\hfill \\ j_a\hfill & j_w\hfill & J_{12}\hfill \end{array}\right\}(1)^{j_a+j_w}`$ (10)
$`\times `$ $`{\displaystyle \underset{nb}{}}\left[{\displaystyle \frac{Z_1(wban)Z(bn)}{ϵ(b)+ϵ(w)ϵ(a)ϵ(n)}}+{\displaystyle \frac{Z_1(wnab)Z(nb)}{ϵ(b)+ϵ(a)ϵ(w)ϵ(n)}}\right]`$ (11)
$`Z^{(\mathrm{corr})}(v^0w^0\left[J_{12}\right]aJ,xJ^{})`$ $`=`$ $`{\displaystyle \underset{vw}{}}\sqrt{[J_{12}][J]}P_{J_{12}}(v^0v,w^0w)\delta (J^{}x){\displaystyle \underset{k}{}}(1)^{j_aj_v+J_{12}+k}`$ (14)
$`\times `$ $`{\displaystyle \underset{i}{}}[{\displaystyle \frac{Z(ix)X_k(vwai)}{ϵ(v)+ϵ(w)ϵ(a)ϵ(i)}}\delta (J,j_i){\displaystyle \frac{1}{[J]}}\left\{\begin{array}{ccc}j_w\hfill & j_i\hfill & k\hfill \\ j_a\hfill & j_v\hfill & J_{12}\hfill \end{array}\right\}`$
$``$ $`{\displaystyle \frac{Z(ia)X_k(vwxi)}{ϵ(v)+ϵ(w)ϵ(x)ϵ(i)}}\left\{\begin{array}{ccc}j_x\hfill & j_i\hfill & J_{12}\hfill \\ j_w\hfill & j_v\hfill & k\hfill \end{array}\right\}\left\{\begin{array}{ccc}j_x\hfill & J\hfill & 1\hfill \\ j_a\hfill & j_i\hfill & J_{12}\hfill \end{array}\right\}(1)^{J+j_wj_i}`$ (19)
$``$ $`{\displaystyle \frac{Z(vi)Z_k(axwi)}{ϵ(a)+ϵ(x)ϵ(w)ϵ(i)}}\left\{\begin{array}{ccc}j_v\hfill & J\hfill & k\hfill \\ j_a\hfill & j_w\hfill & J_{12}\hfill \end{array}\right\}\left\{\begin{array}{ccc}j_x\hfill & J\hfill & 1\hfill \\ j_v\hfill & j_i\hfill & k\hfill \end{array}\right\}(1)^{k+J_{12}+j_w+j_iJ+1}]`$ (24)
In the above equations, the index $`b`$ designates core states, index $`n`$ designates excited states, and index $`i`$ denotes an arbitrary core or excited state. In the sums over $`i`$ in Eqs. (A,24), all terms with vanishing denominators are excluded. The definitions of $`X_k(abcd)`$ and $`Z_k(abcd)`$ are given by Eq.(2.12) and Eq.(2.15) in Ref. Safronova et al. (1996) and $`\mathrm{\Delta }_{ij}`$ is defined at the end of section II in Safronova et al. (1996); $`ϵ(w)`$ is a one-electron DF energy.

The derivative term is just the derivative of the the first-order matrix element with respect to the transition energy. It is introduced to account for the first-order change in transition energy. An auxiliary quantity $`P^{(\mathrm{derv})}`$ is defined by

$$P^{(\mathrm{derv})}(v^0w^0\left[J_{12}\right]aJ,xJ^{})=\underset{vw}{}\sqrt{[J_{12}][J]}P_{J_{12}}(v^0v,w^0w)\delta (J^{}x)\delta (vx)Z^{(\mathrm{derv})}(va)\left\{\begin{array}{ccc}j_x\hfill & J\hfill & 1\hfill \\ j_a\hfill & j_w\hfill & J_{12}\hfill \end{array}\right\}(1)^{j_a+j_w}.$$
(25)
The derivative term $`Z^{(\mathrm{derv})}(va)`$ is given in length and velocity forms by Eqs. (10) and (11) of Ref. Safronova et al. (1999).

The coupled dipole transition matrix element between the initial state $`I`$ and final state $`F`$ in Na-like ions is given by

$`Q^{(1+2)}(IF)`$ $`=`$ $`{\displaystyle \frac{1}{E^{(1)}[F]E^{(1)}[I]}}{\displaystyle \underset{avw}{}}{\displaystyle \underset{J_{12}^{}}{}}C_1^F[vw[J_{12}^{}]a(J)]`$ (26)
$`\times `$ $`\{[ϵ(x)ϵ(vwa)][Z^{(1+2)}[vw\left[J_{12}^{}\right]aJ,xJ^{}]+B^{(2)}[vw\left[J_{12}^{}\right]aJ,xJ^{}]]`$
$`+`$ $`[E^{(1)}[F]+E^{(1)}[I]ϵ(x)+ϵ(vwa)]P^{(\mathrm{derv})}[vw\left[J_{12}^{}\right]aJ,xJ^{}]\}.`$
Here, $`ϵ(vwa)=ϵ(v)+ϵ(w)ϵ(a)`$, $`Z^{(1+2)}=Z^{(1)}+Z^{(\mathrm{RPA})}+Z^{(\mathrm{corr})}`$. (Note that $`Z^{(\mathrm{HF})}`$ vanishes since we start from a Hartree-Fock basis.) The sum over $`vwa,J_{12}^{}`$ is understood as sum over the complex of states with the same $`J`$ and parity. In Eq. (26), we let $`B^{(2)}=B^{(\mathrm{RPA})}+B^{(\mathrm{HF})}`$ +$`B^{(\mathrm{corr})}`$ to represent second-order corrections arising from the Breit interaction. The quantities $`C_1^F[vw[J_{12}^{}]a(J)]`$ are eigenvectors (or mixing coefficients) for particle-particle-hole state $`F`$. The initial state $`I`$ is a single, one-valence state. Using the above formulas and the results for uncoupled reduced matrix elements, we carry out the transformation from uncoupled reduced matrix elements to intermediate coupled matrix elements between physical states.