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# Nearly Degenerate dS Horizons from a 2-D Perspective

## I Introduction

From a theoretical perspective, black holes provide us with an intriguing “laboratory” for examining many aspects of quantum and semi-classical gravity. With regard to such investigations, the thermodynamic properties associated with black hole horizons have played an especially prominent role. In particular, black holes are commonly attributed a temperature that is proportional to the horizon surface gravity and an entropy that is proportional to the horizon surface area . The initial motivation for these identifications was an observed analogy between black hole horizon mechanics and the thermodynamic first and second laws . Nonetheless, this thermodynamic correspondence is generally given a physical status on the basis of Hawking radiation . That is, it has been shown that, when quantum effects are considered, black holes emit thermal radiation and, remarkably, at the exact value of temperature that the analogy suggests.

On the other hand, in a statistical mechanical sense, there are still conceptual difficulties with this thermodynamic picture. For instance, “what is the microscopic origin of the black hole entropy?” has become a popular slogan (paraphrasingly speaking) among gravitational researchers . However, putting this controversial issue aside, one can see that the entropy (and not only the temperature) does, indeed, have a clear physical interpretation. To elaborate, the black hole horizon is essentially a membrane that obstructs the flow of information. That is, an external observer will be unable to access any degrees of freedom from behind the horizon, and just such an obstruction will naturally induce, via coarse-graining effects, an entropy of entanglement . Indeed, direct calculations of this entanglement entropy (e.g., ) have been known to reproduce the Bekenstein-Hawking entropic area law . (Albeit, up to some ambiguity in the proportionality factor. However, it is expected that the correct factor will be reproduced once renormalization effects have properly been accounted for .)

Moreover, there is substantial evidence that any horizon (i.e., any null hypersurface that prevents the accessibility of information) can be attributed a temperature and entropy in the same manner as for a black hole (e.g.,). Although intuitively sensible, this may not be a priori clear for horizons that are observer dependent; most notably, Rindler horizons (which are manifestations of an accelerating observer ) and de Sitter cosmological horizons (which are defined in terms of a given observer’s causal patch of de Sitter space ). On the other hand, the principle of black hole complementarity  implies that the existence (or lack thereof) of a black hole horizon is also an objective feature of the spacetime; for instance, a free-falling observer will detect no horizon at all. Hence, observer dependence should not, after further consideration, be that significant of an issue.

Furthermore, our understanding of horizon thermodynamics is expected to persist in spacetimes with multiple horizons (e.g., charged and/or spinning black holes and Schwarzschild-de Sitter spacetimes), provided that each horizon is treated locally  or as a distinct physical system .***It has recently been conjectured, however, that the temperature in a Schwarzschild-de Sitter spacetime can be given a global meaning . There is, however, a very important caveat to this statement when two (or more) otherwise distinct horizons become degenerate. For such an occurrence, the thermodynamic properties typically become ambiguous and sometimes even ill-defined (for further discussion and references, see ).

This formal breakdown in degenerate-horizon thermodynamics brings us to the problem of how to interpret the degenerate limit of relevant spacetimes; most notably, the extremal limit of a charged and/or spinning black hole and the Nariai limit  of a Schwarzschild-de Sitter spacetime. (Since a degenerate limit naively coincides with a limit of vanishing temperature, this problem can alternatively be viewed as an ambiguity in formulating the third law of horizon thermodynamics .) That such a problem exists is re-enforced when one considers these degenerate limits from a topological perspective. That is, the degenerate solutions (as indicated above) have non-trivial qualitative differences in topology from their non-degenerate counterparts (e.g.,).

The resolution of this degenerate-limit problem is, in some (perhaps naive) sense, really quite simple. One needs only to conjecture that a non-degenerate solution is prohibited from continuously evolving into a degenerate one (and vice versa) . That this should intuitively be the case follows from the topological distinctions mentioned above. (This still does not resolve the related problem of how should the thermodynamic properties in a degenerate spacetime be defined. We will not, however, be addressing this issue in the current paper.But for further discussion and references in an extremal black hole context, see . Rather, our focus is on the “near-degenerate” sector of a particular theory.) To physically motivate this conjecture, one still requires a mechanism for enforcing the proposed censorship. Fortunately, it appears that quantum effects efficiently and naturally serve this purpose. Indeed, recent studies in the context of black hole spectroscopy have directly implied that quantum fluctuations will prevent a charged and/or spinning black hole from ever reaching a precise state of extremality . Also recently, a similar outcome has been obtained by the current author via independent means . As this latter approach is central to the present analysis, let us give a point-by-point recount of the relevant steps and results.
(i) We started off with a Reissner-Nordstrom (i.e., charged and static) black hole in an asymptotically flat spacetime. (The number of dimensions was initially four  but later arbitrary .) The focus was on the near-extremal sector; in particular, the deviations (from extremality) in the black hole entropy and temperature were determined as functions of the deviation in the mass (with the charge regarded as a fixed parameter).
(ii) Subjecting the “fundamental” action to a procedure of reduction and field reparametrization, we obtained a two-dimensional effective model. (The motivation being that quantum back-reaction effects, which are ultimately of interest, can be much more easily addressed in the lower-dimensional theory.) Then following , we expanded the two-dimensional action about the extremal configuration. The resulting theory, which should effectively describe the Reissner-Nordstrom near-extremal sector, turned out to be a two-dimensional anti-de Sitter action; that is, the Jackiw-Teitelboim model .
(iii) A duality was re-established  between the near-extremal Reissner-Nordstrom black hole and the near-massless sector of Jackiw-Teitelboim theory. That is, after appropriate identifications, the thermodynamic deviations (as discussed above) were shown to coincide exactly with the thermodynamics of the two-dimensional black hole solutions.
(iv) The next phase of the analysis concentrated on first-order quantum effects. Here, we began by incorporating the simplest possible matter field having a higher-dimensional pedigree; namely, a massless scalar field that is minimally coupled to the fundamental gravity theory. The same procedure of dimensional reduction, field reparametrization and expansion was then repeated for the revised theory. Interestingly, we found that the revised effective action mimics the theory of a dimensionally reduced BTZ black holeThe BTZ black hole refers to special solutions of 2+1-dimensional anti-de Sitter gravity that exhibit all the properties of black holes . The dimensionally reduced BTZ model was first discussed in . with minimally coupled matter.
(v) Eventually, attentions were focused on the quantum-corrected form of the surface gravity or (equivalently) the temperature. The desired result, at the one-loop level, could be directly extracted from a prior study on the thermodynamics of dimensionally reduced BTZ black holes  (also, ).§§§Actually,  used a form of dimensionally reduced (one-loop) action that has recently been criticized on technical grounds . If the action in question does require (yet unknown) corrections, then it is certainly clear that any quantitative results would have to be closely scrutinized. However, we suggest that the coarse, qualitative features of the spacetime would be less sensitive to any such corrections. Working under the premise that a consistent theory must have a non-negative surface gravity , we were able to establish a finite lower bound on the black hole mass. That is, quantum back-reaction effects will prevent the (two-dimensional) black hole from completely evaporating; rather, the system will “freeze” at a non-vanishing value of mass.
(vi) In view of the prior outcome and the previously established duality, we ultimately argued that quantum back-reaction effects will prevent the Reissner-Nordstrom black hole from ever reaching a state of precise extremality. That is, a non-extremal Reissner-Nordstrom black hole will be unable to continuously evolve into an extremal solution (and vice versa).

The objective of the current paper is to extend the above treatment to the scenario of a nearly degenerate Schwarzschild-de Sitter black hole spacetime. In this case, the two horizons represent the (inner) black hole horizon and the (outer) cosmological horizon of an asymptotically de Sitter spacetime. Also of interest, the point of degeneracy corresponds to the so-called Nariai black hole solution , which can equivalently be regarded as the Schwarzschild-de Sitter solution of maximal mass. For motivation, let us point out that asymptotically de Sitter spacetimes have experienced a recent surge in interest; thanks to, for instance, astronomical observations , possible holographic dualities  and quasi-de Sitter inflationary scenarios . (For a general overview, see .)

The rest of the paper is organized as follows. Section 2 introduces the “fundamental” theory of interest: a Schwarzschild-de Sitter spacetime of arbitrary dimensionality. Here, the focus is on the thermodynamic properties of near-degenerate solutions. In Section 3, we employ a suitable reduction ansatz, as well as other manipulations, to derive an effective two-dimensional model of the near-degenerate sector. We go on to demonstrate a clear thermodynamic duality between this effective description and the originating theory. (Some of this section follows parts of , although the perspective of the cited paper differs substantially from the present one.) In Section 4, we consider one-loop corrections and present an argument as to why back-reaction effects would prevent a degenerate state from ever being reached. Finally, Section 5 contains a brief summary and discussion.

## II The Fundamental Theory

Let us formally begin by writing down the de Sitter gravitational action for a spacetime of arbitrary dimensionality ($`d=n+2>3`$):

$$I^{(n+2)}=\frac{1}{16\pi l^n}d^{n+2}x\sqrt{g^{(n+2)}}\left[R^{(n+2)}2\mathrm{\Lambda }\right],$$
(1)
where $`l^n`$ is the $`n`$+2-dimensional Newton constant (with $`l`$ being the analogue to the Planck length) and $`\mathrm{\Lambda }`$ is the positive cosmological constant. Note that

$$\mathrm{\Lambda }=\frac{n(n+1)}{2L^2},$$
(2)
where $`L`$ is the curvature radius of de Sitter space.

If we assume no electrostatic charges, then the unique static solution of Eq.(1) can be written as follows:

$$ds_{n+2}^2=h(r)dt^2+\frac{1}{h(r)}dr^2+r^2d\mathrm{\Omega }_n^2,$$
(3)
$$h(r)=1\frac{16\pi l^nM}{n𝒱_nr^{n1}}\frac{r^2}{l^2},$$
(4)
where $`M`$ represents the conserved mass  and $`d\mathrm{\Omega }_n^2`$ is an $`n`$-dimensional spherical hypersurface with volume $`𝒱_n=2\pi ^{\frac{n+1}{2}}/\mathrm{\Gamma }\left(\frac{n+1}{2}\right)`$.

The above solution is that of a (non-degenerate) Schwarzschild-de Sitter black hole provided that the mass observable is constrained according to

$$0<M<M_0\frac{n}{(n+1)}\frac{𝒱_n}{8\pi l^n}\left[\left(\frac{n1}{n+1}\right)L^2\right]^{\frac{n1}{2}}.$$
(5)
For $`M`$ within these limits, one can readily verify the existence of exactly two positive, real and distinct horizons; which can be located by solving the polynomial $`h(r=r_H)=0`$. The smaller of this pair (to be denoted as $`r_H=r_{}`$) is a Schwarzschild-like black hole horizon, while the larger is the de Sitter cosmological horizon (which will be denoted as $`r_H=r_+`$).

Of special interest are the upper and lower limits in Eq.(5). Firstly, when $`M=0`$, there is no black hole to speak of and the spacetime corresponds to pure de Sitter space. In this event, there is a single (cosmological) horizon at $`r_+=L`$. Secondly, when $`M=M_0`$, the two horizons coincide and this solution of maximal mass is often referred to as the Nariai  black hole. More explicitly, by solving for $`h(r_H;M=M_0)=0`$, one finds that $`r_{}=r_+=r_0`$, where

$$r_0\sqrt{\frac{n1}{n+1}}L.$$
(6)
Let us also point out that either $`M<0`$ or $`M>M_0`$ results in a naked singularity,To elaborate, the black hole horizon disappears when $`M<0`$ and both horizons vanish if $`M>M_0`$. but these awkward scenarios can (and will) be disregarded on the grounds of cosmological censorship .

Since our current focus is on the case of nearly degenerate horizons, we will now assume that $`M`$ is close to, but always less than, the Nariai value of $`M_0`$. To put this notion on a more quantitative level, let us introduce the following measures of deviation from degeneracy:

$$\mathrm{\Delta }MMM_0,$$
(7)
$$\mathrm{\Delta }r_\pm r_\pm r_0,$$
(8)
while insisting that $`|\mathrm{\Delta }M|<<M_0`$ and $`|\mathrm{\Delta }r_\pm |<<r_0`$. It should be kept in mind that $`\mathrm{\Delta }M<0`$ must always be imposed. On the other hand, it should be clear that one of the horizon shifts will be positive and the other, negative. By our prior convention, this means that $`\mathrm{\Delta }r_+>0`$ and $`\mathrm{\Delta }r_{}<0`$. Moreover, to lowest order in $`\sqrt{\mathrm{\Delta }M}`$, one can employ the horizon condition (i.e., $`h(r=r_H)=0`$) and readily show that

$$\mathrm{\Delta }r_\pm =\pm \frac{L}{n+1}\sqrt{\frac{2|\mathrm{\Delta }M|}{M_0}}.$$
(9)
Let us now consider the thermodynamic properties \- specifically, the Bekenstein-Hawking entropy  and Hawking temperature  \- of these horizons. (For the generalization of these properties to a cosmological horizon, see .) Here, we will employ the standard prescriptions for the entropy and temperature (respectively):

$$S_H=\frac{A_H}{4\mathrm{}l^n}=\frac{𝒱_nr_H^n}{4\mathrm{}l^n},$$
(10)
$$T_H=\frac{\mathrm{}}{2\pi }|\kappa _H|=\frac{\mathrm{}}{4\pi }\left|\frac{dh}{dr}\right|_{r=r_H}=\mathrm{}\left|\frac{4(n1)l^nM}{n𝒱_nr_H^n}\frac{r_H}{2\pi L^2}\right|,$$
(11)
where $`A_H`$ is the surface area and $`\kappa _H`$ is the surface gravity with respect to the horizon at $`r=r_H`$.Note that, here and throughout, the speed of light and Boltzmann’s constant have been set to unity.

Some straightforward calculations reveal that, to lowest order in $`\sqrt{|\mathrm{\Delta }M|}`$ (as appropriate for the near-degenerate regime of interest),

$`\mathrm{\Delta }S_\pm `$ $``$ $`S_\pm (M_0+\mathrm{\Delta }M)S_H(M_0)`$ (12)
$`=`$ $`\pm {\displaystyle \frac{1}{\mathrm{}}}\sqrt{{\displaystyle \frac{n\pi 𝒱_n}{(n1)}}{\displaystyle \frac{r_0^{n+1}}{l^n}}|\mathrm{\Delta }M|},`$ (13)
$`\mathrm{\Delta }T_\pm `$ $``$ $`T_\pm (M_0+\mathrm{\Delta }M)T_H(M_0)`$ (14)
$`=`$ $`2\mathrm{}{\displaystyle \frac{(n1)}{(n+1)}}\sqrt{{\displaystyle \frac{(n1)}{n\pi 𝒱_n}}{\displaystyle \frac{l^n}{r_0^{n+1}}}|\mathrm{\Delta }M|}.`$ (15)
Note that $`S_H(M_0)=𝒱_nr_0^n/4\mathrm{}l^n`$ and $`T_H(M_0)=0`$.\**\**\**Actually, rigorous analysis indicates that $`T=\mathrm{}/2\pi r_0`$ for a Nariai black hole . Nevertheless, our interest is in the near-degenerate regime (rather than the Nariai solution per se), and the naive extrapolation of non-degenerate thermodynamics does indeed suggest a limit of vanishing temperature.

It may be bothersome that the first law of thermodynamics is apparently violated at the cosmological horizon, $`r_H=r_+`$, given that the entropy is increasing ($`\mathrm{\Delta }S_+>0`$) while the mass is decreasing ($`\mathrm{\Delta }M<0`$). However, this paradoxical feature of cosmological horizons can be anticipated and is, in fact, well understood . (Reassuringly, there is no such violation for the black hole horizon, $`r_H=r_{}`$.) Speaking of the first law, one finds that the expected relation of

$$\frac{|\mathrm{\Delta }S_H|}{|\mathrm{\Delta }M|}=\frac{1}{\mathrm{\Delta }T_H},$$
(16)
is not quite obtained; rather, it is off by a simple numerical factor. This slight discrepancy can be viewed as a consequence of treating each of the horizons as an isolated system. Nonetheless, this effect can be accommodated for with a simple rescaling: $`\mathrm{\Delta }M\mathrm{\Delta }M(n1)/(n+1)`$. Hence, we now have (for either horizon)

$$|\mathrm{\Delta }S_H|=\frac{1}{\mathrm{}}\sqrt{\frac{n+1}{n1}}\sqrt{\frac{n\pi 𝒱_n}{(n1)}\frac{r_0^{n+1}}{l^n}|\mathrm{\Delta }M|},$$
(17)
$$\mathrm{\Delta }T_H=2\mathrm{}\sqrt{\frac{n1}{n+1}}\sqrt{\frac{(n1)}{n\pi 𝒱_n}\frac{l^n}{r_0^{n+1}}|\mathrm{\Delta }M|}.$$
(18)
## III The Effective Theory

The next step in our procedure is the dimensional reduction of the fundamental action (1) to an effective two-dimensional theory . The reduction that we have in mind can be obtained by imposing a spherical ansatz:

$$ds_{n+2}^2=ds_2^2(t,x)+\varphi ^2(x,t)d\mathrm{\Omega }_n^2,$$
(19)
which transforms Eq.(1) into the following functional (also see ):

$$I=\frac{𝒱_n}{16\pi l^n}d^2x\sqrt{g}\varphi ^n\left[R+n(n1)\left(\frac{(\varphi )^2}{\varphi ^2}+\frac{1}{\varphi ^2}\right)\frac{n(n+1)}{L^2}\right].$$
(20)
Here, the “dilaton”, $`\varphi `$, can be identified with the radius of the symmetric $`n`$-sphere and all geometric quantities are now defined with respect to the resultant 1+1-dimensional manifold.

It proves to be convenient if the dilaton is redefined in accordance with

$$\psi (x,t)=\left[\frac{\varphi }{l}\right]^{\frac{n}{2}}.$$
(21)
The reduced action (20) can then be reformulated as follows:

$$I=\frac{1}{2G}d^2x\sqrt{g}\left[D(\psi )R+\frac{1}{2}\left(\psi \right)^2+\frac{1}{l^2}V_\mathrm{\Lambda }(\psi )\right],$$
(22)
where the following definitions have been invoked:

$$\frac{1}{2G}\frac{8(n1)𝒱_n}{16\pi n},$$
(23)
$$D(\psi )\frac{n}{8(n1)}\psi ^2,$$
(24)
$$V_\mathrm{\Lambda }(\psi )\frac{n^2}{8}\psi ^{\frac{2n4}{n}}\frac{(n+1)n^2l^2}{8(n1)L^2}\psi ^2.$$
(25)
The above action is an particularly convenient form, as it is now suitable for the implementation of a field reparametrization that eliminates the kinetic term . Following the prescribed methodology, let us redefine the dilaton, metric and “dilaton potential” as follows:

$$\overline{\psi }=D(\psi )=\frac{n}{8(n1)}\psi ^2,$$
(26)
$$\overline{g}_{\mu \nu }=\mathrm{\Omega }^2(\psi )g_{\mu \nu },$$
(27)
$$\overline{V}_\mathrm{\Lambda }(\overline{\psi })=\frac{V_\mathrm{\Lambda }(\psi )}{\mathrm{\Omega }^2(\psi )},$$
(28)
where

$$\mathrm{\Omega }^2(\psi )\mathrm{exp}\left[\frac{1}{2}\frac{d\psi }{\left(dD/d\psi \right)}\right]=𝒞\left[\frac{8(n1)\overline{\psi }}{n}\right]^{\frac{n1}{n}}.$$
(29)
In the last line, $`𝒞`$ represents an arbitrary constant of integration that can (in a general sense) often be fixed via physical arguments. Here, we will follow the fifth section of  (which similarly considers the spherical reduction of an arbitrary-dimensional action) and set $`𝒞=n^2/8(n1)`$.

With the above reparametrizations, the reduced action (22) transforms into the following expression:

$$I=\frac{1}{2G}d^2x\sqrt{\overline{g}}\left[\overline{\psi }R(\overline{g})+\frac{1}{l^2}\overline{V}_\mathrm{\Lambda }(\overline{\psi })\right].$$
(30)
It can readily be seen that the degenerate-horizon limit of the higher-dimensional theory is precisely recovered when $`\overline{V}_\mathrm{\Lambda }(\overline{\psi })=0`$. Denoting this extremal value of the dilaton as $`\overline{\psi }=\overline{\psi }_0`$, we find that (cf, Eqs.(28,25,26))

$$\overline{\psi }_0=\frac{n}{8(n1)}\left[\frac{(n1)L^2}{(n+1)l^2}\right]^{n/2}.$$
(31)
With the above discussion in mind, let us define $`\stackrel{~}{\psi }\overline{\psi }\overline{\psi }_0`$ and appropriately expand the action (30) about the extremal configuration. To first order in $`\stackrel{~}{\psi }`$, such an expansion yields

$$I=\frac{1}{2G}d^2x\sqrt{\overline{g}}\left[\stackrel{~}{\psi }R(\overline{g})+\frac{1}{l^2}\stackrel{~}{V}_\mathrm{\Lambda }(\stackrel{~}{\psi })\right],$$
(32)
where

$`\stackrel{~}{V}_\mathrm{\Lambda }(\stackrel{~}{\psi })`$ $``$ $`{\displaystyle \frac{d\overline{V}_\mathrm{\Lambda }}{d\overline{\psi }}}|_{\overline{\psi }_0}\stackrel{~}{\psi }`$ (33)
$`=`$ $`16{\displaystyle \frac{(n1)^2}{n^2}}\left[{\displaystyle \frac{(n+1)l^2}{(n1)L^2}}\right]^{(n+1)/2}\stackrel{~}{\psi }`$ (34)
$``$ $`2\lambda \stackrel{~}{\psi }.`$ (35)
Note that Eqs.(25,26,28,29,31) were applied in attaining the second to last line and $`\lambda >0`$.

We now drop the various tildes and bars and thus consider the following action:

$$I=\frac{1}{2G}d^2x\sqrt{g}\psi \left[R(g)2\frac{\lambda }{l^2}\right].$$
(36)
We could, in principle, continue on with this form of effective action; essentially, a two-dimensional de Sitter theory of constant curvature . However, it is substantially easier to work with the anti-de Sitter analogue, for which the static solutions are described by the very well-known Jackiw-Teitelboim (JT) black hole . This JT analogue can be obtained with a simple analytic continuation of the length parameter (i.e., $`l^2l^2`$), and so we will subsequently work with

$$I=\frac{1}{2G}d^2x\sqrt{g}\psi \left[R(g)+2\frac{\lambda }{l^2}\right],$$
(37)
where $`\lambda `$ is (still) a positive quantity. Actually, if the reduced action described a fundamental theory, then such a continuation would have to be treated very carefully; especially, in any attempt to extract physically meaningful results about the spacetime. However, in the current analysis, where the reduced theory serves as only an effective description of a reduced phase space, such a procedure should be perfectly viable.

The general solution of this effective JT action (37) can be conveniently expressed in a static, Schwarzschild-like gauge:

$$ds^2=(\lambda \frac{x^2}{l^2}2lGm)dt^2+(\lambda \frac{x^2}{l^2}2lGm)^1dx^2,$$
(38)
$$\psi =\frac{x}{l}.$$
(39)
Here, $`m`$ represents the conserved mass of the JT black hole. Moreover, we can apply the formalism of  (which is applicable to a generic theory of two-dimensional dilaton gravity), to obtain the other thermodynamic properties of relevance; namely, the entropy and the temperature:

$$S_{JT}=\frac{2\pi }{\mathrm{}G}\psi _+,$$
(40)
$$T_{JT}=\frac{\mathrm{}\lambda }{2\pi l}\psi _+,$$
(41)
where $`\psi _+=x_+/l=\sqrt{2lGm/\lambda }`$ is the horizon value of the dilaton field.

Substituting for $`\lambda `$ (35) and $`G`$ (23) into the above expressions, as well as applying the defining relation for $`r_0`$ (6), we are able to derive the following results:

$$S_{JT}=\frac{1}{\mathrm{}}\sqrt{\frac{n\pi 𝒱_n}{(n1)}\frac{r_0^{n+1}}{l^n}m},$$
(42)
$$T_{JT}=2\mathrm{}\sqrt{\frac{(n1)}{n\pi 𝒱_n}\frac{l^n}{r_0^{n+1}}m}.$$
(43)
Let us now make a reasonable identification between the JT black hole mass, $`m`$, and the mass deviation (from degeneracy) of the higher-dimensional model, $`|\mathrm{\Delta }M|`$. It then becomes quite evident that the two theories are closely related. To be explicit (cf, Eqs.(17,18)),

$$S_{JT}=𝒦|\mathrm{\Delta }S_H|,$$
(44)
$$T_{JT}=\frac{1}{𝒦}\mathrm{\Delta }T_H,$$
(45)
where $`𝒦=\sqrt{n1/n+1}`$ is a dimensionless numerical factor. Clearly, we can eliminate the numerical factor, $`𝒦`$, by rescaling an appropriate parameter of the effective theory (such as the effective Planck’s constant). The important point is that $`T_{JT}S_{JT}=\mathrm{\Delta }T_H|\mathrm{\Delta }S_H|`$ and all of the dimensional quantities do indeed coincide precisely. Hence, we have established the anticipated thermodynamic duality: the nearly degenerate sector of Schwarzschild-de Sitter black holes with the near-massless sector of JT theory.

Before proceeding to the next section, let us point out an important property of the JT black hole: as the mass, $`m`$, goes to zero, so does the temperature, $`T_{JT}`$, and the entropy, $`S_{JT}`$. Although this relation is intuitively expected in conventional thermodynamic systems, it is, nevertheless, very unusual in a black hole context (where, typically, a vanishing temperature corresponds to both a finite mass and entropy). It is, in fact, this property of JT black holes that makes them an ideal framework for studying the low-temperature regime of dually related theories.

## IV Quantum Effects

In analogy to our prior studies on near-extremal black holes , we will now invoke one-loop considerations to argue the following: a nearly degenerate Schwarzschild-de Sitter solution will be unable to evolve continuously into a degenerate, Nariai spacetime (and vice versa).

The essence of our argument goes as follows (for a more detailed discussion, see ). We start by considering the simplest possible matter having a higher-dimensional pedigree; namely, a massless scalar field ($`f`$) that is minimally coupled to the $`n`$+2-dimensional de Sitter theory. The revised (total) action can now be expressed as

$$I_{TOT}^{(n+2)}=I^{(n+2)}\frac{\mathrm{}}{16\pi l^n}d^{n+2}x\sqrt{g^{(n+2)}}(^{(n+2)}f)^2,$$
(46)
where $`I^{(n+2)}`$ is the classically defined action of Eq.(1). Again imposing the reduction ansatz of Eq.(19), as well as constraining $`f=f(t,x)`$, we obtain the following reduced form:

$$I_{TOT}=I\frac{\mathrm{}𝒱_n}{16\pi l^n}d^2x\sqrt{g}\varphi ^n(f)^2,$$
(47)
where $`I`$ is the reduced action of Eq.(20).

Following the same pattern of field reparametrization and expansion as described in Section 3, we can eventually write

$$I_{TOT}=I_{JT}\frac{\mathrm{}(n1)𝒱_n}{2\pi n}d^2x\sqrt{\overline{g}}\stackrel{~}{\psi }(\overline{}f)^2,$$
(48)
where $`I_{JT}`$ is the JT action of Eq.(37), and the tilde and bar notation has been resurrected for maximal clarity.

The above result informs us that the dilaton-matter coupling is precisely that obtained in the dimensional reduction (from three to two dimensions) of a BTZ black hole; under the assumption of minimally coupled matter in the three-dimensional theory .††††††The unorthodox factor in front of the above matter action is of no relevance, as this constant can always be absorbed in a rescaling of $`f`$. This observation is important because, as discussed on a rigorous level in , the dimensionally reduced BTZ black hole suffers a formal breakdown as the limit of zero mass is approached (i.e., as $`m0`$). More specifically, at some small but finite value of $`m`$, the surface gravity (or, equivalently, the temperature) will take on a negative value and become increasingly more negative as the $`m=0`$ limit is approached. Significantly, it has been argued that a non-negative surface gravity is a necessary criteria for a consistent black hole solution . On this basis, we have further argued that, because of quantum back-reaction effects, the reduced BTZ black hole will be unable to attain a state of vanishing mass . Obviously, the same conclusion (if valid) must apply to the JT black hole when it is coupled to matter with a higher-dimensional pedigree.

Let us now remind ourselves of the main outcome of Section 3; namely, the near-massless limit of the JT sector is dual (at least at the level of thermodynamics) to the near-degenerate sector of a Schwarzschild-de Sitter black hole. It therefore stands to reason that the censorship of massless JT black holes will translate into the following dual statement: a Schwarzschild-de Sitter black hole will be unable to reach the limit of horizon degeneracy (i.e., the limit $`|\mathrm{\Delta }M|0`$). To put it another way, quantum back-reaction effects will prohibit a nearly degenerate Schwarzschild-de Sitter black hole from ever reaching a precise state of degeneracy. Hence, a non-degenerate Schwarzschild-de Sitter spacetime should never be able to evolve continuously into a Nariai black hole and vice versa.

## V Conclusion

In summary, we have been considering a holographic type of duality  between a nearly degenerate Schwarzschild-de Sitter spacetime (of arbitrary dimensionality) and the near-massless sector of Jackiw-Teitelboim theory . We started out by rigorously demonstrating this dual relationship at the level of horizon thermodynamics. We then went on to argue that, on the basis of this duality and one-loop considerations, the higher-dimensional spacetime will never be able to continuously evolve into a Nariai solution ; that is, a Schwarzschild-de Sitter black hole of maximal mass and perfectly coincident horizons. Let us emphasize that our conclusions in no way undermine the Nariai black hole as a viable solution of a spacetime with a positive cosmological constant. Moreover, the type of censorship discussed here does not apply to more exotic mechanisms, such as quantum tunneling between Nariai and non-degenerate solutions .

It should again be pointed out that the latter part of the paper was based (vicariously through ) on the outcomes of a one-loop analysis of the dimensionally reduced BTZ black hole. This analysis was based, in turn, on a form of dimensionally-reduced action that has been the subject of some recent criticism . In spite of the potentially disturbing implications, we expect that our qualitative outcomes will not be in any jeopardy. To motivate this claim, let us take note of some independent studies in the context of black hole spectroscopy . In these treatments, it was shown, quite generically, that quantum fluctuations will prevent a charged or spinning black hole from ever reaching a state of exact extremality. Although these studies are not directly applicable to the current analysis, their generality does insinuate a similar censorship in any spacetime with potentially degenerate horizons.

Finally, one might wonder if this discontinuity between non-degenerate and degenerate Schwarzschild-de Sitter black holes could have any ramifications in quantum gravity. In this regard, let us take note of the conjectured duality between time evolution in an asymptotically de Sitter spacetime and a suitably defined renormalization-group flow . (This duality can be viewed as a manifestation of the so-called “dS/CFT” holographic correspondence .) Perhaps significantly, it has been suggested that the Nariai solution should correspond to the infrared fixed point of the holographic flow . It is not obvious to us, at the current time, if our findings could play a role in such a context; nonetheless, it could yet prove to be a worthwhile direction of investigation.

## VI Acknowledgments

The author would like to thank V.P. Frolov for helpful conversations.


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# Ab initio study of charge order in Fe3O4

## I Introduction

Based upon its high magnetoresistive properties, magnetite, Fe3O4, is a system of interest for such technological applications as computer memory, magnetic recording, and other ”spintronic” devices. It has been extensively studied for the past 60 yearsWalz , but despite such an extended effort the issue of a possible charge order below the so-called Verwey transition temperature, TV=122 K, has not been understood yetVerwey . Above the Verwey transition temperature, magnetite is thought to be a half-metal with a highest known Tc of 860 K. At the transition temperature, the conductivity of the system decreases abruptly by two orders of magnitude, as a small gap opens up in the density of states spectrum.Park  This first order metal-insulator transition Imada  is associated with a lattice distortion from cubic to monoclinic, which however has not been fully resolved.Izumi ; Zuo ; Paolo  The transition has been viewed as an order-disorder transition in relation to the arrangement of cations on the octahedral sites of the inverse spinel structure whose formal chemical formula can be written as FeA3+ \[ Fe2+, Fe3+ \]BO42-, where $`A`$ and $`B`$ refer to the interstitial, i.e., tetrahedral and octahedral sites, respectively. This simple ionic picture implies that magnetite is a mixed-valent compound. The $`A`$ sublattice is occupied only by Fe3+ cations in a ferromagnetic arrangement, while the $`B`$ sublattice is occupied by both Fe2+ (B1-site) and Fe3+ (B2-site) cations, also in a ferromagnetic manner which, however, is antiferromagnetically aligned to the ferromagnetic order on the $`A`$ sublattice. The oxygen atoms occupy the face-centered-cubic (fcc) close-packed sites. The Fe2+ cation can be viewed as Fe3+ plus an ”extra” electron, hopping freely between the octahedral sites above the Verwey transition, while below the transition these ”extra” electrons become localized or quasi-localized and some kind of long range order sets in on the $`B`$ sublattice. Verwey, who argued that below the transition temperature, TV, the Fe3+ and Fe2+ cations order in alternate (001) planes, looked upon this transition as an electron localization-delocalization transition. The Mössbauer spectra clearly demonstrate existence of two types of localized ions on the octahedral sites.Moss  The low temperature structure is a rhombohedral distortion of the cubic spinel arrangement to the first approximation, rook  but this splits in the ratio 3:1 for the occurance of the Fe2+ and Fe3+ cations on the corner-sharing tetrahedra that are formed by the octahedral sites. This is not consistent with the Anderson condition of minimum electrostatic repulsion, implying the ratio of 2:2. anderson  A recent combined high resolution X-ray and neutron powder diffraction study Paolo  confirmed a small charge disproportionation of about 0.2 electron on the octahedral sites, and a violation of the Anderson condition. The current experimental situation suggests that the long range order present below the Verwey transition is much more complicated than the charge order first proposed by Verwey. Some experiments, claim that there exists no charge order on the octahedral sites.garcia1 ; garcia2

In this paper we present an application of the self-interaction corrected local spin density (SIC-LSD) approximation to Fe3O4. The SIC-LSD method allows the ab-initio realization of valencies through total energy calculations for configurations of Fe2+ and Fe3+ cations. The method includes all bandstructure effects of the delocalized Fe and O electrons, including their hybridization, as well as the electronic structure of the localized Fe electrons. As such this methodology has been able to describe the valencies of the rare earths successfully.Strange  Here, we concentrate on the total energies for different $`d`$ electron configurations on the octahedral sites, defining Fe valencies, and try to establish whether the simple charge order postulated by Verwey is the ground state solution. Apart from the Verwey order we also consider other obvious arrangements of Fe valencies on the octahedral sites. There have been other first-principles studies of magnetite, Sashy ; Anisimov ; Antonov  however, this is the first time that different Fe valencies and charge order scenarios have been studied by an ab initio method. In Refs. Anisimov,  and Antonov, , the LDA+U method has been used to study the Verwey insulating phase albeit in the cubic structure only, and neither the total energies nor other charge order phases have been considered. In Ref. Antonov, , in addition, the optical properties of magnetite have been studied.

The remainder of the paper is organized as follows. In the next section, we briefly present the theoretical background of the SIC-LSD approach. In section III, the technical and computational details regarding the application to magnetite are elaborated upon. In section IV, we present total energy and density of states calculations. We also study the charge order and different Fe valencies on the octahedral sites, and try to establish the ground state configuration. The paper is concluded in section V.

## II Theory

The basis of the SIC-LSD formalism is a self-interaction free total energy functional, $`E^{SIC}`$, obtained by subtracting from the LSD total energy functional, $`E^{LSD}`$, a spurious self-interaction of each occupied electron state $`\psi _\alpha `$PZ81 , namely

$$E^{SIC}=E^{LSD}\underset{\alpha }{\overset{occ.}{}}\delta _\alpha ^{SIC}.$$
(1)
Here $`\alpha `$ numbers the occupied states and the self-interaction correction for the state $`\alpha `$ is

$$\delta _\alpha ^{SIC}=U[n_\alpha ]+E_{xc}^{LSD}[\overline{n}_\alpha ],$$
(2)
with $`U[n_\alpha ]`$ being the Hartree energy and $`E_{xc}^{LSD}[\overline{n}_\alpha ]`$ the LSD exchange-correlation energy for the corresponding charge density $`n_\alpha `$ and spin density $`\overline{n}_\alpha `$.

The SIC-LSD approach can be viewed as an extension of LSD in the sense that the self-interaction correction is only finite for spatially localized states, while for Bloch-like single-particle states $`E^{SIC}`$ is equal to $`E^{LSD}`$. Thus, the LSD minimum is also a local minimum of $`E^{SIC}`$. A question now arises, whether there exist other competitive minima, corresponding to a finite number of localized states, which could benefit from the self-interaction term without loosing too much of the energy associated with band formation. This is often the case for rather well localized electrons like the 3 $`d`$ electrons in transition metal oxides or the 4$`f`$ electrons in rare earth compounds. It follows from minimization of Eq. (1) that within the SIC-LSD approach such localized electrons move in a different potential than the delocalized valence electrons which respond to the effective LSD potential. For example, in the case of magnetite, five (Fe3+) or six (Fe2+) Fe $`d`$ electrons move in the SIC potential, while all other electrons feel only the effective LSD potential. Thus, by including an explicit energy contribution for an electron to localize, the ab-initio SIC-LSD describes both localized and delocalized electrons on an equal footing, leading to a greatly improved description of static Coulomb correlation effects over the LSD approximation.

In order to make the connection between valency and localization more explicit it is useful to define the nominal valency as

$$N_{val}=ZN_{core}N_{SIC},$$

where $`Z`$ is the atomic number (26 for Fe), $`N_{core}`$ is the number of core (and semi-core) electrons (18 for Fe), and $`N_{SIC}`$ is the number of localized, i.e., self-interaction corrected, states (either five or six, respectively for Fe3+ and Fe2+). Thus, in this formulation the valency is equal to the integer number of electrons available for band formation. To find the valency we assume various atomic configurations, consisting of different numbers of localized states, and minimize the SIC-LSD energy functional of Eq. (1) with respect to the number of localized electrons. The SIC-LSD formalism is governed by the energetics due to the fact that for each orbital the SIC differentiates between the energy gain due to hybridization of the orbital with the valence bands and the energy gain upon localization of the orbital. Whichever wins determines if the orbital is part of the valence band or not and in this manner also leads to the evaluation of the valency of elements involved. The SIC depends on the choice of orbitals and its value can differ substantially as a result of this. Therefore, one has to be guided by the energetics in defining the most optimally localized orbitals to determine the absolute energy minimum of the SIC-LSD energy functional. The advantage of the SIC-LSD formalism is that for such systems as transition metal oxides or rare earth compounds the lowest energy solution will describe the situation where some single-electron states may not be Bloch-like. For magnetite, these would be the Fe 3$`d`$ states, but not the O 2$`p`$ states, as trying to localize the latter is energetically unfavourable.

In the present work the SIC-LSD approach, has been implementedTSSW98  within the linear muffin-tin-orbital (LMTO) atomic sphere approximation (ASA) band structure method,oka75  in the tight-binding representation.AJ84  The electron wave functions are expanded in terms of the screened muffin-tin orbitals, and the minimization of $`E^{SIC}`$ becomes non-linear in the expansion coefficients.

## III Calculational details

As mentioned earlier, magnetite crystallizes in the fcc inverse spinel structure with two formula units (14 atoms) in the primitive unit cell, and the space group is Fd$`\overline{3}`$m. In the actual calculations, an additional 16 empty spheres have been used in order to obtain better space filling and to minimize the ASA overlap. Concerning the linear muffin-tin basis functions, we have used $`4s`$, $`4p`$, and $`3d`$ partial waves on all Fe atoms, and treated them as low-waves. Lambrecht  Including also $`4f`$basis functions on the Fe-sites, treated as intermediate waves, is of no substantial importance for the final results. On the oxygens only $`2s`$ and $`2p`$ partial waves have been treated as low-waves, while the $`3d`$waves have been treated as intermediate. On the empty spheres the $`1s`$waves have been considered as low- and the $`2p`$’s as intermediate-waves. The empty spheres are necessary to obtain half-metallic solution with the LSD, whose self-consistent charge densities have been used to start SIC-LSD calculations.

Although, below the Verwey transition, the cubic structure undergoes a monoclinic distortion, we have first explored the charge ordered phases on the basis of the cubic structure and then extended the study to the distorted structure. Since the true monoclinic structure has not been fully resolved, our calculations for the low temperature phase have been performed for two orthorhombic structures, given in Refs. Izumi,  and Paolo, , as closest approximations to the monoclinic structure. In the latter work, the refined atom positions were obtained using a combination of high resolution X-ray and neutron powder diffraction. The respective space groups used are Pmc21 and P2/c, each with 56 atoms in the unit cell. However, for reliable calculations empty spheres have been included, increasing the total number of sites to 104 in the first case, and 120 for the refined structure of Wright et al. Paolo

To make the SIC-LSD calculations feasible, for the orthorhombic set-ups we had to restrict to minimum basis sets, in particular $`4s,4p,3d`$low waves have been used on every Fe-atom, $`2s,2p`$low waves and intermediate $`3d`$waves on all oxygen atoms and only $`1s`$low waves and intermediate $`2p`$waves on the empty spheres. Also, the number of k-points in the irreducible Brillouin zone (BZ) had to be reduced to 18 k-points.

To study charge order, we have implemented three obvious scenarios. First, we have considered the simple Verwey charge order, where it is assumed that the tetrahedral sites are occupied by Fe3+ ions, while on all the octahedral sites Fe alternates between Fe3+ (five $`d`$ electrons move in the SIC-LSD potential) and Fe2+ (six $`d`$ electrons move in the SIC-LSD potential) in the successive (001) planes. Subsequently, we refer to this as Verwey charge order scenario. In the second scenario, we assume that all tetrahedral and octahedral sites are trivalent, namely Fe3+. Finally, in the third scenario we assume all the tetrahedral sites to be Fe3+, and all the octahedral sites to be Fe2+. In what follows, we shall refer to these calculations as scenarios 1-3, respectively.

Note that for a divalent Fe atom one needs to consider six $`d`$ electrons moving in the SIC potential. Five of the electrons fill up the full manifold of one spin component, whilst the sixth electron has the freedom to populate either of the five states of the other spin component (three t2g and two eg states in the cubic symmetry). As a result five separate, self-consistent total energy calculations have to be performed, for all different structures and scenarios involving divalent Fe’s, to find the lowest energy solution. In what follows, only the results of the lowest energy solutions are presented and discussed.

## IV Results and discussion

### IV.1 Densities of states

In Fig. 1 we compare for the cubic structure the LSD total and species-decomposed densities of states (DOS) with the SIC-LSD counterparts where the Verwey charge order has been implemented. In this figure both spin components are displayed. In Fig. 2, we compare separately the LSD spin-decomposed DOS for the tetrahedral and octahedral sites with the respective DOS from the SIC-LSD calculations, where the octahedral sites are additionally split into Fe3+ and Fe2+. The first thing to note about Fig. 1 is that the LSD calculations find half-metallic DOS, while a small band gap opens up in both spin-channels of the SIC-LSD densities of states, as a result of the Verwey charge order implemented on the octahedral sites. The gap is about 0.35 eV, which is more than two times the experimental gap found in photoemission for magnetite below the Verwey transition temperature, but in good agreement with the LDA+U calculation of Anisimov et al., Anisimov  although the SIC-LSD gap has the $`p`$-$`d`$ charge transfer character, while the LDA+U gap occurs between $`d`$ states of the octahedral Fe ions. Note that due to opening of the SIC-LSD gap, the unoccupied Fe 3$`d`$ states have been shifted up in energy, away from the Fermi level, while the occupied Fe 3$`d`$ states appear well below the valence band, which is composed mostly of oxygen 2$`p`$ with a small admixture of Fe $`d`$ states. In the LSD plots, the spin-up Fe 3$`d`$ states occur at the Fermi level, while there is a well defined gap in the other spin-component. In addition, the predominantly oxygen-like valence band is much more structured in the case of LSD, due to strong hybridization with Fe 3$`d`$ states, which appear at the top of the valence band. Looking at all different types of Fe sites in both the calculations (see Fig. 2), it is clear that the Fe-A sites in the SIC-LSD calculations do not contribute to DOS at the Fermi level, so there is a well defined gap in both spin channels for these sites. The A-sites in the LSD calculation exhibit a very small DOS in the spin-up component, and a gap in the other spin channel. The octahedral, B-sites, in the LSD calculations exhibit a gap in one spin component and in the other spin-component well hybridized states can be observed at the Fermi level, giving rise to the half-metallic ground state. Among the octahedral sites in the SIC-LSD calculations, the B-sites occupied by Fe3+ ions show similar DOS to the LSD calculations for the octahedral ions, except for the gap appearing in the SIC-LSD case in both spin-channels, and the localized spin-down Fe3+ states occuring well below the valence bands. Regarding the unoccupied Fe 3$`d`$ states, the spin-up states for the Fe2+ sites lie higher in energy than the corresponding states for the Fe3+ sites. The small peak observed just below the valence band is due to the sixth localized 3$`d`$ state, while the remaining five localized $`d`$states are visible at about 8.0 eV in the other spin component.

In Fig. 3 we show the total and partial Fe- and O-densities of states for the second SIC-LSD scenario, namely for the case where all Fe-sites, tetrahedral and octahedral alike, are 3+. The DOS are half-metallic, with a gap in one spin component and hybridized Fe-O states occuring at the Fermi level in the other spin component. The DOS of localized Fe 3$`d`$ states appear well below the valence band at about 13.0 eV. Note substantial differences of these DOS with respect to the LSD result of Fig. 1. The reason being, that in the LSD all electrons move in the effective LSD potential, while in the 3+ scenario, the Fe 3$`d`$ electrons respond to the SIC potential. Due to this localizing potential the total weight of the occupied 3$`d`$ states is shifted well below the valence band, while in the LSD picture they appear at the top of the valence band, strongly hybridizing with the O 2$`p`$ states. From the A and B-Fe site decomposed spin-polarized DOS in Fig. 4 we can see that the tetrahedral sites do not contribute at the Fermi level. The half-metallic behaviour is entirely due to the hybridization of the unoccupied 3$`d`$ states of the octahedral Fe sites with the oxygen 2$`p`$ states.

Finally, the LSD and SIC-LSD densities of states for the orthorhombic structures (not displayed in this work) show similar features to their counterparts in the cubic structure, when the respective tetrahedral and octahedral ions are compared. Specifically, a small energy gap of about $`0.1eV`$ and insulating solutions are observed in the charge ordered state for both orthorhombic symmetries. Note that in both orthorhombic structures that were studied there are six crystallographically different B-sites which are subsequently referred to as B1, …, B6. Izumi  Nevertheless, we still have only two types of Fe ions, divalent and trivalent. Concerning the tetrahedral (A) sites, there are four different crystallographic positions in the structure with Pmc21 symmetry, but only two A-type positions in the structure with P2/c symmetry.

Detailed comparison of the densities of states for all different crystallographic structures that we have implemented here, reveals that the second scenario in the orthorhombic structure with the Pmc21 symmetry leads to metallic rather than half-metallic DOS. This result is caused by the fact that the Fermi level moves slightly into the Fe-A 3$`d`$ peak, which is unoccupied in the cubic structure. However, for the refined orthorhombic structure of Ref. Paolo , with P2/c symmetry, we again recover a half-metallic solution for the all trivalent configurations. As in the cubic structure, the Fe-A 3$`d`$ peak is fully unoccupied. This appears to indicate a great sensitivity of the half-metallic solution to atom positions in the low temperature structure.

### IV.2 Total energies and charge order

In this subsection we concentrate on the total energies, spin magnetic moments, and charge disproportionation on octahedral sites, obtained for the scenarios studied here. Tables I and II summarize for the cubic and orthorhombic structures, respectively, the spin magnetic moments on Fe-sites and energy differences with respect to the ground state configuration of the most favourable scenario.

Comparing total energies for the LSD and three different SIC-LSD charge order scenarios in either cubic (Table I) or orthorhombic (Table II) structure, one can see that the second scenario, with all Fe’s in the trivalent configuration, is the lowest energy solution. It is followed by the Verwey charge order scenario, then the third scenario, and finally the LSD, which is the most unfavourable result. The significant energy difference of 113 mRy per formula unit (Table I), found between the scenario SIC(1) and scenario SIC(2), renders the simple Verwey ordering highly unlikely as an explanation for the properties in the low temperature phase of magnetite. The last two columns of Table I, $`\mathrm{\Delta }`$EBF and $`\mathrm{\Delta }`$ESIC, representing respectively the loss in band formation/hybridization energy and gain in localization energy, relative to the respective values of the ground state configuration, provide further physical understanding of this finding. Whilst the localization energy favours more localized states, and hence the formation of Fe2+ on the B2 octahedral sites, the loss of band formation energy by far outweighs the gain in localization energy. So, there is a strong competition between localization and band formation/hybridization energies, and in the simple Verwey scenario the loss in band formation energy, due to localization of one additional electron on the B2 octahedral sites, is three times larger than the gain in localization energy. This balance could possibly be reversed by increasing the nearest neighbour Fe (B2-type)-O bond length, which could perhaps be realized in a very distorted structure, although it is not the case for the orthorhombic structures studied here. The expectation is that substantially increased Fe (B2-type)-O bond length would lead to an increase in the localization energy of all six $`d`$ electrons of B2-Fe (with $`2+`$ valency), and a reduction of their hybridization, thus establishing the Verwey phase as the lowest energy solution. However, one should keep in mind that we refer to nominal valencies, and therefore find that already Fe3+ contains more than five $`d`$-electrons (Table III). All in all, Fe3O4 turns out to have mostly intermediate valencies.

Inspecting in detail the other numbers of Table I, where the results for cubic structure are summarized, one can see that because these systems are either insulating or half-metallic their total magnetic moments are integer. The corresponding total spin magnetic moments for LSD, scenario SIC(1) and scenario SIC(2) are equal to 4.0 $`\mu _B`$ per formula unit, while for the third scenario the total spin moment is 2.0 $`\mu _B`$ per formula unit. The latter value results from the fact that for divalent ions, one additional $`d`$ electron becomes localized. The type-resolved octahedral sites spin magnetic moments are substantially larger for the trivalent ions than for the divalent ions in all the SIC-LSD calculations. The spin magnetic moments of the tetrahedral Fe’s are of similar magnitude but opposite sign to the trivalent octahedral ions. As there are twice as many octahedral sites as tetrahedral ones, the total spin magnetic moment of magnetite in all the different scenarios is mostly due to the octahedral sites. The SIC-LSD spin magnetic moments of the oxygens are of the order of 0.02-0.30 $`\mu _B`$, depending on the scenario, while the spin magnetic moments on the empty spheres are still two orders of magnitude smaller. It is interesting that for the scenario with all octahedral ions in divalent configuration all oxygen moments are oppositely polarized to the octahedral Fe moments and are of the order of 0.2-0.3 $`\mu _B`$. This of course is reflected in the much smaller total spin moment of this scenario. For the first and second scenarios the O moments are smaller, between 0.04 and 0.17 $`\mu _B`$, and polarized parallel to the octahedral Fe ions. The oxygen moments calculated within LSD are of the order of 0.1 $`\mu _B`$ and alligned anti-parallel to the octahedral Fe spin magnetic moments.

Turning to Table II (orthorhombic structure), one can see similar behaviour to that of Table I (cubic structure). Except for the LSD, the respective energy differences for different scenarios are slightly smaller, but otherwise comparable to those for the cubic structure. Regarding the type of solution, metallic or otherwise, again the scenario SIC(1) is insulating, for both orthorhombic structures, but the second (all trivalent) scenario for Pmc21 symmetry and LSD for the P2/c symmetry are not 100% spin polarized, as reflected by their respective total spin magnetic moments. Most importantly, however, for the refined atom positions, as reflected by the structure with P2/c symmetry, Paolo  the all trivalent scenario is half-metallic. Also, for the LSD solution in this structure we find only a minute deviation from 100% spin polarization with the DOS at the Fermi level of about 0.24 states per formula unit and the total spin magnetic moment of almost 4.00 $`\mu _B`$ (with the accuracy better than 0.5%). Compared to the other orthorhombic structure Izumi ; Zuo  it appears that the refined atom positions are crucial for the half-metallic solution in the second scenario. Regarding the type-resolved spin magnetic moments, again we see that the trivalent tetrahedral and octahedral sites give rise to comparable values, with substantially smaller moments of the divalent Fe octahedral sites. Also, the oxygen spin moments are similar to those of the cubic structure.

The spin resolved charges for various Fe atoms for all scenarios and structures are given in Tables III and IV. The first thing to note is that except for the LSD scenario the electron charges of both spin components of the tetrahedral Fe’s do not differ too much among various scenarios. The situation is different for the octahedral sites. Especially, in the Verwey charge ordered scenario the different octahedral ions show similar numbers in one spin component, but differ by about 0.42 electron in the other spin component of the cubic structure, which is due to localization of the sixth $`d`$ electron. So, while in the ionic picture the valency of the two octahedral sites (B1 and B2) differs by one, in terms of the charge disproportionation they are only 0.32 electron different. The situation is similar for the orthorhombic structures. For the structure with the Pmc21 symmetry the B1 and B4 sites are divalent, while B2, B3, B5 and B6 sites are trivalent. In the other orthorhombic P2/c structure, the sites B1 to B4 are divalent, while B5 and B6 sites are trivalent. Again, the charge of spin down components of all the octahedral sites is of the order of 5.8-5.9 electron, the spin up charges of the divalent sites are about 2.2-2.3 electron, while for the trivalent sites they are of the order of 1.8 electron for the Pmc21 symmetry. For the P2/c symmetry the spin down charges of the octahedral sites fall between 5.5 to 5.7 electron, while the spin down charges are of the order of 2.0 and 1.6-1.7 electron for the divalent and trivalent octahedral ions respectively. Consequently, the total charge disproportionation between the divalent and trivalent sites is up to 0.5 and 0.6 electron, respectively for the Pmc21 and P2/c symmetries. There is a spread in charges over the octahedral sites of the orthorhombic structures due to the reduced symmetry of these Fe sites. In the orthorhombic structure we also see charge disproportionation in the other three scenarios, namely LSD, scenario SIC(2) and SIC(3) - this of course does not occur in the cubic phase. It is important to note that for the ground state configuration of all trivalent Fe’s we find charge disproportionations of $`0.2`$ and $`0.36`$ electron for the Pmc21 and P2/c symmetries respectively. These calculated charge disproportionations are in better agreement with the recent experimental study by Wright et al.Paolo  than the ones of the Verwey charge ordered state.

## V Conclusions

In summary, in the present application of the first-principles SIC-LSD method to magnetite we have studied three different arrangements of Fe’s on the octahedral sites, namely the simple Verwey order, the case where, like the tetrahedral sites, all the octahedral sites have been occupied by Fe3+, and finally the scenario with all the octahedral sites occupied by the Fe2+ ions. For all these scenarios the tetrahedral sites have been occupied only by Fe3+. Our total energy calculations, both for the cubic and orthorhombic structures, have shown that the second scenario, with all interstitial sites occupied by Fe3+, is the ground state solution, followed by the case of the Verwey charge order. In the latter case, we have calculated magnetite to be insulating with a gap of about 0.35 eV ($``$0.1 eV in the orthorhombic phase), while the Fe3+ scenario, depending on structure, has given rise to half-metallic or metallic (though still with high spin polarization) state. The insulating state for the Verwey scenario indicates that in the SIC-LSD description the O 2$`p`$ bands are filled, as would be the case for the ionic model. However, no ionic charge distribution is obtained as substantial Fe and O bonding and hybridization still occur. Localizing one less Fe $`d`$ electron (second scenario) results in disappearance of the insulating state and emergence of the half-metallic state, which is a non-trivial result, not predicted by the ionic model.

The ground state scenario of all trivalent Fe’s gives a charge disproportionation which is approximately half of what is found in the Verwey charge ordered state in the orthorhombic structure. The values of the ground state scenario are in line with the recent experiments. Paolo ; garcia1 ; garcia2  The charge disproportionation in the ground state is similar to the one obtained from the LSD which would indicate that these charge disproportionations are not of an electronic origin but are determined by the structure. Namely, the inequivalent Fe positions give rise to different charge distributions, whilst the nominal Fe valency remains unaltered.

Obviously we have managed to study only the three simplest charge ordering scenarios, and within these restrictions our results indicate the energetically unfavourable character of Fe2+. We also find the same ground state configuration of all trivalent Fe in both the cubic structure and the distorted orthorhombic structures. The calculations indicate no minority spin electron localization in the distorted structure, only a marginal decrease, in this structure, with respect to the cubic one, of 5% or so, in the energy difference between the ground state and the charge ordered one. This implies that a simple charge ordered state as described by scenario 1 (SIC(1)) is not realized below the Verwey temperature.

Our study has shown that the SIC-LSD is capable to study any kind of static charge order, although realization of more complicated charge arrangements, which might be of relevance to future studies, may be limited by memory and CPU of present computers. Given these limitations that we only studied a simple Verwey charge ordered state, we have concluded that the charge disproportionation below the Verwey temperature is structural in origin and all Fe ions occur in a trivalent state. This does not exclude the possibility that Fe3O4 below the Verwey temperature is described by a much more complicated charge ordered state.

## Acknowledgements

We thank Dr P.G. Radaelli for providing atom positions of the orthorhombic structure with P2/c symmetry, Professor Victor Antonov for useful communication, and Professor P.H. Dederichs for valuable discussions. This work is partially funded by the Training and Mobility Network on ’Electronic Structure Calculation of Materials Properties and Processes for Industry and Basic Sciences’ (contract:FMRX-CT98-0178) and the Research Training Network ’Psi-k f-electron’ (contract:HPRN-CT-2002-00295). This work is partially sponsored by the Division of Materials Sciences and Engineering, Office of Basic Energy Sciences, U.S. Department of Energy, under Contract DE-AC05-00OR227725. The computational work reported here was performed at the Center for Computational Sciences (CCS) at ORNL and at NERSC at LBNL.