format: text

text:
# Optical properties of perovskite alkaline earth titanates : a formulation

## 1 Introduction

The object of our present study is to derive an expression for the optical conductivity as a convolution of the energy resolved joint density of states and an energy-frequency dependent transition rate. The need is to go beyond the usual reciprocal space based formulations and obtain an expression which we can immediately generalize for disordered systems. This would require labelling states by energy and the angular momentum labels ($`\mathrm{},m`$) alone. Once we derive this expression we shall find a representation for the optical conductivity in the minimal basis set of the tight-binding linearized muffin-tin orbitals (TB-LMTO). The generalization to disordered systems will be carried out through the augmented space recursion (ASR) introduced by us earlier for the study of electronic properties of disordered systems -. The ASR carries out the configuration averaging essential to the description of properties of disordered systems, going beyond the usual mean-field approaches and taking into account configuration fluctuations. The input into the ASR method includes the Hamiltonian parameters of the pure constituents, as the starting point of the local spin density approximation (LSDA) iterations for the alloy. It also includes the information about the transition rates of the pure constituents, expressed as functions of the initial and final state energies. The aim of this paper is to reformulate the reciprocal space representation of the transition rate and re-express it in the energy-frequency label representation for the pure constituents. Only when we are confident that this works, can we proceed with the full calculations for the disordered alloy. This communication is an attempt to verify our formulation for a series of alkaline earth titanates in the paraelectric phase, on which extensive theoretical and experimental data of optical properties are available for comparison.

Perovskite structured titanate ferroelectric compounds is, to date, one of the most extensively investigated materials. They are extremely interesting from the viewpoint of solid state theoreticians because their structures are a lot simpler than that of any other ferroelectric material known, and, therefore, prove to be rather simple systems to study and better understand the ferroelectric phenomenon. The titanates are very easily prepared as polycrystalline ceramics, they are chemically and mechanically pretty stable and they exhibit para- to ferroelectric phase transition at or above room temperature. Continued interest in these compounds has led to a wide variety of theoretical and experimental work, specially on lattice vibrations. A less common approach has been those based on electronic structure calculations . Michel-Calendini and Mesnard - have reported band structure of $`BaTiO_3`$ within a linear combination of atomic orbitals (LCAO) method with empirical off-diagonal integrals. The pioneering work on $`SrTiO_3`$ was that of Kahn and Leyendecker . This was followed by an Augmented Plane Wave (APW) calculation by Matheiss  and a self-consistent tight-binding calculation by Soules et al. However, Battaye et al have compared experimental valence-band spectra with these early theoretical predictions and have concluded that the agreement was not satisfying. Pertosa and Michel-Calendini  carried out a modified tight-binding calculation on $`BaTiO_3`$ and $`SrTiO_3`$ and compared their results with X-ray photoelectron spectra. These authors introduced inner orbital interactions. Perkins and Winter  have carried out LCAO calculations on the band structure of $`SrTiO_3.`$ There have been several all-electron, full-potential linearized augmented plane waves (FP-LAPW) studies of the titanates in recent times -. In addition ultrasoft-pseudopotential, local density approximation (LDA) based studies on perovskites have been carried out by King-Smith and Vanderbilt . In comparison, electronic structure calculations on $`CaTiO_3`$ have been fewer. Ueda and coworkers - have used the first-principles tight-binding method to study $`CaTiO_3`$ .

We shall show that for all the three compounds the transition rate, defined by us, is strongly energy and frequency dependent, i.e. it depends upon the energy of both the initial and the final states. We shall compare the theoretical results with experiment.

## 2 Methodology

In recent years a number of methods have been proposed for calculating optical properties within the framework of the LMTO - for both metals and semi-conductors. We shall present here a gauge-independent formalism, following the ideas of Hobbs et al. Since our final aim is to use the augmented space recursion method (ASR) - and study the optical properties of random systems, we shall modify the reciprocal space formulation and obtain an expression in which all states are labelled by their energy and the optical conductivity is expressed as a convolution of the energy resolved joint density of states and an energy-frequency dependent transition matrix. This formulation will then be directly generalized within the ASR.

The Hamiltonian describing the effect of a radiation field on the electronic states of a solid is given by :

$$H=\underset{i=1}{\overset{N}{}}\left\{\frac{1}{2m_e}\left(𝐩_i+\frac{e}{c}𝐀(𝐫_i,t)\right)^2+V(𝐫_i)+e\mathrm{\Phi }(𝐫_i,t)\right\}$$

Here $`e`$ is the magnitude of electronic charge, $`m_e`$ the electronic mass, $`c`$ is the velocity of light and $`\mathrm{}`$ is the Planck’s constant. $`𝐀(𝐫_i,t)`$ and $`\mathrm{\Phi }(𝐫_i,t)`$ are the vector and scalar potentials seen by the $`i`$-th electron because of the radiation field. There are N electrons labelled by $`i`$. The potential $`V(𝐫_i)`$ experienced by the electrons is expressed as an effective independent electron approximation within the LDA of the density functional theory (DFT). For not too large external optical fields, neglecting terms of the order of $`O(|\text{A}|^2)`$, the Hamiltonian reduces to :

$$H=\underset{i=1}{\overset{N}{}}\left\{\frac{1}{2m_e}𝐩_i^2+V(𝐫_i)+\frac{1}{c}𝐣_i𝐀(𝐫_i,t)\right\}$$
(1)
Here ji = (e/m) pi is the current operator. We work in the Coulomb gauge where $`𝐀(𝐫_i,t)`$ = 0 and $`\mathrm{\Phi }(𝐫_i,t)`$ = 0, so that the electric field

$$𝐄(𝐫_i,t)=\frac{𝐀(𝐫_i,t)}{t}$$

In choosing the above equation we have ignored the response of the system. The local electric field is the external field due to the incident radiation as well as the internal field due to the polarization of the medium. Such local field corrections are important for insulators. We intend, as is customary, to introduce the local filed corrections as well as corrections due to the Coulomb hole in our final GW calculations, for which these single-particle picture will form the zeroth starting point.

The Kubo formula then relates the linear current response to the radiation field :

$$j_\mu (t)=\underset{\nu }{}_{\mathrm{}}^{\mathrm{}}𝑑t^{}\chi _{\mu \nu }(tt^{})A_\nu (t^{})$$

The generalized susceptibility is given by :

$$\chi _{\mu \nu }(\tau )=ı\mathrm{\Theta }(\tau )\varphi _0|[j_\mu (\tau ),j_\nu (0)]|\varphi _0$$

where, $`\tau =tt^{}`$ and $`\mathrm{\Theta }(\tau )`$ is the Heaviside step function,

$$\mathrm{\Theta }(\tau )=\{\begin{array}{cc}1\hfill & \text{if }\tau >0\hfill \\ 0\hfill & \text{if }\tau 0\hfill \end{array}$$

$`|\varphi _0`$ is the ground state of the unperturbed system, that is the solid in the absence of the radiation field. In the absence of the radiation field, there is no photocurrent, i.e. $`\varphi _0|j_\mu |\varphi _0`$ = $`0`$. The fluctuation-dissipation theorem relates the imaginary part of the generalized susceptibility to the correlation function as follows :

$$\chi _{\mu \nu }^{\prime \prime }(\omega )=\frac{1}{2}\left(1e^{\beta \omega }\right)S_{\mu \nu }(\omega )$$
(2)
where,

$$\beta =\frac{1}{k_BT}\text{where }k_B\text{ is the Boltzmann constant and }T\text{ the temperature}$$

and

$$\chi _{\mu \nu }^{\prime \prime }(\omega )=\mathrm{}m_{\mathrm{}}^{\mathrm{}}𝑑te^{ız\tau }\chi _{\mu \nu }(\tau )\text{z=}\omega \text{+}ı0^+$$

and,

$$S_{\mu \nu }(\omega )=\mathrm{}m_{\mathrm{}}^{\mathrm{}}𝑑te^{\iota z\tau }\varphi _0|j_\mu (\tau )j_\nu (0)|\varphi _0\text{z=}\omega \text{+}ı0^+$$

An expression for the correlation function, can be obtained via the Kubo-Greenwood expression,

$$S(\omega )=\frac{\pi }{3}\underset{i}{}\underset{f}{}\underset{\mu }{}\varphi _i|j_\mu |\varphi _f\varphi _f|j_\mu |\varphi _i\delta (E_fE_i\mathrm{}\omega )$$
(3)
We have assumed isotropy of the response so that the tensor $`S_{\mu \nu }`$ is diagonal and we have defined $`S(\omega )`$ as the direction averaged quantity $`\frac{1}{3}_\mu S_{\mu \mu }(\omega )`$. The $`|\{\varphi _i\}`$ are the occupied ‘initial’ single electronic states in the ground state while $`|\{\varphi _f\}`$ are the unoccupied single electron ‘final’ excited states in the LDA description.

The imaginary part of the dielectric function is related to the above :

$$ϵ_2(\omega )=\frac{1}{\pi ^2\omega ^2}S(\omega )$$
(4)
We may obtain the real part of the dielectric function $`ϵ_1(\omega )`$ from a Kramers-Krönig relationship.

For crystalline semi-conductors the equation (3) may be rewritten as follows :

$$S(\omega )=\frac{\pi }{3}\underset{j}{}\underset{j^{}}{}_{BZ}\frac{d^3𝐤}{8\pi ^3}\left|\mathrm{\Phi }_{j^{}𝐤}|𝐣|\mathrm{\Phi }_{j𝐤}\right|^2\delta \left(E_j^{}(𝐤)E_j(𝐤)\mathrm{}\omega \right)$$
(5)
Here $`j`$ and $`j^{}`$ refer to band labels : $`j`$ for the occupied valence bands and $`j^{}`$ the unoccupied conduction bands at T=0 K. The $`𝐤`$ is the quantum label associated with the Bloch Theorem. For disordered materials, the Bloch Theorem fails and the expression (5) can no longer be used. Our first aim will be to obtain an alternative expression where the quantum states are directly labelled by energy and frequency, rather than by the ‘band’ and ‘crystal momentum’ indeces. For this, let us examine the following expressions :

$`n(E)`$ $`=`$ $`{\displaystyle \underset{j}{}}{\displaystyle _{BZ}}{\displaystyle \frac{d^3𝐤}{8\pi ^3}}\delta (E_j(𝐤)E)`$ (6)
$`J(E,\omega )`$ $`=`$ $`{\displaystyle \underset{j}{\overset{occ}{}}}{\displaystyle \underset{j^{}}{\overset{unocc}{}}}{\displaystyle _{BZ}}{\displaystyle \frac{d^3𝐤}{8\pi ^3}}\delta (E_j(𝐤)E)\delta (E_j^{}(𝐤)E\mathrm{}\omega )`$ (7)
In the equation (6), the right hand side picks up a factor of 1 whenever a quantum state, labelled by $`\{𝐤,j\}`$ falls in the range E, E+$`\delta `$E. The left-hand side, therefore, is the density of states arising from the bands labelled $`j`$.

In the equation (7), the right-hand side picks up a factor of 1 whenever a quantum state in the filled bands labelled $`j`$ falls in the range E, E+$`\delta `$E and simultaneously a quantum state in the unfilled bands labelled $`j^{}`$ falls in the range E+$`\omega `$, E+$`\omega `$+$`\delta `$E. The left-hand side is then the energy resolved joint density of states :

$$J(E,\omega )=n_v(E)n_c(E+\mathrm{}\omega )$$
(8)
We shall define the energy-frequency labelled Transition rate as :

$`T(E,\omega )`$ =    $`{\displaystyle \underset{j}{}}{\displaystyle \underset{j^{}}{}}{\displaystyle _{BZ}}{\displaystyle \frac{d^3𝐤}{8\pi ^3}}T^{jj^{}}(𝐤)\delta (E_j(𝐤)E)\delta (E_j^{}(𝐤)E\mathrm{}\omega )`$  $`{\displaystyle \underset{j}{}}{\displaystyle \underset{j^{}}{}}{\displaystyle _{BZ}}{\displaystyle \frac{d^3𝐤}{8\pi ^3}}\delta (E_j(𝐤)E)\delta (E_j^{}(𝐤)E\mathrm{}\omega )`$

(9)
Where,

$$T^{jj^{}}(𝐤)=\underset{\mu }{}\left|\text{}\mathrm{\Phi }_{j^{}𝐤}|j_\mu |\mathrm{\Phi }_{j𝐤}\right|^2$$

The expression for $`S(\omega )`$ from equation (5) then becomes,

$$S(\omega )=(\pi /3)𝑑ET(E,\omega )J(E,\omega )$$
(10)
Many earlier workers argued that the transition matrix element is weakly dependent on both E and $`\omega `$. They then assumed it to be constant $`T_0`$ and obtained a simple expression for the correlation function :

$$S_0(\omega )=(\pi /3)T_0𝑑EJ(E,\omega )$$
(11)
We shall investigate the validity of this approximation for the systems under study in this communication. Let us first get an expression for the equation (10) within the TB-LMTO formalism of - : The basis of the LMTO starts from the minimal muffin-tin orbital basis set of a KKR formalism and then linearizes it by expanding around a ‘nodal’ energy point $`E_\nu \mathrm{}^\alpha `$ . The wave-function is then expanded in this basis :

$`\mathrm{\Phi }_{j𝐤}(𝐫)`$ $`=`$ $`{\displaystyle \underset{L}{}}{\displaystyle \underset{\alpha }{}}c_{L\alpha }^{j𝐤}\left[\varphi _{\nu L}^\alpha (𝐫)+{\displaystyle \underset{L^{}}{}}{\displaystyle \underset{\alpha ^{}}{}}h_{LL^{}}^{\alpha \alpha ^{}}(𝐤)\dot{\varphi }_{\nu L^{}}^\alpha ^{}(𝐫)\right]`$
where, $`L`$ is the composite angular momentum index $`(\mathrm{},m)`$, $`j`$ is the band index and $`\alpha `$ labels the atom in the unit cell.

and,

$`\varphi _{\nu L}^\alpha (𝐫)`$ $`=`$ $`ı^{\mathrm{}}Y_L(\widehat{r})\varphi _{\mathrm{}}^\alpha (r,E_\nu \mathrm{}^\alpha )`$
$`\dot{\varphi }_{\nu L}^\alpha (𝐫)`$ $`=`$ $`\text{}ı^{\mathrm{}}Y_L(\widehat{r}){\displaystyle \frac{\varphi _{\mathrm{}}^\alpha (r,E_\nu \mathrm{}^\alpha )}{E}}`$
$`h_{LL^{}}^{\alpha \alpha ^{}}(𝐤)`$ $`=`$ $`(C_L^\alpha E_\nu \mathrm{}^\alpha )\delta _{LL^{}}\delta _{\alpha \alpha ^{}}+\sqrt{\mathrm{\Delta }_L^\alpha }S_{LL^{}}^{\alpha \alpha ^{}}(𝐤)\sqrt{\mathrm{\Delta }_L^{}^\alpha ^{}}`$
$`C_L^\alpha `$ and $`\mathrm{\Delta }_L^\alpha `$ are TB-LMTO potential parameters and $`S_{LL^{}}^{\alpha \alpha ^{}}(𝐤)`$ is the structure matrix. These terms are standard for the LMTO formulation and the reader is referred to the citation  for greater detail. The TB-LMTO secular equation provides the expansion coefficients $`c_{L\alpha }^{j𝐤}`$ via :

$$\underset{L^{}}{}\underset{\alpha ^{}}{}\left[h_{LL^{}}^{\alpha \alpha ^{}}(𝐤)+(E_\nu \mathrm{}^\alpha E^{j𝐤})\delta _{LL^{}}\delta _{\alpha \alpha ^{}}\right]c_{L^{}\alpha ^{}}^{j𝐤}=0$$
(12)
We may now immediately write an expression for the matrix element of the current operator as in equation (9) :

$`\mathrm{\Phi }_{j^{}𝐤}(𝐫)|𝐣|\mathrm{\Phi }_{j𝐤}(𝐫)={\displaystyle \underset{LL^{}}{}}{\displaystyle \underset{\alpha }{}}\overline{c}_{L^{}\alpha }^{j^{}𝐤}c_{L\alpha }^{j𝐤}\{\text{}\varphi _{\nu L^{}}^\alpha (𝐫)|𝐣|\varphi _{\nu L}^\alpha (𝐫)\mathrm{}`$
$`\mathrm{}+\text{}(E^{j𝐤}E_\nu \mathrm{}^\alpha )\varphi _{\nu L^{}}^\alpha (𝐫)|𝐣|\dot{\varphi }_{\nu L}^\alpha (𝐫)\mathrm{}`$
$`\mathrm{}+\text{}(E^{j^{}𝐤}E_\nu \mathrm{}^{}^\alpha )\dot{\varphi }_{\nu L^{}}^\alpha (𝐫)|𝐣|\varphi _{\nu L}^\alpha (𝐫)\mathrm{}`$
$`\mathrm{}+(E^{j𝐤}E_\nu \mathrm{}^\alpha )(E^{j^{}𝐤}E_\nu \mathrm{}^{}^\alpha )\dot{\varphi }_{\nu L^{}}^\alpha (𝐫)|𝐣|\dot{\varphi }_{\nu L}^\alpha (𝐫)\text{}\}`$
We shall now obtain expressions for the right-hand terms by noting the following :

$`𝐣=e\text{}{\displaystyle \frac{d𝐫}{dt}}`$ $`=`$ $`{\displaystyle \frac{e}{ı\mathrm{}}}[𝐫,H]`$
$`\text{}H\varphi _{\nu L}^\alpha (𝐫)`$ $`=`$ $`E_\nu \mathrm{}^\alpha \varphi _{\nu L}^\alpha (𝐫)`$
$`\text{}H\dot{\varphi }_{\nu L}^\alpha (𝐫)`$ $`=`$ $`\varphi _{\nu L}^\alpha (𝐫)+E_\nu \mathrm{}^\alpha \dot{\varphi }_{\nu L}^\alpha (𝐫)`$ (14)
We can write,

$$𝐫=(2\pi /3)^{1/2}r\left[(Y_{1,1}Y_{1,1})\widehat{𝐢}+ı(Y_{1,1}+Y_{1,1})\widehat{𝐣}+2^{1/2}Y_{1,0}\widehat{𝐤}\right]$$

Using the above two equations we get,

$$\varphi _{\nu L^{}}^\alpha (𝐫)^{}𝐫H\varphi _{\nu L}^\alpha (𝐫)d^3𝐫=ı^{\mathrm{}\mathrm{}^{}}E_\nu \mathrm{}^\alpha 𝚪_{LL^{}}_0^{s_\alpha }\varphi _\nu \mathrm{}^{}^\alpha (r)\varphi _\nu \mathrm{}^\alpha (r)r^3𝑑r$$
(15)
where, $`s_\alpha `$ is the atomic sphere radius of the $`\alpha `$-th atom in the unit cell and $`𝚪_{LL^{}}`$ is a combination of Gaunt coefficients  :

$$𝚪_{LL^{}}=\sqrt{\frac{2\pi }{3}}\left[\left(G_{\mathrm{}^{},1,\mathrm{}}^{m^{},1,m}G_{\mathrm{}^{},1,\mathrm{}}^{m^{},1,m}\right)\widehat{𝐢}+ı\left(G_{\mathrm{}^{},1,\mathrm{}}^{m^{},1,m}+G_{\mathrm{}^{},1,\mathrm{}}^{m^{},1,m}\right)\widehat{𝐣}+\sqrt{2}G_{\mathrm{}^{},1,\mathrm{}}^{m^{},0,m}\widehat{𝐤}\right]$$

In order to obtain $`\varphi _{\nu L^{}}^\alpha (𝐫)^{}H𝐫\varphi _{\nu L}^\alpha (𝐫)d^3𝐫`$, we note that $`H=(\mathrm{}^2/2m_e)^2+V(𝐫)`$ so that using the Green’s second identity we can obtain,

$`{\displaystyle }\varphi _{\nu L^{}}^\alpha (𝐫)^{}H𝐫\varphi _{\nu L}^\alpha (𝐫)d^3𝐫=ı^{\mathrm{}\mathrm{}^{}}𝚪_{LL^{}}\{E_\nu \mathrm{}^{}^\alpha {\displaystyle _0^{s_\alpha }}\varphi _\nu \mathrm{}^{}^\alpha (r)\varphi _\nu \mathrm{}^\alpha (r)r^3dr\mathrm{}`$
$`\text{}\mathrm{}+(\mathrm{}^2/2m_e)s_\alpha ^2\varphi _\nu \mathrm{}^\alpha (s_\alpha )\varphi _\nu \mathrm{}^{}^\alpha (s_\alpha )(D_\nu \mathrm{}^{}^\alpha D_\nu \mathrm{}^\alpha 1)\}`$
$`D_\nu \mathrm{}^\alpha `$ is the logarithmic derivative of $`\varphi _\nu \mathrm{}^\alpha (r)`$ at $`r=s_\alpha `$ and are obtained as parameters in the TB-LMTO routines. We define the following integrals :

$`{\displaystyle _0^{s_\alpha }}\varphi _\nu \mathrm{}^{}^\alpha (r)\varphi _\nu \mathrm{}^\alpha (r)r^3𝑑r`$ $`=`$ $`I_{\mathrm{}\mathrm{}^{}}^\alpha `$
$`{\displaystyle _0^{s_\alpha }}\varphi _\nu \mathrm{}^{}^\alpha (r)\dot{\varphi }_\nu \mathrm{}^\alpha (r)r^3𝑑r`$ $`=`$ $`J_{\mathrm{}\mathrm{}^{}}^\alpha `$
$`{\displaystyle _0^{s_\alpha }}\dot{\varphi }_\nu \mathrm{}^{}^\alpha (r)\dot{\varphi }_\nu \mathrm{}^\alpha (r)r^3𝑑r`$ $`=`$ $`K_{\mathrm{}\mathrm{}^{}}^\alpha `$
call,

$$(\mathrm{}^2/2m_e)s_\alpha ^2(D_\nu \mathrm{}^\alpha D_\nu \mathrm{}^{}^\alpha 1)=𝒟_{\mathrm{}\mathrm{}^{}}^\alpha $$

Then the matrix elements for the current operator becomes :

$`_{LL^{},\mu }^{(1)\alpha }=\varphi _{\nu L^{}}^\alpha (𝐫)|j_\mu |\varphi _{\nu L}^\alpha (𝐫)`$ $`=`$ $`{\displaystyle \frac{ı^\mathrm{}\mathrm{}^{}1}{\mathrm{}}}\mathrm{\Gamma }_{LL^{}}^\mu \left[\stackrel{~}{E}I_{\mathrm{}^{}\mathrm{}}^\alpha 𝒟_{\mathrm{}^{}\mathrm{}}^\alpha \varphi _\nu \mathrm{}^\alpha (s_\alpha )\varphi _\nu \mathrm{}^{}^\alpha (s_\alpha )\right]`$
$`_{LL^{},\mu }^{(2)\alpha }=\varphi _{\nu L^{}}^\alpha (𝐫)|j_\mu |\dot{\varphi }_{\nu L}^\alpha (𝐫)`$ $`=`$ $`{\displaystyle \frac{ı^\mathrm{}\mathrm{}^{}1}{\mathrm{}}}\mathrm{\Gamma }_{LL^{}}^\mu \left[\stackrel{~}{E}J_{\mathrm{}^{}\mathrm{}}^\alpha +I_{\mathrm{}^{}\mathrm{}}^\alpha 𝒟_{\mathrm{}^{}\mathrm{}}^\alpha \dot{\varphi }_\nu \mathrm{}^\alpha (s_\alpha )\varphi _\nu \mathrm{}^{}^\alpha (s_\alpha )\right]`$
$`_{LL^{},\mu }^{(3)\alpha }=\dot{\varphi }_{\nu L^{}}^\alpha (𝐫)|j_\mu |\varphi _{\nu L}^\alpha (𝐫)`$ $`=`$ $`{\displaystyle \frac{ı^\mathrm{}\mathrm{}^{}1}{\mathrm{}}}\mathrm{\Gamma }_{LL^{}}^\mu \left[\stackrel{~}{E}J_{\mathrm{}\mathrm{}^{}}^\alpha I_{\mathrm{}^{}\mathrm{}}^\alpha 𝒟_{\mathrm{}^{}\mathrm{}}^\alpha \varphi _\nu \mathrm{}^\alpha (s_\alpha )\dot{\varphi }_\nu \mathrm{}^{}^\alpha (s_\alpha )\right]`$
$`_{LL^{},\mu }^{(4)\alpha }=\dot{\varphi }_{\nu L^{}}^\alpha (𝐫)|j_\mu |\dot{\varphi }_{\nu L}^\alpha (𝐫)`$ $`=`$ $`{\displaystyle \frac{ı^\mathrm{}\mathrm{}^{}1}{\mathrm{}}}\mathrm{\Gamma }_{LL^{}}^\mu [\text{}\stackrel{~}{E}K_{\mathrm{}\mathrm{}^{}}^\alpha +J_{\mathrm{}^{}\mathrm{}}^\alpha J_{\mathrm{}\mathrm{}^{}}^\alpha \mathrm{}`$
$`\mathrm{}𝒟_{\mathrm{}^{}\mathrm{}}^\alpha \dot{\varphi }_\nu \mathrm{}^\alpha (s_\alpha )\dot{\varphi }_\nu \mathrm{}^{}^\alpha (s_\alpha )\text{}]`$
where, $`\stackrel{~}{E}=E_\nu \mathrm{}^\alpha E_\nu \mathrm{}^{}^\alpha `$

The transition term $`T^{jj^{}}(𝐤)`$ has to be written in terms of the normalized wavefunction.

The normalizing factor for the wavefunctions are obtained from :

$`N_𝐤^j`$ $`=`$ $`{\displaystyle d^3𝐫\mathrm{\Phi }_{j𝐤}^{}(𝐫)\mathrm{\Phi }_{j𝐤}(𝐫)}`$
$`=`$ $`{\displaystyle \underset{L}{}}{\displaystyle \underset{\alpha }{}}|\overline{c}_{L\alpha }^{j𝐤}|^2\left\{𝒥_{L\alpha }^{(1)}+2(E^{j𝐤}E_\nu \mathrm{}^\alpha )𝒥_{L\alpha }^{(2)}+(E^{j𝐤}E_\nu \mathrm{}^\alpha )^2𝒥_{L\alpha }^{(3)}\right\}`$
where,

$`𝒥_{L\alpha }^{(1)}`$ $`=`$ $`{\displaystyle _0^{s_\alpha }}\left|\varphi _{\nu L}^\alpha (r)\right|^2r^2𝑑r`$
$`𝒥_{L\alpha }^{(2)}`$ $`=`$ $`{\displaystyle _0^{s_\alpha }}\varphi _{\nu L}^\alpha (r)^{}\dot{\varphi }_{\nu L}^\alpha (r)r^2𝑑r`$
$`𝒥_{L\alpha }^{(3)}`$ $`=`$ $`{\displaystyle _0^{s_\alpha }}\left|\dot{\varphi }_{\nu L}^\alpha (r)\right|^2r^2𝑑r`$
Using the secular equation (12), the expression for the transition term becomes,

$`T^{jj^{}}(𝐤)=\left(N_𝐤^jN_𝐤^j^{}\right)^{1/2}|\text{}{\displaystyle \underset{\mu }{}}{\displaystyle \underset{LL^{}}{}}{\displaystyle \underset{\alpha }{}}\overline{c}_{L^{}\alpha }^{j^{}𝐤}c_{L\alpha }^{j𝐤}\{_{LL^{},\mu }^{(1)\alpha }+(E^{j𝐤}E_\nu \mathrm{}^\alpha )_{LL^{},\mu }^{(2)\alpha }\mathrm{}`$
$`\mathrm{}+(E^{j^{}𝐤}E_\nu \mathrm{}^{}^\alpha )_{LL^{},\mu }^{(3)\alpha }+(E^{j𝐤}E_\nu \mathrm{}^\alpha )(E^{j^{}𝐤}E_\nu \mathrm{}^{}^\alpha )_{LL^{},\mu }^{(4)\alpha }\left\}\text{}\right|^2`$
The equation (10) provides an expression for the optical conductivity where both the transition matrix and the energy resolved joint density of states are expressed as functions of energy and frequency. As we shall show in a subsequent communication, that within the ASR formalism, this is the form in which the information about the constituents are input and the configuration averaged correlation function for the alloy may be expressed as :

$$S(\omega )=(\pi /3)dET^{eff}(E,\omega )J(E,\omega )$$
(20)
where,

$$J(E,\omega )=n_v(E)n_c(E+\omega )[\text{}1+\mathrm{\Lambda }(E,\omega )J(E,\omega )]$$

and,

$$T^{eff}(E,\omega )=T(E,\omega )+\delta T(\text{}E,\omega ,\mathrm{\Sigma }(E,\omega ))$$

where, $`\mathrm{\Sigma }(E,\omega )`$ is the self-energy due to disorder scattering and $`\mathrm{\Lambda }(E,\omega )`$ the corresponding vertex correction. The details of the derivation will be communicated in a subsequent paper .

## 3 Calculational Details and Results

The primitive cell for the ideal perovskite structure $`ABC_3`$ is illustrated in figure 1 (a). For the class of compounds we are interested in, the generic chemical formula is $`ABO_3`$. $`A`$ is a mono or divalent cation, $`B`$ is a tetra or penta-valent metal. In the paraelectric phase there is full cubic symmetry. It can be thought of as lattice of corner sharing oxygen octahedra with inter-penetrating simple cubic lattices of $`A`$ and $`B`$. The $`B`$ cations sit in the centre of the octahedral O cage, while the $`A`$ metal ions sit in the 12-fold coordinated sites between the octahedra. In our case the body centre position is occupied by the Ti atom, the edges by alkaline earth atoms and the face centres by O atoms. The space group is $`O_h^1`$ and the corresponding Brilluoin zone is shown in figure 1 (b). Both the A and B atoms are situated at sites with full cubic ($`O_h`$) point symmetry, while the O atoms have tetragonal ($`D_{4h}`$) symmetry.

The electronic configuration of the alkali earth atoms are as follows :

| Atom | Deep | Shallow | Valence | Unoccupied |
| --- | --- | --- | --- | --- |
|  | Core | Core |  |  |
| Ca | $`1s^22s^22p^63s^23p^6`$ | - | $`4s^2`$ | $`3d4p`$ |
| Sr | $`1s^22s^22p^63s^23p^63d^{10}4s^2`$ | $`4p^6`$ | $`5s^2`$ | $`4d5p4f`$ |
| Ba | $`1s^22s^22p^63s^23p^63d^{10}4s^24p^64d^{10}5s^2`$ | $`5p^6`$ | $`6s^2`$ | $`5d6p4f`$ |
| Ti | $`1s^22s^22p^63s^23p^6`$ | - | $`3d^24s^2`$ | $`4p`$ |
| O | $`1s^2`$ | - | $`2s^22p^4`$ | $`3s3d`$ |

Since we wish to take into account the shallow core states, to include the transitions from these to the conduction band at large enough optical frequencies, the energy range is about 40 eV (3 Ryd) and the single panel LMTO cannot be made to be accurate over this range, we have carried out a two panel calculation, with the $`E_\nu \mathrm{}^\alpha `$ lying in the lower energy range in one panel and in the upper energy range in the other. The minimal basis set used in the two panels are the following :

| $`CaTiO_3`$ | |
| --- | --- |
| Lower Panel | Ca $`4s4p3d`$, Ti $`4s4p3d`$, O $`2s2p(3d)`$ |
| Upper Panel | Ca $`4s4p3d`$, Ti $`4s4p3d`$, O $`3s2p(3d)`$ |
| $`SrTiO_3`$ | |
| Lower Panel | Sr $`5s4p4d(4f)`$, Ti $`4s4p3d`$, O $`2s2p(3d)`$ |
| Upper Panel | Sr $`5s5p4d(4f)`$, Ti $`4s4p3d`$, O $`3s2p(3d)`$ |
| $`BaTiO_3`$ | |
| Lower Panel | Ba $`6s5p5d(4f)`$, Ti $`4s4p3d`$, O $`2s2p(3d)`$ |
| Upper Panel | Ba $`6s6p3d(4f)`$, Ti $`4s4p3d`$, O $`3s2p(3d)`$ |

The states in parentheses are unfilled states which have been downfolded in our calculations. The figure 2 shows the band structure of the three titanates.

Let us first look at the leftmost figure for $`CaTiO_3`$ . The Ca $`3p`$ core level lies around –27 eV and not shown in this figure. The narrow band around –20 eV is the O $`2s`$ band. The nine valence bands just below the Fermi level are derived from hybridized Ti $`4s`$ and O $`2p`$. An indirect band gap appears between the valence band top at the R point and the conduction band minimum at the $`\mathrm{\Gamma }`$ point. $`CaTiO_3`$ shows an indirect band gap ($`\mathrm{\Gamma }`$-R) of 1.6 eV, in the absence of the scissors operation. The experimentally reported indirect gap is 3.5 eV . This discrepancy is characteristic of the Local density Approximation (LDA) upon which the TB-LMTO is based. In the conduction band region we have bands originating from (in ascending order of energy) Ti $`3dt_{2g}`$ triplet, a singlet arising from Ca $`4s`$ and a doublet from Ti $`3de_g`$ . Then comes the bands which originate from the Ca $`3de_g`$ doublet and the Ca $`3dt_{2g}`$ triplet. Finally we have the Ti $`4p`$ and Ca $`4p`$ based bands and finally the band based on Ca $`4s`$. We note that for $`CaTiO_3`$ , Ca and Ti $`3d`$ based bands overlap and hybridize in the conduction region.

For $`SrTiO_3`$ , in the lower panel, the Sr $`4p`$ level now sits almost atop the O $`2s`$ band, giving rise to a rather broad (as compared to $`CaTiO_3`$ ) $`sp`$ hybridized band just below –20 eV. The subsequent analysis of the bands is rather similar to $`CaTiO_3`$ . However, the band gap is now direct and $``$ 1.4 eV. Earlier band structure calculations of Mo et al and Kimura et al yield indirect band gaps of $``$ 1.45 eV and $``$ 1.79 eV respectively. The experimental direct band gap is around 3.2 eV.

For $`BaTiO_3`$ , in the lower panel, the Ba $`5p`$ shallow core level now crosses and lies above the O $`2s`$ band. The band gap is direct and $``$ 1.2 eV. The band structure is almost identical to the pseudopotential calculations of King-Smith and Vanderbilt , whose band gap was also direct and $``$ 1.8 eV. The experimental band gap turns out to be $``$ 3.2 eV .

For all three compounds, our calculations show a characteristic flatness of the lowest conduction band along $`\mathrm{\Gamma }`$ to X. This agrees with earlier works of Cardona , Matheiss , Harrison , Wolfram and Ellialtioğlu  and King-Smith and Vanderbilt . This observed flatness is related to certain unusual features in the density of states and optical conductivity, which appear to be characteristic of pseudo- two-dimensional systems.

Figure 3 shows the densities of states for the three titanates. The densities of states reflect the detailed band structure we have described above. Earlier works on the density of states were based on different methods. Michel-Calendini and Mesnard  and Pertosa and Michel-Calendini  have used parameterized tight-binding and adjusted LCAO based methods for $`BaTiO_3`$ . Their density of states is in agreement with ours, with the band gap difference characteristic of LSDA methods like the TB-LMTO. Similarly, Matheiss  used the LCAO and Perkins and Winter  used the extended Húkel basis for $`SrTiO_3`$ . Again their band structures and densities of states are in agreement with ours, with the exception of the band gap. Even earlier works on $`SrTiO_3`$ by Zook and Castelman  and Soules et al also show reasonable agreement. For $`CaTiO_3`$ we may compare our results with those of Ueda et al, which agree reasonably well with our results.

Figure 4 displays the transition rates $`T(E,\omega )`$ for the three titanates, shown here as functions of the initial energy of the excited electron and the incident photon energy (frequency). It is clear from the figure that the transition rate is strongly dependent on the energy-frequency variables for all the three compounds. The usual assumption of a transition matrix, weakly dependent on energy and frequency is certainly not valid in any of the three cases -.

In figure 5 we compare the imaginary part of the dielectric function with the scaled joint-density of states/$`\omega ^2`$. If the transition rate were independent of energy and frequency, they should be the same. The behaviour of the two are similar, but the relative weights of the structures across the frequency range are clear indications of the energy-frequency dependence of the transition rates.

$`CaTiO_3`$  :

The effect of energy-frequency dependence of the transition rate has a large effect for the optical properties of $`CaTiO_3`$ . If we compare the results reported in  with our figure 6 we note that although in the earlier work the joint density of states does reproduce the peaks at lower frequencies, the relative heights are not replicated. Looking at the lower panel of the figure, we may assign the peak at 4.5 eV to the transitions : O $`2p`$ $``$ Ti $`3d`$-$`t_{2g}`$ at the R and X-points. The next and highest peak arises because of the nearby two unresolved peaks due to the transitions : O $`2p`$ $``$ Ca $`4s`$ at the M-point (at 6.3 eV) and O $`2p`$ $``$ Ca $`3d`$-$`e_g`$ at the M-point (at 6.8 eV). The third peak at 7.5 eV may be assigned to the transitions : O $`2p`$ $``$ Ti $`3d`$-$`t_{2g}`$ at the R-point and O $`2p`$ $``$Ca $`3d`$-$`e_g`$ at the X-point. At higher frequencies, the theory does not tally well with experiment. The peak at 10 eV is not reproduced except as a shoulder. The real part of the dielectric function $`ϵ_1(\omega )`$ is obtained by a Kramers-Krönig transformation from the imaginary part. This is shown in the top panel of figure 6. The discrepancies at high frequencies could be due to the fact that in the scissors type approach we have provided a rigid shift to the conduction bands. In a full fledged many-body GW technique, which is our ultimate aim to produce, the shift, due to the self-energy will turn out to be energy (frequency) dependent.

$`SrTiO_3`$  :

Let us now examine the figure 7. As in the case of $`CaTiO_3`$ , here too, the effect of energy-frequency dependence of the transition rate reproduces the correct relative heights of the peaks in $`ϵ_2(\omega )`$. The shoulder peak at around 4 eV may be attributed to the transitions : O $`2p`$ at $``$ Ti $`3dt_{2g}`$ and O $`2p`$ $``$ Ti $`3de_g`$ both at the $`\mathrm{\Gamma }`$ point. The high peak at 5 eV due to O $`2p`$ $``$ Ti $`3d`$-$`e_g`$ at the $`\mathrm{\Gamma }`$ point. A third shoulder peak at 6 eV is due to the transition O $`2p`$ $``$ Ti $`3d`$-$`e_g`$ also at the $`\mathrm{\Gamma }`$ point. As in the case of $`CaTiO_3`$ , the structure in the high frequency part has both lower heights and are shifted to higher frequencies. The cause is the same as discussed above.

$`BaTiO_3`$ :

Lastly, let us look at figures 6-8. If we compare the shape of the imaginary part of the dielectric function $`ϵ_2(\omega )`$ obtained by our accurate estimate of the transition rate with that of , we note that agreement with experiment  is much better when we take the energy-frequency dependences of the transition matrix into account. The relative weights of the low frequency peaks, at 3.8 eV and 5 eV are correctly reproduced here. The lower peak is attributed to the transition from the O $`2p`$ to the Ti $`3d`$-$`t_{2g}`$ band and from the O $`2p`$ to the Ti $`3d`$-$`e_g`$ band both at the $`\mathrm{\Gamma }`$ points. The next higher peak is the because of the transition from the O $`2p`$ to the Ti $`3d`$-$`e_g`$ band at the $`\mathrm{\Gamma }`$ point. Our present study also indicates a peak around 10 eV and the features at higher frequencies follow the experimental results closely, although the amplitude seems to have been underestimated as compared to the low frequency results. In all cases, although the lower frequency part is much better reproduced, the high frequency structures in the theoretical result is shifted upwards. As before, we argue that this is probably an artifact of the rigid shift of the scissors type approach. A energy-frequency dependent self-energy of the type given by the GW method should provide the necessary correction. In addition, the wrong heights at higher frequencies could also arise from the fact that we have neglected transitions to some of the higher energy conduction bands. A more complete, perhaps a three panel calculation at higher energies, should correct this. Alternatively, we could use the higher order NMTOs , when they are available, since they span a much larger energy range.

## 4 Conclusion

We have proposed here a modified expression for the optical conductivity as a convolution of an energy-frequency dependent transition matrix and the energy resolved joint density of states. The main motivation was to generalize it to disordered systems, where the traditional reciprocal space formulation breaks down due to the failure of Bloch’s Theorem. In order to be confident in our new formulation we have applied it here to the three alkaline earth perovskite titanates in their paraelectric phases. The results are in reasonable agreement with experimental data. The agreement is as good as we can expect from a LDA calculation. This formulation will now form the starting point of a two-fold generalization : first, combining with the ASR to random systems and as then as a starting point for a many-body GW formulation.

## References


text:
# Effective lagrangian approach to structure of selected nuclei far from stability

## I Introduction

The study of nuclei far from the $`\beta `$-stability line has drawn the attention of nuclear physicists. The implications of the structure and reaction cross-sections from these nuclei play an important role in the description of nucleosynthesis processes such as the r-process, which takes place in the region of neutron rich nuclei. In addition to this, these nuclei are the perfect place to test the validity of some successful methods and theories, which have rendered satisfactory results along the stability line for medium-heavy nuclei. The development of new experimental facilities and the implementation of new techniques have already given experimental data for some of these, like the doubly-magic nuclei $`{}_{50}{}^{132}\text{Sn}_{82}^{}`$ and $`{}_{50}{}^{100}\text{Sn}_{50}^{}`$. Some of the new approaches being tested are those of relativistic mean-field models. In this paper we are going to deal with a relativistic mean-field theory derived from the chiral effective lagrangian of Furnstahl, Serot and Tang CEL . This lagrangian, which incorporates the symmetries of QCD, particularly a non-linear realization of chiral symmetry, is built as an effective field theory and contains the lowest lying hadronic degrees of freedom as the main ingredients. Though it reproduces the ground-state properties of stable doubly-magic nuclei, its predictability far from the $`\beta `$-stability region has not been tested, especially the convergence of the calculations as the number of effective terms in the lagrangian increases.

Relativistic mean-field models can account for a large number of bulk properties of nuclei and there are different methods that have produced acceptable results. Recently, Toki, et al. Toki  used a relativistic mean-field approach to calculate properties of nuclei from the proton to the neutron drip lines, extending the calculations to super-heavy nuclei. The good agreement with known experimental data shows how relativistic mean-field models can account for a variety of phenomena in the nuclear many-body system. Toki and his co-workers, using a mean effective lagrangian, have an extensive program underway on applications of this approach to astrophysics, in particular to element formation in supernovas Toki-2 .

The idea of using effective field theories to describe the nuclear problem is an increasing field of study, an account of recent results can be found in Furnstahl1 . The relativistic mean-field approach to the nuclear many-body problem has been successful in describing medium-size nuclei, and its success can be understood under the perspective of effective field theory (EFT) and density functional theory (DFT) Furnstahl ; Ser-Wal . The success of previous relativistic mean-field models, like the original Walecka model Wal-book ; Ser-Wal  and its extensions to include nonlinear couplings of the $`\sigma `$ field, is now understood by applying the ideas of naturalness from EFT Furnstahl2 . A comparison of various mean-field models and an account of their success was presented by Furnstahl, et al Furnstahl3 . In that paper it was shown, using the EFT approach and NDA, why various mean-field approaches have been successful and that the use of different degrees of freedom to describe nuclear properties corresponds to different organizational principles. Thus a description of the nuclear many-body system based on nucleon and meson fields, as in this approach, or an expansion in nucleon densities, as in the Skyrme model, are equivalent. The principles of EFT rely on the fact that there exist natural scales and in order to understand a particular phenomenon it is enough to use probes that can resolve the dynamics at that scale. These probes are the relevant degrees of freedom needed to describe the system. The most general lagrangian density is built from these interacting fields paying attention to symmetries imposed by an underlying theory (QCD in this case) and arranged by some organizing principle, like the naive dimensional analysis (NDA) from Georgi and Manohar NDA-1 ; NDA-2 . The unknown dynamics, of heavier degrees of freedom, is integrated out and appears as coupling constants in the theory. These are determined by fitting the theory to known experimental data. The number of terms in this EFT lagrangian is infinite and, in order to give predictive power to the model, it is necessary to have an organizing principle that groups together terms that contribute at the same level. In this way it is possible to truncate the expansion at some arbitrary order and be certain that all non-redundant terms, of the same order, have already been taken into account.

The inclusion of new interaction terms in the lagrangian aims to give a better description of the energy functional, thus going beyond the Hartree approximation and incorporating exchange-correlation effects. The new terms are non-renormalizable, a distinction with standard RMF models, which truncate the effective lagrangian at this level without any underlying physical justification. A chiral effective lagrangian has been derived by Furnstahl, Serot, and Tang CEL , which incorporates a non-linear realization of chirial symmetry and uses the lowest lying hadronic levels: i) pions, whose field appears as the phase of a chiral rotation of the identity matrix, ii) nucleons, described by isospinor field N, iii) an isoscalar-vector field, whose mass is taken to be equal to the $`\omega `$-meson mass and iv) an isoscalar-scalar field which simulates correlated two-pion exchange with an effective mass around 500 MeV, and v) an isovector field, the $`\rho `$-meson, to take into account the symmetry energy in nuclei. By applying the relativistic mean-field approximation, a set of equations of motion can be derived from the effective lagrangian in which the meson fields act as classical fields.

The connection to DFT is made by considering the expansion of the relativistic mean-field lagrangian as an expansion of the energy functional of the nuclear many-body problem in terms of nucleon densities and auxiliary classical meson fields. According to the principles of DFT Kohn ; DFT-QHD-1 , knowledge of the exact energy functional can be used, by optimizing it with respect to the fermion densities and auxiliary potentials, to calculate the exact ground-state scalar and vector densities, energy, and chemical potential for the fully interacting many-fermion system Many-body . These optimal observables are used here to compare the experimental values with the calculated ones. Other observables are not expected to be well reproduced, but a comparison with some of them is included in this paper in order to understand the extent to which the theory can be applied, as well as to find new directions in which more work needs to be done. In this way the EFT principles combined with DFT methods give an approach to the nuclear many-body problem that uses the simplicity of solving the self-consistent Hartree equations in which new contributions coming from the interacting fields can be incorporated in a systematic and controlled way. The expansion parameters that make the truncation of the effective lagrangian possible in the nuclear structure case are essentially the ratios of mean isoscalar, scalar and vector fields to the nucleon mass $`(1/3)`$ and the ratio of the Fermi momentum to the nucleon mass $`(1/4)`$.

In this paper we study the convergence of the chiral effective lagrangian (CEL) approach to the nuclear many-body problem when extrapolated to selected doubly-magic nuclei far from the $`\beta `$-stability region. The study focuses at how well additional levels of approximation of the energy functional reproduce the above ground-state properties of the selected, spherical, doubly-magic nuclei. In addition to this, we also examine the effect of fitting a larger set of observables, in the mean, along the stability line. We center our attention on the four doubly-magic nuclei $`{}_{50}{}^{132}\text{Sn}_{82}^{}`$, $`{}_{50}{}^{100}\text{Sn}_{50}^{}`$, $`{}_{28}{}^{48}\text{Ni}_{20}^{}`$ and $`{}_{28}{}^{78}\text{Ni}_{50}^{}`$ chosen for their relevance to the nucleosynthesis processes. Here we compare the predictions of the CEL model at various levels of approximation with the most recent experimental results for these nuclei. We compare results of nuclear binding energies for these nuclei and also extend this analysis to neighboring nuclei that differ by one particle or one hole from the doubly-magic nuclei thus comparing the values of the chemical potential. We find in both cases remarkable agreement with recent experimental data. In addition to this we look at the convergence for single-particle levels, both for neutrons and protons. We examine how sensitive these calculated spectra are to the various levels of approximation in the CEL, as new interaction terms come into play. Nuclear densities are also shown for the “proton rich” nucleus $`{}_{50}{}^{100}\text{Sn}_{50}^{}`$ and the neutron rich one $`{}_{50}{}^{132}\text{Sn}_{82}^{}`$. These densities are in very good agreement with other calculations Lalazissis  using the relativistic Hartree Bogoliubov equations. According to the EFT approach used here, the systematic inclusion of interaction terms will approach the true energy functional, going beyond the Hartree level and including exchange-correlation terms. Thus, here we include additional pairing interactions only to the extent they are systematically included through the additional terms in the CEL and the fitting of the constants. The goal of the present work is to study how well the current level of approximation in the CEL reproduces the ground-state properties of the selected nuclei without explicit use of the pairing interactions.

The calculations are done using an independently developed code, which solves the self-consistent Hartree equations at any level of approximation. The code has been tested successfully by reproducing previous calculations. The coupling constants, for each level of approximation, were obtained by Furnstahl, et al. CEL  by fitting in the mean to properties of stable doubly-magic nuclei leading to different parameter sets according to the level of approximation CEL ; Ser-Wal . We use here these results and use the same name for the parameter sets, i.e. W1, Q1, Q2, G1 and G2 in increasing level of approximation, respectively. In addition to these, we include two additional sets: L2 and NLC. The parameter set L2 corresponds to the same level of approximation as the set W1, it contains no non-linear terms in the meson fields. The other parameter set, NLC, has the same level of approximation as Q1. Both L2 and NLC were fit to describe different nuclear properties than those corresponding to the sets W1, Q1, Q2, G1 and G2 111The NLC set describes the deformation of selected medium-weight nuclei deformed . They also differ from these in the number of nuclei used to fit the parameters. The values of the constants used in this paper are given in Table 1, and the fitting procedure is discussed in more detail later in this paper.

Other approaches have been applied to studies of nuclei far from stability with various degrees of success. Neutron and proton skin formation, the reduction of the spin-orbit interaction and the realization of pseudo-spin symmetry are some of the phenomena studied recently by various authors Lenske ; Meng ; skins . Shell-model calculations using the CD-Bonn effective potential modified by the G-matrix and renormalized using the Q-box method have been used to study the importance of the $`{}_{}{}^{1}\text{S}_{0}^{}`$ and $`{}_{}{}^{3}\text{P}_{2}^{}`$ partial waves in reproducing the constancy of the $`2_1^+0_1^+`$ level spacing which is apparent in Sb nuclei England . Some of the methods that have been tested on these nuclei with various degrees of success are the density dependent relativistic Hartree (DDRH) Hofmann ; Lenske , relativistic continuum Hartree Bogoliubov (RCHB) Meng , relativistic Hartree Bogoliubov (RHB) Lalazissis , Hartree-Fock-Bogoliubov Grasso  and relativistic Dirac-Hartree-Bogoliubov (DHB) Carlson . In these methods pairing correlations have been taken into account using a phenomenological force like the Gogny force Meng ; Lalazissis  or a density-dependent zero-range interaction Hofmann . Other authors Estal ; Hofmann  used the BCS approach with a constant pairing strength to take into account the effects of the continuum. Perhaps the most self-consistent approach has been the use of the RHB, in which ph-interactions and pairing correlations have been taken into account in a unified way by solving self-consistently the RHB-equations with the Klein-Gordon equations that describe the meson fields Lalazissis ; Carlson . Other authors have derived new parameter sets of known potentials, e.g. Nilsson Zhang , Groningen Hofmann , to fit the new experimental data of binding energies, single-particle levels, and nuclear radii for these nuclei far from stability. Relativistic mean field models (RMF), which have been successful in describing bulk properties of stable nuclei, are being tested in these new regimes. Some of the models use the $`\sigma \omega `$ lagrangian with linear and non-linear $`\sigma `$ interactions Lalazissis ; Zhang . Applications of DFT to the nuclear many-body problem have been carried out using the QHD-I and QHD-II lagrangians DFT-QHD-1 ; DFT-QHD-2 ; DFT-QHD-3 . Here the exchange-correlations are taken directly from the applications of many-body techniques in infinite nuclear matter, but extensions to nuclei far from stability have not yet been performed in this approach. Direct application of the QHD-II lagrangian to the doubly-magic Sn isotopes to calclulate single-particle level spectrum and nucleon densities can be found in Bachman .

The combination of the fundamental idea of DFT and the realization that an approximation to the exact energy functional can be derived using EFT methods is a new approach to the nuclear many-body problem. As such, it is still in development. To the extent that a sufficient number of terms are retained in the effective lagrangian to provide the correct energy functional, one has actually developed the effective field theory for QCD at the nuclear density domain. Extensions to other density regimes still has to be explored. This paper explores how additional terms in the effective lagrangian contribute to the results for ground-state properties of selected nuclei far from stability. The EFT methods in this chiral effective lagrangian approach have already shown that the coupling constants are all natural CEL , therefore the relevant degrees of freedom have been correctly taken into account and the NDA works. Knowing how well this EFT approach behaves at these extreme cases of nuclei far from stability will give a firmer ground for the theory. Predictions for the properties of these nuclei is also, of course, of direct relevance to experiments, both ongoing and planned GSI , and to element formation in supernovas.

In this paper we see that the increasing level of approximation approaches the total binding energy of the selected nuclei. There is also very good agreement with the binding energies of neighboring nuclei, which differ by one particle or one hole from the doubly-magic nucleus, i.e. the chemical potential. The spins and parities of these nuclei, to the extent to which they have been measured, are also correctly given. In addition, we show the calculated single-particle excitation spectra and examine the effects of additional levels of approximation. Finally, we present the nucleon densities for neutron rich and neutron deficient nuclei predicted with this approach.

The following two sections explain the effective lagrangian used in this paper and describe the calculations, and in the last two sections results are presented and conclusions are drawn.

## II Calculations

The chiral effective lagrangian used here was constructed using the relevant lowest lying hadronic degrees of freedom CEL . The pion field is introduced as the phase of a chiral rotation of the identity matrix in isospin space. A field $`\xi (x)`$ is defined in the following way:

$$\xi (x)=exp(i\pi (x)/f_\pi ).$$

where the pion field $`\pi (x)`$ is defined by $`\pi (x)=\frac{1}{2}\stackrel{}{\tau }\stackrel{}{\pi }`$

Nucleons are included as isospinor fields, $`N(x)`$, in which the upper component corresponds to the proton and the lower component the neutron.

$$N=\left(\begin{array}{c}p(x)\\ n(x)\end{array}\right)$$

To include a contribution to the symmetry energy of nuclear matter, a $`\rho _\mu `$-field is added to the lagrangian.

A non-linear realization of chiral symmetry is considered following the work of Callan, Coleman, Wess, and Zumino CCWZ . A description of the incorporation of chiral symmetry in the nuclear many-body lagrangian can be found in Wal-book ; Ser-Wal . In this formalism, the non-linear realization of the chiral symmetry is defined by a global transformation, L and R, of the subgroups $`SU(2)_L`$ and $`SU(2)_R`$ such that

$$LR:(\xi ,\rho _\mu ,N)(\xi ^{},\rho _\mu ^{},N^{})$$
(1)
where

$`\xi ^{}(x)`$ $`=`$ $`L\xi (x)h^{}(x)=h(x)\xi (x)R^{},`$ (2)
$`\rho _\mu ^{}(x)`$ $`=`$ $`h(x)\rho _\mu (x)h^{}(x),`$ (3)
$`N^{}(x)`$ $`=`$ $`h(x)N(x).`$ (4)
here $`\rho _\mu (x)=\frac{1}{2}\stackrel{}{\tau }\stackrel{}{\rho }_\mu `$.

In addition to the above fields, an electromagnetic field $`A_\mu `$ is included and the electromagnetic structure of the nucleons has been taken into account. Their anomalous magnetic moments, labeled as $`\lambda _p`$ and $`\lambda _n`$ for proton and neutron respectively, then enter. An isoscalar-vector field $`V_\mu `$ is needed to correctly represent the bulk properties of nuclei. This field is treated as a chiral singlet and its mass is taken to be equal to the $`\omega `$-meson mass. Finally, an isoscalar-scalar field $`\varphi `$, again a chiral singlet, is included to incorporate the observed mid-range N-N attraction. Its mass is determined by fitting the calculations to experimental results.

The various interaction terms present in the effective lagrangian have been arranged following the NDA from Georgi and Manohar NDA-1 ; NDA-2 . Details concerning the construction of the chiral effective lagrangian can be found in CEL  where the full effective lagrangian is developed.

In order to solve the equations of motion derived from this lagrangian we apply the relativistic mean-field approximation in which the meson fields become expectation values and thus are treated as classical fields. In this approximation the pseudo-scalar pion field does not contribute because it has no expectation value. The interplay between these fields, particularly the scalar and vector fields, accounts for the bulk properties of nuclei as is well described in Wal-book ; Ser-Wal . For spherically symmetric systems, as is the case for double-magic nuclei, the spatial components of the vector field vanish. The rho isovector field develops only the non-charged component, $`\rho _0`$, since conservation of charge is imposed. The resulting equations of motion consist of a Dirac equation for the nucleons and a system of non-linear, coupled differential equations for the meson fields.

The Dirac hamiltonian for the nucleon fields takes the form:

$`h(x)`$ $`=`$ $`i\stackrel{}{\alpha }\stackrel{}{}+W(x)+{\displaystyle \frac{1}{2}}\tau _3R(x)+\beta (M\mathrm{\Phi }(x))`$ (5)
$`+{\displaystyle \frac{1}{2}}(1+\tau _3)A(x)`$
$`{\displaystyle \frac{i}{2M}}\beta \stackrel{}{\alpha }(f_\rho {\displaystyle \frac{1}{2}}\tau _3\stackrel{}{}R+f_v\stackrel{}{}W)`$
$`+{\displaystyle \frac{1}{2M^2}}(\beta _s+\beta _v\tau _3)^2A`$
$`{\displaystyle \frac{i}{2M}}\lambda \beta \stackrel{}{\alpha }\stackrel{}{}A`$
Here $`\lambda =\frac{1}{2}\lambda _p(1+\tau _3)+\frac{1}{2}\lambda _n(1\tau _3)`$ and the numerical values used for the anomalous magnetic moments are $`\lambda _p=1.793`$, $`\lambda _n=1.913`$.

The mean meson fields are denoted by $`W=g_vV_0`$, $`\mathrm{\Phi }=g_s\varphi _0`$, $`R=g_\rho b_0`$, and $`A=eA_0`$ respectively. The quantities $`f_\rho ,f_v,\beta _s,\beta _v`$ are parameters fit to experiment (see below). The meson field equations become the following:

$`^2\mathrm{\Phi }+m_s^2\mathrm{\Phi }`$ $`=`$ $`g_s^2\rho _s(x){\displaystyle \frac{m_s^2}{M}}\mathrm{\Phi }^2({\displaystyle \frac{\kappa _3}{2}}+{\displaystyle \frac{\kappa _4}{3!}}{\displaystyle \frac{\mathrm{\Phi }}{M}})`$ (6)
$`+{\displaystyle \frac{g_s^2}{2M}}(\eta _1+\eta _2{\displaystyle \frac{\mathrm{\Phi }}{M}}){\displaystyle \frac{m_v^2}{g_v^2}}W^2`$
$`+{\displaystyle \frac{g_s^2\eta _\rho }{2M}}{\displaystyle \frac{m_\rho ^2}{g_\rho ^2}}R^2+{\displaystyle \frac{\alpha _1}{2M}}[(\stackrel{}{}\mathrm{\Phi })^2+2\mathrm{\Phi }^2\mathrm{\Phi }]`$
$`+{\displaystyle \frac{\alpha _2g_s^2}{2Mg_v^2}}(\stackrel{}{}W)^2`$
Here $`\rho _s`$ is the baryon Lorenz scalar density and $`g_s`$, $`m_s`$, $`\kappa _3`$, $`\kappa _4`$, $`\eta _1`$, $`\eta _2`$, $`g_v`$, $`g_\rho `$, $`\alpha _1`$, $`\alpha _2`$ are again parameters fit to experiment. Furthermore,

$`^2W+m_v^2W`$ $`=`$ $`g_v^2[\rho _B(x)+{\displaystyle \frac{f_V}{2M}}\stackrel{}{}(\rho _B^T(x)\widehat{𝐫})]`$ (7)
$`(\eta _1+{\displaystyle \frac{\eta _2}{2}}{\displaystyle \frac{\mathrm{\Phi }}{M}}){\displaystyle \frac{\mathrm{\Phi }}{M}}m_v^2W`$
$`{\displaystyle \frac{1}{3!}}\zeta _0W^3+{\displaystyle \frac{\alpha _2}{M}}(\stackrel{}{}\mathrm{\Phi }\stackrel{}{}W+\mathrm{\Phi }^2W)`$
$`{\displaystyle \frac{e^2g_v}{3g_\gamma }}\rho _{\mathrm{chg}}(x)`$
Here $`\rho _B`$ is the baryon density, $`\rho _B^T`$ is the baryon tensor density, $`\rho _{\mathrm{chg}}`$ is the charge density and $`f_v`$, $`\zeta _0`$ are parameters. In addition,

$`^2R+m_\rho ^2R`$ $`=`$ $`{\displaystyle \frac{1}{2}}g_\rho ^2[\rho _3(x)+{\displaystyle \frac{f_\rho }{2M}}\stackrel{}{}(\rho _3^T(x)\widehat{𝐫})]`$ (8)
$`\eta _\rho {\displaystyle \frac{\mathrm{\Phi }}{M}}m_\rho ^2R{\displaystyle \frac{e^2g_\rho }{g_\gamma }}\rho _{\mathrm{chg}}(x)`$
Here $`\rho _3`$ and $`\rho _3^T`$ are the isovector densities, $`f_\rho `$, $`\eta _\rho `$, $`g_\rho `$ are parameters and $`g_\gamma `$=5.01, is the coupling of the photon to the $`\omega `$-meson. Finally,

$$^2A=e^2\rho _{\mathrm{chg}}(x)$$
(9)
where $`\rho _{\mathrm{chg}}`$ is the charge density. To solve the Dirac equation and obtain the single-particle energy levels one has

$$h\psi _\alpha (x)=E_\alpha \psi _\alpha (x)$$
(10)
The Dirac solutions are expressed as,

$$\psi _\alpha (x)=\left(\begin{array}{c}\frac{i}{r}G_a(r)\mathrm{\Phi }_{\kappa m}\\ \frac{1}{r}F_a(r)\mathrm{\Phi }_{\kappa m}\end{array}\right)\zeta _t$$
(11)
where the $`\mathrm{\Phi }_{\kappa m}`$ is a spin spherical harmonic and t is equal to 1/2 for protons and -1/2 for neutrons. Inserting this into Eq.(10) and using Eq.(5) a set of two coupled first-order differential equations for the G and F functions is obtained:

$$\left(\frac{d}{dr}+\frac{\kappa }{r}\right)G_a(r)[E_aU_1(r)+U_2(r)]F_a(r)U_3G_a(r)=0$$
(12)
$$\left(\frac{d}{dr}\frac{\kappa }{r}\right)F_a(r)+[E_aU_1(r)U_2(r)]G_a(r)+U_3F_a(r)=0$$
(13)
where the single-particle potentials are given by

$`U_1(r)`$ $``$ $`W(r)+t_aR(r)+(t_a+{\displaystyle \frac{1}{2}})A(r)`$ (14)
$`+{\displaystyle \frac{1}{2M^2}}(\beta _s+2t_a\beta _V)^2A(r)`$
$`U_2(r)`$ $``$ $`M\mathrm{\Phi }(r)`$ (15)
$`U_3(r)`$ $``$ $`{\displaystyle \frac{1}{2M}}\{f_VW^{}(r)+t_af_\rho R^{}(r)`$ (16)
$`+A^{}(r)[(\lambda _p+\lambda _n)/2+t_a(\lambda _p\lambda _n)]\}`$
Here the prime indicates a radial derivative; e.g. $`W^\mathrm{`}(r)=dW(r)/dr`$.

Once the single-particle wave functions are calculated, the various densities that appear on the r.h.s. of the meson equations can be obtained. They are defined as follows:

$`\rho _s(x)`$ $`=`$ $`{\displaystyle \underset{\alpha }{\overset{occ}{}}}{\displaystyle \frac{2j_a+1}{4\pi r^2}}\left(G_a^2(r)F_a^2(r)\right)`$ (17)
$`\rho _B(x)`$ $`=`$ $`{\displaystyle \underset{\alpha }{\overset{occ}{}}}{\displaystyle \frac{2j_a+1}{4\pi r^2}}\left(G_a^2(r)+F_a^2(r)\right)`$ (18)
$`\rho _B^T(x)`$ $`=`$ $`{\displaystyle \underset{\alpha }{\overset{occ}{}}}{\displaystyle \frac{2j_a+1}{4\pi r^2}}2G_a(r)F_a(r)`$ (19)
$`\rho _3(x)`$ $`=`$ $`{\displaystyle \underset{\alpha }{\overset{occ}{}}}{\displaystyle \frac{2j_a+1}{4\pi r^2}}(2t_a)\left(G_a^2(r)+F_a^2(r)\right)`$ (20)
$`\rho _3^T(x)`$ $`=`$ $`{\displaystyle \underset{\alpha }{\overset{occ}{}}}{\displaystyle \frac{2j_a+1}{4\pi r^2}}(2t_a)2G_a(r)F_a(r)`$ (21)
where the sum goes over the occupied orbitals. In addition to these, the charge density is composed of two pieces: a direct nucleon charge density and the vector meson contribution

$$\rho _{\mathrm{chg}}\rho _d(𝐱)+\rho _m(𝐱)$$
(22)
The direct part is given by

$`\rho _d(x)`$ $`=`$ $`\rho _p(x)+{\displaystyle \frac{1}{2M}}\stackrel{}{}(\rho _\mathrm{a}^T(x)\widehat{𝐫})`$ (23)
$`+{\displaystyle \frac{1}{2M^2}}[\beta _s^2\rho _B(x)+\beta _v^2\rho _3(x)]`$
and the vector meson contribution arising from the coupling of the neutral vector mesons to the photon (VMD) takes the form

$$\rho _m(x)=\frac{1}{g_\gamma g_\rho }^2R+\frac{1}{3g_\gamma g_v}^2W$$
(24)
Here the point proton density $`\rho _p`$ and nucleon tensor density $`\rho _\mathrm{a}^T`$ are given by

$$\rho _p=\frac{1}{2}(\rho _B+\rho _3)$$
(25)
$$\rho _\mathrm{a}^T=\underset{\sigma }{\overset{occ}{}}\psi _\sigma ^{}(x)i\lambda \beta \stackrel{}{\alpha }\widehat{𝐫}\psi _\sigma (x)$$
(26)
To solve the meson equations a Green’s function method is used. The equations are iterated until a consistent solution for all the meson fields is obtained, that is, we obtain a $`0^{\text{th}}`$-order solution to the meson equations by neglecting all non-linear terms on the r.h.s., and we then use this to obtain a $`1^{\text{st}}`$-order solution, continuing until convergence is achieved. Because NDA guarantees that each additional term on the rhs of Eqs. (6) - (9) is smaller than the previous one, convergence is both expected and obtained.

The whole system of Eqs. (12), (13) and (6) - (9) is solved self-consistently until a global convergence is reached.

The values of the various constants used in this paper are given in Table 1 with a label indicating the parameter set. These values are taken from CEL ; Ser-Wal . The constants were obtained by fitting several nuclear properties CEL . From the 16 constants in 1 the last 3 where determined by fitting to electromagnetic properites of the nucleon. The sets labeled W1, Q1, Q2, G1 and G2 were obtained using a weighted generalized $`\chi ^2`$ defined by

$$\chi ^2=\underset{i}{}\underset{X}{}[\frac{X_{\mathrm{exp}}^{(i)}X_{\mathrm{th}}^{(i)}}{W_X^{(i)}X_{\mathrm{exp}}^{(i)}}]^2$$

to fit a total of 29 observables listed as follows:

* The binding energies per nucleon E/B with W=0.15%;
* The rms charge radii $`r^2_{\mathrm{chg}}^{\frac{1}{2}}`$ with W=0.2%;
* the diffraction-minimum-sharp, d.m.s., radii Rdms with W=0.15%;
* The spin-orbit splittings $`\mathrm{\Delta }E_{SO}`$ of the least-bound proton and neutrons with W=5% for $`{}_{}{}^{16}\text{O}`$, 15% for $`{}_{}{}^{208}\text{Pb}`$, 25% for $`{}_{}{}^{40}\text{Ca}`$ and $`{}_{}{}^{48}\text{Ca}`$, and 50% for $`{}_{}{}^{88}\text{Sr}`$; 222Note that the spin-orbit splitting arises predominantly from the mean isoscalar scalar and vector fields that are determined by the bulk properties Wal-book ; Ser-Wal .
* The proton energy $`E_p(1h_{9/2})`$ and the proton level splitting $`E_p(2d_{3/2})E_p(1h_{11/2})`$ in $`{}_{}{}^{208}\text{Pb}`$ with W=5% and 25%, respectively;
* The surface-energy and symmetry-energy deviation coefficients $`\delta a_2`$ and $`\delta a_4`$ with a weight W=0.08.

The parameter set L2 was obtained by fitting the constants to reproduce the infinite nuclear matter properties Ser-Wal :

* Saturation density $`\rho _B^0=0.1484\text{fm}^3`$.
* Binding energy per nucleon E/B = -15.75 MeV.
* Bulk symmetry energy = 35 MeV.
* rms charge radius of $`{}_{}{}^{40}Ca`$ = 3.482 fm.

## III Results

In this section we show the results of the calculations of several ground-state properties of the nuclei $`{}_{50}{}^{132}\text{Sn}_{82}^{}`$, $`{}_{50}{}^{100}\text{Sn}_{50}^{}`$, $`{}_{28}{}^{48}\text{Ni}_{20}^{}`$, and $`{}_{28}{}^{78}\text{Ni}_{50}^{}`$ and of the neighboring nuclei differing by one particle or one hole. We start by considering results for the total binding energy, which are shown in Fig. 1

The plot is divided in two parts which show different forms of the convergence of the models. On the left are the results of total binding energy using the simplest lagrangian, i.e. with no non-linear terms. The two parameter sets L2 and W1 represent the result of fitting the constants of the model to different nuclear properties. As described in the previous section, the W1 set is fit to more data than L2. The improvement of the results is clear. The experimental result is shown as a long-dash line in the plot. The error bars are of the same size as the thickness of the line showing the experimental value. The experimental results are taken from Web , except for $`{}_{28}{}^{48}\text{Ni}_{20}^{}`$ where we use the value quoted in Brown . On the right side of Fig. 1 are the results obtained from the more elaborate lagrangians, which in general include different non-linear interactions as shown in the previous section (see Eqns. (6) - (9)). The first two points, corresponding to the NLC and Q1 parameter sets, represent the same level of approximation of the lagrangian. We see here, again, that the use of an extended set of observables in the fitting procedure dramatically improves the results. In this case, the Q1 set already gives an excellent result for all nuclei.

As we move to the right on this part of the plot, we see the effect of additional interaction terms in the lagrangian. The inclusion of a fourth-order vector field term in the lagrangian, see Eq.(7) and Table 1, gives a larger binding energy. This effect is further balanced by additional non-linear terms in the G1 and G2 sets. At this level, the sets G1 and G2 give almost the same results and cannot be differentiated. Since both sets correspond to the same level of approximation, we are looking here at the sensitivity of the results to the variations of the fitted constants. The same features are verified for all the nuclei tested. Figure 2 shows the percentage deviation in estimating the total binding energy of the selected nuclei. We observe that it lies below approximately 1% in all cases. In all cases the parameter set Q1 gives the smallest deviation. Extending the parameter set to G1 and G2, while validating the NDA and the assumption of ”naturalness” as discussed in , does not significantly improve the quality of the fit to this quantity for the nuclei shown. For the four doubly-magic nuclei tested we obtain better agreement for the case of the Sn-isotopes than for those of Ni.

For the Sn isotopes, we extended the calculations of the total binding energy to cover the entire range of even-even nuclei. Figure 3 shows the results for the G2 parameter set for the isotopes $`{}_{50}{}^{100}\text{Sn}_{50}^{}`$ \- $`{}_{50}{}^{132}\text{Sn}_{82}^{}`$. The percentage deviation in this extended case is shown in Figure 4. Here we observe that the deviation for the three sets Q1, G1 and G2 is in absolute value less than 1%. In general, all three parameter sets give less binding energy than observed. For all parameter sets shown in this figure, G1 gives overall the smallest deviation, except for the two nuclei $`{}_{50}{}^{100}\text{Sn}_{50}^{}`$ and $`{}_{50}{}^{132}\text{Sn}_{82}^{}`$, which lie at the extreme edges of the plot. This would imply that there is indeed improved convergence overall in going from Q1 to the extended parameter sets G1 and G2, and G1 gives better results than G2 over the entire range.

From this figure we can observe the effects of the accuracy of the isovector contributions to the effective lagrangian. Following, for example, the G1 results we observe that in the center of the plot there is essentially a constant deviation from the experimental values, while this increases close to the edges of the isotope range. A study of the problem of the isovector contribution to the description of finite nuclei has been presented recently by Furnstahl Furnstahl-isovector .

We can conclude that a more sophisticated lagrangian, fit to stable nuclear properties, can reproduce ground-state total binding energies of nuclei far from stability.

It is important to note that even though the constants of the model were fit using only stable doubly-magic nuclei, the results for binding energies of these nuclei far from stability are remarkably good.

Figures 5 through 10 show the level structure of neighboring nuclei differing by a single particle or hole, relative to the doubly-magic nuclei. They are separated in isotopes and isotones. The core nucleus is plotted in the center of the plot marked with $`0^+`$. On the left we have put neighboring nuclei with one more particle. On the right the corresponding nucleus with one less particle is shown. When available, we include the experimental values. These results were obtained using the G2 parameter set, although the G1 set gives very similar ground state binding energies. In all these cases there is excellent agreement with the experimental data Web .

In the case of $`{}_{50}{}^{131}\text{Sn}_{81}^{}`$ the above reference gives as ground-state a value of $`\frac{3}{2}^+`$, but recent experimental results from Bhattacharyya, et al. Bhatt  indicate that the ground-state is in fact $`\frac{11}{2}^{}`$ in accord with our results.

We have applied the chiral effective lagrangian to calculate the ground-state properties of selected doubly-magic nuclei. The inclusion of additional interaction terms in the effective lagrangian, consistent with NDA, gives results that approach asymptotically to the experimental value for the total binding energy. We extended this calculations to neighboring nuclei, differing by one particle or one hole, and determined the binding energy relative to the doubly-magic one and found an overall agreement of better than 1% for the total binding energy of the doubly-magic nuclei and better than 10% for the relative binding energy of the neighboring nuclei. In this latter case, the spin and parities of the ground-states are correctly predicted.

Single-particle excitation spectra for the nuclei $`{}_{50}{}^{133}\text{Sn}_{83}^{}`$ and $`{}_{51}{}^{133}\text{Sb}_{82}^{}`$ have been measured by Hoff, et al. Hoff  and by Sanchez-Vega et al. Sanchez . The level spectra for these nuclei is shown as a function of parameter set in Figs. 11 and 12. Here we chose only the G2, G1 and Q1 sets since these give the best results for the total binding energy of $`{}_{50}{}^{132}\text{Sn}_{82}^{}`$. From the discussion of the DFT approach we do not expect these single-particle and single-hole excitation spectra to be well reproduced, though we observe that there is a slow convergence of the results with higher levels of approximation. This might indicate the need for many more terms in the lagrangian. On the other hand the excellent agreement shown in Fig 3 for the total binding energy, and Figs. 5 and 6 for the ground-state properties (i.e. chemical potential leading to the neighboring single-particle and single-hole nuclei) suggests that the current level of approximation is enough to reproduce the ground-state observables the theory is designed for. We observe that increasing levels of approximation give better results in the level spacing, e.g. Fig 11 though the ordering is essentially independent of the level of approximation. Note that in the case of $`{}_{51}{}^{133}\text{Sb}_{82}^{}`$ we do not include results for the Q1 parameter set for levels above 2d5/2. This is because the program used did not find those states to be bound, a problem that is not present in the case of $`{}_{50}{}^{133}\text{Sn}_{83}^{}`$. This feature is expected since the higher order terms included in the G1 and G2 parameter sets do not only contribute to the bulk properties of the nuclei but also improve the description of the single-particle spectra.

In Figs. 13 and 14 we show the results for the neutron and proton densities of $`{}_{50}{}^{132}\text{Sn}_{82}^{}`$ and $`{}_{50}{}^{100}\text{Sn}_{50}^{}`$. In both cases the density of neutrons is always higher in the interior of the nuclei. This is particularly interesting in the case of $`{}_{50}{}^{100}\text{Sn}_{50}^{}`$ since there are an equal number of neutrons and protons implying that the protons are pushed out, due to the Coulomb potential, forming a thin layer at the surface. In contrast, in the neutron rich case the neutrons extend far out and form a neutron layer. In Fig. 15 we compare the neutron densities of these two doubly-magic Sn nuclei. These results are in good agreement with calculations made using other approaches Lalazissis .

The calculations of the nuclear properties using the DFT approach do not include the contributions of pairing interactions. Even though most modern calculations use some type of pairing, as mentioned before, the goal of this study is to determine the convergence of the results for the optimal observables as new interaction terms are included. Extending these calculations beyond these observables gives less satisfactory results, as has been seen in the single-particle and single-hole excitation spectra of neighboring nuclei, Figs 11 and 12. Although beyond the original purpose of the paper, it is interesting to compare the experimental values of the two-neutron separation energy $`S_{2N}`$ for the series of nuclei $`{}_{50}{}^{100}\text{Sn}_{50}^{}`$ \- $`{}_{50}{}^{136}\text{Sn}_{86}^{}`$ with our calculated results. We give results for G2 only, since G1 gives essentially the same values. To make a reasonable comparison, we extract the configuration energy contribution coming from the mean-fields by eliminating from the experimental data the pairing contributions. To do this we use a simple solvable pairing model Fetter-Walecka  of j-dependent strength $`G_j`$ corresponding to a pure pairing force. The result of the model is that $`S_{2N}`$ is related to the number of particles in the j-th sub-shell by the formula:

$$S_{2N}=2\epsilon _{\text{eff}}(j)+G_j(2j+52n)$$

where n is the number of particles in the j-th shell. Fitting the experimental data to this formula, which indeed goes through all the experimental points, gives the values of the configuration energy $`2\epsilon _{\text{eff}}(j)`$ and $`G_j`$ shown in Table 2.

To obtain the calculated configuration energy $`\epsilon _{eff}(j)`$ using the present approach, we calculated it using two methods. In one case we put only one particle in the j-th sub-shell, while the other lower shells and sub-shells where filled, and determined the total binding. Extracting the contribution from the lower filled shells and sub-shells, to the total binding energy, gave the configuration energy. In the second case the j-th sub-shell was completely filled. We proceeded as before and caclulated the total binding energy and subtracted from it the contribution from all the lower filled shells and sub-shells. This final result was averaged by dividing it by the total number of neutrons in that j-th sub-shell, $`2j+1`$. Both methods gave essentially the same result. Figure 16 shows the comparison between the extracted and calculated configuration energies. The plot shows that, though not quantitatively, the present approach reproduces the level ordering.

The inclusion of pairing correlations is a subject that goes beyond the scope of the present study, but it is recognized that some sort of pairing has to be included to obtain a more complete description of nuclear observables. Work on this subject has shown that in the case of standard RMF models the approach using the DHB seems to be the most straight forward way to include such effects Carlson . The role of pairing in this EFT approach is currently under investigation by the author.

## IV Conclusions

From the results shown in this paper we draw the following conclusions:

1. As additional interaction terms are included in the effective lagrangian, following the prescriptions given by naive dimensional analysis, the calculated results of ground-state properties of selected nuclei far from stability converge to the observed experimental values. The overall agreement, averaged over all tested nuclei is better than 1% in the total binding energy. The relative ground-state binding energy of neighboring nuclei, differing by one particle or one hole, are well reproduced, with a relative error of better than 10%. The spin and parity of these nuclei, where measured, is also correctly reproduced.
2. The effect of fitting the constants of the Chiral Effective Lagrangian to a large number of observables greatly improves the results for the total binding energy of these nuclei far from stability.
3. Nucleon densities calculated with this approach are in agreement with previous works.
4. The effective field theory and density functional theory approach provides a predictive framework for dealing with QCD in the strong-coupling, nuclear physics regime Many-body .
5. Additional interactions to reproduce the effect of pairing are needed to extend the theory to reproduce additional ground-state properties.

I will like to thank Dr. J. D. Walecka for his support and advice, Dr. R. J. Furnstahl for his useful insight on the subject and Dr. B. D. Serot for his comments on the paper. This work is supported in part by DOE grant DE-FG02-97ER41023.