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# First-principles investigation of the assumptions underlying Model-Hamiltonian approaches to ferromagnetism of 3𝑑 impurities in III-V semiconductors

## I Introduction: electronic structure as a tool for constraining model Hamiltonians

The prospect of manipulating the electron spin to store and transport information in semiconductor devices has led to renewed interest in the physics of transition metal (TM) impurities in semiconductors - an area which was intensively studied in the eighties alexrev ; expt\_rev ; multiplets\_expt . Current interest expt ; dms ; nahill ; mark ; yujun ; min ; chelikowsky\_gan ; chelikowsky\_gaas ; mirbt ; HKY ; cdgep2 ; model\_dietl1 ; model\_macdonald ; model\_bhatt ; model\_amit ; model\_dietl2  in achievement of ferromagnetism (FM) at ambient temperatures has led to the investigation of the mechanism that stabilizes FM in transition-metal doped semiconductors. One useful approach to obtain an understanding of the electronic properties of these systems is the first principles electronic structure approach where one focuses on the explicit electronic and spin wavefunctions of the system. Variational minimization of the total energy, determines within the underlying approximations of the spin density functional theory some of the basic features of the states involved, such as the extent of localization, the magnitude of the spin interactions as well as the identity of disorder and compensating defects (antisites; interstitials). However, the approach does have the drawback of underestimating the extent of electron correlations in addition to being a zero-temperature approach. While comparison with experiment (e.g. ferromagnetic temperature vs. alloy composition HKY ) can be used to assess the extent to which electron correlations are underestimated, the first-principle results have to be generally mapped onto a model Hamiltonian to calculate finite temperature properties.

While model Hamiltonians model\_dietl1 ; model\_macdonald ; model\_bhatt ; model\_amit ; model\_dietl2  have been widely used to describe the properties of these systems, the underlying assumptions in choosing a particular form for the Hamiltonian are rarely justified in their own right. Generally model\_dietl1 ; model\_macdonald ; model\_bhatt ; model\_amit ; model\_dietl2 , one renormalizes away the electronic degree of freedom and retains only the spin degree of freedom for the transition metal impurity. One then assumes a local interaction between the transition metal impurity and the free carrier (usually RKKY-like), and then solves for various physical properties of these systems.

In the present work we use first-principles calculations to examine whether the assumptions made in model Hamiltonian treatments are consistent with an ab-initio description of the electronic structure of these systems. Our detailed results are then cast in the language of a simple electronic structure model, which could be used in an informed construction of model Hamiltonians.

We start by identifying the main physical quantities that come into play in determining the electronic structure of these systems. When a trivalent cation site such as Ga of a III-V semiconductor is replaced by divalent Mn, an acceptor level (denoted as E(0/-)) is generally created in the band gap. If the Fermi level $`ϵ_F`$ lies below this E(0/-) level, then Mn is charge neutral, i.e., its formal oxidation +3 equals that of the Ga atom being replaced. In this case there is a hole in the Mn-related orbital. If, on the other hand, the Fermi level is above E(0/-), then the Mn-related orbital captures an electron from the Fermi sea (i.e. creating a hole there), becoming negatively charged (i.e. oxidation state Mn2+). In this case the hole resides in the Fermi sea. The Mn-induced hole for $`ϵ_F<`$ E(0/-) features prominantly in contemporary theories of ferromagnetism

The model Hamiltonians involve three entities - the host crystal states, the transition metal atom, and the impurity-induced hole state. There are approximations made at various levels which involve decoupling various degrees of freedom. At the first level, one decouples the orbital degrees of freedom associated with the transition metal atom, describing it with a localized spin-only part. The spin is interacting with a hole system through a local exchange interaction. At the next level of approximation, one reduces the problem to that of the transition metal spin interacting with the hole spin, assuming that the host crystal is unperturbed. The main assumptions made in such approaches, which we wish to examine, are:

(i) The hole resides in a bulk-like, hydrogenic, delocalized state. This picture is based on the assumption that the perturbing potential $`V_{Mn}(r)`$-$`V_{Ga}(r)`$ generated by the impurity is dominated by a long-ranged Coulomb part, as a result of which only a small percentage of the charge resides in the Wigner-Seitz cell and the rest is distributed over a large portion of the host crystal. In this ”host-like hole” picture, one reduces the problem to a quasi-hydrogenic form in which the acceptor state is designated via quantum numbers ($`s`$, $`p`$ …) of the host lattice. In such cases the wavefunction of the acceptor level is delocalized, and can essentially be constructed from the host crystal $`\mathrm{\Gamma }`$ states. This picture is motivated by the fact that divalent, post transition metal atom elements such as Zn2+ form in III-V semiconductors quasi-hydrogenic acceptor states baldereschi  with small binding energies. Similarly, extrinsic $`p`$-type doping of II-VI dilute magnetic semiconductor CdMnTe old\_dietl  also form hydrogenic hole states. However, unlike Zn in GaAs or extrinsic $`p`$-type CdMnTe, the Mn atom introduced into III-V’s has chemically active $`d`$ orbitals alexrev , so it is not obvious that the acceptor state it forms in GaN, GaP or GaAs would qualify as a delocalized host-like hydrogenic state. Indeed, the microscopic features determining the localization of the hole wavefunction, such as the $`d`$-character of the acceptor level must be considered. Such interactions could change the symmetry ($`t_2`$ vs. $`e`$) of the hole state, hence its coupling to the host. The pertinent quantum designation of the hole state is impurity-like ($`t_2`$, $`e`$) not host-like effective-mass model\_macdonald .

(ii) The host valence band maximum (VBM) levels are unperturbed by the transition metal impurity. In this view, the host band structure represented in the model Hamiltonian could be described by a $`k`$.$`p`$ model, valid for the pure host crystal and is decoupled from the part of the Hamiltonian involving the host + hole system. However, since one of the symmetry representations of the Mn $`d`$ orbitals in tetrahedral sites ($`t_2`$, $`e`$) is the same as that of the zincblende VBM ($`t_2`$), such states could couple, hence become mutually perturbed.

(iii) The spin of the hole couples to the spin of the transition metal impurity via an interatomic local exchange interaction $`J_{pd}`$. As only the spin degree of freedom of the transition metal atom is considered, while the orbital degree of freedom is ignored, the free carriers feel the effective magnetic field produced by the transition metal impurity spin. This is modelled as a local exchange interaction, $`J_{pd}`$, between the transition metal impurity and the spin of the free carrier. Hence, the magnitude of $`J_{pd}`$ determines the energy scale of ferromagnetic ordering. Areas visited by the free carrier are rendered ferromagnetic. However certain materials ferro\_insulating  are found to show activated behavior in their transport implying no free charge carriers, yet they exhibit ferromagnetism. The current model which requires delocalized carriers cannot explain ferromagnetism in such systems.

In what follows, we use first principles calculations to examine the validity of assumptions (i)-(iii) for 3$`d`$ impurities V, Cr, Mn, Fe, Co and Ni in GaAs, as well as for Mn and Cr in GaN, GaP and GaSb. We then construct a qualitative model that explains our numerical results. We find that

(i) The Mn-induced hole could have significant 3$`d`$ character. The assumption of a ”delocalized hydrogenic hole” is not supported by first-principle calculations. The depth of the acceptor level (reflecting its localization) and the coupling of the 3$`d`$ impurity orbitals to the hole change markedly with the host crystal in the series GaN $``$ GaP $``$ GaAs $``$ GaSb. The hole generated by introducing Mn in GaN is found to have significant 3$`d`$ character, while in GaSb the hole is found to have primarily host character. Further, the symmetry of the hole depends on the combination of the host crystal with the impurity atom. For example while in GaAs:Co the hole has dominantly $`t_2`$ character, the corresponding isoelectronic impurity ZnSe:Fe has a hole with $`e`$ symmetry.

(ii) The presence of the transition metal impurity perturbs the valence band of the host semiconductor. The extent of the perturbation depends on the relative position of the impurity generated levels (referenced to the valence band maximum of the host) which have the same symmetry as the valence band maximum. In GaAs:V which has levels with $`e`$ symmetry in the bandgap, the perturbation is small, while for GaAs:Mn the perturbation is large.

(iii) The interaction between the spin of the TM atom and the spin of the host-like hole has a predominantly non-local part. This is evidenced by the strong stabilization of the ferromagnetic state for Mn and Cr pairs in GaAs at $``$ 8 $`\AA `$ separation. This interaction induces a spin-polarization of the host-like states. The direction of the spin-polarization depends on the relative energy position of the cation vacancy generated (host-like) states with respect to the impurity states. Furthermore, the band-theoretic description of Cr in GaP shows a partially occupied mid-gap band, and the wavefunctions associated with this mid-gap state are localized. Yet, even in the absence of free carriers, our total energy calculations predict a ferromagnetic ground state to be strongly stabilized, while no long range magnetic order is expected.

## II Earlier Electronic structure Calculations

There have been considerable earlier first-principles nahill ; mark ; yujun ; min ; chelikowsky\_gan ; chelikowsky\_gaas ; mirbt ; HKY  work on the electronic structure of these systems. One of the most well-studied systems is Mn in GaAs, which is found to be half-metallic nahill ; mark ; yujun ; chelikowsky\_gaas ; mirbt . The GaAs cell with one Mn atom in it has a net magnetic moment of 4 $`\mu _B`$ nahill ; yujun ; chelikowsky\_gaas ; mirbt , with part of the moment residing on the As neighbors of the Mn atom. The hole state is found to be strongly hybridized with the transition metal state, and has been referred to as a hybridized band of holes chelikowsky\_gaas . The Mn atom and its four nearest neighbors are found to account for most of the density of states at the valence band edge chelikowsky\_gaas . Since only the first shell of As atoms surrounding Mn are affected by the spin polarization of the Mn atom, the interactions are believed to be short-ranged chelikowsky\_gaas . The first principle results have been interpreted by Ref. nahill  as suggestive of a $`d^5`$/$`d^6`$ electron configuration on Mn nahill . LDA+U calculations min  have been used to obtain a description of the electronic structure consistent with photoemission.

First-principle calculations have been used earlier to elucidate the magnetism in these systems. Mahadevan and Zunger cdgep2  developed a simple model of interaction of the cation-vacancy generated states with the transition metal states to understand how ferromagnetism results when Mn is doped into the chalcopyrite semiconductor CdGeP2. Sato and Katayama-Yoshida HKY  have calculated the energy difference between ferromagnetic and the random alloy to determine which impurity could give rise to ferromagnetism. They found that at low concentrations V, Cr, and Mn doping in III-V stabilized the ferromagnetic state, while, Fe, Co and Ni doping stabilized the magnetically disordered state. Mirbt, Sanyal and Mohn mirbt  showed that the interaction of the transition metal impurity with the As dangling bond states could result in a spin polarization of the hybridized dangling bond states. The partial occupancy of these spin-polarized levels results in ferromagnetism. Sanvito, Ordejon and Hill nahill  found an decrease of the spin-splitting of the valence band maximum of the GaAs host with impurity concentration. This is in contrast with what is expected from the mean-field Kondo Hamiltonian traditionally used to describe these systems kondoiivi . They attribute the deviation to a breakdown of the mean-field approximation, while they say that the Kondo Hamiltonian is good enough to provide a description of the ferromagnetism. Schilfgaarde and Mryasov mark  have used the total energies obtained from first-principle calculations for different materials to extract exchange interaction strengths. They find a decrease of the exchange interactions with concentration which prompts them to suggest that the picture model\_dietl1 ; model\_macdonald ; model\_bhatt ; model\_amit ; model\_dietl2  of carrier-mediated ferromagnetism is not valid for these systems.

We build on the current understanding of the electronic and magnetic properties that exists in the literature. However, we focus our calculations specifically on the examination of the features (i)-(iii) assumed as ”input” to most model Hamiltonian theories.

## III Method of Calculations

We have carried out first-principle electronic structure calculations using density functional theory, within the momentum space total energy pseudopotential method ihmzunger , using ultra-soft pseudopotentials usp  as implemented in the VASP vasp  code. The Ga pseudopotentials that we used for GaAs and GaP did not include the Ga 3$`d`$ states in the valence. While this is usually a good approximation for GaAs and GaP, it has been found that for GaN not retaining Ga 3$`d`$ states in the valence leads to erroneous results for some physical properties such as optimized lattice constant, cohesive energy fiorentini . We therefore used ultra-soft pseudopotentials which included Ga $`d`$ states in the basis for GaN. We studied transition metal impurities - V, Cr, Mn, Fe, Co and Ni in 64 atom supercells of zincblende GaSb, GaAs, GaP and GaN. In Table I we compare the calculated lattice constants of pure III-V using PW91 GGA exchange functional pw91  with the experimental values expt\_lattice . We have fixed the equilibrium lattice constant of the supercells at the calculated values of the pure host given in Table I. The basis sets had a cutoff energy for plane waves equal to 13.3 Ry for GaSb, GaAs and GaP and 29.4 Ry for GaN. We used a Monkhorst Pack grid of 4x4x4 k-points which includes $`\mathrm{\Gamma }`$. The cell-internal positions of the atoms were allowed to relax to minimize the forces. The equilibrium transition metal-to-As bond lengths in GaAs were 2.47, 2.47, 2.48, 2.44, 2.36 and 2.34 $`\AA `$ for V, Cr, Mn, Fe, Co and Ni respectively.

The $`d`$ partial density of states as well as the local moment at the transition metal were calculated within a sphere of radius of 1.2 $`\AA `$ about the atoms and have been broadened with a gaussian of 0.2 eV full width at half maximum. The total energy differences between the ferromagnetic and the antiferromagnetic spin arrangements were computed for TM pairs at first and fourth neighbor separations for a parallel and an anti-parallel arrangement of their spins to determine whether a specific transition metal impurity resulted in a ferromagnetic state or not.

LDA vs. GGA: In order to compare LDA capz  and GGA pw91  exchange functionals, we consider the case of Co impurity in GaAs, where earlier LDA work mirbt  suggests a nonmagnetic ground state. Using the experimental lattice constant of 5.65 $`\AA `$ for GaAs, we find that the GGA calculations lead to a magnetic ground state with a moment of 2 $`\mu _B`$. The energy of this state is strongly stabilized by $``$ 150 meV compared to the nonmagnetic state. Using LDA exchange functional we find that while the nonmagnetic state is stabilized for a 2x2x2 Monkhorst Pack grid as used in the earlier work mirbt , the magnetic state with the moment of 2 $`\mu _B`$ is stabilized by $``$ 40 meV for a 4x4x4 Monkhorst Pack k-points grid. These observations are consistent with the fact that GGA calculations have a greater ability to stabilize a magnetic ground state than LDA calculation. For other impurities - Cr and Mn in GaAs, the LDA and GGA results are found to give the same ground state. We use the GGA exchange functional throughout this work.

The introduction of various transition metal impurities lead to defect levels in the band gap of the semiconducting host. We compute the formation energies of the transition metal impurities in various charge states $`q`$. The formation energy for a defect comprising of atoms $`\alpha `$ in the charge state $`q`$ was computed using the expression cuinse2

$`\mathrm{\Delta }H_f^{\alpha ,q}(ϵ_f,\mu )`$ $`=`$ $`E(\alpha )E(0)+{\displaystyle \underset{\alpha }{}}n_\alpha \mu _\alpha ^a+q(E_v+ϵ_F),`$ (1)
where $`E(\alpha )`$ and $`E(0)`$ are, respectively the total energies of a supercell with and without the defect $`\alpha `$. $`n_\alpha `$ denotes the number of atoms of defect $`\alpha `$ transferred in or out of the reservoir, while $`\mu _\alpha ^a`$ denotes their chemical potentials.

Total energies: The total energies of the charged supercells were computed by compensating any additional charge on the impurity atom by a uniform jellium background and have been corrected for interactions between charges in neighboring cells using the Makov and Payne correction payne . We use the static dielectric constant values - 15.69 for GaSb, 12.4 for GaAs, 11.11 for GaP and 10.4 for GaN landolt . The quadrupole moment of the isolated defects was calculated as the difference between the moments of the supercell with the charged defect and that with the neutral defect.

Transition energies: The defect transition energy $`ϵ(q,q^{})`$ is the value of the Fermi energy $`ϵ_F`$ at which $`\mathrm{\Delta }H^{\alpha ,q}(ϵ_f)`$=$`\mathrm{\Delta }H^{\alpha ,q^{}}(ϵ_f)`$. The zero of the Fermi energy is chosen as the valence band maximum $`E_v`$ of the pure host.

Chemical potential limits: As the reservoir supplying the atoms could be elemental solids, or compounds formed from the elements, we express $`\mu _\alpha ^a`$ as the sum of the energy of the element in its most stable structure $`\mu _\alpha ^s`$, and an additional energy $`\mu _\alpha `$ i.e $`\mu _\alpha ^a`$ = $`\mu _\alpha ^s`$ \+ $`\mu _\alpha `$. The stable structures we considered for the elements were nonmagnetic body-centred cubic (bcc) for V, antiferromagnetic bcc for Cr, the antiferromagnetic face-centred cubic (fcc) for Mn, ferromagnetic bcc for Fe, ferromagnetic hexagonal for Co, ferromagnetic fcc for Ni and the nonmagnetic base-centred orthorhombic structure for Ga.

The required ranges of $`\mu _\alpha `$ are determined by $`\mu _{Ga}`$ $``$ 0; $`\mu _{TM}`$ $``$ 0; $`\mu _{Sb,As,P,N}`$ $``$ 0 (no precipitation of solid elements) and by the formation energies of the semiconducting host and competing binary phases formed between the elements of the semiconductor and the transition metal impurity. This could be the most stable NiAs phase of MnAs in the case of GaAs:Mn and the MnP phase of CrAs for GaAs:Cr.

The energies E($`\alpha `$), E(0), and $`\mu _\alpha `$ entering Eq.(1) are calculated within the density functional formalism discussed earlier. No correction for the band gap underestimation was made. Changing the k-point mesh from 2x2x2 to 4x4x4 changed the formation energies by $``$ 20 meV. We used a plane wave cutoff of 13.3 Ry for the calculations involving Mn in GaAs. Increasing the cutoff to 29.4 Ry, changed the formation energies by $``$ 10 meV.

## IV Results of Density Functional Calculations

We now divide the main features of the first principle calculations into three main entities introduced in Section I:

A. The nature of the impurity-induced level in the gap

B. The impurity-induced valence-band resonances

C. The perturbed host VBM

Then, in section V, we will provide a simple model that explains all of our numerical results qualitatively.

### IV.1 The Nature of the impurity-induced level in the gap

Figure 1 shows the transition-metal local DOS for V, Cr, Mn, Fe, Co and Ni in GaAs, projected into irreducible representations $`t_2`$ and $`e`$ and spin directions + and -. The VBM is at the zero of the energy. The GGA band gap of pure GaAs is found to be 0.3 eV; all the impurities V-Ni introduce levels into this band gap. We first discuss the nature of these gap levels, and then the circumstances how and when a hole is present in them.

From Fig. 1 we see that the sequence of levels occupied for Cr in GaAs are $`t_+`$, $`e_+`$, $`t_{}`$ and $`t_+`$ in the order of increasing energy. For a free atom one would expect levels of one spin channel to be filled up before levels of the other spin channel; the deviation that one observes here reflects solid state effects. The two sets of $`t_+`$ and $`t_{}`$ levels that we find for each impurity are suggestive of bonding/antibonding combinations arising from hybridization. We therefore determined the atoms on which each of the $`t_2`$ states are localized by computing atom-projected DOS. Bonding states with a large wavefunction amplitude on the TM site are referred to as ”Crystal Field Resonances” (CFR) alexrev , whereas antibonding $`t_2`$ states with low contribution on the TM which are localized instead on the four nearest As atoms are referred to as the ’Dangling Bond Hybrid’ (DBH). The full explanation of the genesis of these states will be provided in Sec. V. We see that,

1. Symmetry of gap levels and lowest unoccupied levels: Substituting Cr, Mn and Co in GaAs introduce levels with up-spin character and $`t_2`$ symmetry in the band gap. These levels are partially occupied by 1, 2 and 2 electrons for neutral Cr, Mn and Co, respectively: Cr0 ($`t_+^1`$), Mn0 ($`t_+^2`$) and Co0 ($`t_+^2`$). The levels introduced by V0 ($`e_+^2`$) and Fe0 ($`t_+^3e_+^2`$) are fully occupied. The first unoccupied levels have $`t_+`$ and $`e_{}`$ symmetry for V and Fe respectively.

2. d character of gap levels: The transition metal projected partial density of states for different transition metal impurities in GaAs given in Fig. 1 indicates that the gap level/first unoccupied level is strongly $`d`$-like for the early transition metal impurities V and Cr, while for the heavier 3$`d`$ elements e.g. Mn these levels have less $`d`$ character. An increased $`d`$ character of the gap level would imply increased spatial localization of the wavefunction in the vicinity of the impurity.

3. Degree of localization of gap levels: We quantify the degree of localization by plotting in Fig. 2 the charge Q(R1)=$`_{R_1}^{R_1+\mathrm{\Delta }}\psi ^2r^2𝑑r`$ enclosed between concentric spheres with radius $`R_1`$ and $`R_1+\mathrm{\Delta }`$ centered about the impurity atom. The integrated charge between the spheres is plotted as a function of R1. For comparison, we show also the result expected for a homogeneous charge distribution (electron gas), where the charge density at any point in the cell is given by reciprocal volume $`\frac{1}{V}`$. We see that Q(R1) for the TM impurities has little similarity to the results for an electron gas. Changing the impurity from Mn to Cr in GaAs, we see an increase in the charge density localized in the vicinity of the impurity. We find that till a radius which includes second neighbors of the TM atom, the integrated charge for Cr is higher than for Mn. Further, we find that the enclosed charge in the vicinity of the impurity atom is higher in GaN:Mn than in GaAs:Mn and the decay of the wavefunction is faster.

4. The negative exchange splitting of the gap levels: Having established the identity of the gap levels, we now investigate their spin splittings. In Fig. 3 we have plotted the spin splittings of the CFR and DBH levels at $`\mathrm{\Gamma }`$ point for the impurities V-Co in GaAs obtained from an analysis of their eigenvalues/eigenfunctions. For V and Cr the spin splitting of the DBH levels is positive i.e. $`t_+^{DBH}`$ states are at lower energies compared to $`t_{}^{DBH}`$. However, for Mn, Fe and Co the splitting is negative with the $`t_{}^{DBH}`$ states at lower energies compared to $`t_+^{DBH}`$. A similar negative exchange splitting was observed earlier for the Te states in MnTe mnte , the Ce states in CeFe2 cef2 , and the Mo states in Sr2FeMoO6 sfmo . The explanation was that the $`p`$ states of Te in CdTe, the $`d`$ states of Ce in CeFe2 and the $`d`$ states of Mo in Sr2FeMoO6 are sandwitched in between the 3$`d`$ states of the transition metal atom. The $`p`$-$`d`$ hybridization results in an exchange splitting of these states opposite in direction to that on the transition metal atom. Indeed we see from Fig. 1 that for the cases where the DBH states are bracketed by the spin split CFR states, the spin splitting is negative.

5. Enhanced exchange splitting for $`t^{CFR}`$ states: From Fig. 3, we see that the exchange splitting of the $`t^{CFR}`$ states is larger than that of the $`e^{CFR}`$ states for Mn, Fe and Co impurities.

Having discussed the existence of impurity-induced levels in the band gap of the host semiconductor, we next discuss the location of these levels.

6. Acceptor transitions for gap levels: Single particle LDA or GGA levels do not have any rigorous meaning. We thus calculate transition energies, $`ϵ`$($`q`$,$`q^{}`$) which correspond to the value of the Fermi energy $`ϵ_F`$ at which the defect changes from a charge state $`q`$ to $`q^{}`$. Table II provides the calculated and measured multiplets\_expt  acceptor/donor transition energies for various transition metal impurities in GaAs. The calculated acceptor levels for Mn and Cr in GaSb, GaAs, GaP and GaN are plotted in Fig. 4 where the host band edges are aligned according to their calculated unstrained valence band offsets boffset . We see that as the electronegativity of the host crystal increases in the sequence GaSb $``$ GaAs $``$ GaP $``$ GaN, its bulk ionization energy (= position of VBM with respect to vacuum) increases. The acceptor level is thus farther away from the VBM of GaN than it is from the VBM of GaAs. Thus, GaN:Mn and GaP:Cr have more localized hole states whereas GaSb:Mn has more delocalized holes. This behavior, whereby the acceptor energy level does not follow the host valence band energy (as in the case of hydrogenic impurities) characterizes localized states fazzio .

7. Multiplet states and violation of isovalency rule: We use the level occupancies (Fig. 1) as well as the net magnetic moments that we obtain for different transition metal impurities in GaAs (Table III) to obtain the multiplet configuration describing the ground state. These are given in Table III. We also provide the multiplet configuration observed from experiment multiplets\_expt  and find that there is agreement in all cases. It is interesting to compare the ground state multiplets of two isoelectronic cases - ZnSe:Fe2+ and GaAs:Co3+ in their neutral charge states. In both cases we expect an electron configuration of $`d^6`$. Normally, one would expect to find equal multiplets for isoelectronic cases alexrev  (isovalency rule). This expectation is based on the fact that we are looking at a low transition metal impurity concentration regime where basic crystal field theory ideas are expected to be sufficient to explain the observed ordering of energy levels. However, we find in GaAs:Co3+ the configuration 3T2, i.e the hole is in the $`t^{DBH}`$ level ($`t_{CFR+}^3e_{CFR+}^2e_{CFR}^2t_{DBH}^3𝐭_{\mathrm{𝐃𝐁𝐇}+}^\mathrm{𝟐}`$), whereas in ZnSe:Fe2+ we find 5E, i.e the hole is in the $`e_{CFR}`$ level ($`t_{CFR+}^3e_{CFR+}^2t_{DBH}^3t_{DBH+}^3𝐞_{\mathrm{𝐂𝐅𝐑}}^\mathrm{𝟏}`$). The reason for the difference is that the stronger $`p`$-$`d`$ hybridization for GaAs:Co pushes the $`t_+^{DBH}`$ levels to higher energies, so that the $`e_{}^{CFR}`$ levels are occupied first and the hole resides in the $`t_+^{DBH}`$ level. We thus conclude that the isovalency rule is not applicable, and one cannot assume that the hole is in a ”generic” $`d`$ state.

8. FM vs. AFM ground state and their relation to the symmetry of the gap levels: Having summarized the nature of the level induced in the gap by the introduction of the transition metal impurity, we now analyze when a ferromagnetic state is favored. In Table III we provide the energy difference between the ferromagnetic and antiferromagnetic energies for two TM atoms at nearest $`\mathrm{\Delta }`$ENN and fourth neighbor $`\mathrm{\Delta }`$E4NN fcc positions in a 64 atom supercell of GaAs. We find that (a) when the level in the gap is fully occupied as in V0 and Fe0, the favored ground state is antiferromagnetic. (b) When the level in the gap is partially occupied and has $`t_2`$ symmetry as in Cr0, Mn0, the ferromagnetic state is lower in energy. This is also the case for electron doped V- in GaAs which is strongly ferromagnetic. Although Co0 (3T2) also has a hole in the $`t_2`$ level, the system is at the brink of a ferromagnetic-to-nonmagnetic transition. (c) When the level in the gap has $`e`$ symmetry, as in the case of electron doped Fe-, the stability of the FM state is weaker. Evidently the symmetry of the hole carrying state strongly determines the magnetic order. We conclude that FM is stabilized strongly only when the hole resides in the level with $`t_2`$ symmetry. (Note , viz. Sec. V, that in $`T_d`$ symmetry $`t_2`$ states are strongly bonded to their neighboring atoms, whereas the lobes of the $`e`$ orbitals point in between the nearest-neighbor atoms.)

### IV.2 The impurity-induced valence-band resonances

Figure 1 shows that in addition to the gap levels, the introduction of a transition metal atom gives rise to resonance levels that lie deep within the valence band of the host semiconductor. In most model Hamiltonian theories model\_dietl1 ; model\_macdonald ; model\_bhatt ; model\_amit ; model\_dietl2 , one usually ignores the orbital degree of freedom of the transition metal impurity, and the presence of the impurity is included only as a localized spin of value 5/2. In our calculations we find that the degree of localization of such deep resonances (thus, the possibility of depicting them as local point-like spin) varies sharply with the position of the impurity in the periodic table. For heavier TM such as Fe and Mn, the deeper resonance level has significant TM $`d`$ character (being Crystal-Field Resonances), while for the early TM impurities in GaAs, one finds that the deeper $`t_2`$ levels have significantly less TM character (being Dangling Bond Hybrids). This is discussed next.

1. Anticrossing of the two $`t_2`$ levels in different host materials: Level anticrossing is evident when keeping the impurity atom fixed, and, changing the host semiconductor. Considering the example of Mn, we find that by changing the host from GaSb to GaN, the DBH and the CFR exhibit anticrossing. This is not the only difference: We find that the exchange splitting of the DBH levels is in the same direction as the CFR levels (positive) in GaN:Mn, in contrast to GaAs:Mn. Further, in GaN:Mn the $`t_+^{CFR}`$ levels lie above the $`e_+^{CFR}`$ levels, unlike the case in GaAs:Mn. The reason is evident from Fig. 4 which shows that the VBM of GaN is much deeper than the VBM of GaAs. Since the free Mn2+ ion has its $`d`$ orbitals above the GaN VBM, but below the VBM of GaSB or GaAs, an anticrossing occurs along the GaN $``$ GaP $``$ GaAs $``$ GaSb series. This is illustrated in Fig. 5 which shows that in GaN:Mn for the up spin channel, the upper $`t_2`$ is more localized than the lower $`t_2`$, whereas in GaAs:Mn the localization sequence is reversed. This clarifies a confusion that existed in the literature dietl\_rev  regarding the question of whether the gap level is localized or not. Our result shows that the answer depends on the host. These results also clarify the nature of the acceptor transition for Mn in different materials. GaN:Mn can be viewed as a $`d^4`$-like case since its configuration is $`e_{CFR+}^2t_{CFR+}^2`$ (hole in $`t_+^{CFR}`$), and the (0/-) acceptor transition is from a Mn configuration $`d^4`$ to $`d^5`$. On the other hand for Mn in GaP, GaAs and GaSb we have the configuration ($`d^5`$ \+ hole), i.e. $`e_{CFR+}^2t_{CFR+}^3t_{DBH}^3t_{DBH+}^2`$ and the acceptor transition is from a Mn configuration of ($`d^5`$+hole) to $`d^5`$.

2. Occupancy of the valence band resonances and comparison with photoemission: Table III gives the calculated occupancy of the crystal field resonances of the 3$`d`$ impurities in GaAs (in square brackets). These levels are found to have a configuration of ”$`d^5`$” for Cr, Mn and Fe. Experimentally the position of these levels can be detected by valence band photoemission fujimori . By suitably tuning the photon energy so that the photo-ionization cross-section is maximum for the TM-related states, an electron can be ionized from these deep CFR levels. Kobayashi et al. fujimori  used resonant valence band photoemission and showed that the the CFR levels for Mn in GaAs are located at $`E_v`$ \- 4 eV. A direct comparison of the position of these levels with the single-particle density of states calculated for GaAs:Mn places these energies at $`E_v`$ \- 2-3 eV. The LDA error in the position of these states is because of the self-interaction correction (SIC) that places these energies too high sicref . As pointed out earlier zungeriivi  for the 3$`d`$ states in II-VI’s, the experimental result should be compared with the total energy difference between the configurations $`d^4`$ and $`d^5`$ and not with the bare single particle eigenvalues. Alternatively, the LDA error can be empirically corrected by using the simplified LDA+U version of SIC. In Fig. 6 we plot the Mn $`t_+^{CFR}`$ partial density of states as a function of U for GaAs:Mn. As $`U`$ increases, the position of the Mn $`t^{CFR}`$ level is pushed deeper into the GaAs valence band. Agreement with XPS for the $`t_+^{CFR}`$ being at $`E_v`$-4 eV occurs for U $``$ 2 eV. At the same time, the Mn character of the DBH state at $`ϵ_F`$ (not shown) decreases with increasing $`U`$. As the DBH hole becomes more delocalized, the EFM-EAFM stabilization energy (insert to Fig. 6) is reduced; a ”host-like hole” obtained for unphysically large U leads to nearly vanishing FM stabilization energy. Clearly, the picture of ”host like hole” is invalid for GaAs:Mn, since for the $`U`$ that leads to agreement with XPS the DBH hole is still localized to some extent, whereas for very large $`U`$, when the hole is delocalized, there is no ferromagnetism.

### IV.3 The perturbed host VBM

Having studied the impurity-induced levels in the gap and deep in the host valence band, we next examine the perturbation of the host states, especially the host valence band maximum by the presence of the impurity atom. Figure 7 shows the up and down spin band dispersions for 3 $`\%`$ Cr doped GaP supercell (panels (a) and (b)). The band dispersion of the GaP host without the impurity has been provided in panel (c) for comparison. The thickness of the lines depicting these bands has been made proportional to the Cr $`d`$ character of the states. We see that Cr introduces a new band within the band gap of GaP. In a band-theoretic picture, this system is metallic, with the Fermi energy within the impurity band. Interestingly, (1) the host band dispersions are significantly altered by the presence of the impurity. In particular the VBM is found to have significant TM $`d`$ character for the 3$`\%`$ Cr concentration represented by the supercell. (2) A Cr-induced spin-splitting of the valence band maximum is observed. Effects (1) and (2) suggest that the host VBM is sufficiently perturbed by the transition metal.

Another way of detecting perturbations in the host bands is to examine the host projected DOS of the system containing the impurity. In Fig. 8 we have plotted the As $`p`$ partial density of states projected onto different As atoms labelled 1-4 for a GaAs supercell containing 2 Mn atoms. The As atom labelled 1 has one Mn nearest neighbor, while the As atom labelled 2 has two Mn nearest neighbors. The As atoms show a strong polarization which increases with the number of Mn neighbors. The As atoms labelled 3 and 4 which are far away from the Mn atoms show a reduced polarization.

To pictorially see the perturbation in the VBM states, we compare in Fig. 9 the wavefunction squared along two chains in the (110) plane for the valence band maximum of the pure GaAs host (panel (a)) as well as the VBM (i.e. state below DBH) of the system with the Mn impurity in the up (panel (b)) and down (panel (c)) spin channels. The upper chain in panels (b) and (c) contains the perturbing Mn impurity. The perturbation of the VBM in the presence of the impurity can be assessed by comparing the perturbed charge density for each spin channel with the unperturbed charge density of the host lattice. We find that the perturbations are significant in the chain containing the Mn atom, while in adjoining chains, the perturbation is limited in extent. Further the perturbations are stronger in the up spin channel than in the down spin channel.

To evaluate the 3$`d`$-induced spin-splitting in the VBM, we reference the up and down spin VBM eigenvalues of the impure system to the corresponding VBM of the pure host semiconductor. This is done by aligning the average potentials on Ga atoms far away from the impurity for the two systems. The presence of the impurity band with $`t_2`$ symmetry above the VBM for Mn and Cr impurities complicates the identification of the valence band maximum. We associate the highest occupied triply degenerate eigenvalues at $`\mathrm{\Gamma }`$ point with the impurity band, and the next deeper set as $`E_v^+`$. The shift with respect to the pure host $`\mathrm{\Delta }E_v^+`$=$`E_v^+`$(GaAs:Mn)-$`E_v`$ (GaAs) and $`\mathrm{\Delta }E_v^{}`$=$`E_v^{}`$(GaAs:Mn)-$`E_v`$ (GaAs) is given in Table IV for the impurities V, Cr and Mn in different host semiconductors. We find that the perturbation of the host VBM is smaller in the down spin channel compared to the up spin channel. This is consistent with what we find from the charge density plotted in Fig. 9. The spin splitting of the valence band maximum depends strongly on the transition metal impurity and host semiconductor combination. Considering the case of impurities in GaAs, we find that while the spin splitting associated with the introduction of V is only 0.06 eV, it increases to 0.39 eV for Mn. Keeping the impurity fixed (Mn), and varying the semiconductor host (GaAs to GaN), we find the splitting decreases from 0.39 eV to 0.1 eV. The small valence band splittings in the case of V in GaAs as well as Mn in GaN compared with that for Mn in GaAs is because of the larger energy separation between the interacting $`t_2`$ states in the former cases compared to the latter.

### IV.4 Summary of the electronic structure as obtained by density functional

We are now in a position to examine whether the physical picture of the electronic structure of 3$`d`$ impurities as assumed in model Hamiltonian theories (reviewed in Sec. I) is consistent with first-principles calculations (outlined in Sec. IV).

(i) The nature of the TM-induced hole state: A 3$`d`$ impurity in a III-V semiconductor generates two sets of states with $`t_2`$ symmetry, and one set of states with $`e`$ symmetry in each spin channel. While one set of $`t_2`$ states are localized on the TM atom (CFR), the other are localized on the host anion atoms next to the impurity (DBH). These states CFR and DBH exhibit anticrossing for a fixed TM as a function of the host anion GaN $``$ GaP $``$ GaAs $``$ GaSb, or for a fixed host as a function of the impurity V $``$ Mn. The localization of the hole state decreases as we move from Mn in GaN to Mn in GaP, and then to Mn in GaSb. Not all impurities introduce holes. In GaAs, V0 and Fe0 have no hole; Cr0, Mn0 and V- have $`t_2`$ holes; and Fe- has an $`e`$ hole. In all cases, however, the hole is non-hydrogenic, manifesting significant admixture of 3$`d`$ character and showing deep acceptor levels whose energies do not follow the host VBM. This implies that the neglect of the short-range part of the impurity potential and the consequent expansion of the acceptor wavefunction in terms of a single host wavefunction are questionable. The effective mass of the hole state is therefore different from that of the host, as observed in recent experiments optical\_prl . The exchange splitting of the CFR states is different for the $`t_2`$ states from that for the $`e`$ states. While the splitting for the $`e`$ states is larger than that for the $`t_2`$ states for V and Cr in GaAs, the order is reversed for Mn, Fe and Co. This reversal in the order of the spin splitting of the CFR states is accompanied by a reversal in the sign of the spin splitting of the DBH states. The identity of the hole state - both the symmetry as well as the character depends on the impurity-host combination. While the hole carrying orbital for Fe in ZnSe has $`e`$ symmetry, the hole is found to be located in an orbital with $`t_2`$ symmetry for the isovalent doping of Co in GaAs.

(ii) The nature of the host VBM: The introduction of the transition metal perturbs the valence band of the host crystal. We find this perturbation to be large when the state in the gap has $`t^{DBH}`$ character. This is because the effective coupling is larger since the DBH states have strong host character. We find that the VBM is spin-split in the presence of 3$`d`$ impurity, and that the VBM in the up-spin channel is perturbed more strongly than in the spin down channel in the presence of the impurity.

(iii) Ferromagnetism and symmetry: Impurities with fully occupied DBH-like $`t_2`$ gap states such as V0, Fe0 show antiferromagnetism. Partial occupation of the $`t^{DBH}`$ as in Cr0, Mn0 or V- show ferromagnetism. Partially occupied $`e`$-like level like in Fe- show weak or no ferromagnetism.

(iv) Ferromagnetism and hole localization: Using LDA+U as an artificial device to explore the consequences of delocalized host-like-hole states we find (insert to Fig. 8) that in this limit there is reduced ferromagnetism.

We find that despite the well known GGA-LDA band gap error, as well as the underestimation of the location of deep CFR states due to SIC, these first principle calculations provide us with the correct spin multiplets. LDA+U changes some details (CFR locations), but does not alter the basic picture emerging from GGA/LDA when the hole is DBH-like as in GaAs:Mn.

## V  Simple Model of the Electronic Structure of 3$`d`$ impurities in GaAs

### V.1 The Model

Most of the results of the density functional study of the electronic structure of 3$`d`$ impurities in III-V’s (Sec III) can be captured by a simple model. The electronic structure of substitutional 3$`d`$ in III-V semiconductors can be understood as arising from the interaction of the host cation vacancy (= anion dangling bonds) with the crystal-field and exchange split orbitals of a 3$`d`$ ion.

(a) The dangling bonds for a column III cation vacancy $`V_{III}`$: A cation vacancy for a column III element gives rise to a fully-occupied $`s`$-like $`a_1`$ level located deep in the host valence band, and a partially-occupied $`p`$-like $`t_2`$ level located just above the host valence band maximum, with wavefunction amplitude localized primarily on the neighboring atoms baraff . This is evident from the wavefunction squared of the Ga vacancy dangling bond state shown in the (110) plane in Fig. 10. The neutral vacancy $`V_{III}^0`$ has a deficiency of 3 electrons, i.e the orbital configuration is $`a_1^2t_2^3(p)`$, where $`p`$ denotes its major orbital character. Spin-polarization splits this $`t_2(p)`$ vacancy level into spin-up \[$`t_+(p)`$\] and spin-down \[$`t_{}(p)`$\] states, but the splitting is small (90 meV at the $`\mathrm{\Gamma }`$ point) on account of the rather delocalized nature of these pure host dangling bond orbitals.

(b) The crystal-field split TM 3$`d`$ orbitals: The tetrahedral crystal-field of the zincblende host splits the TM $`d`$ levels into $`e(d)`$ and $`t_2(d)`$, with $`e`$ below $`t_2`$ in the point-ion limit balhausen ; the crystal-field (CF) splitting of the ion is denoted by $`\mathrm{\Delta }_{CF}`$($`t_2`$-$`e`$). Exchange interactions further split these levels into spin-up (+) and spin-down (-), with exchange-splittings $`\mathrm{\Delta }_x(e)`$\[$`e_{}`$(d)-$`e_+`$(d)\] and $`\mathrm{\Delta }_x(t)`$\[$`t_{}`$(d)-$`t_+`$(d)\].

The energy levels of a cation-substituted TM in a III-V semiconductor can be thought of alexrev  as the result of hybridization between the anion dangling bonds generated by a column III cation vacancy $`V_{III}`$ \[(i) above\], and the crystal-field and exchange split $`d`$ levels of a TM ion placed at the vacant site \[(ii) above\]. There are two limiting cases: When the 3$`d`$ levels are well below the host cation dangling bonds (e.g. Mn in GaAs, Fig. 11), or when the 3$`d`$ levels are well above the host cation dangling bonds (e.g. V in GaAs, Fig. 12). The dangling bond states are shown on the right hand side of Fig. 11 and 12, while the crystal field and exchange split TM $`d`$ levels are shown on the left hand side of Fig. 11 and 12. The levels generated after hybridization are shown in the central panel. The $`t_2(p)`$ levels of the anion dangling bond hybridize with the $`t_2(d)`$ levels of the transition metal. In contrast, the $`e(d)`$ level of the TM ion remains largely unperturbed since the host does not have localized $`e`$ states in this energy range, available for significant coupling. Considering the examples of Mn in GaAs and GaN, we plot the charge density of the $`e`$ and the $`t_2`$ states in the (110) plane in Fig. 13. It is evident that the $`e`$ states for Mn in GaAs are essentially nonbonding, while in GaN, as a result of the reduced Mn-Mn separation, there is weak interaction between the Mn atoms. The hybridization in the $`t_2`$-channel creates bonding, transition-metal localized ”Crystal-Field Resonances” (CFR): $`t_+^{CFR}`$, $`t_{}^{CFR}`$, as well as the host-anion localized antibonding ”Dangling Bond Hybrids” (DBH): $`t_+^{DBH}`$, $`t_{}^{DBH}`$, whereas the $`e`$-channel creates the non-bonding $`e_+^{CFR}`$ and $`e_{}^{CFR}`$ states. This model explains the existence of two sets of $`t_+`$ and $`t_{}`$ levels that we found in Fig. 1. The available electrons for occupation of these levels are N=(n-1)+6 for a $`d^n`$s2 transition metal atom (three electrons are used to complete the anion dangling bond state to $`t_2^6`$($`p`$), leaving $`d^{n1}`$ at the transition metal ion.) For GaAs:V (Fig. 12) the ordering of levels after hybridization is

$$t_+^{DBH}<t_{}^{DBH}<e_+^{CFR}<t_+^{CFR}<e_{}^{CFR}<t_{}^{CFR}$$

with increasing energy. Hence for V we have N=(n-1)+6=8 electrons occupy the DBH and CFR levels. Thus, V has the configuration ($`t_{DBH+}^3t_{DBH}^3e_{CFR+}^2`$), as seen in Fig. 1 and Table III.

The order of levels for

$$\text{GaAs:Mn   is }(t_{CFR+}^3<e_{CFR+}^2<t_{DBH}^3<t_{DBH+}^2)\text{,}$$

$$\text{GaAs:Fe   is }(t_{CFR+}^3<e_{CFR+}^2<t_{DBH}^3<t_{DBH+}^3)\text{,}$$

$$\text{GaAs:Co   is }(t_{CFR+}^3<e_{CFR+}^2<e_{CFR}^2<t_{DBH}^3<t_{DBH+}^2)$$

(Fig. 11). The number of electrons (n-1)+6 is 10, 11 and 12 for Mn, Fe and Co respectively. This agrees with Fig. 1 showing that Mn and Fe in GaAs have the ordering of levels shown in Fig. 11, with fully-filled $`t_+^{CFR}`$ and $`e_+^{CFR}`$ levels and 2, 1 and 0 holes in the $`t_+^{DBH}`$ level. By an analysis of the density of states obtained within our first principle calculations, we have determined (Table III) the energy minimizing orbital configurations for the transition metal impurities V, Cr, Mn, Fe and Co in GaAs in fully relaxed configurations. The first unoccupied orbital for each impurity has been indicated in boldface in Table III. The simple model of Figs. 11, 12 gives the same result.

### V.2 Qualitative consequences of the simple model

1. Level anticrossing: The model explains how the hopping interaction between the $`t_2`$ states on the transition metal impurity with the cation-vacancy states generates a pair of $`t_2`$ states in each spin channel. The bonding-antibonding character of these states is determined by the relative separation of the interacting levels as well as their interaction strengths. Hence as depicted in Fig. 14, one could by a suitable choice of the TM impurity change the character of the gap levels. When the orbital energy of the 3$`d`$ ion lies below the host dangling bond, we have a ”CFR-below-DBH” situation, illustrated in Fig. 11. In this case one has CFR states in the valence band of the semiconductor while the gap levels are more delocalized with dominant weight in the dangling bonds. This is the case for GaAs:Fe, Mn, and Co. Conversely, when the orbital energy of the 3$`d`$ ion lies above the host dangling bond, we have the ”CFR-above-DBH” situation, illustrated in Fig. 12. In this case the gap level is CFR-like.

While Fig. 1 illustrates anticrossing when changing the 3$`d`$ atom, but keeping the host fixed, e.g. GaAs, Fig. 5 suggests that there is also anticrossing when keeping the 3$`d`$ atom fixed e.g. Mn, but changing the host crystal GaN $``$ GaP $``$ GaSb. Indeed, as the anion dangling bond becomes deeper (GaSb $``$ GaAs $``$ GaP $``$ GaN) or the TM $`d`$ level becomes shallower (Mn $``$ V), there will be a DBH-CFR anticrossing, resulting in the level ordering shown in Fig. 12. The CFR-above-DBH is exemplified by GaAs:V (see Fig. 1) which has a shallow $`d`$ level and by GaN:V, Cr and Mn which have a deep semiconductor VBM boffset . For GaAs:V, this level anti-crossing results in a reduced $`\mathrm{\Delta }_x`$($`t_2`$) exchange splitting compared to the cases where this crossing did not occur (Cr and beyond). For Mn in III-V’s we see a reversal between hole-in-DBH case for GaAs:Mn with $`[t_+^3e_+^2t_{}^0e_{}^0]_{CFR}`$ $`(𝐭_+^\mathrm{𝟐}t_{}^3)_{DBH}`$ configuration to the case of hole-in-CFR $`[𝐭_+^\mathrm{𝟐}e_+^2t_{}^0e_{}^0]_{CFR}`$ $`(t_+^3t_{}^3)_{DBH}`$ for GaN:Mn. As the CFR is much more localized than DBH, this is reflected by a change in acceptor level depth.

2.  Negative exchange splitting in the DBH manifold and low-spin configurations: For Co,Fe and Mn in GaAs the special position of the Ga-vacancy level $`t_{}`$(p) between the exchange-split TM ion levels $`t_+`$(d) and $`t_{}`$(d) (Fig. 11), results in a hybridization-induced exchange splitting of the DBH states (Fig. 3), opposite in direction to the splitting on the CFR levels (Fig. 3). This results from the fact that $`t_{}^{DBH}`$ is pushed down by $`t_{}`$($`d`$)-$`t_{}`$($`p`$) coupling more than the $`t_+`$($`d`$)-$`t_+`$($`p`$) coupling pushes $`t_+^{DBH}`$ up. Such a negative exchange splitting was also observed in bulk MnTe mnte , CeF2 cef2  and Sr2FeMoO6 sfmo . As seen in Table III, the negative exchange splitting leads to the DBH orbital configuration ($`t_{}^3𝐭_+^\mathrm{𝟐}`$) and ($`t_+^3t_{}^3`$) for Mn and Fe, respectively. This corresponds to a low-spin configurations for Mn with a moment of 4. Co, on the other hand, has a configuration of \[$`t_+^3`$$`e_+^2`$$`e_{}^2`$\]CFR ($`t_{}^3𝐭_+^\mathrm{𝟐}`$)DBH, so $`\mu `$=2$`\mu _B`$. Note that the moment $`\mu `$=4 for GaAs:Mn is a consequence of $`\mathrm{\Delta }_x<0`$: the $`e_+^2t_+^3`$ CFR levels give a spin of 5/2, and the $`t_{}^{DBH}`$-below-$`t_+^{DBH}`$ gives a configuration $`t_{}^3t_+^2`$, so the total spin is 4/2, and $`\mu `$=4. Had $`t_{}^{DBH}`$ been above $`t_+^{DBH}`$, we would have had the configuration $`t_+^3t_{}^2`$ with S=3, and $`\mu `$=6. As a result of the negative exchange splitting of the DBH states, one finds that the exchange splitting for the more delocalized $`t^{CFR}`$ levels is larger than that for the more localized $`e^{CFR}`$ levels.

3.  Migration of the d-holes into the DBH acceptor states of GaAs:Cr, Mn and Co: The $`d^{n1}`$ configuration of the trivalent TM ion corresponds to $`d^3`$ for Cr and $`d^4`$ for Mn in GaAs and thus to 2 and 1 hole respectively, relative to $`d^5`$. However, since for these impurities the $`t_+^{CFR}`$ and $`e_+^{CFR}`$ levels are deeper in energy than the $`t^{DBH}`$ levels (Fig. 11), it is energetically favorable for the $`d`$ holes to ”float” into the higher $`t^{DBH}`$ levels. As a result, we find that GaAs:Cr ($`d^3`$) has a configuration $`[t_+^3e_+^2]_{CFR}`$$`(t_{}^3t_+^1)_{DBH}`$ with two holes in the DBH, while for GaAs:Mn ($`d^4`$) we find $`[t_+^3e_+^2]_{CFR}`$$`(t_{}^3t_+^2)_{DBH}`$ with one hole, and GaAs:Fe ($`d^5`$) has a closed-shell configuration of $`[t_+^3e_+^2e_{}^0]_{CFR}`$$`(t_+^3t_{}^3)_{DBH}`$. One expects Co ($`d^6`$) to have a configuration $`[t_+^3e_+^2e_{}^1]_{CFR}`$$`(t_{}^3t_+^3)_{DBH}`$, i.e. a ground state multiplet $`{}_{}{}^{5}E`$ with a hole in $`e^{CFR}`$. However, we find that the lowest energy configuration for Co is $`[t_+^3e_+^2e_{}^2]_{CFR}`$$`(t_{}^3t_+^2)_{DBH}`$ with a hole in the DBH level i.e. ground state multiplet $`{}_{}{}^{3}T_{2}^{}`$. The migration of the holes from the TM-localized deep CFR levels into the dangling-bond manifold for Cr, Mn and Co in GaAs creates partially occupied $`p`$-$`d`$ hybridized states at the Fermi level with significant delocalized As $`p`$ character.

4. Perturbation of the valence band maximum of the host: The valence band maximum of the pure host has $`t_2`$ symmetry. Hence, they can interact with the states with the same symmetry on the dangling bonds as well as the TM ion. The consequent spin splitting of the VBM must depend on the relative separation of the levels involved as well as the coupling strength. Our analysis for different TM-host combinations suggests that when the gap level has $`t^{DBH}`$ character the spin-splitting of the VBM is large ($``$ 0.4 eV for Mn in GaAs). Changing the host semiconductor from GaAs to GaN, increases the energy separation between the dangling bond levels generated by the Ga vacancy and the valence band levels. Consequently the perturbation of the valence band levels resulting in the observed spin-splitting is smaller ($``$ 0.1 eV for Mn in GaN). This VBM spin-splitting of the impure system has been traditionally used to estimate the exchange interaction strength $`J_{pd}`$ between the hole and the transition metal atom. We see that the spin splittings of the VBM of the impure system is grossly underestimates the spin-splitting of the impurity band (DBH,CFR) as seen in Figs. 1,3 and 5.

## VI Conclusions

We have analyzed the basic electronic structure of 3$`d`$ transition metal impurities in III-V semiconductors. We find that the introduction of a 3$`d`$ impurity is accompanied by the introduction of a pair of states with $`t_2`$ symmetry in addition to nonbonding states with $`e`$ symmetry. Not all 3$`d`$ impurities introduce holes. The basic symmetry and character of the hole state depends strongly on the semiconductor-impurity combination. We find that the hole has significant 3$`d`$ character. We have constructed a microscopic model which captures the basic aspects of the electronic structure of transition metal impurities in semiconductors. The elements of this model are the relative separation of the dangling bond and transition metal levels, the $`p`$-$`d`$ hybridization strength and the crystal-field and exchange splittings of the transition metal levels. We model a change in these interaction strengths by changing the semiconducting host, keeping the transition metal impurity fixed, - Mn. We find that while the hole introduced by Mn has significant 3$`d`$ character in GaN, it is more delocalized in GaAs. The symmetry ($`e`$ vs. $`t_2`$), the character (DBH vs. CFR) as well as the occupancy of the gap level, determine the magnetic ground state favored by the transition metal impurity. When the hole has dominantly host character, an exchange splitting is induced on the hole states which is opposite in direction to that on that the transition metal atom. The nature of the exchange coupling $`J_{pd}`$ that exists between between the transition metal atom and the hole comes out automatically from such a microscopic model. The perturbation of the host valence band is not directly related to the coupling strength $`J_{pd}`$. When the hole has primarily DBH character, one finds the perturbation of the host valence band is larger. The basic picture that emerges from our first-principles calculations could be used to replace the more naive model-Hamiltonian treatments which have assumed a host-like-hole picture, an unperturbed valence band and that the spin of the hole couples to the spin of the TM via a local exchange interaction.

This work was supported by the U.S. DOE, Office of Science, BES-DMS under contract no. DE-AC36-99-G010337.


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# Some notes about matrices, 5

As usual, let $`𝐑`$, $`𝐂`$ be the real and complex numbers, and for each positive integer $`n`$ let $`𝐑^n`$, $`𝐂^n`$ be the real and complex vector spaces of $`n`$-tuples of real and complex numbers, respectively. We write $`GL(𝐑^n)`$, $`GL(𝐂^n)`$ denote the general linear groups of invertible real and complex-linear transformations on $`𝐑^n`$, $`𝐂^n`$, respectively, and $`SL(𝐑^n)`$, $`SL(𝐂^n)`$ for the subgroups of $`GL(𝐑^n)`$, $`GL(𝐂^n)`$ consisting of linear transformations with determinant equal to $`1`$. Also, $`O(𝐑^n)`$, $`U(𝐂^n)`$ are the subgroups of $`GL(𝐑^n)`$, $`GL(𝐂^n)`$ of orthogonal and unitary linear transformations on $`𝐑^n`$, $`𝐂^n`$, respectively, which are the linear transformations which preserve the standard Euclidean norm, or, equivalently, the standard inner products on $`𝐑^n`$, $`𝐂^n`$, which is the same as saying that they are invertible linear transformations whose inverses are equal to their adjoints, and $`SO(𝐑^n)`$, $`SU(𝐑^n)`$ are the special orthogonal and unitary groups, which are the subgroups of $`O(𝐑^n)`$, $`U(𝐂^n)`$ of linear transformations which also have determinant equal to $`1`$.

Let us write $`𝒮(𝐑^n)`$, $`𝒮(𝐂^n)`$ for the real vector spaces of self-adjoint linear transformations on $`𝐑^n`$, $`𝐂^n`$. We write $`𝒮_+(𝐑^n)`$, $`𝒮_+(𝐂^n)`$ for the open convex cones in $`𝒮(𝐑^n)`$, $`𝒮(𝐂^n)`$ consisting of linear transformations which are positive-definite. Furthermore, we write $`(𝐑^n)`$, $`(𝐂^n)`$ for the subsets of $`𝒮_+(𝐑^n)`$, $`𝒮_+(𝐂^n)`$ of linear transformations with determinant equal to $`1`$.

Of course $`GL(𝐑^n)`$, $`GL(𝐂^n)`$ are open subsets of the vector spaces of all linear transformations on $`𝐑^n`$, $`𝐂^n`$, respectively, which can be defined by the condition that the determinant is nonzero. One can think of $`SL(𝐑^n)`$, $`SL(𝐂^n)`$ as hypersurfaces in $`GL(𝐑^n)`$, $`GL(𝐂^n)`$, and indeed they are regular or smooth hypersurfaces because the equation that the determinant be equal to $`1`$ is nondegenerate on these subsets, which is to say that the gradient of the determinant, as a function on the vector space of linear transformations on $`𝐑^n`$ or $`𝐂^n`$, is nonzero at every invertible linear transformation. Similarly, $`(𝐑^n)`$, $`(𝐂^n)`$ are smooth hypersurfaces in the open sets $`𝒮_+(𝐑^n)`$, $`𝒮_+(𝐂^n)`$.

There are natural actions of $`GL(𝐑^n)`$, $`GL(𝐂^n)`$ on $`𝒮(𝐑^n)`$, $`𝒮(𝐂^n)`$, defined by

(1)
$$AT^{}AT$$

when $`A`$ is a self-adjoint linear transformation on $`𝐑^n`$ or $`𝐂^n`$ and $`T`$ is an invertible linear transformation on the same space. If $`T`$ is an invertible linear mapping on $`𝐑^n`$ or $`𝐂^n`$, then this action takes $`𝒮_+(𝐑^n)`$ onto itself or $`𝒮_+(𝐂^n)`$ onto itself, as appropriate. Similarly, if $`T`$ lies in $`SL(𝐑^n)`$ or in $`SL(𝐂^n)`$, then this action takes $`(𝐑^n)`$ onto itself or $`(𝐂^n)`$ onto itself, as appropriate.

The exponential of a linear transformation $`A`$ on $`𝐑^n`$ or on $`𝐂^n`$ is defined by

(2)
$$\mathrm{exp}A=\underset{j=0}{\overset{\mathrm{}}{}}\frac{A^n}{j!},$$

and is always an invertible linear transformation on the same space. When $`A`$ is self-adjoint, $`\mathrm{exp}A`$ is self-adjoint and positive-definite, and indeed the exponential defines a one-to-one mapping of $`𝒮(𝐑^n)`$, $`𝒮(𝐂^n)`$ onto $`𝒮_+(𝐑^n)`$, $`𝒮_+(𝐂^n)`$, respectively. If we write $`𝒮_0(𝐑^n)`$, $`𝒮_0(𝐂^n)`$ for the linear subspaces of $`𝒮(𝐑^n)`$, $`𝒮(𝐂^n)`$ consisting of self-adjoint linear transformations with trace $`0`$, then the exponential is a one-to-one mapping of $`𝒮_0(𝐑^n)`$, $`𝒮_0(𝐂^n)`$ onto $`(𝐑^n)`$, $`(𝐂^n)`$, respectively.

Next we look at some of these objects in terms of vector calculus.

For linear transformations on $`𝐑^n`$ or on $`𝐂^n`$, the differential of the exponential mapping at the origin is equal to the identity. Explicitly, for each linear transformation $`A`$ on $`𝐑^n`$ or on $`𝐂^n`$, we have that

(3)
$$\left(\frac{d}{dt}\mathrm{exp}(tA)\right)_{t=0}=A.$$

Similarly, for the second differential, if $`A`$, $`B`$ are linear transformations on $`𝐑^n`$ or on $`𝐂^n`$, then

(4)
$$\left(\frac{^2}{st}\mathrm{exp}(sA+tB)\right)_{s,t=0}=\frac{1}{2}(AB+BA).$$

Let us define a Riemannian metric on $`𝒮_+(𝐑^n)`$, $`𝒮_+(𝐂^n)`$ as follows. If $`P`$ is a positive-definite self-adjoint linear transformation on $`𝐑^n`$ or on $`𝐂^n`$, then tangent vectors to $`𝒮_+(𝐑^n)`$, $`𝒮_+(𝐂^n)`$ at $`P`$ are given simply by self-adjoint linear transformations $`A`$, $`B`$ on $`𝐑^n`$ or on $`𝐂^n`$, and we define the inner product of these two tangent vectors at $`P`$ by

(5)
$$A,B_P=tr(P^1AP^1B),$$

where $`trC`$ denotes the trace of a linear transformation $`C`$. Using standard properties of the trace it is easy to see that this is a positive-definite symmetric bilinear form in $`A`$, $`B`$, and it depends smoothly on $`P`$, so that we get a Riemannian metric on $`𝒮_+(𝐑^n)`$ or on $`𝒮_+(𝐂^n)`$, as appropriate.

Suppose that $`T`$ is an invertible linear mapping on $`𝐑^n`$ or on $`𝐂^n`$, and consider the mapping $`\tau =\tau ^T`$ on $`𝒮_+(𝐑^n)`$ or $`𝒮_+(𝐂^n)`$, as appropriate, defined by

(6)
$$\tau (P)=T^{}PT.$$

If $`A`$, $`B`$ are self-adjoint linear transformations on $`𝐑^n`$ or on $`𝐂^n`$, which we view as tangent vectors to $`𝒮_+(𝐑^n)`$ or $`𝒮_+(𝐂^n)`$ at $`P`$, then $`d\tau _P(A)`$, $`d\tau _P(B)`$, which are the images of $`A`$, $`B`$ as tangent vectors at $`P`$ under the differential of the mapping $`\tau `$, are self-adjoint linear transformations on $`𝐑^n`$ or $`𝐂^n`$ given by

(7)
$$d\tau _P(A)=T^{}AT,d\tau _P(B)=T^{}BT,$$

and they are viewed as tangent vectors to $`𝒮_+(𝐑^n)`$ or $`𝒮_+(𝐂^n)`$ at $`\tau (P)`$. One can check that

(8)
$$d\tau _P(A),d\tau _P(B)_{\tau (P)}=A,B_P,$$

which is to say that the Riemannian metrics on $`𝒮_+(𝐑^n)`$, $`𝒮_+(𝐂^n)`$ are invariant under the actions of $`GL(𝐑^n)`$, $`GL(𝐂^n)`$ that we have defined.

Of course the usual flat Riemannian metrics are defined as follows. If $`T`$ is an element of $`𝒮(𝐑^n)`$ or of $`𝒮(𝐂^n)`$, then again two tangent vectors $`A`$, $`B`$ to $`𝒮(𝐑^n)`$ or $`𝒮(𝐂^n)`$ at $`T`$ are given by self-adjoint linear transformations on $`𝐑^n`$ or $`𝐂^n`$, as appropriate, and their inner product in the standard flat Riemannian metric is given by the usual inner product, namely

(9)
$$trAB.$$

The flatness of this Riemannian metric is reflected in the fact that it does not depend on the point $`T`$ in the space.

The metrics that we have defined on $`𝒮_+(𝐑^n)`$, $`𝒮_+(𝐂^n)`$ reduce exactly to the standard flat metric at the identity operator $`I`$. The differential of the exponential function at the zero operator is equal to the identity mapping,

(10)
$$d\mathrm{exp}_0(A)=A,$$

as we have noted previously, and thus the standard flat metric on the tangent space of $`𝒮(𝐑^n)`$ or $`𝒮(𝐂^n)`$ at $`0`$ agrees with the metric that we have defined on $`𝒮_+(𝐑^n)`$ or $`𝒮_+(𝐂^n)`$, respectively, at the identity operator $`I`$ with respect to the correspondence given by the differential of the exponential function. We would like to show that in fact this agreement works to another term in the Taylor expansion.

Basically this means that if $`T`$ is a self-adjoint linear transformation on $`𝐑^n`$ or on $`𝐂^n`$, which we think of as being near the origin, and if $`A`$, $`B`$ are two self-adjoint linear transformations on the same space, which we think of as tangent vectors to $`𝒮(𝐑^n)`$ or $`𝒮(𝐂^n)`$ at $`T`$, then the images of $`A`$, $`B`$ under the differential of the exponential map at $`T`$ have inner product with respect to the Riemannian metric defined above at the exponential of $`T`$ which agrees to second order with the inner product of $`A`$ in the standard flat metric on $`𝒮(𝐑^n)`$ or $`𝒮(𝐂^n)`$. Explicitly, this means that

(12) $`d\mathrm{exp}_T(A),d\mathrm{exp}_T(B)_{\mathrm{exp}T}`$
$`=tr(\mathrm{exp}(T))(d\mathrm{exp}_T(A))(\mathrm{exp}(T))(d\mathrm{exp}_T(B))`$
agrees with

(13)
$$trAB$$

up to terms of order $`O(T^2)`$. This is not difficult to check, using the facts that $`\mathrm{exp}(T)=IT+O(T^2)`$,

(14)
$$d\mathrm{exp}_T(A)=A+\frac{1}{2}(TA+AT)+O(T^2),$$

and similarly for $`B`$.

As a consequence, if $`C`$ is any self-adjoint linear transformation on $`𝐑^n`$ or $`𝐂^n`$, then

(15)
$$\mathrm{exp}(tC)$$

satisfies the equation for geodesics in the space of positive-definite linear transformations at $`t=0`$. Basically this is because the line $`tC`$ satisfies the equation for geodesics in the flat space of self-adjoint linear transformations at the origin. Of course we are also using the fact that the standard flat metric on the space of self-adjoint linear transformations around $`0`$ agrees with the Riemannian metric on the space of positive-definite metrics around the identity operator $`I`$ with respect to the exponential mapping as well as they do.

In fact, we get that

(16)
$$\mathrm{exp}(tC)$$

satisfies the equation for geodesics in the space of positive-definite matrices for all real numbers $`t`$. For a fixed real number $`t_0`$, the statement that this curve satisfies the equation for geodesics at $`t_0`$ is equivalent to the statement that $`\mathrm{exp}((t_0+t)C)`$ satisfies the equation for geodesics at $`t=0`$. This is in turn equivalent to the statement that $`T^{}\mathrm{exp}(tC)T`$ satisfies the equation for geodesics at $`t=0`$ when $`T=\mathrm{exp}(t_0C/2)`$, and this follows from the fact that $`\mathrm{exp}(tC)`$ satisfies the equation for geodesics at $`t=0`$, since transformations of the form $`PT^{}PT`$ are isometries on the spaces of positive-definite matrices and therefore preserve geodesics.

Thus exponentials of straight lines through the origin in the spaces of self-adjoint linear transformations give rise to geodesics through the identity operator $`I`$ in the corresponding spaces of positive-definite linear transformations. By standard results about uniqueness of initial value problems for ordinary differential equations this accounts for all of the geodesics in the spaces of positive definite linear transformations which pass through the identity operator $`I`$. Using mappings of the form $`PT^{}PT`$ one can move these curves to other places and thereby account for all of the geodesics in the spaces of positive-definite linear transformations.


text:
# Detection of a Fully-resolved Compton Shoulder of the Iron K𝛼 Line in the Chandra X-ray Spectrum of GX 301-2

## 1 Introduction

When a high energy photon propagating through a low-temperature ($`<`$ 105 K) medium undergoes Compton scattering with the constituent electrons, the energy of the photon is modified in a way that depends on the scattering angle and the electron velocity distribution. In the limit where the electrons are at rest, a fraction of the photon energy is transferred to the electron according to the Compton formula,

$$E_1=\frac{E_0}{1+\left(E_0/m_ec^2\right)\left(1\mathrm{cos}\theta \right)},$$
(1)
where $`E_0`$ is the energy of the incoming photon, $`E_1`$ is the energy of the outgoing photon, $`\theta `$ is the angle between the incoming and outgoing photons, and $`m_ec^2`$ is the electron rest-mass energy (= 511 keV). The maximum energy shift per scattering due to the electron recoil is, therefore, $`\mathrm{\Delta }E_{\mathrm{max}}=2E_0^2/(m_ec^2+2E_0)`$ for photons that are back-scattered ($`\theta `$ = 180). An X-ray emission line propagating through a medium with substantial Compton optical depth ($`\tau _{\mathrm{Compton}}`$ $`>`$ 0.1) has a non-negligible probability of interacting with an electron, resulting in down-scattering of photons and, hence, producing a discernible ”Compton shoulder” between $`E_0`$ and $`E_0\mathrm{\Delta }E_{\mathrm{max}}`$.

X-ray emission lines at higher energies are ideal for studying the properties of the Compton shoulders, since the Compton scattering opacity relative to that of photoelectric absorption is larger for higher energy photons. The iron K$`\alpha `$ fluorescent line complex at $`E_0`$ = 6.40 keV, therefore, is particularly promising, and can be produced over an extremely wide range in column density, which makes it ideal for diagnosing the physical properties of a cold medium irradiated by X-rays (Hatchett & Weaver, 1977; Basko, 1978; Illarionov et al., 1979; George & Fabian, 1991; Sunyaev & Churazov, 1996; Matt, 2002). The energy shift of an iron line photon due to a single Compton scattering $`\mathrm{\Delta }E_{\mathrm{max}}`$ = 156 eV (see eq.(1) ) is, however, at best, comparable to the spectral resolving power of past X-ray detectors in orbit. Previous detections of the Compton shoulder are unresolved (see, e.g., Molendi, Bianchi & Matt 2003) and, in many cases, they are statistically marginal as well (Iwasawa, Fabian & Matt, 1997; Matt & Guainazzi, 2003). The high spectral resolution of 33 eV (FWHM) at 6.4 keV attained by the High Energy Transmission Grating Spectrometer (HETGS) (Canizares et al., 2000) onboard the Chandra X-ray Observatory (Weisskopf et al., 2000) enables us, for the first time, to resolve the Compton shoulder of the iron K$`\alpha `$ line (see, e.g., Kaspi et al. 2002; Bianchi et al. 2002).

The X-ray binary pulsar GX 301$``$2 is one of the most promising targets for studying the Compton shoulder associated with the 6.4 keV iron K$`\alpha `$ line. The system consists of an accreting magnetized neutron star in a highly eccentric orbit ($`e`$ = 0.46; Sato et al. 1986; Koh et al. 1997), embedded in the stellar wind from a B2 super-giant companion star (Bord et al., 1976). X-ray continuum photons from the neutron star ionize the K-shell electrons of iron in the wind, a fraction of which is followed by fluorescence emission of the 6.4 keV line. Previous observations of the system have shown an intense iron line with an equivalent width as large as $``$ 1 keV (White & Swank, 1984; Leahy et al., 1989; Tashiro et al., 1991; Endo et al., 2002). Given the large mass-loss rate of the companion (Parkes et al., 1980), a substantial fraction of the 6.4 keV photons can subsequently undergo Compton scattering prior to escaping the wind.

In this Letter, we present spectral analysis results of the properties of the iron K$`\alpha `$ line and its Compton shoulder observed in GX 301$``$2 with the Chandra HETGS. As we show, the detection of the fully-resolved Compton shoulder provides a unique opportunity to investigate in detail the physical state and geometrical distribution of cold ($`<`$ 105 K) material surrounding an X-ray source. In § 2, we describe the observation and the procedures adopted for data reduction. Some basic spectral measurements and observed quantities are also discussed. In § 3, we describe our Monte Carlo simulator used for the spectral analyses. Finally in § 4, we present our measurements and discuss the implications of the results.

## 2 Observation and Data Reduction

Chandra observed GX 301$``$2 at three different orbital phases: (1) $`\varphi `$ = 0.167–0.179, (2) $`\varphi `$ = 0.480–0.497, and (3) $`\varphi `$ = 0.970–0.982, hereafter referred to as intermediate (IM), near-apastron (NA), and pre-periastron (PP) phases (Pravdo et al., 1995), respectively. We focus primarily on the spectrum of the PP-phase, during which the X-ray luminosity, absorbing column density, and the iron line equivalent width are the highest (Endo et al., 2002). The observation of the PP-phase was performed on 2002 February 3 12:34:10 UT and continued for $``$ 40 ksec. All of the data were processed using CIAO v2.2.1. Since the zeroth order image was severely piled-up, the centroid was determined by finding the intersection of the streak events and the dispersed events. We apply a standard spatial filter and an order sorting mask to extract only the first order events. The exposure map and effective area were calculated based on the extraction region described above. Since we are interested mainly in the properties of the iron line, we use data only from the High-Energy Grating (HEG) for the analysis, since it has a higher resolving power ($`\mathrm{\Delta }E_{\mathrm{FWHM}}`$ = 33 eV at 6.4 keV) and larger effective area (20 cm2) in the iron K line region.

The X-ray light curve in the 1.0–10.0 keV band extracted from the HEG events is shown in the top panel of Fig. 1. An X-ray outburst is seen in the first half of the observation. Hence, we have chosen to divide the data into the first and second halves as indicated by the vertical dotted line, and have extracted spectra from each data segment separately. The observed 2–10 keV fluxes are 13.2 $`\times `$ 10-10 erg cm-2 s-1 and 9.0 $`\times `$ 10-10 erg cm-2 s-1 during the first and second halves, respectively. A blow-up of the iron K$`\alpha `$ line spectra are shown in the bottom panels of Fig. 1. In addition to the intense iron K$`\alpha `$ line at 6.4 keV, a shoulder extending towards the low energy side down to $``$ 6.24 keV is clearly seen in the data. The equivalent widths of the iron K$`\alpha `$ lines including the shoulders are 643 $`\pm `$ 20 eV and 486 $`\pm `$ 18 eV for the first and second halves, respectively. The width of the shoulder ($`\mathrm{\Delta }E`$ $``$ 160 eV) precisely matches what is predicted by eq. (1), which strongly indicates that the feature is formed primarily through single Compton scattering of the iron K$`\alpha `$ photons. Changes in the shape of the Compton shoulder as well as in the shoulder flux relative to the un-scattered line flux, can be seen between the spectra of the first and second halves.

## 3 Monte Carlo Simulation

The Compton shoulder can be used to infer various physical parameters that characterize the scattering medium. The flux ratio of the shoulder to the line is determined by the metal abundance and the optical thickness of the scattering cloud. Its energy distribution, on the other hand, is sensitive to the temperature and the geometrical distribution of the scattering electrons. A discernible change in the profile shown in Fig. 1 implies that these physical parameters are variable between the first and second halves of the observation.

In order to obtain some quantitative information from the spectra, we have constructed a Monte Carlo simulator to compute the emergent spectrum from an X-ray source surrounded by a cloud. We assume a spherical distribution of material motivated by the observed correlation between the iron emission line strength and its corresponding edge depth during the IM, NA, and PP phases. This assumption also significantly simplifies the simulation. The cloud consists of H, He and astrophysically abundant metals (C, N, O, Ne, Na, Mg, Al, Si, S, Cl, Ar, Ca, Cr, Fe and Ni), and all of the metal abundances (Z $`>`$ 2) are allowed to vary together relative to the cosmic values of Feldman (1992). We account for photoelectric absorption and subsequent fluorescent emission, as well as Compton scattering by free electron. The angular-dependence of the Compton scattering cross section is fully accounted for and the electrons are assumed to have a Maxwellian energy distribution. The photons may suffer multiple interactions and are traced until they completely escape the cloud. The energy distribution of the emergent photons are then histogrammed to produce a spectrum.

Fig. 2 shows some of the results from the simulations for the iron line and its Compton shoulder with varying hydrogen column density ($`N_\mathrm{H}`$) and electron temperature ($`kT_\mathrm{e}`$). The original iron K$`\alpha _1`$ and K$`\alpha _2`$ photons are assumed to be distributed according to the K-shell photoionization rate at each radius from the central continuum source. The distribution of the original iron K photons is also calculated with the simulator, in which a power-law X-ray source with a photon index of 1.0 is assumed. In the upper panels of Fig. 2, one can see an increase in the scattered flux relative to the narrow line flux as $`N_\mathrm{H}`$ is increased. The lower panels of Fig. 2 show the temperature dependence of the shape of the Compton shoulder. More smearing is seen at higher $`kT_\mathrm{e}`$. Photons between 6.24 keV and 6.40 keV are due primarily to single-scattered photons, and the component below 6.24 keV result from multiple-scattering, which are important even at moderate optical depths.

## 4 Discussion

We performed spectral fits based on the simulation for the iron line and the Compton shoulder. A fits file of ”table models” were generated from the results of the simulations, which were then incorporated into XSPEC v11.2. The parameters of the model are $`N_\mathrm{H}`$, $`kT_\mathrm{e}`$, and the metal abundances. The radial dependence of the intrinsic K$`\alpha `$ line emissivity is fixed to what one expects from a photon index of $`\mathrm{\Gamma }=1.0`$. We have confirmed that this assumption produces at most a 5 % error in the emergent line profile for $`\mathrm{\Gamma }`$ between 0.0 and 2.0.

### 4.1 Metal Abundance

We first attempt to determine the metal abundances from the total PP-phase spectrum. In doing this, we note that two independent constraints between the abundance and the hydrogen column density are available, as described below. The first one arises from the observed intensity ratio of the shoulder to the narrow line. For a given ratio, an increase in column density must be accompanied by an increase in abundance and, hence, the two parameters are correlated as shown in Fig. 3. The other constraint originates from the observed equivalent width of the line. In this case, the abundance is anti-correlated with the column density. From these two constraints (see Fig. 3), the metal abundance is determined to be 0.65–0.82 times of the cosmic value (Feldman, 1992), assuming $`\mathrm{\Gamma }`$ = 1.0. The slope, however, is not well-measured due to the limited bandpass of the Chandra gratings. If we allow a range in $`\mathrm{\Gamma }`$ of 1.0–1.5, which has been seen in previous hard X-ray observations (Pravdo et al., 1995; Orlandini et al., 2000), the metal abundance is determined to be 0.65–0.90 times of the cosmic. Note that this is consistent with that of typical OB-stars (Daflon et al., 2001).

### 4.2 Hydrogen Column Density and Electron Temperature

Adopting the metal abundance of 0.75 cosmic derived in § 4.1, we find the values for $`N_\mathrm{H}`$. The derived values are listed in Table 1, and the models are shown by the lines superimposed on the data in Fig. 1. The difference in the observed Compton profile can be described by a change in the column density, which results in a variation in the number-of-scatterings distribution even at these moderate optical depths. We have also obtained upper-limits (90 % confidence levels) to $`kT_\mathrm{e}`$ of $`<`$ 3.4 eV and $`<`$ 0.6 eV for the first- and second-half spectra, respectively. Interestingly, the derived electron temperatures are consistent with that expected for the stellar wind being cooled via adiabatic expansion from the surface of the companion star with a photospheric temperature of $``$ 2 eV (Bord et al., 1976). Interestingly, the column density as inferred from the Compton profile, in fact, reproduces the spectrum in the entire HEG bandpass for a power-law photon index of 1.0. Fig. 4 shows the observed spectra overlaid with the simulated spectra. Reduced chi-squared values of 1.30 and 0.95 were obtained for the first and second halves spectra, respectively. Though some residual flux still remain, the simulations, which are based on parameters derived from the line and Compton shoulder, provide fairly good descriptions of the broadband data. Assuming a distance of 1.8 kpc (Parkes et al., 1980), the absorption-corrected X-ray luminosities in the 2–10 keV are 3.5 $`\times `$ 1036 erg s-1 and 1.6 $`\times `$ 1036 erg s-1 for the first and second halves, respectively.

### 4.3 Future Prospects

We have demonstrated through our quantitative analysis of the Chandra HETGS data of GX 301$``$2 that the Compton shoulder provides a sensitive diagnostic for the physical conditions of cold material irradiated by X-ray photons. The substantial improvement in the spectral resolution (6 eV at 6 keV) and the effective area ($``$ 300 cm2 at 6 keV) accessible with the X-ray Spectrometer (XRS) onboard the Astro-E2 observatory, which is planned to be deployed in 2005, will allow us to study the Compton shoulder profile in various classes of X-ray sources, such as a molecular cloud irradiated by a proto-star, an accretion disk swirling around a compact object, and a dusty torus surrounding an active galactic nucleus. More detailed geometrical information can be obtained by studying the energy distribution and, hence, the scattering angle distribution in the circumsource medium. Compton scattering by electrons in bound systems produces spectral signatures that are distinct from those produced by free electrons (Sunyaev & Churazov, 1996; Vainshtein et al., 1998; Sunyaev, Uskov & Churazov, 1999), which may be detectable with future X-ray spectrometers.

SW is supported by research fellowships of the Japan Society for the Promotion of Science for young Scientists. MS was supported by NASA through the Chandra Fellowship Program.