text:
# Effective Spin Models for Spin-Phonon Chains by Flow Equations

## I Introduction

The interest in the spin-Peierls (SP) transition  has been renewed by the discovery of the first inorganic SP substance CuGeO3 . The SP instability of quasi one-dimensional spin systems is the analogon of the Peierls instability of quasi one-dimensional metals towards lattice modulations with a wave vector $`2k_F`$. Due to the coupling of the lattice degrees of freedom to the $`d=1`$ magnetic degrees of freedom the system can lower its energy by undergoing a phase transition into a dimerized state. The loss in elastic energy is overcompensated by the gain in the magnetic energy.

Most theoretical studies of SP transitions rely on an *adiabatic* treatment of the phonons (e. g. Ref. ). This means that the energy of the phonons, that are associated with the lattice distortion, should be low compared with the spin-spin exchange coupling. In addition to the occurrence of a *pre-existing soft phonon*, one observes a phonon softening in the organic SP compounds. Furthermore, the phonon energy $`\omega `$ should be small compared with the resulting gap $`\mathrm{\Delta }`$ in the spin excitation spectrum .

It has been recently emphasized , that CuGeO3 does not fulfill these conditions. Even more, a *phonon hardening* by about $`5\%6\%`$ is observed . Uhrig  has developed a flow equation approach  which is not founded on adiabaticity. The comparison with the DMRG data of Bursill et al.  has shown that the flow equation method works well, especially in the limit of small $`J/\omega `$ (cf. Fig. 1 in Ref. ). In this paper we extend this approach. Details will be given below.

## II Flow equation approach

The method of our choice is the flow equation approach introduced by Wegner . This method is similar to Fröhlich’s approach , which projects a Hamilton operator to an effective Hamiltonian in one step applying an unitary transformation. Wegner modified the Fröhlich transformation as he uses an infinite number of infinitesimal unitary transformations.

The model we study reads

$`(\mathrm{})`$ $`=`$ $`_\text{S}+_{\text{SB}}+_\text{B}`$ (2)
$`_\text{S}`$ $`=`$ $`{\displaystyle \underset{i}{}}(J_1(\mathrm{})𝐒_i𝐒_{i+1}+J_2(\mathrm{})𝐒_i𝐒_{i+2})`$ (3)
$`_\text{B}`$ $`=`$ $`{\displaystyle \underset{i}{}}\left[\omega (\mathrm{})b_i^{}b_i+{\displaystyle \frac{\mu (\mathrm{})}{2}}(b_i^{}b_i^{}+b_ib_i)\right]`$ (4)
$`_{\text{SB}}`$ $`=`$ $`{\displaystyle \underset{i}{}}(𝒜_i(\mathrm{})b_i^{}+𝒜_i^{}(\mathrm{})b_i).`$ (5)
Here $`𝐒_i`$ stands for the $`S=1/2`$ spin operator on site $`i`$ and $`b_i`$ ($`b_i^{}`$) destroys (creates) a phonon on site $`i`$. $`_\text{S}`$ is the Hamiltonian of a frustrated spin chain or $`J_1`$-$`J_2`$ model. If the frustration parameter $`\alpha J_2/J_1`$ exceeds a critical value of $`\alpha =\alpha _\text{c}=0.241167(5)`$, then the model undergoes a quantum phase transition from a gapless state to a gapped phase . We start with a Hamilton operator (2) consisting of pure spin ($`_\text{S}`$) and phonon ($`_\text{B}`$) parts and a spin-phonon coupling term $`_{\text{SB}}`$ and use flow equations to decouple the spin-phonon system.

The continuous transformation is parameterized by a flow parameter $`\mathrm{}[0,\mathrm{}]`$. So $`(\mathrm{}=0)`$ stands for the original Hamiltonian as given. We will end up with the effective Hamiltonian $`(\mathrm{}=\mathrm{})`$ which is more “diagonal” in the way that the direct spin-phonon coupling has been rotated away. The infinitesimal generator $`\eta (\mathrm{})`$ defines the unitary transformation via

$`{\displaystyle \frac{\text{d}(\mathrm{})}{\text{d}\mathrm{}}}=[\eta (\mathrm{}),(\mathrm{})].`$ (6)
A choice of $`\eta (\mathrm{})`$ proposed by Wegner is

$`\eta (\mathrm{})=[_\text{d}(\mathrm{}),(\mathrm{})],`$ (7)
where $`_\text{d}`$ is the part of the Hamiltonian which is regarded as diagonal. By choosing $`_\text{d}(\mathrm{})_\text{S}(\mathrm{})+_\text{B}(\mathrm{})`$ and the “off-diagonal” interaction part as $`_{\text{od}}(\mathrm{})_{\text{SB}}(\mathrm{})`$, our generator reads $`\eta (\mathrm{})[_\text{d},_{\text{od}}]=[_\text{S}+_\text{B},_{\text{SB}}]`$. In Chapter IV we present an alternative choice of $`\eta `$, while the canonical version (7) is used throughout the main part of this paper.

As initial conditions we choose

$`J_1(0)=J\text{and}J_2(0)=0.`$ (8)
So the untransformed pure spin part is the normal Heisenberg Hamiltonian. As we will see later on, for non-zero values of the flow parameter $`\mathrm{}`$ long range spin-spin interactions arise. As a consequence, the next-nearest neighbour coupling constant $`J_2`$ in the effective spin model is finite. The phonon part $`_\text{B}=_\text{B}^{(\omega )}+_\text{B}^{(\mu )}`$ includes a non-boson-number conserving term $`_\text{B}^{(\mu )}`$. This choice is due to the fact, that the generator $`\eta =[_\text{S}+_\text{B}^{(\omega )},_{\text{SB}}]`$ would produce terms proportional to $`b_ib_i`$ ($`b_i^{}b_i^{}`$) anyway. So for our purpose it is convenient to embed this terms in $``$ and renormalize $`\mu (\mathrm{})`$. Henceforth, we choose

$`\omega (0)\omega _0=1\text{and}\mu (0)=0`$ (9)
and give all coupling constants in units of $`\omega _0`$.

$`_{\text{SB}}`$ describes the coupling between spin and phonon system. The spin-phonon coupling mainly influences neighbouring sites. Hence the coupling operator $`𝒜_i(0)`$ typically consists of nearest neighbour spin products. An appropriate choice for $`𝒜_i(0)`$ is the difference coupling

$`𝒜_i(0)=g(𝐒_i𝐒_{i+1}𝐒_i𝐒_{i1}),`$ (10)
which does not contribute to the undistorted phase due to the translational invariance , i. e. $`𝒜_i(0)`$ vanishes. According to Ref. , $`𝒜_i`$ should be normal-ordered, i. e. $`𝒜_i(0)𝒜_i(0)𝒜_i(0)`$. This is guaranteed by the specific choice (10). By choosing different coupling operators, various mechanisms of how the lattice distortions influence the exchange integral $`J`$ can be investigated. In the case of the difference coupling, the exchange coupling directly depends on the “position” of a spin between the neighbouring ones. For CuGeO3 this corresponds to changes of two neighbouring Cu–O–Cu binding angles, i. e. one of them is enlarged on expense of the other one.

Sometimes a local coupling $`_{\text{SB}}^{\text{loc}}=g_i𝐒_i𝐒_{i+1}(b_i^{}+b_i)`$ is used in connexion with CuGeO3 (see e. g. Ref. ): Single harmonic degrees of freedom directly modify the magnetic interaction. In Ref.  the gap due to dimerization was investigated by means of a high order perturbation expansion. A flow equation approach to this coupling type will be presented elsewhere .

Applying the unitary transformation, not only the coupling constant in (10) changes ($`ga(\mathrm{})`$). Additionally longer range and multiple site interactions arise. Their $`\mathrm{}`$-dependent coupling constants are denoted by $`b_n(\mathrm{})`$. The aim of this approach is to disentangle phonons and spins. Hence in the limit $`\mathrm{}\mathrm{}`$ the coupling operator $`𝒜_i(\mathrm{})`$ vanishes, i. e. $`a(\mathrm{})=0`$ and $`b_n(\mathrm{})=0`$.

We introduce the Liouville operator $`𝔏`$ for the commutation with $`_\text{S}`$: $`𝔏𝒪:=[_\text{S},𝒪]`$. In extension to Ref.  the Liouville operator $`𝔏(\mathrm{})`$, the phonon frequencies $`\omega (\mathrm{})`$ and $`\mu (\mathrm{})`$ are $`\mathrm{}`$-dependent. We choose for the generator $`\eta `$

$`\eta (\mathrm{})={\displaystyle \underset{i}{}}\{`$ $`\left[(𝔏+\omega )𝒜_i\mu 𝒜_i^{}\right]`$ $`b_i^{}+`$ (11)
$`\left[(𝔏\omega )𝒜_i^{}+\mu 𝒜_i\right]`$ $`b_i\}`$ (12)
according to $`\eta =[_\text{S}+_\text{B},_{\text{SB}}]`$. The general flow equation (6) leads to a flow equation for the coupling operator $`𝒜_i(\mathrm{})`$ by investigating the terms linear in phonon operators of $`[\eta (\mathrm{}),(\mathrm{})]`$

$$\frac{\text{d}𝒜_i}{\text{d}\mathrm{}}=\left\{\left[(𝔏+\omega )^2\mu ^2\right]𝒜_i2\mu 𝔏𝒜_i^{}\right\}.$$
(13)
Due to the complicated structure of Eq. (13) we restrict ourselves to a subspace of operators, which are allowed to appear in $`𝒜_i(\mathrm{})`$. A systematic choice is to consider all terms arising in $`𝒜_i(0)`$ and $`𝔏𝒜_i(0)`$. The following table summarizes the resulting set of operators.

| coefficient | spin operator |
| --- | --- |
| $`a(\mathrm{})`$ | $`𝐒_i𝐒_{i+1}𝐒_{i1}𝐒_i`$ |
| $`b_0(\mathrm{})`$ | $`i𝐒_{i1}(𝐒_i\times 𝐒_{i+1})`$ |
| $`b_1(\mathrm{})`$ | $`i[𝐒_i(𝐒_{i+1}\times 𝐒_{i+2})+𝐒_{i2}(𝐒_{i1}\times 𝐒_i)]`$ |
| $`b_2(\mathrm{})`$ | $`i[𝐒_i(𝐒_{i+1}\times 𝐒_{i+3})+𝐒_{i3}(𝐒_{i1}\times 𝐒_i)]`$ |
| $`b_3(\mathrm{})`$ | $`i[𝐒_{i+2}(𝐒_i\times 𝐒_{i1})+𝐒_{i2}(𝐒_i\times 𝐒_{i+1})]`$ |

In next order in $`𝔏`$ the operators arising in $`𝔏^2𝒜_i(0)`$ are included leading to 14 additional three spin operators of the type $`(𝐒_i\times 𝐒_j)(𝐒_k\times 𝐒_l)`$ and five additional long range two spin operators. Eq. (13) can now be divided in a set of differential equations for the spin-phonon coupling constants $`a(\mathrm{})`$ and $`b_n(\mathrm{})`$.

The truncation of the coupling operator $`𝒜_i`$ in order $`n`$ (by constructing the operator space with all terms appearing in $`𝒜_i(0)`$, $`𝔏𝒜_i(0)`$, $`𝔏^2𝒜_i(0)`$, $`\mathrm{}`$, $`𝔏^n𝒜_i(0)`$) neglects effects of order $`n+1`$ in $`J`$. We note here, that in this step no expansion in $`g`$ occurs. As the contribution to the flow of the neglected operators corresponding to higher order contributions in $`J`$ is small compared to the one of the leading order terms, we expect the flow equations to converge for $`\mathrm{}\mathrm{}`$. This actually is the case except for large values of $`J/\omega `$.

For the phonon frequencies we find

$`{\displaystyle \frac{\text{d}\omega }{\text{d}\mathrm{}}}`$ $`=`$ $`{\displaystyle \underset{i}{}}\left([(𝔏+\omega )𝒜_i,𝒜_i^{}]+[𝒜_i,(𝔏+\omega )𝒜_i^{}]\right)`$ (15)
$`{\displaystyle \frac{\text{d}\mu }{\text{d}\mathrm{}}}`$ $`=`$ $`2{\displaystyle \underset{i}{}}[𝔏𝒜_i\mu 𝒜_i^{},𝒜_i].`$ (16)
Only nearest and next-nearest neighbour spin products are kept and their mean field value, denoted by the outer brackets $``$, is inserted.

The flow equations for $`J_1(\mathrm{})`$ and $`J_2(\mathrm{})`$ can be extracted from $`[\eta ,_{\text{SB}}]`$

$`{\displaystyle \underset{i}{}}`$ $`\left\{[(𝔏+\omega )𝒜_i,𝒜_i^{}]+\text{h.c.}\right\}b^{}b`$ (17)
$`+`$ $`{\displaystyle \underset{i}{}}`$ $`\left\{[𝔏𝒜_i\mu 𝒜_i^{},𝒜_i]+\text{h.c.}\right\}b^{}b^{}`$ (18)
$``$ $`{\displaystyle \underset{i}{}}`$ $`\left\{𝒜_i^{}\left[(𝔏+\omega )𝒜_i\mu 𝒜_i^{}\right]+\text{h.c.}\right\}.`$ (19)
The quadratic boson terms are replaced by their expectation values. This is systematic in the sense of an expansion in $`g`$. This mean-field step neglects fluctuation effects of order $`g^2`$. As these terms only arise in $`g^2`$-terms, the total error is of order $`g^4`$ (cf. Ref. ). We note here, that these expectation values are $`\mathrm{}`$-dependent due to the $`\mathrm{}`$-dependence of $`\omega `$ and $`\mu `$. Finally, $`\frac{\text{d}J_1}{\text{d}\mathrm{}}`$ ($`\frac{\text{d}J_2}{\text{d}\mathrm{}}`$) is equal to the (next) nearest neighbour part of (17), respectively.

## III Results

Having collected all flow equations, the set of differential equations (9 in order $`𝔏`$ and 28 in order $`𝔏^2`$) have to be solved numerically. This is done via a standard fifth-order Runge-Kutta routine with adaptive step size control. The change of the $`\mathrm{}`$-dependent coupling constants for two succeeding Runge-Kutta steps is computed for all couplings. Convergence is assumed if the sum of the changes squared is less than $`10^9`$ in units of $`\omega _0`$. Fig. 1 shows for $`J/\omega _0=0.6`$ and $`g/\omega _0=0.3`$ the flow of all 9 parameters. For intermediate values of $`\mathrm{}`$ the additional four spin coupling terms arise ($`b_n(\mathrm{})0`$). As $`\mathrm{}`$ becomes larger, all spin-phonon coupling constants vanish, i. e. $`_{\text{SB}}0`$. $`J_1`$ and $`J_2`$ reach their effective values in the limit $`\mathrm{}\mathrm{}`$ and thus give rise to a frustration $`\alpha _{\text{eff}}=J_2^{\text{eff}}/J_1^{\text{eff}}`$ in the decoupled spin model. This procedure is very intuitive in the sense that a flow diagram like Fig. 1 shows, how the dressing of the spins with phonons induces a frustration $`\alpha _{\text{eff}}>0`$.

As a by-product, we find an increased phonon frequency in the effective phonon part of the model. This phonon hardening can be interpreted qualitatively as a level repulsion between the high energy phonon system and the low energy spin system. Recently, it has been pointed out by Gros and Werner  that this feature is consistent with the RPA-approach by Cross and Fisher to the spin-Peierls transition. Fig. 2 shows for four values of $`J`$ the effective phonon frequencies in dependence of $`g`$. As an appropriate measure of the phonon hardening, the frequency $`\lambda _{\text{ph}}\sqrt{\omega _{\text{eff}}^2\mu _{\text{eff}}^2}`$ of the diagonalized version $`_\text{B}_i\lambda _{\text{ph}}\beta _i^{}\beta _i+\lambda _{\text{ph,0}}`$ is depicted.

The phase diagram of the spin-Peierls anti-ferromagnetic chain of spins interacting with phonons has been investigated by Bursill et al. via DMRG , by Uhrig via flow equations in leading order in $`g/\omega `$ and $`J/\omega `$ , by Weiße et al. via fourth order perturbation theory and Lang-Firsov transformation  and by Sun et al. via mean field and renormalization group methods . In Fig. 3 results of various flow equation approaches are shown. In Fig. 4, we compare our results to those of the other approaches.

Our calculation is based on the idea that the transition into the ordered phase does not occur due to the softening of a phonon but due to the tendency of the effective spin model towards dimerization. Phonon-induced frustration above its critical value $`\alpha _{\text{eff}}>\alpha _\text{c}`$ drives the dimerization. The phase transition line is therefore determined by solving

$`\alpha _\text{c}\left(\underset{\mathrm{}\mathrm{}}{lim}\alpha \right)|_{g,J}=0`$ (20)
for fixed values of $`J`$ with respect to $`g`$. In this way we find the critical spin-phonon coupling $`g_\text{c}`$ in dependence of the nearest neighbour spin coupling $`J`$. For values of $`J/\omega `$ up to $`0.35`$ the extended flow equation approach improves the results from Ref. . For intermediate values of $`J/\omega `$ the curve crosses the DMRG result and predicts critical couplings, which must be considered as too low. It is interesting that the result of Ref.  gives a good description of $`g_\text{c}`$ up to $`J/\omega 10`$ although it is systematic only to order $`g^2/\omega ^2`$ and $`g^2J/\omega ^3`$. We presume that the two leading orders comprise already the main competition between dimerization and delocalization. Further orders start to build in resonance effects. But they do not succeed for all $`J/\omega `$ because the effective interactions are restricted to small distances only in our ansatz. It is not uncommon (cf. mean field treatments) that the leading orders yield physically reasonable though not accurate results whereas systematic improvements are difficult to implement (see Ref.  for an expansion in the inverse coordination number as example).

The inclusion of the next order in the systematic expansion by Weiße et al. leads to slight improvements for $`J/\omega <0.15`$ which is an estimate of the convergence radius of the series expansion. But the higher order terms produce too large critical couplings even for intermediate values of $`J/\omega `$ . Furthermore, Weiße et al. used the Lang-Firsov transformation to combine adiabatic and antiadiabatic effects in their theory. This leads actually to an additional increase of the critical couplings for intermediate $`J/\omega `$ (cf. Fig. 6 in Ref. ). We conclude that the extended flow equation approach used here has important advantages over the systematic series expansion. This is due to its renormalizing property, i. e. the feedback of the $`\mathrm{}`$-dependence of all couplings. In this way the region of validity is increased up to $`J/\omega 0.35`$.

For values of $`J/\omega <1`$ Sun et al. use $`g_\text{c}/\omega =\sqrt{J/(2\omega )}`$ . This is smaller by about a factor $`1/\sqrt{2}`$ than the first order result obtained by Kuboki and Fukuyama , who find $`g_\text{c}/\omega =\sqrt{\alpha _\text{c}/(1/2\alpha _\text{c})J/\omega }\sqrt{J/\omega }`$. As can be seen from Figure 4, the results of Sun et al. do not compare so well with those of the other approaches. For $`J/\omega >2`$ they find critical couplings $`g_\text{c}/\omega 0.6`$, which are about twice as large as the $`g_\text{c}`$-values computed by DMRG . For increasing $`J/\omega `$, Sun et al. predict decreasing $`g_\text{c}`$ above $`J/\omega 5`$ (not shown) in contrast to the DMRG data.

While for not too large values of $`J/\omega `$ the extension of the flow equation approach to higher orders in $`g/\omega `$ provides a fast method to retrieve data as precise as DMRG calculations, the large $`J/\omega `$ regime cannot be described so easily. At $`J/\omega 0.77`$ the effective Hamiltonian is no longer hermitian and the description breaks down. The next systematic extension is to enlarge the operator subspace for $`𝒜_i(\mathrm{})`$ to order $`𝔏^2`$. The result once again improves the calculations in order $`𝔏`$ for small $`J/\omega `$, but cannot circumvent the “downturn” at $`J/\omega 0.4`$. We will argue below that the inclusion of longer range interactions is necessary for $`J/\omega >0.35`$.

## IV Modifications

To enlarge the region of validity of the flow equation approach to larger $`J`$s, we introduce some modifications. In a first attempt the restriction to a given operator subspace can be dropped for intermediate terms arising in (13-17) via $`𝔏𝒜_i`$. This circumvents the downturn of the phase transition line but leads to too large critical couplings $`g_\text{c}(J)`$. As these modifications changed the solutions of the differential equations drastically the influence of longer range interactions present in these intermediate terms can be judged as important. To include them in a systematic way two additional couplings $`J_3`$ and $`J_4`$ are introduced. They correspond to spin interactions $`𝐒_i𝐒_{i+3}`$ and $`𝐒_i𝐒_{i+4}`$. The flow equations for $`J_3(\mathrm{})`$ and $`J_4(\mathrm{})`$ can be extracted from (17). As the critical coupling $`\alpha _\text{c}`$ is only known for the $`J_1`$-$`J_2`$-model we combine these four couplings to two effective couplings $`J_1^{\text{sw}}(\mathrm{})`$ and $`J_2^{\text{sw}}(\mathrm{})`$ and thus $`\alpha ^{\text{sw}}(\mathrm{})=J_2^{\text{sw}}/J_1^{\text{sw}}`$. This is done by using linear spin wave theory . The effective couplings $`J_1^{\text{sw}}`$ and $`J_2^{\text{sw}}`$ are chosen such that the spin wave dispersion with $`J_1^{\text{sw}}`$ and $`J_2^{\text{sw}}`$ equals the one for $`J_1`$, $`J_2`$, $`J_3`$ and $`J_4`$. Thus we obtain

$`J_1^{\text{sw}}`$ $`=`$ $`\sqrt{(J_1+9J_3)(J_1+J_3)}`$ (22)
$`J_2^{\text{sw}}`$ $`=`$ $`\sqrt{{\displaystyle \frac{J_1+J_3}{J_1+9J_3}}}(J_2+4J_4)`$ (23)
$`\alpha ^{\text{sw}}`$ $`=`$ $`{\displaystyle \frac{J_2^{\text{sw}}}{J_1^{\text{sw}}}}={\displaystyle \frac{J_2+4J_4}{J_1+9J_3}}.`$ (24)
The curve of Fig. 3 denoted with $`\alpha ^{\text{sw}}`$ is the solution of $`\alpha _\text{c}\alpha _{\mathrm{}\mathrm{}}^{\text{sw}}=0`$. The downturn does not occur any more, but the critical couplings are too large. As $`\frac{\text{d}J_3}{\text{d}\mathrm{}}`$ and $`\frac{\text{d}J_4}{\text{d}\mathrm{}}`$ are solved separately from all other coupling constants, i. e. $`J_3`$ and $`J_4`$ do not couple to the other differential equations, another method denoted with $`\text{d}^{\text{sw}}`$ is introduced. Differentiating (22) and (23) one finds $`\frac{\text{d}J_1^{\text{sw}}}{\text{d}\mathrm{}}`$ and $`\frac{\text{d}J_2^{\text{sw}}}{\text{d}\mathrm{}}`$. These two derivatives do depend on all $`J_n`$ and $`\frac{\text{d}J_n}{\text{d}\mathrm{}}`$ ($`n=1,\mathrm{},4`$). They are calculated in each Runge-Kutta step. This provides a coupling of $`J_3`$ and $`J_4`$ to the other flow equations. The results from this procedure show again the downturn at $`J/\omega _00.4`$ and produce worse data for small $`J/\omega `$ than the unmodified approach.

The inclusion of long range interaction terms modifies the results drastically. So they are important and have to be treated correctly. It seems that one has to extend the flow equation approach to very high orders in the Liouville operator $`𝔏`$, i. e. the subspace for the coupling operator $`𝒜_i(\mathrm{})`$ should be fairly large, if one wants accurate data for large values of $`J/\omega `$. For $`J/\omega <0.35`$, however, the method presented works very accurately.

Due to the complicated spin commutators and products in the flow equations an extension to higher orders in $`𝔏`$ is cumbersome. A further hint of how this could be achieved more easily shall be given. Recently non-standard choices of the generator $`\eta `$ have been used successfully . The main point is to introduce a quantum number $`𝒬`$ and define the generator via $`\eta (\mathrm{})=[𝒬,(\mathrm{})]`$. Thus $`[_{\text{eff}},𝒬]=0`$, i. e. $`𝒬`$ is conserved with respect to $`_{\text{eff}}`$. For our problem we introduce the phonon number $`𝒬=_ib_i^{}b_i`$. With this choice the generator reads $`\eta =_i(𝒜_ib_i^{}𝒜_i^{}b_i)`$ and does not contain the Liouville operator. The flow equations (for $`T=0`$) are pretty simple

$`{\displaystyle \frac{\text{d}𝒜_i}{\text{d}\mathrm{}}}`$ $`=`$ $`(𝔏+\omega )𝒜_i`$ (26)
$`{\displaystyle \frac{\text{d}\omega }{\text{d}\mathrm{}}}`$ $`=`$ $`2[𝒜_i,𝒜_i^{}]`$ (27)
$`[\eta ,_{\text{SB}}]`$ $`=`$ $`2{\displaystyle \underset{i}{}}𝒜_i^{}𝒜_i.`$ (28)
We investigated these flow equations in order $`𝔏`$ and $`𝔏^2`$. The results are similar to those of the standard choice of $`\eta `$. Although the standard choice (7) leads to slightly better results for small couplings $`J/\omega `$, the alternative generator could be used to investigate very large subspaces for $`𝒜_i(\mathrm{})`$, as only $`𝔏`$ enters linearly in (26) and it is absent in (27,28).

## V Summary

We used the flow equation method to rotate the spin-phonon coupling of a spin-Peierls Hamiltonian away. In this way we derived effective spin and phonon models. The spin-phonon coupling induces longer range interactions, i. e. produces a non-vanishing frustration, and renormalizes the original couplings. The effective phonon frequency is enlarged. This corresponds to the phonon hardening observed for CuGeO3. The phase diagram describing the transition from a gapped to an ungapped state is compared with DMRG results. For large values of $`J/\omega `$ the results deviate. In this regime very long range interactions appear to be relevant and the transformation of the spin-Peierls chain onto a rather local effective spin model must be considered as not sufficient. The flow equation and the DMRG results coincide for $`J/\omega <0.35`$.

## VI Acknowledgements

The authors are indebted to R. J. Bursill for providing additional DMRG data and acknowledge helpful discussions with H. Fehske, U. Löw, E. Müller-Hartmann and A. Weiße. This work was supported by the DFG through SFB 341 and SP 1073.


format: text

text:
# A new population of soft X-ray weak quasars

## 1 Introduction

The broad band properties of quasars have been investigated in recent years through multiwavelength observations of several quasar samples: the mean Spectral Energy Distribution (SED) of quasars was estimated for a sample of optically selected, X–ray bright quasars by Elvis et al. (1994); the X-ray properties of optically selected quasars were determined for several large samples by using the Einstein all–sky survey (Avni & Tananbaum 1986, Wilkes et al. 1994) and the ROSAT all–sky survey (Green et al. 1995, Brinkmann et al. 1998, Yuan et al. 1999). The results of all these works were essentially that quasars emit a significant fraction of their bolometric luminosity (several % or more) in the X–ray band. An indicator widely used in the literature, in order to measure the X–ray emission relative to the optical, is the “Optical to X index” $`\alpha _{OX}`$ defined as:

$$\alpha _{OX}=\frac{\mathrm{log}(\mathrm{L}(2500\mathrm{\AA })/\mathrm{L}(2\mathrm{k}\mathrm{e}\mathrm{V}))}{\mathrm{log}(\nu (2500\mathrm{\AA })/\nu (2\mathrm{k}\mathrm{e}\mathrm{V}))}$$
(1)
where L and $`\nu `$ are the monochromatic luminosity and the rest–frame frequency. The above authors find on average $`\alpha _{OX}`$ 1.5, with a dispersion $`\sigma (\alpha _{OX})0.2`$. Moreover, this index is found to increase slightly with redshift and luminosity. Together with these “normal” quasars, a minority of objects is found to be very weak in the X rays ($`\alpha _{OX}1.8`$): many of these sources are Broad Absorption Line quasars (BAL), while others are optically normal objects111In this paper “normal quasars” refers to objects selected with standard color techniques. Their mean SED is derived from Elvis et al. (1994), normalizing the X-ray emission in order to have $`\alpha _{OX}=`$ 1.5. The optical line spectrum is derived from Francis et al. (1991)..

As one can easily estimate from Fig. 1, X-ray weak sources are a few per cent of the entire population of quasars.

Recent works suggest that the origin of the X–ray weakness of BALs is absorption rather than an intrinsically weak emission (Brandt et al. 2000). At the same time, BALs have no optical reddening, hence their optical colours are those typical of normal quasars: for this reason they have been detected by “standard” surveys based on U and B colour excesses.

Our search for a new population of soft-X-ray weak quasars is motivated by several results that suggest the existence of objects other than BALs with a mismatch between optical and X-ray classificationi, and/or optical colours redder than normal quasars:

* The optical identifications of the HELLAS sources (hard X–ray selected) indicate that some objects with very hard X–ray spectra are type 1 AGNs in the optical (Fiore et al. 1999).
* The optical and infrared photometry of a sample of flat spectrum radio quasars shows that a significant fraction of radio–selected objects have redder colours than “normal” quasars (Webster et al. 1995). A similar conclusion, even if based on a much smaller sample, has been reached by Kim & Elvis (1998) who searched for red quasars among soft X–ray selected sources.
* An X–ray study of a sample of very luminous, high redshift quasars performed by the ASCA satellite revealed the existence of several objects with heavy obscuration in the 2-10 keV band (Reeves et al. 1997).
* A comparison between the absorbing column density NH, measured through X–ray analysis, and the optical reddening EB-V, measured through the Balmer decrement, performed on a sample of local Seyfert galaxies (Maiolino et al. 2001a), shows that for a large fraction of AGNs the EB-V/NH ratio is much lower than Galactic. The same conclusion is also suggested by the comparison between the X–ray and mid-IR emission of AGN–dominated Luminous Infrared Galaxies (Risaliti et al. 2000).

The basic idea of our work is that BAL quasars could be the tail of a population of X-ray weak quasars. In this view BALs would be extreme objects because, despite of their strong absorption in the X rays, their optical colours are typical of normal (i.e. blue) quasars. Between the two extremes of “normal” and BAL quasars, a population of objects could exist, with a strong X–ray absorption but a low optical reddening, enough to change slightly the optical colours (and, therefore, to exclude the sources from colour–based surveys) but the associated extinction would not be enough to obscure completely the optical broad lines. According to this scheme, this new class of objects should be classified type 1 AGNs if observed in the optical, but absorbed (type 2–like) if observed in the X–rays. In the following we will refer with “blue quasars” to colour-selected quasars, and with “red quasars” to the new population described above.

The best way to search for red quasars in the optical is by means of spectroscopic selection. The basis of the work described here is a cross-correlation of grism-selected samples of quasars with optical and X-ray surveys. We studied the optical colours and the X-ray to optical flux ratio of these objects and compared them with a sample of blue quasars.

The paper is organized as follows: in Sect. 2 we analyze the selection criteria adopted for the composition of the most studied quasar samples and we define the characteristics of the quasar population that could have been missed, then we describe our search for X–ray weak quasars, performed by cross–correlating spectroscopically selected quasar samples with the WGACAT catalogue of ROSAT observations (White et al. 1995). In Sect. 3 we present our results and in Sect. 4 we discuss their physical interpretation. In Sect. 5 we analyze the consequences of our study for several relevant arguments concerning AGNs and the X–ray background, and the future work in order to define the properties of this new population of objects.

Throughout this paper we adopt the cosmological parameters H$`{}_{0}{}^{}=50`$ km s-1 Mpc-1 and q$`{}_{0}{}^{}=0.5`$.

## 2 Sample selection and X-ray data

### 2.1 Colour-based selection

The optical emission of “classical” quasars is characterized by two major features: an optical–UV excess in the continuum and several strong, broad emission lines. The technique used in most quasar surveys consisted in an automatic selection of a reasonably large sample of quasar candidates, followed by spectroscopic observations. Since quasars are rare objects and the spectroscopy is very time consuming, an efficient primary selection is needed. For this reason the color selection used in most surveys is very stringent: for example, in the PG survey a color U-B $`<0.44`$ is required and, although this is a very blue color, the efficiency of the selection is less than 10%, the vast majority of candidates being blue stars or white dwarfs.

This kind of selection automatically excludes objects with intrinsically redder spectra or with some absorption along the line of sight: for example, assuming a galactic dust–to–gas ratio, a typical quasar at z=1 with a very blue continuum would be excluded by the PG selection criterion if it is obscured by a rest frame column density higher than $`2\times 10^{21}`$ cm-2.

### 2.2 Broad line-based selection

The considerations made above suggest that the best way to search in the optical for red or moderately absorbed quasars is by means of a spectroscopic selection. The technique used in spectroscopic surveys is usually a two-step selection, with a first step at low resolution.

We have studied two spectroscopic samples of quasars. The first one is the Palomar Transit Grism sample (PT, Schneider et al. 1994), composed by $``$ 1000 objects selected only by means of emission line criteria, without any requirement about the continuum colours. Data available for these sources are the redshift, an r4 magnitude and the flux, equivalent width and physical width of the line used for the selection. The search technique was optimized in order to discover many high–redshift quasars, nevertheless most of the sources are at low or intermediate redshift. The redshift distribution of the sample is plotted in Fig. 2.

The second sample we used in our work is the Hamburg Quasar Sample (HS, Hagen et al. 1995, Engels et al. 1998, Hagen et al. 1999). In this case a first selection of the objects was performed by using a color criterion (see Hagen et al. 1999 for details), while a second filter consisted in the requirement of broad emission lines in the observed spectrum. Even if a colour selection is still present in this sample, the requirements on the colours are less stringent than in “classical” quasar samples, like the PG, and therefore many quasars with slightly redder colours can be included.

### 2.3 Cross-correlation with the X-ray catalogue.

The X-ray catalogue that we used for the cross–correlation with the optical samples is the WGACAT, obtained by analyzing all the fields observed in pointing mode by the ROSAT PSPC instrument.

We found that 180 sources of the PT and 85 of the HS are in the WGACAT fields. Among the 180 PT sources, we made a further selection in order to exclude objects with apparent magnitude E$`>`$18 and absolute O magnitude M$`{}_{O}{}^{}>`$ -22222E and O magnitudes are obtained from the APM digital catalogue.. A luminosity cut is required to avoid contamination from the host galaxy. The optical brightness cut is due to our interest in X-ray weak objects: we therefore exclude the sources that would be undetected in the WGACAT even if their optical-to-X ratio were normal: indeed, in these cases we would only obtain X-ray upper limits that are useless to constrain the X-ray properties of these sources. The brightness cut could bias the sample in favor of objects with large $`\alpha _{OX}`$. However, our control sample is the PG, with an even stronger brightness cut. So the “differential” effect cannot be spurious.

The final sample contains 30 PT quasars.

In the following we compare the X–ray properties of these sources, relative to their optical emission, with the analogous properties of the PG quasar sample. The PG sample is used as reference both because it is the best studied quasar sample and because it is selected according to the “historical” definition of quasars (i.e. compact objects with high luminosity and a strong UV excess).

Among the 30 PT sources, only 9 are detected in the WGACAT, while for the remaining 21 only an upper limit is available. Among the HS sources, that are on average brighter than the PT sources, about half are detected. The upper limits have been estimated at the 90% confidence level, taking into accout the vignetting and the PSF of the ROSAT PSPC instrument. Further details are gven in the Appendix.

### 2.4 Definition of an optical–to–X index

The simplest way to compare the samples would be that of calculating the $`\alpha _{OX}`$ index for line-selected sources, as defined in Eq. 1, and following the prescriptions given in previous works (Green et al. 1995, Wilkes et al. 1994). On the other hand, the calculation of $`\alpha _{OX}`$ poses several problems in the extrapolations needed: in particular, the monochromatic flux at E=2 keV is strongly dependent not only on the WGACAT count rate (that is the only information directly available), but also on the spectral properties of the source. The standard method consists in assuming a powerlaw spectrum with spectral index $``$ 1-1.5, that is typical for quasars in the ROSAT energy band. However, we suspect that our sources are much more absorbed in the X rays than normal quasars: this would imply a possible photoelectric cutoff and/or a much flatter spectral index.

An analogous problem arises in the optical, even if in this case the errors should be lower.

For these reasons we define a new optical–to–X index, by using directly the available data: for the HS sample we use the B magnitude for the optical and the WGACAT count rates for the X rays, while for the PT sample we use the O and E magnitudes obtained from the APM sky catalogue and the WGACAT count rates.

In order to perform a homogeneous comparison, we took the PG quasars in the WGACAT ($`70`$) and we defined the count rates and the upper limits in the same way as for the HS and PT samples. The B magnitudes are directly available in the literature (Schmidt & Green 1983), while the O and E magnitudes were calculated from the B and V magnitudes assuming the quasar template of Francis et al. (1991). We note that this extrapolation is much safer than those discussed above, because these bands are much closer to B and V than 2500 Å.

The optical–X index used in this work is defined as follows:

$$I_{OX}=\mathrm{log}\frac{10^{(20m)/2.5}}{\varphi (\mathrm{cts}\mathrm{s}^1)}$$
(2)
where m is the optical magnitude and $`\varphi `$ the ROSAT count rate. Since the optical magnitude does not always refer to the same band, we define a different IOX for each band and compare only same-band indices. Finally, we note that in our definition we do not take into account the K correction, even if many of our sources are at intermediate or high redshift. We discuss this point in detail in the next Section.

## 3 X-ray properties of emission line selected AGNs

In order to understand the physical properties of the selected objects, we divide our sources in two groups, to be studied separately: the HS sample and the PT sample. This division is necessaray since the two parent samples have different redshift distributions (Fig. 2) and selection criteria.

### 3.1 Analysis of the HS sample

In Fig. 3 we plot the IOX distribution for the entire HS sample (Fig. 3a) and for three redshift intervals. We note that no object in the HS sample is at redshift z$`<0.1`$ and that high redshift sources are on average weaker in the X-rays than intermediate redshift ones. A dependence of the $`\alpha _{OX}`$ index (as defined in Eq. 1) with the redshift is suggested by several statistical studies of large quasar samples, as reminded in the Introduction. For this reason the comparison of the high–redshift HS objects with the PG comparison sample could be not strictly correct, because the latter is composed mostly of low–redshift sources. However, the redshift dependence that has been proposed in the literature (a factor $`3`$ between z=0 and z $`>`$1, Yuan et al. 1999) is much weaker than the effect found in the HS sample, where the X–ray emission of a significant fraction of objects is more than one order of magnitude lower, with respect to the optical, than in normal quasars.

Since the HS is a flux–limited sample, the redshift dependence of the IOX distribution could be due either to a real dependence on evolution or to a luminosity effect. This issue will be discussed further in Sect. 4.

### 3.2 Considerations on the K correction

For logarithmic indicators, as our IOX index, the K correction is $`(\gamma _1\gamma _2)\mathrm{log}(1+\mathrm{z})`$, where $`\gamma _1`$ and $`\gamma _2`$ are the spectral index of the X–ray and optical spectrum respectively (assuming a powerlaw spectrum, F$`{}_{\nu }{}^{}\nu ^\gamma `$). Assuming a standard quasar spectrum, with $`\gamma _1=2`$ and $`\gamma _2=1.5`$, the K correction is 0.15 at z=1 and 0.24 at z=2, much lower than the observed effect.

It is well known, for example from the analysis of the X–ray emission of BAL quasars (e.g. Gallagher et al. 1999), that X–ray weak quasars have on average flatter X–ray spectra than normal quasars. This is also found in low-luminosity AGNs: if the complex 2-10 keV spectra of heavily absorbed Seyfert 2s is fitted with a simple powerlaw, the photon index varies between $`0.5`$ and $`1.5`$ (see for example Turner et al. 1997 and Maiolino et al. 1998). Therefore, the X–ray spectral index of our objects could be significantly lower than the canonical value of 2, and this effect goes in the direction of lowering and perhaps inverting the k–correction for IOX.

We conclude that a physical effect different from the K correction is responsible for the unusually high values of IOX.

### 3.3 Analysis of the PT sample

The IOX distribution for the PT sources is plotted in Fig. 4 for two diffent cuts in magnitude. A highly significant difference between our sample and the PG quasars is evident even in the E $`<`$ 18 sample: more than half of the objects are underluminous in the X-rays of at least a factor 5 with respect to a “normal” quasar. The X-ray weakness is however more significant in the small E$`<`$ 17 subsample. The increase of the discrepancy with brightness shows that grism selection is indeed effective in finding out X-ray weak quasars, but in the case of the PT sample the flux limits in the WGACAT are too high to investigate the correlation between the optical and X-ray emission.

## 4 Selection effects and interpretation

The results presented above suggest the existence of a class of AGNs with broad lines in the optical/UV but with an X-ray emission much lower than expected from the optical flux and a PG-based extrapolation.

The quasars of the HS sample show a significant correlation of their broad-band properties with redshift (or, analogously, with luminosity, since the sample is flux–limited). We performed a KS test on the distributions plotted in Fig. 3, and we found that the z$`<`$1 and 1$`<`$z$`<2`$ distributions are different at a level of confidence of 96%, while the z$`<1`$ and z$`>2`$ distributions differ at 99%.

We note that the level of significance of the lower limits on IOX is the same at all redshifts, because both the optical and the X–ray parent samples are flux limited at constant fluxes. The increase of IOX with redshift can therefore be due to a “luminosity effect”: optically more luminous quasars are on average weaker in the soft X-rays (with respect to the optical emission).

In Fig. 5 we show the O-E colour for the HS sample, obtained from of the Palomar All Sky Survey (POSS). The theoretical lines represent the typical O-E colour of quasars in function of the redshift, for three different values of optical extinction. Since the blue colour excess is still one of the main selection criteria here, more than half of the HS quasars do not have, on average, colours redder than normal quasars. However, another $``$25% of the sources have an O-E colour that corresponds in normal quasars to an optical extinction A$`{}_{V}{}^{}>1`$. This is a further indication that also quasars with a relevant absorption were selected in the Hamburg Quasar Survey. In Fig. 6 we show the IOX distributions for the HS objects with z$`<2`$ and located respectively below (upper panel) and above (lower panel) the AV=1 line in Fig.5. Redder objects are clearly also on average weaker in the X-rays. This results confirm one of our main working hypotheses, i.e. that X-ray weak quasars are missed in surveys based on a strong colour selection.

Sources at z $`>2`$ are significantly X-ray weaker than normal quasars, irrespectively of their optical colour. This is in agreement with the “luminosity effect” discussed above. Again, this class of objects could easily have been missed by colour-based surveys, since the U-B criterion becomes inefficient at z$`>`$2.2.

Since the HS survey is still biased towards blue objects, this result could imply that a non negligible population of “red” quasars could exist, analogously to what found by Webster et al. (1995) for flat-spectrum radio quasars.

The discussion made above for the HS quasars can be repeated for the PT quasars. In this case, even if we are able to find a significant fraction of X-ray weak quasars, the result is weaker, due to the fainter optical magnitudes of these sources.

The O-E colour distribution for the PT sample is similar to that of the HS, revealing a significant fraction of objects redder than normal quasars (Fig. 7). This result confirms that spectroscopic selection is able to find quasars that would be missed in classical color-based surveys.

## 5 Discussion and conclusions

The X–ray and optical analysis of the HS and PT samples, presented in the previous Sections, points out the existence of a population of X–ray weak AGNs, with optical colours not very different from “normal” quasars, but red enough to be missed by classical colour–based surveys.

Our results on the IOX distribution imply that at least 50% of our objects are significantly weaker in the soft X rays than normal “blue” quasars.

The high IOX measured in our sources could be due to an intrinsic X-ray weakness, or to a low A$`{}_{V}{}^{}/`$NH value. Several considerations make the first hypothesis unlikely:

* Soft X-ray emission is a general feature present in all known classes of AGNs (except for BALs, but see the next paragraph). Moreover, since the strong emission lines detected in the optical require a powerful UV source, it is unlikely that a physical process provides an intense UV emission without any significant tail in the soft X rays.
* As briefly mentioned in the Introduction, BAL AGNs, that are the only sources similar to ours with respect to the X/optical properties, are likely to be heavily absorbed rather than intrinsically weak. This is suggested (a) by the correlation between the X to optical ratio and the C IV absorption features (Brandt et al. 2000) and (b) by detailed analysis of the X–ray emission of some BAL quasars, that shows an absorbed spectrum in the 2-10 keV band (Gallagher et al. 1999).

On the other hand, there are several indications that a low A$`{}_{V}{}^{}/`$NH (relative to the Galactic value) could be common to several classes of sources (see the Introduction). Moreover, this possibility is supported by the correlation between high IOX values and high O-E colours, suggesting a common physical origin of the two phenomena.

Current models of the circumnuclear medium of AGNs do not clarify which physical process can be responsible for an A$`{}_{V}{}^{}/`$NH value substantially lower than Galactic. Qualitatively, a high absorption in the X rays, together with a low extinction in the optical can be due to two different reasons: a low dust–to–gas ratio or a size distribution of dust grains different from the standard one. For a more detailed discussion on this issue, the reader is referred to Maiolino et al. 2001b.

Whatever the physical origin of the low A$`{}_{V}{}^{}/`$NH, the main conclusion of this discussion is that a population of quasars does exist, with X-ray properties of type 2 AGNs and optical spectrum of type 1s. In Fig. 8 we propose a simple classification scheme for AGNs in the AV \- NH plane. In this diagram, “blue” quasars and BALs are the objects revealed by classic, colour-based optical surveys. The line-selected objects are located in the “X-ray type 2 zone” (N$`{}_{H}{}^{}>`$ a few 1022 cm-2) but in the “optical type 1 zone” (A$`{}_{V}{}^{}<23`$). “ROSAT red quasars” refers to the soft X-ray selected objects of Kim & Elvis (1998). It is worth noting that even in the “optical type 2 zone” a relevant number of objects could have low A$`{}_{V}{}^{}/`$NH: for example, comparing the near IR broad lines with the X-ray spectrum of the type 2 AGN IRAS 05189-2524, we estimated an A$`{}_{V}{}^{}/`$NH substantially lower than Galactic (Severgnini et al. 2000).

###### Acknowledgements.

This work has made use of data obtained through the VizieR Service for Astronomical Catalogues at CDS, Strasbourg, France, and the APM Catalogues provided by the Institute of Astronomy, Cambridge, UK. The authors acknowledge partial financial support by the Italian Space Agency (ASI) under grant ARS-99-15 and by the Italian Ministry for University and Research (MURST) under grant Cofin98-02-32.

## Appendix A Evaluating upper limits from the WGACAT catalogue

Here we discuss how to obtain a correct estimation of the upper limits (in counts s-1) for a non-detection in the WGACAT catalogue.

The basic selection criterion in the WGACAT is the request of a signal-to-noise ratio higher than 2. This implies that, if the background counts are B, the minimum number of counts for a detected source, $`S_m`$, is obtained from the equation:

$$S_m=2\sqrt{S_m+B}$$
(3)
In case of a non-detection, a 90% upper limit is obtained multiplying $`S_m`$ by a correction factor a, such that a source with $`aS_m`$ counts has a probability $`<`$10% to be undetected (i.e. to fall below the detection limit $`S_m`$). This factor is therefore obtained solving the equation:

$$\sigma \sqrt{aS_m+B}=S_m(a1)$$
(4)
where $`\sigma =1.25`$ is the number of standard deviations corrisponding to a 1-sided probability of 90%. We found that typical values for this correction are $`a1.651.7`$.

The crucial point in order to obtain a correct value of $`aS_m`$ is the estimation of B.

For each undetected source, we calculated the background counts for a nearby detected source and we re-scaled this value for the vignetting snd PSF of the PSPC instrument.

A tabulation of the vignetting as function of the distance from the center of the field of view, $`y(r)`$, can be obtained directly from the WGACAT. To obtain the PSF we calculated the background counts B for a large number of randomly selected sources (about 10% of the WGACAT) and we fitted the dependence from the radius with a 3rd order polynomial, P(r). Finally we re-scaled the background counts of the nearby detected source with the ratio $`[P(r_1)y(r_1)]/[P(r_2)y(r_2)]`$, where $`r_1`$ and $`r_2`$ are the distances from the center of the undetected and the detected source, respectively.


text:
# Mechanism of resonant x-ray magnetic scattering in NiO

## I introduction

Resonant x-ray scattering has recently attracted much interest as a useful tool to investigate magnetic and orbital orders. The resonant enhancement for magnetic Bragg reflections has been observed in transition-metal compounds using synchrotron radiation with photon energy around the $`K`$ edge. Also the resonant enhancement for the prohibited Bragg reflection corresponding to the orbital order has been observed in LaMnO3.  The resonant scattering is described by a second order process that a photon is virtually absorbed by exciting a core electron to unoccupied states and then emitted by recombining the excited electron with the core hole. Therefore, for the $`K`$ edge, the $`4p`$ states are involved in the dipolar process, while the $`3d`$ states are involved in the quadrupolar process. Since the $`4p`$ states are highly extended in space, they are rather sensitive to electronic structure at neighboring sites. This character is now well recognized in the resonant scattering for the orbital order in LaMnO3; at the beginning, proposed was a mechanism that the intensity comes from the $`4p`$ states modified by the intra-atomic Coulomb interaction with the $`3d`$ electrons constituting the orbital order, but the subsequent studies of treating the $`4p`$ states as a band have revealed that the $`4p`$ states of Mn is mainly modified by the Jahn-Teller distortion via the oxygen potential on the neighboring sites, not by the intra-atomic Coulomb interaction.

In this paper, we study the mechanism of the resonant x-ray scattering for the magnetic order (RXMS) in NiO. We analyze the recent experiment of Neubeck et al., paying special attentions to the band effects of the $`4p`$ states. In NiO, Ni atoms form an fcc lattice. It is a type II antiferromagnet (AF) with the Néel temperature $`T_\mathrm{N}=523`$ K. The order parameter is characterized by a wavevector $`𝐐`$, which is directed to one of four body-diagonals in the fcc lattice. Therefore there exist four domains ($`K`$ domains). The spin vector lies in the plane perpendicular to the AF modulation direction so that there are three possible directions ($`S`$ domains). For example, the spins are directed to $`(1,1,2)`$, $`(2,1,1)`$, or $`(1,2,1)`$ in the $`K`$ domain of $`𝐐=(\frac{1}{2},\frac{1}{2},\frac{1}{2})`$. In total, we have 12 domains. In the RXMS experiment for NiO, the $`K`$ domain is specified, but the $`S`$ domains are mixed.

For generating the RXMS intensity, orbitals have to coupled to the magnetic order; in the dipolar process, the $`4p`$ states have to couple to the $`3d`$ states. Since such couplings are usually much smaller than those to the Jahn-Teller distortion in LaMnO3, the mechanism is much subtler than that for the orbital order in LaMnO3. The spin polarization alone in the $`4p`$ band cannot give rise to the RXMS intensity; if the amplitudes of exciting electron are summed for up and down spins, the total becomes the same at each site in the absence of the orbital moment. This leads to the cancellation of the amplitudes between different magnetic sublattices. The spin-orbit interaction in the $`4p`$ band may break this cancellation,  but its effect will be shown to be negligibly small.

As discussed in our previous paper for CoO, we propose that two couplings are effective to make the $`4p`$ states couple to the magnetic order: the intra-atomic Coulomb interaction between the $`4p`$ and $`3d`$ states, and the mixing of the $`4p`$ states with the $`3d`$ states of neighboring Ni atoms. To substantiate this observation, we use a tight-binding model for the $`4p`$ states, treating the $`3d`$ states within a cluster model. We will show that these couplings actually give rise to the RXMS spectra in agreement with the recent experiment. A caution is to be made on the intra-atomic Coulomb effect; without treating the $`4p`$ states as a band, the Coulomb interaction gives rise to too large RXMS intensities. Thus the $`4p`$ band effect has a role of reducing the effect of the Coulomb interaction. We have also a clear peak in the pre-$`K`$-edge region, which will be shown to come from the quadrupolar process. Since the $`3d`$ states strongly couple to the magnetic order, having this peak is not surprising. The present cluster model analysis, a slight extension of an atomic model analysis, reproduces well the experimental spectra.

This paper is organized as follows. In Sec. II, the present model is described, and the electronic structure is calculated on the basis of this model. In Sec. III, the formulation of the RXMS spectra is developed, and the calculated results are discussed in comparison with experiments. Section V is devoted to concluding remarks. In the Appendix, the geometrical factors are given in explicit forms.

## II 3D STATES

For describing the $`3d`$ states mixing to the $`2p`$ states of neighboring O sites, we start by the following model Hamiltonian:

$`H_0`$ $`=`$ $`{\displaystyle \underset{im\sigma }{}}E_d(m)d_{im\sigma }^{}d_{im\sigma }+H_{3d3d}^I`$ (1)
$`+`$ $`\zeta _{3d}{\displaystyle \underset{i}{}}{\displaystyle \underset{mm^{}\sigma \sigma ^{}}{}}m\sigma |\mathrm{}𝐬|m^{}\sigma ^{}d_{im\sigma }^{}d_{im^{}\sigma ^{}}`$ (2)
$`+`$ $`{\displaystyle \underset{j\mathrm{}\sigma }{}}E_{2p}p_{j\mathrm{}\sigma }^{}p_{j\mathrm{}\sigma }+{\displaystyle \underset{}{}}{\displaystyle \underset{\sigma \mathrm{}m}{}}(t_{im,j\mathrm{}}^{2p,3d}p_{j\mathrm{}\sigma }^daggerd_{im\sigma }+H.c.).`$ (3)
Operators $`d_{im\sigma }`$ and $`p_{j\mathrm{}\sigma }`$ represent the annihilation of an electron with spin $`\sigma `$ in the $`3d`$ state $`m`$ of the Ni site $`i`$ and of an electron with spin $`\sigma `$ in the $`2p`$ state $`\mathrm{}`$ of the O site $`j`$, respectively. The first term describes the energy of the $`3d`$ level. We take account of a point charge crystal-field splitting ($`10Dq`$) such that $`E_d(e_g)=E_d+6Dq`$, $`E_d(t_{2g})=E_d4Dq`$. The second term, $`H_{3d3d}^I`$, represents the intra-atomic Coulomb interaction between the $`3d`$ states on Ni sites. Although the explicit form is omitted here, the matrix elements are written in terms of the Slater integrals $`F^0(3d,3d)`$, $`F^2(3d,3d)`$, and $`F^4(3d,3d)`$. The third term represents the spin-orbit interaction of the $`3d`$ states. The fourth term represents the energy of the $`2p`$ level of O. The relative energy is given by the charge-transfer energy $`\mathrm{\Delta }`$ defined by $`\mathrm{\Delta }=E_dE_{2p}+nU`$ for the $`d^n`$ configuration with $`U=F^0(3d,3d)\frac{2}{63}F^2(3d,3d)\frac{2}{63}F^4(3d,3d)`$. The last term represents the mixing of the Ni $`3d`$ states with the O $`2p`$ states. The mixing parameters $`t_{im,j\mathrm{}}^{2p,3d}`$ are defined by the Slater-Koster integrals, $`(pd\sigma )_{2p,3d}`$, $`(pd\pi )_{2p,3d}`$. Most parameter values are assumed to be consistent with a previous cluster-model analysis and our previous electron correlation calculation. They are listed in Table I. We evaluate the atomic values within the Hartree-Fock (HF) approximation. For $`F^0(3d,3d)`$, we use a rather smaller value than the atomic one by considering screening effects in solids, while for $`F^2(3d,3d)`$ and $`F^4(3d,3d)`$ we use the atomic values with multiplying a factor 0.8.

The ground state is calculated within this Hamiltonian as follows. We assume that each cluster consisting of a Ni atom and surrounding six O atoms is subjected to a molecular field coming from neighboring clusters; the exchange energy in the mean-field approximation is given by $`H_{\mathrm{ex}}=J(𝐐)𝐒𝐒`$, where $`𝐒`$ represent the spin operator for the $`3d`$ states, and $`J(𝐐)`$ is the Fourier transform of the exchange constant with the AF modulation vector $`𝐐`$. Since the Néel temperature $`T_\mathrm{N}`$ is given by $`T_\mathrm{N}=|J(𝐐)|S(S+1)/(3k_\mathrm{B})`$ in the mean field approximation, the exchange energy is expressed as

$$H_{\mathrm{ex}}=\frac{3|𝐒|}{2S(S+1)}k_\mathrm{B}T_\mathrm{N}S_\eta ,$$
(4)
with the $`\eta `$ axis pointing to one of the directions $`(1,1,2)`$, $`(2,1,1)`$, or $`(1,2,1)`$. We put $`S=1`$, $`|𝐒|=1`$ for Ni atoms, and use the experimental value for $`T_\mathrm{N}`$. Then we make numerical calculations, assuming that the ground state is given by a linear combination of the $`3d^8`$ configurations (45 states) and $`3d^9\underset{¯}{L}`$ configuration (360 states) in each cluster, where $`\underset{¯}{L}`$ indicates a state that a hole is in the $`2p`$ states of neighboring O sites. Diagonalizing the Hamiltonian matrix ($`405\times 405`$ dimensions), we obtain the ground state that the weight of being in the $`3d^8`$ configuration is 0.865 with the orbital moment $`L_\zeta =0.316`$. This value is consistent with the value $`L_\zeta =0.32`$ in the recent polarization analysis of nonresonant magnetic-scattering  and in the LDA$`+U`$ calculation. Note that the calculated value of the orbital moment is sensitive to the assumed value of $`10Dq`$.

In the quadrupolar process of the RXMS, an electron is excited from the $`1s`$ state to the $`3d`$ states in the intermediate states. Such excited states are numerically calculated in a similar way to that for the ground state. We diagonalize the Hamiltonian matrix within the space of the $`1s^13d^9`$ configuration (10 states) and the $`1s^13d^{10}\underset{¯}{L}`$ configuration (36 states), assuming that an attractive interaction $`V_{3d}^c4`$ eV works between the $`3d`$ electron and the core hole only in the core hole site. The energy of the core-hole is adjusted such that a peak in the pre-K-edge region is located at $`\mathrm{}\omega =8330`$ eV in the RXMS spectra (see Sec. IV).

## III 4P STATES

The RXMS involves a virtual process of a transition from the $`1s`$ state to the $`4p`$ states at Ni sites in the dipolar process, so that the $`4p`$ states are to be studied in detail. This section is devoted to the study of the $`4p`$ states in connection with the $`K`$-edge absorption spectra.

We use a tight-binding model for the $`4p`$ states. Although many other states such as $`4s`$ state at Ni sites and $`3s`$ state at O sites are mixed in such a rather-high-energy region, this model makes sense as an effective model for simply taking account of the $`4p`$ band effects; the $`4p`$ states keep their atomic character inside the atomic sphere even in solids. As relevant couplings to the magnetic order, we introduce the intra-atomic Coulomb interaction between the $`4p`$ and the $`3d`$ states, and the mixing of the $`4p`$ states with the $`3d`$ states in neighboring Ni atoms. Thereby a part of the Hamiltonian concerning the $`4p`$ states is given by

$`H_1`$ $`=`$ $`{\displaystyle \underset{in\sigma }{}}E_{4p}a_{in\sigma }^{}a_{in\sigma }+{\displaystyle \underset{}{}}{\displaystyle \underset{\sigma nn^{}}{}}(t_{in,i^{}n^{}}^{4p,4p}a_{in\sigma }^{}a_{i^{}n^{}\sigma }+\mathrm{H}.\mathrm{c}.)`$ (5)
$`+`$ $`\zeta _{4p}{\displaystyle \underset{i}{}}{\displaystyle \underset{nn^{}\sigma \sigma ^{}}{}}n\sigma |\mathrm{}𝐬|n^{}\sigma ^{}a_{in\sigma }^{}a_{in^{}\sigma ^{}}`$ (6)
$`+`$ $`H_{4p3d}^I+{\displaystyle \underset{\sigma nm}{}}(t_{in,i^{}m}^{4p,3d}a_{in\sigma }^{}d_{i^{}m\sigma }+H.c.),`$ (7)
where $`a_{in\sigma }`$ represents the annihilation of an electron with spin $`\sigma `$ in the $`4p`$ state $`n`$ on Ni site $`i`$. The first and the second terms describe the $`4p`$ bands. The transfer integral $`t_{in,i^{}n^{}}^{4p,4p}`$ is written in terms of the Slater-Koster parameters, $`(pp\sigma )_{4p,4p}`$ and $`(pp\pi )_{4p,4p}`$. We have the $`4p`$ band width $`20`$ eV, assuming $`(pp\pi )_{4p,4p}3.5`$ eV for the nearest-neighbor Ni-Ni distance, and the half of this value for the next-nearest-neighbor distance, with an empirical relation $`(pp\pi )_{4p,4p}(pp\sigma )_{4p,4p}/4`$. The value of $`E_{4p}`$ is adjusted such that the peak in the $`K`$-edge absorption is located at $`\mathrm{}\omega =8437`$ eV. The third term represents the spin-orbit interaction in the $`4p`$ states. The HF atomic value is used for $`\zeta _{4p}`$. The fourth term $`H_{4p3d}^I`$ represents the intra-atomic Coulomb interaction between the $`4p`$ states and the $`3d`$ states. The matrix elements are written in terms of the Slater integrals, $`F^0(4p,3d)`$, $`F^2(4p,3d)`$, $`G^1(4p,3d)`$, and $`G^3(4p,3d)`$. By the same reason as in $`H_{3d3d}^I`$, the HF atomic values are used for $`F^2(4p,3d)`$, $`G^1(4p,3d)`$, and $`G^3(4p,3d)`$ with multiplying a factor 0.8. The value of $`F^0(4p,3d)`$ is rather ambiguous, since it can be absorbed into the value of $`E_{4p}`$. The last term describes the mixing of the $`4p`$ states with the $`3d`$ states of neighboring sites. The mixing parameter $`t_{in,i^{}m}^{4p,3d}`$ is written in terms of the Slater-Koster parameters, $`(pd\sigma )_{4p,3d}`$ and $`(pd\pi )_{4p,3d}`$. We assume $`(pd\sigma )_{4p,3d}1.0`$ eV together with an empirical relation $`(pd\pi )_{4p,3d}(pd\sigma )_{4p,3d}/2`$. Although this mixing is much smaller than the transfer between the $`4p`$ states, it is not neglected in the RXMS spectra, since it makes the $`4p`$ states couple to the magnetic order. The parameter values are listed in Table I.

We numerically calculate the $`4p`$ band as follows. The $`H_1`$ together with $`H_0`$ is represented in each Ni site within the space of states that one electron is in the $`4p`$ states with the $`3d`$ electrons in the ground state (6 states) and that a $`3d`$ electron is added to become the $`3d^9`$-configuration (10 states). Such states in different Ni sites are coupled through the second and the last terms in Eq. (7), so that they form a band. Considering two Ni atoms in the unit cell due to the AF order, the Hamiltonian matrix has $`32\times 32`$ dimensions for each wave vector, which is numerically diagonalized.

In the final state of the $`K`$-edge absorption and the intermediate states of RXMS, there is a hole in the $`1s`$ state, which attracts the $`4p`$ electron. Assuming that the core-hole potential works only within the core-hole site, we solve the potential problem with respect to a local Green’s function defined by

$$\mathrm{\Pi }_{0n\sigma ;0n\sigma }(\omega )=i_{\mathrm{}}^{\mathrm{}}T\left(b_{0\sigma }^{}(t)a_{0n\sigma }(t)a_{0n^{}\sigma ^{}}^{}b_{0\sigma ^{}}(0)\right)\mathrm{e}^{i\omega t}dt,$$
(8)
where $`b_{0\sigma }`$ is the annihilation operator of the $`1s`$ state with spin $`\sigma `$ at site $`0`$, $`\mathrm{}`$ the average over the ground state, and $`T`$ the time ordering. Taking account of the multiple scattering due to the core-hole potential, we have

$$\mathrm{\Pi }_{0n\sigma ;0n\sigma }(\omega )=\underset{n^{\prime \prime }\sigma ^{\prime \prime }}{}\mathrm{\Pi }_{0n\sigma ;0n^{\prime \prime }\sigma ^{\prime \prime }}^{(0)}(\omega )[IV_{4p}^c\mathrm{\Pi }^{(0)}(\omega )]_{0n^{\prime \prime }\sigma ^{\prime \prime };0n^{}\sigma ^{}}^1,$$
(9)
with

$$\mathrm{\Pi }_{0n\sigma ;0n\sigma }^{(0)}(\omega )=\underset{R}{}\frac{0n\sigma |RR|0n^{}\sigma ^{}}{\omega (E_R+ϵ_{\mathrm{core}}E_g)+i\mathrm{\Gamma }/2}.$$
(10)
Here the state $`|R`$ represents the $`4p`$ band with energy $`E_R`$ discussed above, and $`ϵ_{\mathrm{core}}`$ is the core hole energy. The life-time broadening width $`\mathrm{\Gamma }`$ and the core-hole potential $`V_{4p}^c`$ are set to be $`1.7`$ eV, and $`3`$ eV, respectively.

The spectral function of the local Green’s function, $`I(\omega )=_{n\sigma }(1/\pi )\mathrm{Im}\mathrm{\Pi }_{0n\sigma ;0n\sigma }(\omega )`$, is proportional to the $`K`$-edge absorption spectra and the fluorescence spectra. Figure 7 shows $`I(\omega )`$ in comparison with the $`K`$ edge fluorescence experiment. The solid and the broken lines represent the spectra for $`V_{4p}^c=0`$ and $`3`$ eV, respectively. The attractive interaction enhances the intensity in the low-energy side. It consists of two peaks. The peak in low-energy region corresponds to the $`K`$-edge peak in the experimental spectra. We are mainly interested in the energy region of this peak in the RXMS spectra. Th peak in high energy region may correspond to the peak around $`\mathrm{}\omega =8365`$ eV in the experimental spectra, but the calculated peak is too large. This discrepancy may come from using the $`4p`$ tight-binding model; in reality, it is likely to become much broader through the mixing to other states such as the $`4s`$ state of Ni and $`3s`$ states of O.

## IV RESONANT X-RAY MAGENTIC SCATTERING

### A Procedure of calculation

The magnetic scattering amplitude has been reviewed by several authors.  We summarize here the expression of the amplitude in a form suitable to the present calculation. The scattering geometry is shown in Fig. 7; photon with frequency $`\omega `$, momentum $`𝐤_i`$ and polarization $`\mu `$ ($`=\sigma `$ or $`\pi `$) is scattered into the state with momentum $`𝐤_f`$ and polarization $`\mu ^{}`$ ($`=\sigma ^{}`$ or $`\pi ^{}`$). For the system with two magnetic sublattices $`A`$ and $`B`$ in the AF order, the cross section for elastic scattering at magnetic Bragg peaks is given by

$$\frac{d\sigma }{d\mathrm{\Omega }^{}}|_{\mu \mu ^{}}\left|T_{\mu \mu ^{}}^A(𝐆,\omega )T_{\mu \mu ^{}}^B(𝐆,\omega )\right|^2,$$
(11)
with

$`T_{\mu \mu ^{}}^\eta (𝐆,\omega )=`$ $``$ $`{\displaystyle \frac{i\mathrm{}\omega }{mc^2}}\left({\displaystyle \frac{1}{2}}𝐋^\eta (𝐆)𝐀^{\prime \prime }+𝐒^\eta (𝐆)𝐁\right)`$ (12)
$`+`$ $`J_{\mu \mu ^{}}^\eta (𝐆,\omega )+L_{\mu \mu ^{}}^\eta (𝐆,\omega ).`$ (13)
where $`𝐆=𝐤_f𝐤_i`$ is the scattering vector.

The first term in eq. (13) represents a non-resonant term, where $`m`$ and $`c`$ are the electron mass and the velocity of photon, respectively. $`𝐀^{\prime \prime }`$ and $`𝐁`$ are given by

$`𝐀^{\prime \prime }`$ $`=`$ $`𝐀^{}(𝐀^{}\widehat{𝐆})\widehat{𝐆},𝐀^{}=4\mathrm{sin}^2\theta (\widehat{\mathit{ϵ}}^{}\times \widehat{\mathit{ϵ}}),`$ (14)
$`𝐁`$ $`=`$ $`\widehat{\mathit{ϵ}}^{}\times \widehat{\mathit{ϵ}}+(\widehat{𝐤}_f\times \widehat{\mathit{ϵ}}^{})(\widehat{𝐤}_f\widehat{\mathit{ϵ}})(\widehat{𝐤}_i\times \widehat{\mathit{ϵ}})(\widehat{𝐤}_i\widehat{\mathit{ϵ}}^{})(\widehat{𝐤}_f\times \widehat{\mathit{ϵ}}^{})\times (\widehat{𝐤}_i\times \widehat{\mathit{ϵ}}),`$ (15)
where $`\widehat{\mathit{ϵ}}`$ and $`\widehat{\mathit{ϵ}}^{}`$ are the initial and scattered polarizations, and $`\widehat{𝐤}_i`$, $`\widehat{𝐤}_f`$, and $`\widehat{𝐆}`$ are normalized vectors of $`𝐤_i`$, $`𝐤_f`$, and $`𝐆`$. $`𝐋^\eta (𝐆)`$ and $`𝐒^\eta (𝐆)`$ stand for the Fourier transform of the orbital and spin angular momentum densities, which values are known from the recent non-resonant RXS experiment:  $`|𝐋(𝐆)|(|𝐒(𝐆)|)=0.26(0.82)`$, $`0.24(0.60)`$, and $`0.12(0.20)`$ for $`𝐆=(\frac{1}{2},\frac{1}{2},\frac{1}{2})`$, $`(\frac{3}{2},\frac{3}{2},\frac{3}{2})`$, and $`(\frac{5}{2},\frac{5}{2},\frac{5}{2})`$, respectively. We insert these experimental values into Eq. (13). The local moments of orbital and spin are give by $`𝐋^\eta (𝐆)`$ and $`𝐒^\eta (𝐆)`$ with $`𝐆0`$. The above experimental values are consistent with the present ground-state calculation in Sec. II.

The second term in Eq. (13) represents the resonant contribution from the dipolar process. It is expressed by a second-order process that a photon is virtually absorbed by exciting the $`1s`$ electron to the $`4p`$ states and then emitted by recombining the excited electron with the $`1s`$ core hole. The corresponding amplitude is expressed as

$$J_{\mu \mu ^{}}^\eta (𝐆,\omega )=\underset{\alpha \alpha ^{}}{}(P^\mu ^{})_\alpha M_{\alpha \alpha ^{}}^\eta (\omega )P_\alpha ^{}^\mu ,$$
(16)
with the scattering tensor

$$M_{\alpha \alpha ^{}}^\eta (\omega )=\underset{\mathrm{\Lambda }}{}\frac{m\omega _{\mathrm{\Lambda }g}^2g|x_\alpha |\mathrm{\Lambda }\mathrm{\Lambda }|x_\alpha ^{}|g}{\mathrm{}\omega (E_\mathrm{\Lambda }E_g)+i\mathrm{\Gamma }/2}.$$
(17)
The geometrical factors $`P^\mu `$, $`P^\mu ^{}`$ are given in explicit forms in the Appendix. In Eq. (17), $`\omega _{\mathrm{\Lambda }g}=(E_\mathrm{\Lambda }E_g)/\mathrm{}`$, and $`x_\alpha `$’s stand for the dipole operators, $`x_1=x`$, $`x_2=y`$, and $`x_3=z`$ in the coordinate frame fixed to the crystal axes. The ground state $`|g`$ has an energy $`E_g`$. The intermediate state $`|\mathrm{\Lambda }`$ consists of an excited electron on the $`4p`$ states and a hole on the $`1s`$ state with energy $`E_\mathrm{\Lambda }`$. In the presence of the core-hole potential, it is convenient to rewrite the scattering tensor in terms of the local Green’s function defined in Sec. III. We have

$$M_{\alpha \alpha ^{}}^\eta (\omega )=A_p^2m\omega _c^2\underset{\sigma }{}\mathrm{\Pi }_{0\alpha \sigma ,0\alpha \sigma }(\omega ),$$
(18)
where site $`0`$ is to belong to sublattice $`\eta `$, and $`\mathrm{}\omega _c8350`$ eV. The $`A_p`$ is the dipole matrix element defined by $`A_p=4p|r|1s=_0^{\mathrm{}}R_{4p}(r)rR_{1s}(r)r^2dr`$ with $`R_{1s}(r)`$ and $`R_{4p}(r)`$ being the radial wavefunctions for the $`1s`$ and $`4p`$ states. We evaluate it as $`A_p=1.52\times 10^{11}`$ cm within the HF approximation in the $`3d^8`$ configuration of a free Ni ion. The amplitudes at A and B sublattices are nearly cancelled out, leading to an antisymmetric form for the difference:

$$M^A(\omega )M^B(\omega )=\left(\begin{array}{ccc}\hfill 0& \hfill a& \hfill c\\ \hfill a& \hfill 0& \hfill b\\ \hfill c& \hfill b& \hfill 0\end{array}\right),$$
(19)
with $`a`$, $`b`$, and $`c`$ being some complex numbers.

The third term in Eq. (13) represents the resonant contribution from the quadrupolar process. The corresponding amplitude is expressed as

$$L_{\mu \mu ^{}}^\eta (𝐆,\omega )=\underset{\gamma \gamma ^{}}{}(Q^\mu ^{})_\gamma N_{\gamma \gamma ^{}}^\eta (\omega )Q_\gamma ^{}^\mu ,$$
(20)
with the scattering tensor,

$$N_{\gamma \gamma ^{}}^\eta (\omega )=\frac{k^2}{12}\underset{\mathrm{\Lambda }^{}}{}\frac{m\omega _{\mathrm{\Lambda }^{}g}^2g|z_\gamma |\mathrm{\Lambda }^{}\mathrm{\Lambda }^{}|z_\gamma ^{}|g}{\mathrm{}\omega (E_\mathrm{\Lambda }^{}E_g)+i\mathrm{\Gamma }/2}.$$
(21)
The geometrical factors, $`Q^\mu `$, $`Q^\mu ^{}`$, are given in explicit forms in the Appendix. In Eq. (21), $`k`$ is the wavevector of the incident (and scattered) photon, $`4.2\times 10^8`$ cm-1, $`\omega _{\mathrm{\Lambda }^{}g}=(E_\mathrm{\Lambda }^{}E_g)/\mathrm{}`$, and $`z_\mu `$’s stand for the quadrupole operators, $`z_1=(\sqrt{3}/2)(x^2y^2)`$, $`z_2=(1/2)(3z^2r^2)`$, $`z_3=\sqrt{3}yz`$, $`z_4=\sqrt{3}zx`$, and $`z_5=\sqrt{3}xy`$ in the coordinate frame fixed to the crystal axes. The intermediate states $`|\mathrm{\Lambda }^{}`$ consist of an excited electron on the $`3d`$ states and a hole on the $`1s`$ states with energy $`E_\mathrm{\Lambda }^{}`$, which are evaluated by following the procedure described in Sec II. The scattering amplitude $`N_{\gamma \gamma ^{}}^\eta (\omega )`$ contains the square of the quadrupole matrix element $`A_d=3d|r^2|1s=_0^{\mathrm{}}R_{3d}(r)r^2R_{1s}(r)r^2dr`$, with $`R_{3d}(r)`$ being the radial wavefunction of a free Ni ion. We evaluate it as $`A_d=2.10\times 10^{20}`$ cm2 within the HF approximation in the $`3d^8`$ configuration. Similar to the dipolar process, the scattering tensors $`N^A(\omega )`$ and $`N^B(\omega )`$ are nearly cancelled out, leading to an antisymmetric form for the difference:

$$N^A(\omega )N^B(\omega )=\left(\begin{array}{ccccc}\hfill 0& \hfill d& \hfill e& \hfill f& \hfill g\\ \hfill d& \hfill 0& \hfill h& \hfill p& \hfill q\\ \hfill e& \hfill h& \hfill 0& \hfill r& \hfill s\\ \hfill f& \hfill p& \hfill r& \hfill 0& \hfill t\\ \hfill g& \hfill q& \hfill s& \hfill t& \hfill 0\end{array}\right),$$
(22)
with $`dt`$ being some complex numbers. Note that this difference would vanish if the spin-orbit interaction in the $`3d`$ states were absent. This is consistent with the prediction by Loversey.

### B Calculated results

In this subsection, we discuss the RXMS spectra in comparison with the recent experiment of Neubeck et al. In their experiment, the $`K`$ domain of $`𝐐=(\frac{1}{2},\frac{1}{2},\frac{1}{2})`$ is selected, but the contributions from different $`S`$ domains are not separated. Fortunately the relative volumes for three $`S`$ domains have been determined such that $`0.55(S_1)`$, $`0.4(S_2)`$, $`0.05(S_3)`$ for $`𝐐=(\frac{1}{2},\frac{1}{2},\frac{1}{2})`$, $`0.63(S_1)`$, $`0.37(S_2)`$, $`0(S_3)`$ for $`𝐐=(\frac{3}{2},\frac{3}{2},\frac{3}{2})`$, and $`0.26(S_1)`$, $`0.33(S_2)`$, $`0.41(S_3)`$ for $`𝐐=(\frac{5}{2},\frac{5}{2},\frac{5}{2})`$. In the following, we average the spectra over three $`S`$ domains multiplying the weights of these relative volumes.

Figure 7 shows the spectra thus calculated as a function of photon energy for $`𝐆=(\frac{1}{2},\frac{1}{2},\frac{1}{2})`$. The azimuthal angle $`\psi `$ is set to be zero such that the scattering plane contains the $`(1,1,0)`$ crystal axis, corresponding to the experimental situation. The left panels show the spectra for the $`\sigma \sigma ^{}`$ channel. Only one peak is found at $`\mathrm{}\omega =8330`$ eV in the pre-$`K`$-edge region, in agreement with the experiment. Since the dipolar process is forbidden in this polarization, this peak arises from the quadrupolar process. A strong anti-resonant dip is seen in the low energy side of the peak, which comes from an interference of the non-resonant process with the quadrupolar process. The experimental intensity in the high energy side of the peak is much smaller than the calculated intensity. This discrepancy may be related to the lack of absorption correction on the experimental spectra, which correction should make the intensity in the high energy side the same as that in the low energy side. This observation conversely suggests the size of the absorption correction. The right panels show the spectra for the $`\sigma \pi ^{}`$ channel. Similar to the $`\sigma \sigma ^{}`$ channel, we find a sharp peak at $`\mathrm{}\omega =8330`$ eV, which arises from the quadrupolar process. The intensity for the energy far below $`\mathrm{}\omega =8330`$ eV is much smaller than the value for the $`\sigma \sigma ^{}`$ channel. In addition, we have several structures in the high-energy side of the peak. As plotted by the long-dashed line, the non-resonant process and the quadrupolar process cannot give rise to sufficient intensities, indicating that the intensity mainly comes from the dipolar process. We have checked the effect of the spin-orbit interaction in the $`4p`$ band by calculating the spectra with neglecting that interaction; no visible change is found. We have a peak around $`\mathrm{}\omega =8346`$ eV, in agreement with the experiment. To this peak, the intra-atomic Coulomb interaction between the $`4p`$ and the $`3d`$ states contributes substantially (compare the solid line with the dashed one). The experimental intensity, which is smaller than the calculated one, should be enhanced by absorption correction. We should emphasize here that the dipolar contribution becomes more than $`10`$ times as large as the present values, too large in comparison with the experimental one, if the transfer of the $`4p`$ electron to neighboring sites is neglected.  Therefore, the $`4p`$ band effect is very important for reproducing the experimental spectra. A large peak at $`\mathrm{}\omega 8365`$ eV is regarded as an artifact of using the tight-binding model, as mentioned in Sec. III.

Figure 7 shows the spectra as a function of photon energy, at $`\psi =0`$ for $`𝐆=(\frac{3}{2},\frac{3}{2},\frac{3}{2})`$. The left panels show the spectra for the $`\sigma \sigma ^{}`$ channel. The spectral shape is quite similar to that for $`𝐆=(\frac{1}{2},\frac{1}{2},\frac{1}{2})`$. The right panels show the spectra for the $`\sigma \pi ^{}`$ channel. The non-resonant intensity is larger than that for $`𝐆=(\frac{1}{2},\frac{1}{2},\frac{1}{2})`$. We find a sharp peak at $`\mathrm{}\omega =8330`$ eV, which arises from the quadrupolar process. In the high-energy side of this peak, we also have several structures arising from the dipolar process; a peak around $`\mathrm{}\omega =8346`$ eV agrees well with the experiment.

Figure 7 shows the spectra as a function of photon energy for $`𝐆=(\frac{5}{2},\frac{5}{2},\frac{5}{2})`$. The azimuthal angle $`\psi `$ is now set to be $`270^{}`$, corresponding to the experimental situation. The right panels show the spectra for the $`\sigma \pi ^{}`$ channel. For the peak at $`\mathrm{}\omega 8330`$ eV, an anti-resonant dip now moved to the high-energy side. We also find a broad peak around $`\mathrm{}\omega 8340`$ eV, owing to the dipolar process.

Figure 7 shows the spectra as a function of the azimuthal angle $`\psi `$ for $`𝐆=(\frac{1}{2},\frac{1}{2},\frac{1}{2})`$, in comparison with the experiment. The lowest panel shows the intensity of the peak at $`\mathrm{}\omega =8346`$ eV in the main-$`K`$-edge region for the $`\sigma \pi ^{}`$ channel. We multiply a factor such that the calculated values at $`\psi =0`$ becomes close to the experimental one. The variation resembles to a dependence of $`\mathrm{sin}^2\psi `$, consistent with the dominant contribution of the dipolar process. The top and middle panels show the intensities of the peaks at $`\mathrm{}\omega =8330`$ eV in the pre-$`K`$-edge region for $`\sigma \sigma ^{}`$ and the $`\sigma \pi ^{}`$ channels, respectively. We multiply a same factor in both cases such that the values at $`\psi =0`$ become close to the experimental ones. The variation in the top panel looks simply a $`90^{}`$-shift of the curve in the lowest panel. This is a little surprising, since we expect a more complex shape from the quadrupolar process. The curve in the middle panel has an extra peak. This may be related to the fact that the dipolar contribution remains in this peak. Such an extra peak is not clear in the experiment.

## V CONCLUDING REMARKS

We have studied the RXMS around the $`K`$ edge in the antiferromagnet NiO, treating the $`4p`$ states as a band and the $`3d`$ states as localized states. We have proposed a mechanism that the $`4p`$ states are coupled to the magnetic order through the intra-atomic Coulomb interaction between the $`4p`$ and $`3d`$ states, and through the $`p`$-$`d`$ mixing to the $`3d`$ states of neighboring Ni atoms. Thereby the orbital moment is induced in the $`4p`$ states, giving rise to the RXMS intensity in the dipolar process. The calculated spectra in the present model have reproduced well the experimental ones. Different from previous analyses, the effect of the spin-orbit interaction in the $`4p`$ band is found negligibly small within the present model. This reminds us of the magnetic circular dichroism (MCD) for the $`K`$-edge absorption in the ferromagnetic metals Fe, Co, and Ni.  It is known that the MCD intensity is mainly generated by the orbital moment induced in the $`4p`$ band through the mixing to the $`3d`$ states of neighboring atoms, not through the spin-orbit interaction in the $`4p`$ band.

We have also obtained a peak in the pre-$`K`$-edge region, in agreement with a previous analysis in the atomic model. This arises from the quadrupole process, showing a contrast to the pre-$`K`$-edge peak in the resonant scattering for the orbital order in LaMnO3. The latter is predicted to be generated by the dipolar process, where the states of $`p`$ symmetry (seen from the Mn atoms) have weights in the pre-$`K`$-edge region by mixing to the $`3d`$ states of neighboring Mn atoms. Usually the intensity of the quadrupolar process is much smaller than that of the dipolar process, but the dipolar contribution cannot become large in the present case because of a weak coupling of the $`4p`$ states to the magnetic order.

Furthermore, we have discussed the azimuthal-angle dependence of the spectra. The curve for the pre-$`K`$-edge peak, which comes from the quadrupolar process, looks simply a $`90^{}`$-shift of the curve for the main-$`K`$-edge peak, which comes mainly from the dipolar process.

Finally, we would like to stress again that the tight-binding model is a first approach for taking account of the $`4p`$ band effects. More realistic band calculations are desirable for obtaining more quantitative results.

###### Acknowledgements.

We would like to thank W. Neubeck for kindly informing the experimental data for NiO prior to publication. This work was partially supported by a Grant-in-Aid for Scientific Research from the Ministry of Education, Science, Sports and Culture, Japan.

## A Geometrical factor

We summarize here the expressions of geometrical factors for the dipolar and quadrupolar processes. The detailed derivation is given in Ref. . For the scattering vectors $`𝐆=(\frac{1}{2},\frac{1}{2},\frac{1}{2})`$, $`(\frac{3}{2},\frac{3}{2},\frac{3}{2})`$, and $`(\frac{5}{2},\frac{5}{2},\frac{5}{2})`$, the geometrical factor $`P^\mu `$ ($`\mu =\sigma `$ or $`\pi `$) for incident photon in the dipolar process is given by

$`\left(P^\sigma \right)_1`$ $`=`$ $`(\mathrm{cos}\beta \mathrm{cos}\psi +\mathrm{sin}\psi )/\sqrt{2},`$ (A1)
$`\left(P^\sigma \right)_2`$ $`=`$ $`(\mathrm{cos}\beta \mathrm{cos}\psi \mathrm{sin}\psi )/\sqrt{2},`$ (A2)
$`\left(P^\sigma \right)_3`$ $`=`$ $`\mathrm{sin}\beta \mathrm{cos}\psi ,`$ (A3)
$`\left(P^\pi \right)_1`$ $`=`$ $`\left[\mathrm{sin}\theta (\mathrm{cos}\beta \mathrm{sin}\psi \mathrm{cos}\psi )+\mathrm{cos}\theta \mathrm{sin}\beta \right]/\sqrt{2},`$ (A4)
$`\left(P^\pi \right)_2`$ $`=`$ $`\left[\mathrm{sin}\theta (\mathrm{cos}\beta \mathrm{sin}\psi +\mathrm{cos}\psi )+\mathrm{cos}\theta \mathrm{sin}\beta \right]/\sqrt{2},`$ (A5)
$`\left(P^\pi \right)_3`$ $`=`$ $`(\mathrm{sin}\theta \mathrm{sin}\beta \mathrm{sin}\psi +\mathrm{cos}\theta \mathrm{cos}\beta ),`$ (A6)
where with $`\beta =\mathrm{arccos}\sqrt{1/3}`$, and $`\theta `$ represents the Bragg angle. The azimuthal angle $`\psi =0`$ corresponds to the scattering plane containing the $`(1,1,0)`$ crystal axis. The geometrical factor $`P^\mu ^{}`$ ($`\mu ^{}=\sigma ^{}`$ or $`\pi ^{}`$) for the scattered photon is given by replacing $`\mathrm{sin}\theta `$ by $`\mathrm{sin}\theta `$ in Eqs. (A3) and (A6).

Also, the geometrical factor $`Q^\mu `$ ($`\mu =\sigma `$ or $`\pi `$) for incident photon in the quadrupolar process is given by

$`\left(Q^\sigma \right)_1`$ $`=`$ $`\mathrm{cos}\theta \mathrm{cos}\beta \mathrm{cos}2\psi \mathrm{sin}\theta \mathrm{sin}\beta \mathrm{sin}\psi ,`$ (A7)
$`\left(Q^\sigma \right)_2`$ $`=`$ $`(\sqrt{3}/2)\mathrm{cos}\theta \mathrm{sin}^2\beta \mathrm{sin}2\psi +(\sqrt{3}/2)\mathrm{sin}\theta \mathrm{sin}2\beta \mathrm{cos}\psi ,`$ (A8)
$`\left(Q^\sigma \right)_3`$ $`=`$ $`\mathrm{cos}\theta \mathrm{sin}\beta (\mathrm{cos}\beta \mathrm{sin}2\psi +\mathrm{cos}2\psi )/\sqrt{2}`$ (A9)
$``$ $`\mathrm{sin}\theta (\mathrm{cos}2\beta \mathrm{cos}\psi \mathrm{cos}\beta \mathrm{sin}\psi )/\sqrt{2},`$ (A10)
$`\left(Q^\sigma \right)_4`$ $`=`$ $`\mathrm{cos}\theta \mathrm{sin}\beta (\mathrm{cos}\beta \mathrm{sin}2\psi \mathrm{cos}2\psi )/\sqrt{2}`$ (A11)
$``$ $`\mathrm{sin}\theta (\mathrm{cos}2\beta \mathrm{cos}\psi +\mathrm{cos}\beta \mathrm{sin}\psi )/\sqrt{2},`$ (A12)
$`\left(Q^\sigma \right)_5`$ $`=`$ $`\mathrm{cos}\theta [1(1/2)\mathrm{sin}^2\beta ]\mathrm{sin}2\psi (1/2)\mathrm{sin}\theta \mathrm{sin}2\beta \mathrm{cos}\psi ,`$ (A13)
$`\left(Q^\pi \right)_1`$ $`=`$ $`(1/2)\mathrm{sin}2\theta \mathrm{cos}\beta \mathrm{sin}2\psi \mathrm{cos}2\theta \mathrm{sin}\beta \mathrm{cos}\psi ,`$ (A14)
$`\left(Q^\pi \right)_2`$ $`=`$ $`(\sqrt{3}/4)\mathrm{sin}2\theta \mathrm{sin}^2\beta \mathrm{cos}2\psi (\sqrt{3}/2)\mathrm{cos}2\theta \mathrm{sin}2\beta \mathrm{sin}\psi `$ (A15)
$``$ $`(\sqrt{3}/2)\mathrm{sin}2\theta [1(3/2)\mathrm{sin}^2\beta ],`$ (A16)
$`\left(Q^\pi \right)_3`$ $`=`$ $`(1/2\sqrt{2})\mathrm{sin}2\theta \mathrm{sin}\beta (\mathrm{cos}\beta \mathrm{cos}2\psi \mathrm{sin}2\psi )`$ (A17)
$`+`$ $`\mathrm{cos}2\theta (\mathrm{cos}2\beta \mathrm{sin}\psi +\mathrm{cos}\beta \mathrm{cos}\psi )/\sqrt{2}`$ (A18)
$``$ $`(3/4\sqrt{2})\mathrm{sin}2\theta \mathrm{sin}2\beta ,`$ (A19)
$`\left(Q^\pi \right)_4`$ $`=`$ $`(1/2\sqrt{2})\mathrm{sin}2\theta \mathrm{sin}\beta (\mathrm{cos}\beta \mathrm{cos}2\psi +\mathrm{sin}2\psi )`$ (A20)
$`+`$ $`\mathrm{cos}2\theta (\mathrm{cos}2\beta \mathrm{sin}\psi \mathrm{cos}\beta \mathrm{cos}\psi )/\sqrt{2}`$ (A21)
$``$ $`(3/4\sqrt{2})\mathrm{sin}2\theta \mathrm{sin}2\beta ,`$ (A22)
$`\left(Q^\pi \right)_5`$ $`=`$ $`(1/2)\mathrm{sin}2\theta [1(1/2)\mathrm{sin}^2\beta ]\mathrm{cos}2\psi `$ (A23)
$`+`$ $`(1/2)\mathrm{cos}2\theta \mathrm{sin}2\beta \mathrm{sin}\psi (3/4)\mathrm{sin}2\theta \mathrm{sin}^2\beta .`$ (A24)
The geometrical factor $`Q^\mu ^{}`$ ($`\mu ^{}=\sigma ^{}`$ or $`\pi ^{}`$) for scattered photon is given by replacing $`\mathrm{sin}\theta `$ and $`\mathrm{sin}2\theta `$ by $`\mathrm{sin}\theta `$ and $`\mathrm{sin}2\theta `$, respectively, in Eqs. (A13) and (A24).