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# Theoretical Study of Electron-Phonon Interaction in 𝑍𝑟𝐵₂ and 𝑇𝑎𝐵₂

## I introduction

The search for superconductivity in the transition-metal diborides $`ZrB_2`$ and $`TaB_2`$ has proven to be elusive since the first reports of superconductivity in $`ZrB_2`$ Gasparov et al. (2001) and $`TaB_2`$ Kaczorowski et al.  with superconducting transition temperatures $`T_c=5.5K`$ and $`T_c=9.5K`$, respectively. The subsequent experimental efforts Yamamoto et al. ; Rosner et al. (2001) to make $`ZrB_2`$ and $`TaB_2`$ superconducting by applying external pressure and/or hole doping have also proven to be futile. Such an outcome for $`ZrB_2`$ and $`TaB_2`$ seems somewhat surprising given that under similar conditions $`Nb_xB_2`$ Yamamoto et al.  and $`Mo_{0.96}Zr_{0.04}B_2`$ Muzzy et al.  are found to superconduct with $`T_c=8.5K`$ and $`T_C=5.9K`$, respectively.

To be able to understand the superconducting properties or lack thereof of the transition-metal diborides $`ZrB_2`$ and $`TaB_2`$ within the conventional BCS theory of superconductivity one needs to know the electron-phonon interaction in these systems. In particular, the strength of the electron-phonon interaction in $`ZrB_2`$ and $`TaB_2`$, as reflected in the average electron-phonon coupling constant $`\lambda `$, can be used to predict the possibility of superconductivity in the diborides. Experiments, based on point-contact spectroscopy Yanson et al. ; Naidyuk et al. (2002), indicate $`\lambda `$ to be less than $`0.1`$ for both $`ZrB_2`$ and $`TaB_2`$, and thus preclude the possibility of superconductivity in these diborides. Here, we like to point out that the experimental determination of $`\lambda `$, as carried out in Refs. Yanson et al. ; Naidyuk et al. (2002), is more reliable for $`ZrB_2`$ than for $`TaB_2`$.

Previous theoretical estimates of $`\lambda `$ Rosner et al. (2001, 2002), based on only zone-center sampling of the electron-phonon matrix elements, also indicate $`ZrB_2`$ and $`TaB_2`$ to have a weak electron-phonon coupling with $`\lambda <0.2`$. However, it turns out that in the transition-metal diborides the estimates of $`\lambda `$ based on zone-center sampling of the electron-phonon matrix elements corresponding to the optical $`E_{2g}`$ mode is not reliable Singh (2003a, b). Thus, a detailed analysis of the electron-phonon interaction using a more representative Brillouin zone sampling of the electron-phonon matrix elements is clearly needed to better understand the lack of superconductivity in $`ZrB_2`$ and $`TaB_2`$. The present work is a step in that direction.

Using density-functional-based methods we have studied (i) the electronic structure, (ii) the phonon density of states (DOS), (iii) the electron-phonon interaction, and (iv) the solutions of the isotropic Eliashberg gap equation for $`ZrB_2`$ and $`TaB_2`$ in $`P6/mmm`$ crystal structure. We have calculated the electronic structure of $`ZrB_2`$ and $`TaB_2`$ with experimental lattice constants Rosner et al. (2001, 2002) $`a`$ and $`c`$, as given in Table I, using full-potential linear muffin-tin orbital (LMTO) method. For studying the electron-phonon interaction we used the full-potential linear-response program of Savrasov Savrasov (1996); Savrasov and Savrasov (1996) to calculate the dynamical matrices and the Hopfield parameters, which were then used to calculate the phonon DOS, $`F(\omega )`$, the electron-phonon coupling $`\lambda `$, including the partial $`\lambda _𝐪`$, and the Eliashberg function, $`\alpha ^2F(\omega )`$, for $`ZrB_2`$ and $`TaB_2`$. Subsequently, we have numerically solved the isotropic Eliashberg gap equation Allen and Dynes (1975); Allen and Mitrovic (1982); Allen  for a range of $`\mu ^{}`$ to obtain the corresponding superconducting transition temperature $`T_c.`$

Based on our calculations, described below, we find that the electron-phonon coupling in $`ZrB_2`$ is much weaker than in $`TaB_2`$. In particular, we find that the average electron-phonon coupling constant $`\lambda `$ is equal to $`0.15`$ for $`ZrB_2`$ and $`0.73`$ for $`TaB_2`$. The solutions of the isotropic Eliashberg gap equation indicate no superconductivity for $`ZrB_2`$ but a superconducting transition temperature $`T_c`$ of around $`12K`$ for $`TaB_2`$ with $`\mu ^{}0.16`$.

## II Theoretical Approach and computational details

Within Migdal-Eliashberg theory of superconductivity Allen and Dynes (1975); Allen and Mitrovic (1982), first-principles calculations of superconducting properties require the knowledge of (i) the ground-state electronic structure, (ii) the vibrational spectrum and (iii) the electron-phonon matrix elements of the solid. The phonon spectrum and the electron-phonon matrix elements are then used to calculate the Eliashberg functions from which the superconducting properties of the materials can be calculated. In particular, by solving the fully anisotropic or the isotropic gap equation the superconducting transition temperature can be calculated.

The density-functional theory provides a reliable framework for implementing from first-principles the Migdal-Eliashberg approach for calculating the superconducting properties of metals as outlined above. Such an approach has been implemented by Savrasov using the LMTO formalism and the linear response method, the details of which are given in Refs. Savrasov (1996); Savrasov and Savrasov (1996) . In the following, we briefly outline the approach used in the present calculations. We follow the notation used in Refs. Savrasov (1996); Savrasov and Savrasov (1996).

We calculate the ground-state electronic structure of the transition-metal diborides $`ZrB_2`$ and $`TaB_2`$ using the full-potential linear muffin-tin orbital method in the generalized-gradient approximation of the density-functional theory. The linear response approach is used to evaluate the dynamical matrices and the electron-phonon matrix elements within the density-functional theory as implemented using the LMTO formalism. It amounts to self-consistently evaluating the changes in the electronic structure due to atomic displacements associated with the phonon mode $`\omega _{𝐪\nu }`$. Once the changes in the wave function, density and the effective potential are known, the phonon density of states

$$F(\omega )=\underset{𝐪\nu }{}\delta (\omega \omega _{𝐪\nu }),$$
(1)
and the electron-phonon matrix elements

$$g_{𝐤+𝐪j^{},𝐤j}^{𝐪\nu }=<𝐤+𝐪j^{}|\delta ^{𝐪\nu }V_{eff}|𝐤j>,$$
(2)
can be evaluated. The electron-phonon matrix elements can be interpreted as the scattering of electron in state $`|𝐤j>`$ to state $`|𝐤+𝐪j^{}>`$ due to perturbing potential $`\delta ^{𝐪\nu }V_{eff}`$, which arises due to the phonon mode $`\omega _{𝐪\nu }`$. Note that Eq. 2 has to be corrected for the incomplete basis set as described in Ref. Savrasov (1996). From the electron-phonon matrix elements we can calculate the phonon linewidth $`\gamma _{𝐪\nu }`$

$$\gamma _{𝐪\nu }=2\pi \omega _{𝐪\nu }\underset{𝐤jj^{}}{}|g_{𝐤+𝐪j^{},𝐤j}^{𝐪\nu }|^2\delta (ϵ_{𝐤j}ϵ_F)\delta (ϵ_{𝐤+𝐪j^{}}ϵ_F).$$
(3)
Occasionally, it is useful to define a phonon mode dependent electron-phonon coupling $`\lambda _{𝐪\nu }`$ as

$$\lambda _{𝐪\nu }=\frac{\gamma _{𝐪\nu }}{\pi N(\epsilon _F)\omega _{𝐪\nu }^2},$$
(4)
where $`N(\epsilon _F)`$ is the electronic density of states at the Fermi energy. Now we can combine the electronic density of states, phonon spectrum and the electron-phonon matrix elements to obtain the Eliashberg function $`\alpha ^2F(\omega )`$ defined as

$$\alpha ^2F(\omega )=\frac{1}{2\pi N(ϵ_F)}\underset{𝐪\nu }{}\frac{\gamma _{𝐪\nu }}{\omega _{𝐪\nu }}\delta (\omega \omega _{𝐪\nu })$$
(5)
Finally, the Eliashberg functions can be used to solve the isotropic gap equation Allen and Dynes (1975); Allen and Mitrovic (1982); Allen

$$\mathrm{\Delta }(i\omega _n)=\underset{n^{}}{\overset{|\omega _n^{}|<\omega _c}{}}f_n^{}S(n,n^{})\mathrm{\Delta }(i\omega _n^{})$$
(6)
to obtain the superconducting properties such as the superconducting transition temperature $`T_c.`$ The function $`S(n,n^{})`$ used in the gap equation is defined by

$$S(n,n^{})\lambda (nn^{})\mu ^{}\delta _{nn^{}}\underset{n^{\prime \prime }}{}s_ns_{n^{\prime \prime }}\lambda (nn^{\prime \prime })$$
(7)
and $`f_n=1/|2n+1|`$ with $`s_n`$ representing the sign of $`\omega _n.`$ The electron-phonon coupling $`\lambda (\nu )`$ is given by

$$\lambda (\nu )=_0^{\mathrm{}}𝑑\omega \alpha ^2F(\omega )\frac{2\omega }{\omega _\nu ^2+\omega ^2}.$$
(8)
Before describing our results in detail, we provide some of the computational details which are similar to our study of the electron-phonon interaction in $`MgB_2`$, $`NbB_2`$ and $`TaB_2`$ Singh (2003b, a).

The charge self-consistent full-potential linear muffin-tin orbital calculations were carried out with the generalized gradient approximation for exchange-correlation of Perdew *et al* Perdew and Wang (1992); Perdewa et al. (1996) and 484 $`𝐤`$-points in the irreducible wedge of the Brillouin zone. For $`TaB_2`$, the basis set used consisted of $`s,`$ $`p,`$ $`d`$ and $`f`$ orbitals at the $`Ta`$ site and $`s,`$ $`p`$ and $`d`$ orbitals at the $`B`$ site. In the case of $`ZrB_2`$, we included $`s`$, $`p`$ and $`d`$ orbitals at the $`Zr`$ site. In all cases the potential and the wave function were expanded up to $`l_{max}=6`$. The muffin-tin radii for $`Ta`$, $`B`$, and $`Zr`$ were taken to be $`2.5,`$ $`1.66,`$ and $`2.3`$ atomic units, respectively.

The calculation of dynamical matrices and the Hopfield parameters for $`ZrB_2`$ and $`TaB_2`$ were carried out using a $`6\times 6\times 6`$ grid resulting in $`28`$ irreducible $`𝐪`$-points. The Brillouin zone integrations for charge self-consistency during linear response calculations were carried out using a $`12\times 12\times 12`$ grid of $`𝐤`$-points. The Fermi surface was sampled more accurately with a $`36\times 36\times 36`$ grid of $`𝐤`$-points using the double grid technique as outlined in Ref. Savrasov and Savrasov (1996). In case of $`TaB_2,`$ for a couple of $`𝐪`$-points we had to sample the Fermi surface using a $`48\times 48\times 48`$ grid of $`𝐤`$-points to get converged acoustic-mode frequencies.

## III results and discussion

In this section we describe the results of our calculations of the electronic structure, the linear response and the solutions of the isotropic Eliashberg gap equation for $`ZrB_2`$ and $`TaB_2.`$ Our results for $`ZrB_2`$ and $`TaB_2`$ are described in terms of (i) the density of states (DOS), (ii) the phonon density of states $`F(\omega )`$, (iii) the Eliashberg function $`\alpha ^2F(\omega )`$, and (iv) the superconducting transition temperature $`T_c`$ obtained from the solutions of the isotropic Eliashberg gap equation.

### III.1 The Density of States

The electronic structure of $`ZrB_2`$ Rosner et al. (2002); Shein and Ivanovskii  and $`TaB_2`$ Rosner et al. (2001); Shein and Ivanovskii ; Singh  has been studied previously. Our full-potential results for the electronic structure of $`ZrB_2`$ and $`TaB_2`$ are in agreement with earlier calculations. For example, in Fig. 1 we show the total densities of states for $`ZrB_2`$ and $`TaB_2`$ calculated at the experimental lattice constants using the full-potential LMTO method as described earlier. The agreement with earlier calculations of the densities of states for $`ZrB_2`$ Rosner et al. (2002) and $`TaB_2`$ Rosner et al. (2001) is excellent. We find that the total DOS at the Fermi energy is equal to $`3.72st/Ry`$ and $`12.52st/Ry`$ for $`ZrB_2`$ and $`TaB_2`$, respectively. In $`ZrB_2`$, the relatively low DOS at the Fermi energy leads to a weak electron-phonon coupling in this system. However, at the Fermi energy the $`d`$-electrons are present in substantial amount in both $`ZrB_2`$ and $`TaB_2`$, indicating a more active role for $`Zr`$ and $`Ta`$ atoms in determining the lattice- dynamical as well as the possible superconducting properties of these diborides.

### III.2 The Phonon Density of States

In Fig. 2 we show the phonon DOS $`F(\omega )`$ of $`ZrB_2`$ and $`TaB_2`$ calculated using the full-potential linear response program as described earlier. As is clear from Fig. 2, the phonon DOS for both $`ZrB_2`$ and $`TaB_2`$ can be separated into three distinct regions. Based on our analysis of the eigenvectors, we find that the first region, with a peak in phonon DOS at $`32meV`$ in $`ZrB_2`$ and $`22meV`$ in $`TaB_2`$, is dominated by the motion of the transition-metal atoms $`Zr`$ and $`Ta`$ respectively. Note that the shift of the first region in the phonon DOS towards lower frequency for $`TaB_2`$ in comparison to $`ZrB_2`$ is due to the higher mass of $`Ta.`$ In the second region, the phonon DOS around $`6070`$ $`meV`$ in $`ZrB_2(TaB_2)`$ results from the coupled motion of $`Zr(Ta)`$ and the two $`B`$ atoms. However, the peaks in the phonon DOS at $`78meV`$ in $`ZrB_2`$ and $`75meV`$ in $`TaB_2`$ correspond to the in-plane $`BB`$ motion. The phonon DOS in the third region, which extends from $`94meV`$ to $`102meV`$ in $`ZrB_2`$ and from $`100meV`$ to $`107meV`$ in $`TaB_2`$, results from the displacements of all the three atoms. Not surprisingly, the phonon DOS of $`ZrB_2`$ and $`TaB_2`$ are similar to the phonon DOS of $`NbB_2`$ if we make allowance for the difference in the masses of the transition-metal atoms Singh (2003b).

### III.3 The Eliashberg Function

The main purpose of the present study is to examine the strengths of the electron-phonon interaction in $`ZrB_2`$ and $`TaB_2`$ in order to better understand the lack of superconductivity in these diborides. To this end, we show in Fig. 3 the Eliashberg function $`\alpha ^2F(\omega )`$ of $`ZrB_2`$ and $`TaB_2`$ calculated as described earlier. A comparison of $`\alpha ^2F(\omega )`$ of $`ZrB_2`$ and $`TaB_2`$ shows that the electron-phonon coupling in $`ZrB_2`$ is much weaker than in $`TaB_2`$. In particular, the average electron-phonon coupling constant $`\lambda `$ is equal to $`0.15`$ for $`ZrB_2`$ and $`0.73`$ for $`TaB_2`$.

From Fig. 3, we also see that in the case of $`ZrB_2`$ the phonon mode with peak at $`78meV`$, which corresponds to the in-plane $`BB`$ motion, couples to the electrons more than the phonon mode with peak at $`32meV.`$ However, in $`TaB_2`$ it is the phonon mode corresponding to the displacements of the transition-metal atom $`Ta`$, with a peak at $`22meV`$, which couples more strongly to the electrons. Such a change in $`\alpha ^2F(\omega )`$ clearly indicates a more active role for the transition-metal atoms in deciding the normal as well as the superconducting state (if any) properties of the transition-metal diborides. Our calculated $`\alpha ^2F(\omega )`$ for $`ZrB_2`$ agrees with the point-contact spectroscopy results of Refs. Yanson et al. ; Naidyuk et al. (2002). However, in our opinion, the experimentally obtained $`\alpha ^2F(\omega )`$ for $`TaB_2`$ in Ref. Naidyuk et al. (2002) is underestimated, and it is in disagreement with the present result. In Table II we have listed the Hopfield parameter $`\eta ,`$ the electron-phonon coupling constant $`\lambda `$, and the various averages of the phonon frequencies for $`ZrB_2`$ and $`TaB_2`$.

### III.4 The Superconducting Transition Temperature

The possibility of superconductivity in $`ZrB_2`$ and $`TaB_2`$ within the present approach can be checked by solving numerically the isotropic gap equation Allen and Mitrovic (1982); Allen  using the calculated Eliashberg function $`\alpha ^2F(\omega )`$. The results of such a calculation for $`TaB_2`$ are shown in Fig. 4 for a range of values of $`\mu ^{}.`$ From Fig. 4 we find that for $`\mu ^{}0.16`$ the $`T_c`$ for $`TaB_2`$ is equal to $`12K`$. A similar calculation for $`ZrB_2`$ using the calculated Eliashberg function yields a $`T_c`$ of less than $`10^5K`$.

Our results show that $`ZrB_2`$ is unlikely to show superconductivity, in agreement with experiments Layarovska and Layarovski (1979). In addition, the calculated Eliashberg function for $`ZrB_2`$ agrees well with the corresponding Eliashberg function obtained from point-contact spectroscopy Yanson et al. ; Naidyuk et al. (2002). However, our calculations predict $`TaB_2`$ to superconduct with a $`T_c12K`$ but so far no superconductivity Yamamoto et al.  has been found (except for Ref. Gasparov et al. (2001)). Although our calculated values of $`\alpha ^2F(\omega )`$ and consequently $`\lambda `$ can be improved upon by including more q-points in the linear response calculations but it is unlikely to change the main conclusions of the present work. Thus, the reasons for the lack of superconductivity in $`TaB_2`$ need to be explored further.

### III.5 Convergence of Phonon Density of States, Eliashberg Function and Superconducting Transition Temperature

The first-principles study of superconducting properties of solids as carried out above is computationally demanding. In particular, the requirement of electronic self-consistency for phonon wave vector $`𝐪`$ and mode $`\nu `$ makes the computational effort prohibitive unless one makes a judicious choice of $`𝐪`$ vectors. However, one must ensure that the calculated results are converged with respect to the number of $`𝐪`$ vectors. To demonstrate the convergence of our calculated phonon density of states $`F(\omega ),`$ Eliashberg functions $`\alpha ^2F(\omega )`$ and the superconducting transition temperature $`T_c,`$ we have carried out two sets of calculations using the double-grid technique as outlined in Ref. Savrasov (1996); Savrasov and Savrasov (1996). We have used two $`𝐪`$ grids (i) a $`4\times 4\times 4`$ grid with $`12`$ irreducible $`𝐪`$-points and (ii) a $`6\times 6\times 6`$ grid with $`28`$ irreducible $`𝐪`$-points. All the results described so far correspond to the second grid with $`28`$ $`𝐪`$-points. Below we show a comparison of $`F(\omega ),`$ $`\alpha ^2F(\omega )`$ and $`T_c`$ calculated using the two grids with $`12`$ and $`28`$ $`𝐪`$-points, respectively.

In Fig. 5 we compare $`F(\omega )`$ calculated using the two grids with $`12`$ and $`28`$ $`𝐪`$-points, respectively. In general, dynamical matrices and consequently the phonon spectrum do not require a very fine $`𝐤`$-mesh for convergence. However, the increase in the number of $`𝐪`$-points has understandably reduced the peak heights at $`\omega `$ approximately equal to $`30meV`$, $`75meV`$ and $`95meV`$ for $`ZrB_2`$ and $`20meV`$, $`70meV`$ and $`100meV`$ for $`TaB_2.`$

The convergence of $`\alpha ^2F(\omega )`$ is shown in Fig. 6, where we have plotted $`\alpha ^2F(\omega )`$ calculated using the two grids with $`12`$ and $`28`$ $`𝐪`$-points, respectively. For $`ZrB_2`$ the differences are small in magnitude except at around $`20meV,`$ while for $`TaB_2`$ the effects due to small number of $`𝐪`$-points are reduced with the use of the $`28`$ $`𝐪`$-point grid. We also see that the integrated values such as the electron-phonon coupling constant $`\lambda `$ do not change appreciably between the two sets of calculations ($`\lambda `$ changes by $`0.01`$ for $`ZrB_2`$ and $`0.005`$ for $`TaB_2`$).

As $`F(\omega )`$ and $`\alpha ^2F(\omega )`$ do not change significantly between the two sets of calculations, we do not expect a significant change in the solutions of the isotropic gap equation. Consequently, the calculated $`T_c`$ should be similar in the two cases. In Fig. 7, we show the $`T_c`$ obtained for the two sets of calculations, and the difference of less than $`1^0K`$ between the two sets of calculations confirms the convergence of $`F(\omega )`$, $`\alpha ^2F(\omega )`$ and $`T_c`$.

## IV conclusions

We have studied electron-phonon interaction in $`ZrB_2`$ and $`TaB_2`$ in $`P6/mmm`$ crystal structure using full-potential, density-functional-based methods. we find that the electron-phonon coupling in $`ZrB_2`$ is much weaker than in $`TaB_2`$. In particular, we find that the average electron-phonon coupling constant $`\lambda `$ is equal to $`0.15`$ for $`ZrB_2`$ and $`0.73`$ for $`TaB_2`$. The solutions of the isotropic Eliashberg gap equation indicate no superconductivity for $`ZrB_2`$ but a superconducting transition temperature $`T_c`$ of around $`12K`$ for $`TaB_2`$ with $`\mu ^{}0.16`$.


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# Atomic data from the Iron Project

## 1 Introduction

Ne-like Fe xvii attracts great astrophysical interest with some of the most prominent spectral lines in the X-ray and the EUV regimes. These lines are abundantly evident from diverse sources such as the solar corona and other stellar coronae (e. g. Brickhouse et al. 2001), and active galactic nuclei (e. g. Lee et al. 2001). Fe xvii also plays a role in benchmarking laboratory experiments and theoretical calculations. Recent Iron Project (IP, Hummer et al. 1993) work has included the computation of collision strengths and rate coefficients by electron impact excitation of Fe xvii and diagnostics of laboratory and astrophysical spectra (Chen and Pradhan 2002; Chen, Pradhan and Eissner 2002 – hereafter CPE02). Spectral analysis moreover requires transition probabilities for observed allowed and forbidden transitions. Transition probablities are also required to account for radiative cascades from higher levels that contribute to level populations; cascades generally proceed via strong dipole allowed transitions, and may entail fairly highly excited levels. Therefore a fairly large and complete set of data is needed for astrophysical models of Fe xvii.

Smaller sets of transitions are available from other sources. An evaluated compilation of data, obtained by various investigators using different approximations, can be found in the National Institute for Standards and Technology database (NIST: www.nist.gov). A previous set of non-relativistic data for Fe xvii was obtained by M. P. Scott under the Opacity Project (OP 1995, 1996), which are accessible through the OP database, TOPbase (Cunto et al. 1993). These results are in LS coupling and consider only the dipole allowed $`LS`$ multiplets; no relativistic effects are taken into account.

The present calculations are carried out for extensive sets of oscillator strengths, line strengths, and transition probabilities of dipole allowed, intercombination, and forbidden electric quadrupole and octopole, magnetic dipole and quadrupole fine structure (FS) transitions in Fe xvii up to $`n10`$. Transitions of type E1 are obtained in the relativistic Breit-Pauli R-matrix method developed under the Iron Project. Configuration mixing type atomic structure calculations, using codes SUPERSTRUCTURE (Eissner et al. 1974) and GRASP (Parpia et al. 1996) which is based upon the multiconfiguration Dirac-Fock (MCDF) method, are employed for the forbidden E2, E3, and M1, M2 transitions. One of the primary tasks is the spectroscopic identification of levels and lines of E1 transitions. We apply the recently developed techniques (Nahar and Pradhan 2000) for a reasonably complete spectroscopic dataset to Fe xvii.

## 2 Formulation

We employ the relativistic Breit-Pauli R-matrix (BPRM) approach in a collision type calculation for bound states followed by computing radiative processes: Scott and Burke 1980, Scott and Taylor 1982, Hummer et al. 1993, Berrington et al. 1995. Unlike calculations in $`LS`$ coupling, when radiative transition amplitudes vanish unless $`\mathrm{\Delta }S=0`$, intermediate coupling calculations include intercombination lines.

Details of this close coupling (CC) approach to radiative processes are discussed in earlier papers, such as in the first large scale relativistic BPRM calculations for bound-bound transitions in Fe xxiv and Fe xxv (Nahar and Pradhan 1999), Fe v (Nahar et al. 2000), Ar XIII and Fe XXI (Nahar 2000). However, in the present work, electric octopole and magnetic dipole transitions are included for the first time in the IP series. A brief outline for the formulations is henceforth given.

The wavefunction $`\mathrm{\Psi }(\mathrm{E})`$ for the ($`N`$ \+ 1) electron system with total spin and orbital angular momenta symmetry $`SL\pi `$ or total angular momentum symmetry $`J\pi `$ is expanded in terms of ‘frozen’ $`N`$-electron target ion functions $`\chi _i`$ and vector coupled collision electrons $`\theta _i`$,

$$\mathrm{\Psi }_\mathrm{E}(\mathrm{e}+\mathrm{i}\mathrm{o}\mathrm{n})=𝒜\underset{\mathrm{i}}{}\chi _\mathrm{i}(\mathrm{𝑖𝑜𝑛})\theta _\mathrm{i}+\underset{\mathrm{j}}{}\mathrm{c}_\mathrm{j}\mathrm{\Phi }_\mathrm{j}(\mathrm{e}+\mathrm{i}\mathrm{o}\mathrm{n}),$$
(1)
in some specific state $`S_iL_i\pi _i`$ or level $`J_i\pi _i`$, index $`i`$ marking channels $`S_iL_i(J_i)\pi _ik_i^2\mathrm{}_i(SL\pi `$ or $`J\pi )`$ with energy $`k_i^2`$ of the colliding electron. The second sum expands correlation functions $`\mathrm{\Phi }_\mathrm{j}`$ as products with $`N`$ \+ 1 bound orbital functions that (a) compensate for the orthogonality conditions between the continuum and the bound orbitals, and (b) represent additional short-range correlation that is often of crucial importance in scattering and radiative CC calculations for each $`SL\pi `$.

In IP work we restrict the ($`N`$ \+ 1)-electron Breit-Pauli Hamiltonian to

$$H_{N+1}^{\mathrm{BP}}=H_{N+1}^{\mathrm{NR}}+H_{N+1}^{\mathrm{mass}}+H_{N+1}^{\mathrm{Dar}}+H_{N+1}^{\mathrm{so}},$$
(2)
where $`H_{N+1}^{\mathrm{NR}}`$ is the non-relativistic Hamiltonian

$$H_{N+1}^{\mathrm{NR}}=\underset{i=1}{\overset{N+1}{}}\left\{_i^2\frac{2Z}{r_i}+\underset{j>i}{\overset{N+1}{}}\frac{2}{r_{ij}}\right\};$$
(3)
among the three trailing relativistic terms mass-velocity correction, $`H^{\mathrm{mass}}=\frac{\alpha ^2}{4}_ip_i^4`$, and Darwin term, $`H^{\mathrm{Dar}}=\frac{Z\alpha ^2}{4}_i^2(\frac{1}{r_i})`$. do not break $`LS`$ symmetry while improving energy positions, whereas the spin-orbit interaction, $`H^{\mathrm{so}}=Z\alpha ^2_i\frac{1}{r_i^3}𝐥_𝐢.𝐬_𝐢.`$, splits terms $`LS`$ into fine-structure levels labelled by $`J\pi `$. This Hamiltonian does not include two-body spin-spin, mutual spin-orbit and spin-other-orbit terms nor non-fine structure contributions such as orbit-orbit interaction.

R-matrix solutions of coupled equations to total symmetries $`LS`$ are recoupled in a pair coupling scheme on adding spin-orbit interaction to obtain (e + ion) states of total $`J\pi `$, in the end yielding ($`N`$ \+ 1)-electron solutions

$$H_{N+1}^{\mathrm{BP}}\mathrm{\Psi }=\mathrm{E}\mathrm{\Psi }.$$
(4)
Rather than dealing with positive energies ($`E>\mathrm{\hspace{0.17em}0}`$) as in ordinary collision processes we focus on an eigenvalue problem ($`E<\mathrm{\hspace{0.17em}0}`$) for the electron described by $`\theta `$, leading to discrete bound states $`\mathrm{\Psi }_\mathrm{B}`$.

The transition matrix element for radiative bound-bound excitation or de-excitation can be reduced to the line strength as

$`S^{\mathrm{X}\lambda }(ij)`$ $`=`$ $`\left|\mathrm{\Psi }_jO^{\mathrm{X}\lambda }\mathrm{\Psi }_i\right|^2,S(ji)=S(ij).`$ (5)
For electric (X=E) multipole transitions in the length formulation (and long wave-length approximation),

$`O^{\mathrm{E}\lambda }=b^{[\lambda ]}{\displaystyle \underset{p=1}{\overset{N+1}{}}}\mathrm{C}^{[\lambda ]}(p)r_p^\lambda ,b^{[\lambda ]}=\sqrt{{\displaystyle \frac{2}{\lambda +1}}}`$ (6)
Transition probabilities $`A`$ and absorption oscillator strengths ($`f`$-values) between bound states $`i`$ and $`j`$ and excitation energy $`E_{ij}=E_jE_i`$ are written in terms of the line strength $`S`$, observing that Eq. (3) implies scaling of energies in units of Ry $`={\displaystyle \frac{\alpha ^2}{2}}m_{\mathrm{el}}c^2=13.6`$ eV, hence time unit $`\tau _0=\mathrm{}/\mathrm{Ry}=4.83810^{17}`$ s:

$`f_{ij}`$ $`=`$ $`{\displaystyle \frac{E_{ji}}{3g_i}}S^{\mathrm{E1}}(ij),g_if_{ij}=g_jf_{ji}=(gf)_{ij}`$ (7)
$`A_{ji}^{\mathrm{E1}}\tau _0`$ $`=`$ $`\alpha ^3{\displaystyle \frac{g_i}{g_j}}E_{ji}^2f_{ij}`$ (8)
in the case of electric dipole radiation E$`\lambda =`$E1. The symbols in these equations have their usual meaning, in particular $`g_j`$ and $`g_i`$ being the statistical weights of the upper and lower states respectively. Hypervirial identities arising from the commutator $`[rH]_{}`$ yield alternative formulations, velocity formulation for a start, that probe the radial wave functions less far out. With $`H^{\mathrm{NR}}`$ it leads to simple substitutions of $`r^\lambda `$ in eq. (6) — but to additional terms of order $`\alpha ^2`$ for $`H^{\mathrm{BP}}`$! BPRM ignores such ‘velocity’ terms: they are not large enough though for Fe xvii to render comparison of length with velocity results a useless tool (yet better left to NR-results). In the magnetic dipole case the radiative operator to the line strength expression (5) reads

$$O^{\mathrm{M1}}=\underset{p}{}\mathrm{l}(p)+2\mathrm{s}(p)+\alpha ^2\left\{\frac{^2}{r_p^2}+\mathrm{}+\underset{p^{}>p}{}\frac{\mathrm{}}{r_{p^{}p}}\right\};$$
(9)
where the sum runs over electron coordinates, $`l`$ and $`s`$ are the orbital and spin operators respectively. Details on the correction of relative BP order can be found in O ii work of 1981 by Eissner and Zeippen. Magnetic quadrupole ($`\lambda `$=2) radiation is treated to lowest order, i. e.

$$O^{\mathrm{M}\lambda }=b^{[\lambda ]}\underset{p}{}r_p^{\lambda 1}\left[\mathrm{C}^{[\lambda 1]}(p)\times \left\{\mathrm{l}(p)+(\lambda +1)\mathrm{s}(p)\right\}\right]^{[\lambda ]}.$$
(10)
The lifetime of a level can be computed as

$`\tau `$ $`=`$ $`{\displaystyle \frac{1}{A_k}},`$ (11)
$`\mathrm{where}A_k`$ $`=`$ $`{\displaystyle \underset{i}{}}A_{ki}`$
is the total radiative transition probability for level $`k`$, i. e.

$$g_iA_{ki}^{\mathrm{E1}}=2.6774\times 10^9\mathrm{s}^1(E_iE_k)^3S^{\mathrm{E1}}(i,k)$$
(12)
(the observed rate) in the electric dipole case E1. The Einstein coefficients for spontaneous decay by higher order multipole radiation that need be considered for transitions down to the 10 Å range read as follows:
electric quadrupole (E2) and magnetic dipole (M1)

$`g_jA_{ji}^{\mathrm{E2}}`$ $`=`$ $`2.6733\times 10^3\mathrm{s}^1(E_jE_i)^5S^{\mathrm{E2}}(i,j)`$ (13)
and
$`g_jA_{ji}^{\mathrm{M1}}`$ $`=`$ $`3.5644\times 10^4\mathrm{s}^1(E_jE_i)^3S^{\mathrm{M1}}(i,j);`$ (14)
electric octopole (E3) and magnetic quadrupole (M2)

$`g_jA_{ji}^{\mathrm{E3}}`$ $`=`$ $`1.2050\times 10^3\mathrm{s}^1(E_jE_i)^7S^{\mathrm{E3}}(i,j)`$ (15)
and
$`g_jA_{ji}^{\mathrm{M2}}`$ $`=`$ $`2.37268\times 10^2\mathrm{s}^1(E_jE_i)^5S^{\mathrm{M2}}(i,j).`$ (16)
In approximations like BP one should be careful with the radiative magnetic operators about terms of order $`\alpha ^2`$, in particular in $`O^{\mathrm{M1}}`$, which cannot connect different configurations by its leading term $`l+2s`$ because the (tensor-) radial portion reduces to trivial 1; superstructure does add both 1-body and 2-body contributions of Breit-Pauli order to M1 but not to M2.

## 3 Computation

BPRM calculations span several stages of computation (Berrington et al. 1995). We take radial Fe xviii wavefuntions from superstructure (Eissner et al. 1974) as input to STG1 to compute Slater, magnetic and multipole integrals — obtained with Thomas-Fermi scaling parameters $`\lambda _{nl}`$ of 1.3835, 1.1506, 1.0837, 1.0564, 1.0175, 1.0390 for orbitals $`nl=`$ 1s, 2s, 2p… 3d, which leads to excited levels 2s22p$`{}_{}{}^{5}^2`$P$`{}_{1/2}{}^{}{}_{}{}^{\mathrm{o}}`$ and 2s2p$`{}_{}{}^{6}^2`$S1/2 at 0.9403 and 9.8092 Rydbergs above the ground state 2s22p$`{}_{}{}^{5}^2`$P$`{}_{3/2}{}^{}{}_{}{}^{\mathrm{o}}`$ (while including correlation terms from 6 configurations: 2s22p$`{}_{}{}^{4}3l`$ and 2s2p$`{}_{}{}^{5}3l`$ — ‘1s2’ suppressed for brevity); the excitation energies above the ground state compare with NIST data of 0.93477 and 9.7023 Ry respectively. Other excited levels of Fe viii lie too high to play a role as parent for any Fe xvii bound states (50 Ry separating M- from L-shell: level 2s22p43s 4P5/2 at 57.01 Ry), and therefore need not be considered for radiative calculations. Radial integrals for the partial wave expansion in Eq. 1 are specified for orbitals $`0\mathrm{}9`$ as a basis of NRANG2 = 11 ‘continuum’ functions — sufficient for bound electrons with $`n<10`$ at a radius RA = 2.3750 \[Bohr radii $`a_0`$\] of the $`R`$-matrix box.

Along with the target description STG2 input specifies which collisional Fe xvii symmetries $`LS`$ eventually contribute to 0 $`J`$ 7 or 8 of even and odd parities, namely $`0L`$ 7 or 8, and multiplicities $`(2S+1)`$=1, 3. The second term in Eq. (1), on bound state correlation functions, is specified to include all possible ($`N`$ \+ 1)-particle configurations from a vacant 2s shell to maximum occupancies 2s2, 2p6, 3s2, 3p2, and 3d2.

Stage RECUPD transforms to collisional symmetries $`J7`$ or 8 in a pair-coupling representation, and the (e + ion) Hamiltonian $`R`$-matrices for each total $`J\pi `$ are diagonalized in STGH employing observed target energies.

In STGB fine structure bound levels are found through the poles in the (e + ion) Hamiltonian, searched over a fine mesh of effective quantum number $`\nu `$: $`\mathrm{\Delta }\nu `$ = 0.001. The mesh is orders of magnitude finer than the typical $`\mathrm{\Delta }\nu `$ = 0.01 required to find $`LS`$ energy terms. Intermediate coupling calculations therefore need orders of magnitude more CPU time than calculations in $`LS`$ coupling. Since the fine structure components of higher excited states are more densely packed, a mesh finer than $`\mathrm{\Delta }\nu `$ = 0.001 is essential to avoid missing any levels.

Spectroscopically identifying a large number of fine structure levels poses a major challenge, as the BP Hamiltonian is labelled only by the total angular momentum and parity, i. e. by $`J\pi `$, which is incomplete for unique identification. Complete identification of levels is needed for various spectral diagnostics and spectrocopic applications in a lab. A new procedure has been developed and encoded in the program PRCBPID to identify these levels by a complete set of quantum numbers through analysis of coupled channels in the CC expansion (Nahar & Pradhan 2000). This procedure generally yields unambiguous level identification for most levels. However, for mixed levels where the identification is to some extent arbitrary, we assign levels in descending multiplicity $`(2S+1)`$ and total angular orbital momentum $`L`$. The full spectroscopic designation reads $`C_t(S_tL_t\pi _t)J_tnlJ(SL)\pi `$, where $`C_t`$, $`S_tL_t\pi _t`$, $`J_t`$ are the configuration, parent term and parity, and total angular momentum of target states, $`nl`$ are the principal and orbital quantum numbers of the outer or valence electron, and $`J`$ and $`SL\pi `$ are the total angular momentum, term and parity of the ($`N`$+1)-electron system. The procedure also establishes a correspondence between the fine structure levels and their proper $`LS`$ terms, and enables completeness checks to be performed as exemplified below.

STGBB can compute radiative data for transitions of type E1 and E2; the code exploits methods developed by Seaton (1986) to evaluate the outer region ($`>\mathrm{𝚁𝙰}`$) contributions to the radiative transition matrix elements. However, present work reports only E1 transitions from STGBB. Results for other types of transitions are obtained from superstructure, first optimizing the energy functional over the lowest 49 terms $`LS`$ (Chen et al. 2002, CPE02). They arise from 15 configurations: 2s22p6, 2s22p$`{}_{}{}^{5}3l`$, 2s22p$`{}_{}{}^{5}4l`$, 2s12p$`{}_{}{}^{6}3l`$, and 2s12p$`{}_{}{}^{6}4l`$; the scaling parameters $`\lambda _{nl}`$ for the Thomas-Fermi-Dirac-Amaldi type potential of orbital $`nl`$ are listed in table 1 of CPE02. Much effort was devoted to choosing scaling parameters to optimise the target wavefunctions of the M-shell levels. The primary criteria in this selection are agreement with the observed values for (a) level energies and fine structure splittings within the lowest terms $`LS`$, and (b) $`f`$-values for a number of the low lying dipole allowed transitions. Another practical criterion is that the calculated coefficients $`A`$ should be variationally stable.

Experimental energy level differences are employed in the calculation of all types of transition probabilities wherever available, ensuring proper phase space (or energy) factors for $`f`$ or $`A`$; only a small number of Fe xvii levels are spectroscopically observed though.

In addition to over 26,000 electric dipole transitions we have computed $`A^{\mathrm{E2}}`$, $`A^{\mathrm{M1}}`$, $`A^{\mathrm{E3}}`$ and $`A^{\mathrm{M2}}`$ for more than 3000 forbidden transitions among the first 89 levels. About half of the computed forbidden transition probabilities are larger than $`10^3`$s-1. Selected transtions (Table 7) are compared with various other calculations. Results by Safronova et al. (2002, private communication) are included for comparison.

## 4 Results

We first describe the BPRM calculations for the energy levels and E1 dipole and intercombination transitions in Fe xvii and then discuss higher multipole order radiation.

### 4.1 Fine structure levels

A total of 490 bound fine structure energy levels of Fe xvii are obtained from interacting channels, or Rydberg series

$$E=E_t\frac{z^2}{\nu ^2},\nu =n\mu _{l\pm 1/2}(t)$$
(17)
with series limits $`E_t`$ at the 3 Fe xviii ‘target’ levels 2s22p52P$`{}_{3/2,1/2}{}^{}{}_{}{}^{\mathrm{o}}`$, 2s2p$`{}_{}{}^{6}^2`$S1/2, for symmetries 0 $`J`$ 7 (both parities), implying series orbitals 0 $`l`$ 8. In intermediate coupling language we consider bound state levels of Fe xvii to angular momenta $`L`$ 8 of singlet and triplet symmetries (multiplets to high $`L`$ may thus be incomplete). Series are kept below effective quantum numbers $`\nu =11`$ measured from the target ground state. These are the most detailed close coupling calculations to date for the ion.

Table 1 tentatively matches the 52 spectroscopically observed levels from NIST with identified levels from our calculations (the level index $`I_J`$, in ascending energy order within a given symmetry $`J\pi `$, is most useful for reference in subsequent tables). Calculated effective quantum numbers $`\nu _\mathrm{c}`$ of the first 14 entries differ from observation within numerical uncertainties and errors due to neglect of two-body magnetic effects: typically $`\mathrm{\Delta }\mu \mathrm{\Delta }\nu =.0005`$. The abrupt jump to .0027 at level 15 and typical values of 0.002 thereafter can be explained by the effect of M-shell target levels, for good reasons not included in our calculation. Results from SUPERSTRUCTURE for Fe xviii reveal that the set of M-shell levels, comprising 105 levels, begins at 57.08 Ry above the Fe xviii ground state, and with the binding energy of 92.76 Ry for a 2p electron, from the first entry of Table 1, a first quasi-degenerate state lies an adequate 35.68 Ry below the ground state. We see that such homologous states do not seriously affect the accuracy of our calculation. More important is that M-shell target configurations do not render it incomplete: a binding energy of about 40 Ry for a 3s electron taken from entries 2–5 of Table 1 would lead to true new levels beginning (60-40) Ry above the ionization limit. It is also worth noting at 2–5 entries that the 4 quantum defects are close enough for mere differences in the Coulomb environment, as s-electrons are not affected by ordinary spin-orbit coupling. Way down the table agreement deteriorates. While $`\mathrm{\Delta }\mu 0.005`$ may be considered acceptable and a value 0.01 needs some explanation, the attempts with the 7d and more so 8d levels are an utter failure, 8d off by 0.13 and 0.04, not to speak of a negative ‘observed’ quantum defect of the second 8d level. Such binding energies $`E_\mathrm{o}`$ are unlikely.

A complete set of energy levels to Fe xvii is available electronically. As in recent work (e. g. Nahar et al. 2000) the energies are presented in two formats: (i) in $`LS`$ term order for spectroscopy and completeness check, and (ii) in $`J\pi `$ order for practical applications. In the term format (i) the fine structure components of a $`LS`$ term are grouped together according to the same configuration, useful for spectroscopic diagnostics. It also checks for completeness of a set of energy levels that should belong to same $`LS`$ value and detects any missing level. Table 2a presents a sample of the table containing total sets of energies. The table contains partial sets of levels of Fe xvii. The columns specify the core $`C_t(SL\pi J)_t`$, the label $`nl`$ of the outer electron, total angular momentun $`J`$, energy in Rydbergs, the effective quantum number $`\nu `$ of the valence electron, and possible term designations $`LS`$ of the level. No effective quantum number is assigned to an equivalent electron state.

The top line of each set in Table 2a gives the number Nlv of expected fine structure levels, spin and parity of the set ($`{}_{}{}^{2S+1}L_{}^{\pi }`$), and the values of $`L`$; the total angular quantum numbers $`J`$ associated with each $`L`$ are quoted parenthetically. This line is followed by the set of BPRM energy levels of same configurations. Nlv(c), at the end of the set, specifies the total number of $`J`$-levels obtained. If Nlv = Nlv(c) for a set, the calculated energy set is complete. Correspondence of couplings and completeness of levels is established by the program PRCBPID, which detects and prints missing levels. Each level of a set is further identified by all possible terms $`LS`$ (specified in the last column of the set). Multiple $`LS`$ terms are arranged according to multiplicity $`(2S+1)`$ and $`L`$ as mentioned above. It may be noted that levels are grouped consistently, closely spaced in energies and effective quantum numbers, confirming proper designation of terms $`LS`$. The effective quantum number ($`\nu `$) is expressed upto two significant digits after the decimal point; the main object is to show the consistency of fine structure components in the $`LS`$ grouping. Each level may be assigned to one or more $`LS`$ terms in the last column. For a multiple designation Hund’s rule of decreasing multiplicity $`(2S+1)`$ and $`L`$ is applied for further arrangement. One reason for specifying all possible terms is that the order of calculated and measured energy levels may not exactly match. Another reason is that although our term order arrangement may not apply to all cases for complex ions, it is nonetheless useful in order to establish completeness of fine structure components of a given $`LS`$ multiplet.

Format (ii) keeps the fine structure levels together as they emerge in the computational procedure: for a given symmetry $`J\pi `$ and in energy order as shown for $`0^\mathrm{e}`$ in table 2b, which adds up to Nlv = 20 levels, after the self-explanatory header line. This format should be more convenient for easy implementation in astrophysical or other plasma modeling codes requiring large numbers of energy levels and associated transitions. Here of course we have a set small and transparent enough for assignment by hand rather than by the new code (note how different spin-orbit strength is reflected in the small difference between the quantum defects $`\mu _\mathrm{p}`$ of the two series — here we are facing merely p3/2 with $`t`$=1 and p1/2 with $`t`$=2 because of $`J`$=0). The levels are identified by core configuration $`C_t`$ and level $`(SLJ)_t`$, the outer electron quantum number $`nl`$, total $`J`$, energy against the ionization threshold $`t`$=1, effective quantum number $`\nu `$ associated with the respective series limit $`t`$, and a term designation.

### 4.2 Oscillator strengths for E1 transitions

The 490 bound fine structure energy levels of Fe xvii give rise to 26,222 dipole allowed and intercombination E1 transitions. The complete set, available electronically, contains calculated transition probabilities $`A`$, oscillator strengths $`f`$, and line strengths $`S`$ and the level energies.

A sample subset of transitions, generated by code ”stgbb”, is presented in Table 3a. The first record of the raw stgbb output file FVALUE specifies the nuclear charge number $`Z=26`$, $`N`$=9 electrons in the core ion Fe xviii, and processing directives (e. g. 0 – perturbative channel coupling between RA and $`\mathrm{}`$ disabled, 1 – Buttle correction activated). The next two records, headers for the subsequent Fe xvii transition array data, identify this array as a pair ($`\mathrm{}\mathrm{\hspace{0.17em}2}J_1\pi _1,\mathrm{}\mathrm{\hspace{0.17em}2}J_2\pi _2`$) of symmetries ($`\pi `$=0 for even and =1 for odd parity), here the electric dipole transition $`J_1=0^\mathrm{e}J_2=1^\mathrm{o}`$. stgb had computed $`N_{J_i}=`$ 20 levels of the first symmetry (decoded in Table 2b), $`N_{J_k}=`$ 47 to the second, hence $`20\times 47`$ subsequent records, each prefaced by a pair Ii and Ik of level indices (in energy order for the respective symmetry). Their bound state energies $`E_i`$ and $`E_k`$ below the Fe xviii ground state are shown in columns 3 and 4 in reduced units $`z^2`$ Ry. The radiative result in the last three columns are the $`gf`$-values of the transition $`(`$see Eq. (7)$`)`$ in length and velocity form and the coefficient $`A`$ for spontaneous emission $`(`$derived in the length form, see Eq. (8)$`)`$. The signs of $`gf`$ are in accord with Eq. (7) and would reverse on swapping the order of symmetries $`J\pi `$. Complete spectroscopic identification of the transitions can be deduced from tables of type 2b. For the largest listed value, 2.301$`10^{13}`$/s at (Ii,Ik = 1,5) and associated with excitation energy 60.846 Ry, Table 2b verifies the initial level as the Fe xvii ground state; we have not presented the odd-parity $`J`$=1 section but can identify Ii=5 as a low lying state from tables 1 or 6 as 2s22p53d 1P$`{}_{}{}^{\mathrm{o}}{}_{1}{}^{}`$; this transition reappears in Table 5 with energy-adjusted 2.28(13)/s.

Table 3b, dealing with the same transition array but taken from standard STGBB output (”stgbb.out”) that provides more physics information of the transitions, makes interesting reading about the internal workings of the $`R`$-matrix method. While the radial wave solutions for principal quantum number values 2 or 3 lie entirely inside the R-matrix sphere with radius RA, they have most nodes outside at values $`n10`$. The composition of the dipole transition amplitude D (before normalization) therefore changes from dominant interior contributions DI to large outside portions DA as $`n`$ and $`n^{}`$ increase. Perturbatively computed coupling contributions DP between the propagation range for DA and infinity equally increase, to stay only just small enough at $`n=11`$ to be neglected as in Table 2a (IPERT=0) and in fact most large scale calculations (whereas vital in collisional work!); unlike Buttle contributions DB, which compensate for the rigid logarithmic boundary condition at RA, their computation can be fairly time consuming. Especially transition (15,29) = $`(^2`$P1/2 8p 0$`{}_{}{}^{\mathrm{e}}_{}^{2}`$P1/2 7d 1$`{}_{}{}^{\mathrm{o}})`$ reveals a subtle balance among the constituents and between the amplitudes in length and velocity formulation.

The complete table of $`f`$, $`S`$, and $`A`$ for the E1 transitions in Fe XVII that will be available electronically has slightly different format than Table 3a to match with the similar files for other ions (e.g. for Fe XXI, Nahar 2000). A sample is presented in Table 4. The top line specifies the nuclear charge (Z = 26) and number of electrons in the ion, $`N_{elc}`$ (= 10). It is followed by sets of oscillator strengths belonging to pairs of symmetries, $`J_i\pi _iJ_k\pi _k`$. Each set starts with the transitional symmetries expressed in the form of $`2J_i\pi _i`$ and $`2J_k\pi _k`$, e.g., Table 4 presents partial transitions for the pair of symmetries, $`J=o^eJ=1^o`$. The next line provides the number of bound levels of each symmetry, $`N_{Ji}`$ and $`N_{Jk}`$ as in Table 3a, which is followed by $`N_{Ji}\times N_{Jk}`$ number of transitions. The first two columns are the energy level indices, $`I_i`$ and $`I_k`$, the third and the fourth columns are the absolute energies, $`E_i`$ and $`E_k`$, in Rydberg unit. The fifth column is the $`gf_L`$. where $`f_L`$ is the oscillator strength in length form, and $`g=2J+1`$ is the statistical weight factor of the initial or the lower level. A negative value for $`gf`$ means that $`i`$ is the lower level, while a positive one means that $`k`$ is the lower level. Column six is the line strength (S) and the last column is the coefficient $`A_{ki}(sec^1)`$ for spontaneous emission.

Line strength results from BPRM are used to compute a set of transition probabilities $`A`$ and $`f`$-values for Fe xvii with observed energy separation in favour of the more uncertain calculated energies, exploiting that $`S`$ does not depend on level energies (the procedure is commonly employed and was first adopted in NIST compilations). The astrophysical models also in general use the observed transition energies for the relevant $`f`$ and $`A`$ data. They are more appropriate for comparison or spectral diagnostics.

Coefficients $`A`$ and $`gf`$-values have been reprocessed for all the allowed transitions ($`\mathrm{\Delta }J=0,\pm 1`$) among the observed levels. A partial set of these transitions is presented in Table 5. The set comprises 342 transitions of Fe xvii (the set is also available electronically). The reprocessed transitions are moreover ordered according to configuration $`C`$ and multiplet $`LS`$. This enables one to obtain the $`f`$-values for each multiplet $`LS`$ and check for completeness of the associated levels. Completeness however also depends on the observed set of fine structure levels since the transitions in the set correspond only to the observed levels (NIST). The $`LS`$ multiplets serve various comparisons with other calculations and experiment where fine structure transitions can not be resolved. The level index, $`I_i`$, for each energy level in the table is given next to the $`g`$-value (e. g. $`g_i:I_i`$) for a easy pointer to the complete $`f`$-file.

BPRM coefficients $`A`$ are compared with other calculations in Table 6, and with available NIST data. Safronova et al. (2001) obtained data of E1, E2, M1 and M2 type for transitions $`2l3l^{}`$ of Fe xvii using relativistic many-body perturbation theory (MBPT). Present results agree reasonably well yet with noticeable scatter compared to and also within (a)–(e), in particular for the decay of level 17 (for labels see Table 7): 2s22p53d 3P$`{}_{1}{}^{\mathrm{o}}`$2s22p$`{}_{}{}^{6}^1`$S0. Because of poorer consistency for intercombination transitions — as would happen when varying the strength of multiplet mixing — one might go for inclusion of all magnetic interactions among the valence electrons: after all there are 8 of them in this sequence, while BPRM ignores magnetic 2-body contributions (accounting only for interaction with the two closed-shell 1s electrons). The result marked by $``$ looks encouraging — until one repeats the same short calculation without such terms: $`8.2710^{10}`$/s looks sobering besides the tabulated $`8.8910^{10}`$/s. This way Bhatia and Doschek’s (1992) coefficient falls into place, leaving the Cornille et al. result — also from superstructure— the odd case out. The blanks for Cornille et al. in the last two transitions are not incidental, since they did not include configurations 2s2p$`{}_{}{}^{6}3l`$ which become degenerate to 2s22p$`{}_{}{}^{5}3l^{}`$ in the high Z limit, according to Layzer’s scaling laws (Layzer 1959), that it is essential to include all the configurations of the complex in order to correctly reproduce the terms of the Z-expansion of the non-relativistic energy. FS splitting of course is a different matter, and if 2-body magnetic interaction with the closed K shell is omitted the effective spin-orbit parameter $`\zeta _{2\mathrm{p}}=0.620`$ Ry (0.1484 $`Z^4`$/cm) goes up to the ‘bare’ value of 0.684 Ry (or 0.1644 $`Z^4`$/cm). (For the effective spin-orbit parameter $`\zeta `$ for an orbital, see Blume and Watson 1962, Eissner et al. 1974.) So much about a mute point of interpreting scatter. For electric dipole transitions the BPRM code in its present state is as good as other good approaches but readily delivering far larger data sets than anything to date.

Among forbidden transitions, discussed in the next section, there is one class for which it is obvious that one must draw very different conclusions, that is for transitions between levels of a FS multiplet: to start with, the splitting changes significantly on including 2-body FS contributions.

### 4.3 Forbidden transitions M1, E2, and M2, E3

We extend the behavioural study of computed radiative decay in Table 8 to a selection of forbidden transitions; a complete set will be published in electronic format, available from the CDS library for some 3000 transitions between the 89 Fe xvii-levels. Table 8 along with Table 7 probes the quality of the target representations — especially term coupling, which is crucial in the collisional application (CPE02). Larger uncertainties are confined to intercombination lines, but there they can increase uncomfortably with higher radiative multipole type. Moreover the table assesses the influence of 2-body finestructure contributions neglected in the current BPRM work. Magnetic interaction between valence shell electrons is always present in the MCDF work with GRASP, activated for the superstructure column ss+ but switched off in ss-: follow the trend from ss- via ss+ to full relativistic MCDF.

At wave lengths of 10 Å $``$ 911 Å/100 (hence $`E_{ij}^2=10^4`$ Ry) Eqs (1516) versus (1314) suggest a close look at decay by electric octopole and magnetic quadrupole radiation for transitions with such a lowest path. We can indeed expect rates around $`10^6`$/s, which would be competitive with E2 and M1 decay around Fe with $`Z_{\mathrm{eff}}20`$ along the Ne-isoelectronic sequence, as the scaling laws show: inserting (6) for E$`\lambda `$ and (10) for M$`\lambda `$ into the line strength expression (5) yields scaling of $`A`$ as $`Z^8`$ for both E3 and M2 (and $`Z^6`$ for E2 and M1); for transitions within a principal shell ($`n`$ = 0) though scaling of E$`\lambda `$ drops by a factor of $`Z^2`$, and octopole transitions become negligible. The E3 results in Table 8 are most satisfactory and perfectly understood. To start with the two bottom entries, one of them apparently contradicting this statement, Table 7 identifies levels 87 and 89 as multiplet mixing companions with $`J=\mathrm{\hspace{0.17em}3}`$ to terms 4f 3F and 1F. Therefore the intercombination decay of 87 becomes rather sensitive to magnetic coupling, $`A`$ converging from right to left as much as one can reasonably expect when MCDF works with a slightly different target. This is borne out by 56, the only other troubling level for E3, as Table 7 places it marginally differently (unfortunately no experiment has yet decided). M2 is a different matter, a factor of 2.5 in the poor case (18,1) difficult to reconcile with the lowest order radiative operator as adopted in superstructure.

For E2 vs M1 the picture turns very varied as early as for $`\mathrm{\Delta }n0`$: distinguishing between intercombination transitions (with factors like $`\alpha ^2Z^2`$ and $`\alpha ^2Z^3`$) and direct transition becomes a more persistent companion. For direct transitions between main shells both $`A`$ scale as $`Z^6`$, the time coefficient favouring E2. Next come radiative BP corrections to M1 remembered from the classical case of 1s2s 3S decay. We verified the Bhatia and Doschek entries, converting to $`A`$ without those corrections with the help of an expedient tool: superstructure prints both the full line strength $`S^{\mathrm{M1}}`$ and BP-deficient $`S_0^{\mathrm{M1}}`$. Then $`A(9,1)`$ drops to less than its tenth, from its ss+ result 3.31$`\times 10^3`$ sec-1 — albeit only half what MCDF is telling: greater discrepancies are associated with differences between SS+ and SS- results and rather crowded fields in Table 7 for the respective $`J\pi `$, so BP may be stretched beyond its limits. The trends for E2 type transitions look perfect.

For electric dipole transitions, both direct and spin-flip, Table 8 gives $`A`$ in velocity form as a second entry to the more firmly established length results, as a measure of good target description $`(`$with the proviso after Eq. (7)$`)`$. They compare encouragingly for the EIE work.

Turning briefly towards astrophysical and laboratory implications from Table 8, apart from selected spontaneous emission coefficients for dipole-allowed transitions it gives results to magnetic dipole and electric quadrupole radiation — and some magnetic quadrupole and electric octopole transitions of the same magnitude of some $`10^6`$ s-1: of course this high multipole decay mode can compete only for transitions with very short wave length, i. e. to the ground state. It may influence the modeling of line emissions. In astronomy and in laboratory photoionized plasmas the M2 decay from level 2 has long been observed as a prominent line. The population of level 2 is fed by cascading from 2p53s, 2p53p, and 2p53d and higher configurations. Accurate M2 transition probabilities are the key to modeling this line. Moreover it has important plasma diagnostics potential.

## 5 Conclusions

¿From large-scale state-of-the-art calculations in Breit-Pauli approximation we obtain energy levels with principal quantum number up to $`n=\mathrm{\hspace{0.17em}10}`$ and radiative transition probabilities of Fe xvii. All levels have been identified in spectroscopic notation and checked for completeness. The set of results far exceeds the currently available experimental and theoretical data.

Radiative data for most electric dipole transions as well as level positions agree within 10% and in most cases far better with available theoretical and experimental work of quality. This indicates that for these highly charged ions higher order relativistic and QED effects omitted in the BPRM calculations may lead to an error not exceeding the estimated uncertainty.

We have obtained a consistent set of coefficients $`A`$ for E2 and M1 type transitions and compared our superstructure and MCDF calculations and with other calculations in the literature. Most results for $`A^{\mathrm{E2}}`$ and $`A^{\mathrm{M1}}`$ lie well inside 20–30% of uncertainty. However, numerically very small coefficients can differ from 50% to a factor of two: M2 and in particular E3 results are highly sensitive to the physics included and numerics (e. g. cancellation effects and numerical instabilities). Large differences are found between the superstructure and MCDF calculations. Especially the magnetic quadrupole results are hard to assess, suggesting further study of this issue.

All data are available electronically. Part of the $`f`$-values have been reprocessed using available observed energies for better accuracy. The new results should be particularly useful for the analysis of X-ray and Extreme Ultraviolet spectra from astrophysical and laboratory sources where non-local thermodynamic equilibrium (NLTE) atomic models with many excited levels are needed.

###### Acknowledgements.

This work was partially supported by U.S. National Science Foundation (AST-9870089) and the NASA ADP program; WE enjoyed part-support by Sonderforschungsbereich 392 of the German Research Council. The computational work was largely carried out on the Cray T94 and Cray SV1 at the Ohio Supercomputer Center in Columbus, Ohio.


text:
# Raman scattering from a superconductivity-induced bound state in 𝑀𝑔𝐵₂

## Abstract

It is shown that the sharp peak in the $`E_{2g}`$ Raman spectrum of superconducting $`MgB_2`$ is due to a bound state caused by the electron-phonon coupling. Our theory explains why this peak appears only in the spectra with $`E_{2g}`$ symmetry and only in the $`\sigma `$ but not $`\pi `$ bands. The properties of the bound state and the Raman spectrum are investigated, also in the presence of impurity scattering.

PACS numbers:74.70.Ad, 74.25.Nf, 74.25.Kc

Electronic Raman scattering in superconductors probes the density and, to some extent, the momentum dependence of quasi-particle excitations across the gap. As a result the spectra are usually dominated by broad pair breaking peaks reflecting the magnitude and anisotropy of the gap as well as scattering processes of the quasi-particles. Experimental spectra in the two-gap superconductor $`MgB_2`$ show the typical features of a dirty s-wave superconductor. A new and surprising feature in the $`E_{2g}`$ spectrum is a sharp peak near the larger of the two gaps which in our opinion cannot be explained as a pair breaking peak because of the large impurity scattering rate of quasi-particles in the present $`MgB_2`$ samples. Below we will argue that this peak is the analogue of the magnetic resonance peak observed in high-Tc cuprates where the electron-phonon interaction takes over the role of the Heisenberg interaction and strongly scatters the excitations across the gap.

Neglecting the momenta of the incident and scattered photons the differential Raman cross section can be written as

$$\frac{d^2R}{d\omega d\mathrm{\Omega }}=\frac{e^4}{\pi c^4}(1+n(\omega ))\chi ^{\prime \prime }(\omega ).$$
(1)
$`e`$ is the charge of an electron, $`n(\omega )`$ the Bose distribution function, $`\omega `$ the difference in frequency between incident and scattered light, and $`\chi ^{\prime \prime }`$ the imaginary part of a retarded Green’s function $`\chi `$ at zero momentum. The corresponding Matsubara function is

$$\chi (i\omega _n)=_0^\beta 𝑑\tau e^{i\omega _n\tau }T_\tau \rho (\tau )\rho (0),$$
(2)
where $`\beta `$ is the inverse temperature $`1/T`$, $`\omega _n=2n\pi T`$ are bosonic Matusbara frequencies, $`T_\tau `$ the time ordering operator, and $`\rho `$ an effective density operator with momentum zero. In the following we will be interested in spectra related to the $`E_{2g}`$ symmetry of $`D_{6h}`$, the point group of $`MgB_2`$. $`\rho `$ has then the form

$$\rho =\underset{𝐤\sigma n}{}\gamma _n(𝐤)c_{\sigma n}^{}(𝐤)c_{\sigma n}(𝐤)+R(b+b^{}),$$
(3)
$$\gamma _n(𝐤)=\left(\frac{^2ϵ_n(𝐤)}{k_x^2}\frac{^2ϵ_n(𝐤)}{k_y^2}\right).$$
(4)
$`c_{\sigma n}^{}(𝐤)`$ and $`c_{\sigma n}(𝐤)`$ are creation and annihilation operators for electrons with momentum $`𝐤`$, spin direction $`\sigma `$, band label $`n`$, and energy $`ϵ_n(𝐤)`$. $`MgB_2`$ has only one Raman-active $`𝐪=0`$ phonon, and this phonon has $`E_{2g}`$ symmetry. Its frequency is denoted by $`\mathrm{\Omega }`$, its creation and annihilation operators by $`b^{}`$ and $`b`$, respectively, and the corresponding element of the phononic Raman tensor by $`R`$. Without loss of generality we assume that this phonon transforms as the first basis vector of the two-dimensional $`E_{2g}`$ representation in accordance with Eq.(4).

For the evaluation of $`\chi `$ we use the Hamiltonian $`H=H_0+H^{}`$ with

$`H_0`$ $`=`$ $`{\displaystyle \underset{𝐤\sigma n}{}}ϵ_n(𝐤)c_{\sigma n}^{}(𝐤)c_{\sigma n}(𝐤)+{\displaystyle \underset{𝐪j}{}}\mathrm{\Omega }_j(𝐪)(b_j^{}(𝐪)b_j(𝐪)+{\displaystyle \frac{1}{2}})`$ (5)
$``$ $`{\displaystyle \underset{n}{}}(\mathrm{\Delta }_nc_n^{}(𝐤)c_n^{}(𝐤)+h.c.),`$ (6)
$`H^{}={\displaystyle \underset{\mathrm{𝐤𝐪}n}{}}g_{nj}(\mathrm{𝐤𝐪})c_{\sigma n}^{}(𝐤+𝐪)c_{\sigma n}(𝐤)(b_j(𝐪)+b_j^{}(𝐪))`$ (7)
$`+{\displaystyle \underset{\genfrac{}{}{0pt}{}{\mathrm{𝐤𝐪}\sigma }{nn^{}}}{}}V_{nn^{}}(\mathrm{𝐤𝐪})c_{\sigma n}^{}(𝐤)c_{\sigma n^{}}(𝐪).`$ (8)
$`\mathrm{\Delta }_n`$ is the gap parameter for s-wave superconductivity in the band $`n`$, $`\mathrm{\Omega }_j(𝐪)`$ the frequency of a general phonon with momentum $`𝐪`$ and branch label $`j`$, $`g`$ the coupling constant for intraband electron-phonon scattering and $`V`$ a random potential for intraband impurity scattering. Interband phonon scattering can be neglected in $`H^{}`$ because only zero momentum transfers occur in the approximation used below.

In a first step we perform an infinite summation over bubble diagrams by introducing the irreducible Green’s function $`\stackrel{~}{\chi }`$. $`\stackrel{~}{\chi }`$ contains all diagrams to $`\chi `$ which cannot be decomposed into two parts by cutting one phonon line. The average over impurities yields impuritiy lines with similar properties as phonon lines. However, bubble diagrams connected by impurity lines are not possible in this case so that the above definition of irreducibility is appropriate. Analytically, one obtains

$$\chi =\stackrel{~}{\chi }_{11}+(\stackrel{~}{\chi }_{12}+R)D(R+\stackrel{~}{\chi }_{21}),$$
(9)
$$D=D^{(0)}+D^{(0)}\stackrel{~}{\chi }_{22}D.$$
(10)
The omitted frequency and momentum arguments in the Green’s functions in Eqs.(9) and (10) are $`i\omega _n`$ and $`0`$, respectively. $`\stackrel{~}{\chi }_{11}`$ denotes the irreducible Green’s function associated with the two vertices $`\gamma _n(𝐤)`$. Similarly, the vertices in the functions $`\stackrel{~}{\chi }_{12}`$ and $`\stackrel{~}{\chi }_{22}`$ are $`\gamma _n(𝐤)`$ and $`g_n(𝐤0)`$, and two times $`g_n(𝐤0)`$, respectively. The free phonon progator $`D^{(0)}`$ is given by $`2\mathrm{\Omega }/(\omega _n^2+\mathrm{\Omega }^2)`$.

A sensible approximation for the evaluation of $`\stackrel{~}{\chi }`$ is the ladder approximation plus the corresponding self-energy corrections where the interaction lines are due to phonons or impurities. Only that part of the interaction can contribute in the ladder diagrams which transforms in the same way as the vertices $`\gamma `$ and $`g`$. This means in our case that only the $`E_{2g}`$ component of the phonon-mediated interaction, which usually is considered to be neglegible in a s-wave superconductor, would enter. We therefore will evaluate $`\stackrel{~}{\chi }`$ only in the presence of random impurities using the Born approximation and the dirty limit for each band. Assuming that the vertices and the interaction can be evaluated right on the Fermi surface, expanding $`\gamma `$ and $`g`$ in terms of Fermi surface harmonics of $`E_{2g}`$ symmetry, $`\mathrm{\Phi }_L^{(n)}(𝐤)`$, normalized as in Eq.(1) of Ref.,

$$\gamma _n(𝐤)=\underset{L}{}\alpha _{1L}^{(n)}\mathrm{\Phi }_L^{(n)}(𝐤),$$
(11)
$$g_n(𝐤0)=\underset{L}{}\alpha _{2L}^{(n)}\mathrm{\Phi }_L^{(n)}(𝐤),$$
(12)
and assuming that the interaction is diagonal in $`L`$ we obtain

$$\stackrel{~}{\chi }_{ij}(i\omega _n)=\underset{Ln}{}\alpha _{iL}^{(n)}\alpha _{jL}^{(n)}N_F^{(n)}\stackrel{~}{\chi }(i\omega _n,\mathrm{\Delta }_n,\tau _n^1).$$
(13)
$`N_F^{(n)}`$ is the density of states at the Fermi surface for one spin direction due to the band $`n`$ and $`1/\tau _n`$ an effective scattering rate. After an analytic continuation $`i\omega _n\omega +i\eta `$ the imaginary part of the Green’s function $`\stackrel{~}{\chi }`$, which is independent of $`L`$, becomes

$`Im\stackrel{~}{\chi }(\omega ,\mathrm{\Delta },\tau ^1)={\displaystyle \frac{8\mathrm{\Delta }\omega }{\omega +2\mathrm{\Delta }}}\mathrm{\Theta }(\omega 2\mathrm{\Delta }){\displaystyle \frac{\tau ^1}{\omega ^2+\tau ^2}}`$ (14)
$`({\displaystyle \frac{(\omega 2\mathrm{\Delta })^2}{4\mathrm{\Delta }\omega }}E(\alpha )+{\displaystyle \frac{\tau ^2+\omega ^2+4\mathrm{\Delta }\omega }{\tau ^2+\omega ^2+2\mathrm{\Delta }\omega }}F(\alpha )`$ (15)
$`+{\displaystyle \frac{8\mathrm{\Delta }^2\omega ^2}{(\omega ^2+\tau ^2)^24\mathrm{\Delta }^2\omega ^2}}\mathrm{\Pi }(N,\alpha )),`$ (16)
with

$$\alpha =(\omega 2\mathrm{\Delta })/(\omega +2\mathrm{\Delta }),$$
(17)
$$N=\frac{1+\alpha ^2\omega _1}{1+\omega _1},$$
(18)
$$\omega _1=\tau ^2(14\mathrm{\Delta }^2/(\omega ^2+\tau ^2))/(\omega 2\mathrm{\Delta })^2.$$
(19)
$`\mathrm{\Theta }`$ is the theta function and $`F`$, $`E`$, and $`\mathrm{\Pi }`$ are complete elliptical integrals of the first, second, and third kinds, respectively. The existence of only two gaps in the experimental spectra as well as theoretical arguments suggest that the dirty limit applies even within the two-band complex of $`\sigma `$ and $`\pi `$ bands (denoted by the index $`\rho `$ in the following) and that the interband impurity scattering between $`\sigma `$ and $`\pi `$ bands is neglegible. As a result $`\mathrm{\Delta }_n`$ and $`\tau _n^1`$ can be considered to be the same within the manifold of $`\sigma `$ or $`\pi `$ bands. Introducing then the effective couplings

$$\lambda _{ij}^{(\rho )}=\underset{\genfrac{}{}{0pt}{}{L}{n\rho }}{}\alpha _{iL}^{(n)}\alpha _{jL}^{(n)}N_F^{(n)},$$
(20)
we obtain

$$\stackrel{~}{\chi }_{ij}(\omega )=\underset{\rho =\sigma ,\pi }{}\lambda _{ij}^{(\rho )}\stackrel{~}{\chi }(\omega ,\mathrm{\Delta }_\rho ,\tau _\rho ^1).$$
(21)
Choosing for the first function $`\mathrm{\Phi }_1^{(n)}(𝐤)`$ the properly normalized function $`\gamma _n(𝐤)`$, the summations over $`L`$ collapse to one term $`L=1`$ if either $`i`$ or $`j`$ is equal to 1. In the clean limit $`1/\tau 0`$ Eq.(16) reduces to the analytical formula Eq.(16) of Ref.().

Using the tight-binding fit to the band structure of Ref., $`eV`$ as energy and the lattice constant $`a`$ as length units, we find $`N_F^{(1)}=0.049`$, $`N_F^{(2)}=0.109`$, $`N_F^{(3)}=0.101`$, $`N_F^{(4)}=0.104`$, where $`n=1,2`$ denote the light and heavy $`\sigma `$ bands and $`n=3,4`$ the $`\pi `$ bands. In the case of $`\pi `$ bands we have scaled the published tight-binding parameters slightly in order to reproduce the correct densities. Furthermore, we obtain $`\alpha _1^{(1)}=0.101`$, $`\alpha _1^{(2)}=0.261`$, $`\alpha _1^{(3)}=2.531`$, $`\alpha _1^{(4)}=2.376`$, and thus $`\lambda _{11}^{(\sigma )}=0.008`$, and $`\lambda _{11}^{(\pi )}=1.238`$. The rather small values for $`\alpha _1^{(1)}`$, $`\alpha _1^{(2)}`$, and $`\lambda _{11}^{(\sigma )}`$ reflect the fact that the $`\sigma `$ bands are rather isotropic in the ab-plane near their narrow cylindrical Fermi surfaces and thus cannot contribute much in the $`E_{2g}`$ channel. As a consequence we may safely put $`\lambda _{11}^{(\sigma )}=\lambda _{12}^{(\sigma )}=\lambda _{21}^{(\sigma )}=0`$. The $`\sigma `$ contribution to $`\stackrel{~}{\chi }`$ arises then solely from the coupling of the phonon to the light and its spectral features are determined by the dimensionless electron-phonon coupling constant $`\lambda =\frac{2}{\mathrm{\Omega }}\lambda _{22}^{(\sigma )}`$ and the scattering rate $`1/\tau _\sigma `$.

We will first consider the $`\sigma `$ contribution to $`\stackrel{~}{\chi }`$ and drop the index $`\sigma `$ everywhere in order to simplify the notation. Fig.1 shows the real (dashed lines) and imaginary (solid lines) part of $`\stackrel{~}{\chi }`$ for the gap $`2\mathrm{\Delta }=110cm^1`$ and two scattering rates $`1/\tau =0`$ and $`1/\tau =200cm^1`$. In the clean case the imaginary part $`\stackrel{~}{\chi ^{\prime \prime }}`$ exhibits a square root singularity if $`\omega `$ approaches $`2\mathrm{\Delta }`$ from above. Impurity scattering transforms this singularity into a step at $`2\mathrm{\Delta }`$ with height $`2\pi \mathrm{\Delta }\tau `$, and produces for sufficiently strong scattering a very broad minimum near $`1/\tau `$. The real part $`\stackrel{~}{\chi }^{}`$ shows in the clean case a square root singularity below $`2\mathrm{\Delta }`$ and finite and positive values above $`2\mathrm{\Delta }`$. Taking impurity scattering into account $`\stackrel{~}{\chi }^{}`$ becomes much more symmetric around $`2\mathrm{\Delta }`$ compared to the clean case,

exhibiting there a logarithmic singularity and negative values over a large region above $`2\mathrm{\Delta }`$.

The curves in Fig. 1 suggest that the phonon Green’s function $`D`$ will develop a bound state inside the gap, and that this will occur for all values for $`\lambda `$ and $`1/\tau `$. The frequency of the bound state, $`\omega _b`$, is determined by the vanishing of the denominator of $`D`$, i.e., by the equation,

$$\omega _b^2=\mathrm{\Omega }^2+\mathrm{\Omega }^2\lambda \stackrel{~}{\chi }^{}(\omega _b,\mathrm{\Delta },1/\tau ).$$
(22)
Expanding the denominator of $`D`$ around $`\omega _b`$ one finds for the spectral weight $`Z_b`$

$$Z_b=\frac{2\mathrm{\Omega }}{2\omega _b\lambda \mathrm{\Omega }^2\stackrel{~}{\chi }^{}(\omega _b,\mathrm{\Delta },1/\tau )/\omega _b}.$$
(23)
Fig.2 shows $`\omega _b`$ and $`Z_b`$ as a function of $`\lambda `$ for the two scattering rates $`1/\tau =0`$ and $`1/\tau =200cm^1`$. $`\omega _b`$ approaches zero at $`\lambda _{CDW}=0.50`$ and $`0.47`$, respectively. This means that for $`\lambda >\lambda _{CDW}`$ the superconducting state is unstable against the formation of a charge density wave with $`E_{2g}`$ symmetry. For $`\lambda <\lambda _{CDW}`$ $`\omega _b`$ and $`Z_b`$ increase and decrease rapidly with decreasing $`\lambda `$ approaching their limiting values $`1`$ and $`0`$ in an exponential (for $`1/\tau 0`$) or powerlawlike (for $`1/\tau =0`$) manner.

One peculiar feature of $`D`$ is that any background imaginary part in its self-energy, for instance due to $`\pi `$ electrons, will be diminuished by the factor $`1/Z_b`$ near $`2\mathrm{\Delta }`$. This means that the bound state will not be broadened

and disappear in $`\chi ^{\prime \prime }`$ for small $`\lambda `$’s, even in the presence of strong impurity scattering, but instead will sharpen and loose weight when $`\omega _b`$ approaches 1. To make the situation more realistic one should allow for broadening effects due to inhomogenieties etc. which may be taken into account by folding $`\stackrel{~}{\chi }^{}`$ with a Gaussian with a width $`\delta `$. Fig.3 shows $`\chi ^{\prime \prime }`$ for three different $`\lambda `$ and a width of $`\delta =10cm^1`$. The employed large scattering rate $`\tau ^1=200cm^1`$ has wiped out completely the usual pair breaking peak due to the square root divergence of $`\chi ^{\prime \prime }`$ at $`2\mathrm{\Delta }`$. On the other hand, the electron-phonon coupling accumulates spectral weight near $`2\mathrm{\Delta }`$ and produces a pronounced bound state inside the gap at larger couplings.

Figs.2 and 3 allow to estimate a realistic value for $`\lambda `$. Identifying $`\omega _b`$ with the observed sharp peak in the $`E_{2g}`$ spectrum we have $`\omega _b=104\pm 1cm^1`$ whereas a recent tunneling experiment gave for the gap $`2\mathrm{\Delta }=114\pm 6cm^1`$. This suggest that $`\omega _b`$ is different from $`2\mathrm{\Delta }`$, i.e., the sharp peak should not be identified with the gap, and the ratio $`\omega _b/2\mathrm{\Delta }`$ is $`0.91\pm 0.06`$. Fig.2 indicates then that $`\lambda `$ must be smaller than $`0.3`$. Comparing the intensities of the bound state and the phonon line in Fig.3 with the experimental curve one finds that $`\lambda `$ must be near the interval between 0.15 and 0.20. These values are substantially smaller than the value 0.38 obtained from band structure calculations.

Additional evidence for the importance of the electron-phonon coupling in the $`E_{2g}`$ spectrum comes from the experimental result that the two $`A_{1g}`$ and the $`E_{1g}`$ spectra do not show any pronounced peak near $`2\mathrm{\Delta }`$. We explain this by the fact that, according to group theory, $`MgB_2`$ has no $`𝐪=0`$ phonons with such symmetries so that no

bound states can be formed. Further support for the present theory comes from the absence of a peak near the gap of about 47 $`cm^1`$ in the $`\pi `$ bands. LDA calculations show that the coupling of $`\pi `$ electrons to the $`E_{2g}`$ phonon is by a factor 3 or 4 smaller than for $`\sigma `$ electrons. We find that the bound state structure near the $`\pi `$ gap is invisible for such a coupling which explains its absence in the experimental spectra. Using $`\lambda _{12}^{(\pi )}=\lambda _{21}^{(\pi )}=0`$, $`\lambda _{22}^{(\pi )}/\lambda _{22}^{(\sigma )}=1/3`$, $`\lambda _{11}^{(\pi )}/R^2=1/400`$, $`\lambda =0.16`$, $`\mathrm{\Omega }=620cm^1`$, $`\delta =5cm^1`$, a $`\pi `$ gap of $`43cm^1`$ and a somewhat reduced $`\sigma `$ gap of $`96.5cm^1`$, accounting for the finite temperature of the experimental data, the resulting Raman cross section is shown as the dashed line in Fig.4, together with the experimental $`E_{2g}`$ spectrum. The dashed line reproduces well the main features of the experimental curve, especially at small frequencies. The quantitative discrepancy in the phonon region suggests that only part of the phonon broadening is caused by the electron-phonon coupling and that anharmonicity and deviations from the assumed constant density of states may play a role. The theoretical superconductivity-induced hardening of the phonon frequency in Fig.4 is 5 $`cm^1`$ and thus somewhat smaller than the experimental value of $`710cm^1`$.

In conclusion, we have shown that the $`E_{2g}`$ spectrum in superconducting $`MgB_2`$ can be understood as a superposition of a phonon line coupled strongly to $`\sigma `$ electrons creating hereby a bound state in the gap, and a background due to rather uncorrelated $`\pi `$ electrons. This means that $`MgB_2`$ is to our knowledge the first s-wave superconductor where a bound state in the superconducting gap due to residual interactions has been observed and identified. The obtained electron-phonon coupling constant $`\lambda 0.2`$ for $`\sigma `$ electrons is only half of the band structure value, a discrepancy, which presently is not well understood.

The author thanks O. Dolgov, J. Kortus and I. Mazin for useful discussions.


text:
# Vector meson production and nucleon resonance analysis in the Giessen coupled-channel model

## 1 Introduction

The reliable extraction of nucleon resonance properties from experiments where the nucleon is excited via either hadronic or electromagnetic probes is one of the major issues of hadron physics. The goal is to be finally able to compare the extracted masses and partial-decay widths to predictions from lattice QCD and/or quark models (see references in Refs. ).

Basically all information about nucleon resonances identified so far from experiment stems from analyses of pion-induced $`\pi N`$ and $`2\pi N`$ production and from pion photoproduction, see  and references therein. However, it is well known that, for example, in the case of the $`S_{11}(1535)`$ the consideration of the $`\eta N`$ final state is inevitable to extract its properties reliably, and similar effects can be expected for higher-lying resonances and different thresholds. On the other side, quark models predict a much richer resonance spectrum than has been found in $`\pi N`$ and $`2\pi N`$ production so far, giving rise to speculations that many of these resonance states only couple weakly to the $`\pi N`$ final state (“missing” resonances). For a consistent and reliable identification of these resonances and their properties, the consideration of unitarity effects are inevitable and as many final states as possible have to be taken into account simultaneously. With this aim in mind we have developed in Refs.  a unitary coupled-channel effective Lagrangian model (Giessen model) that incorporates the final states $`\gamma N`$, $`\pi N`$, $`2\pi N`$, $`\eta N`$, $`K\mathrm{\Lambda }`$, $`K\mathrm{\Sigma }`$, and in particular $`\omega N`$. This model is used for a simultaneous analysis of all available experimental data on photon- and pion-induced reactions on the nucleon in the energy range $`m_N<\sqrt{s}<2`$ GeV. The premise is to use the same Lagrangians for the pion- and photon-induced reactions allowing for a consistent analysis, thereby generating the background dynamically from Born, $`u`$\- and $`t`$-channel contributions without new parameters.

Here, we only point out some aspects of our results; all the details can be found in Refs. .

## 2 The Giessen Model

In the Giessen model the Bethe-Salpeter equation for the scattering amplitude $`𝒯`$ is solved by the $`K`$-matrix approximation, where the intermediate particles are set on their mass shell. By a partial-wave decomposition in total spin $`J`$, parity $`P`$, and isospin $`I`$, which is performed in a generalized and uniform way for all final-state combinations (see Refs.  for details), one arrives at an algebraic equation relating the decomposed $`𝒯_{fi}`$ and the potential $`𝒱_{fi}`$ (in a schematic notation): $`𝒯_{fi}^{IJ\pm }=[𝒱^{IJ\pm }/(1\mathrm{i}𝒱^{IJ\pm })]_{fi}`$. Hence unitarity is fulfilled as long as $`𝒱`$ is Hermitian. Furthermore, in the effective Lagrangian approach generating the potential $`𝒱`$, gauge invariance is fulfilled in a straightforward way .

The nucleon resonance properties are extracted by a $`\chi ^2`$ minimization procedure using a total of about 6800 experimental data points, comprising partial-wave analyses for $`\gamma /\pi N\pi N`$, $`\pi N2\pi N`$, and total and differential cross section and polarization data for all other reactions (see Refs. ); a good simultaneuos description of all channels is achieved. As examples, we show the resulting total cross sections of $`\eta N`$, $`K\mathrm{\Lambda }`$, and $`\omega N`$ production in Fig. 1.

In these reactions and in particular in $`\omega N`$ production, strong evidence for important $`P`$-wave contributions is found, mainly steming from the $`P_{11}(1710)`$ and $`P_{13}(1900)`$ resonances, where the latter one is especially important in the pion-induced reactions. In $`K\mathrm{\Lambda }`$ photoproduction also a clear threshold effect is visible due to the opening of the $`\omega N`$ final state. Note that in $`\omega N`$ photoproduction, we furthermore observe a large contribution of the $`\pi `$ $`t`$-channel exchange. In Fig. 2,

the $`\pi N`$ inelastic partial-wave cross sections for $`I=\frac{1}{2}`$ are shown, emphasizing the importance of the inclusion of final states apart from $`\pi N`$ and $`2\pi N`$ in a unitary model. In the $`J^P=\frac{1}{2}^{}(S_{11})`$, $`\frac{1}{2}^+(P_{11})`$, and $`\frac{3}{2}^+(P_{13})`$ partial waves the consideration of the $`\eta N`$ and $`\omega N`$ final states are particularly important.

## 3 Outlook

The next step towards a further improvement of the model is the inclusion of spin-$`\frac{5}{2}`$-resonance effects, see Ref. . Furthermore, investigations concerning a detailed inclusion of all individual $`2\pi N`$ final states ($`\rho N`$, $`\pi \mathrm{\Delta }`$, …) are in progress.

## Acknowledgments

This work was supported by DFG and GSI Darmstadt.