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# 1 Introduction

## 1 Introduction

The dynamics of the massless superstring modes of the various superstring theories admit a description in terms of ten-dimensional effective supergravities. The latter include, in particular, an infinite tower of $`\alpha ^{}`$ corrections. From the world-sheet perspective, the equations of the target-space fields are vanishing conditions for the sigma model beta functions, i.e. conditions for conformal invariance. In this approach, $`\alpha ^{}`$ is the loop-counting parameter in the sigma-model perturbation theory. At zeroth order in $`\alpha ^{}`$, the vanishing of the beta functions is equivalent to the field equations of ordinary supergravity theories. Terms linear or higher in $`\alpha ^{}`$ are associated with corrections involving quadratic or higher polynomials in the spacetime curvature and their supersymmetric completions.

For generic heterotic-string backgrounds the $`\alpha ^{}`$-corrections to sigma-model couplings are not known. As a result, most configurations relevant to string theory that have appeared in the literature, like the compactifications of , the five-brane  and various five-brane intersections , are solutions of ordinary supergravity theories. In cases where there is sufficient world-volume supersymmetry, one can argue that higher-order corrections are absent, see  for a general argument. In general however, the investigation of stringy effects requires taking the $`\alpha ^{}`$ corrections into account. One such background is the heterotic five-brane  which emerges at one loop in sigma-model perturbation. This and other related results have been extended to three loops in .

The low-energy dynamics of the heterotic string is given by $`N=1`$ supergravity in ten dimensions. The bosonic fields of the theory are the spacetime metric $`G`$, the NS three-form field strength $`H`$, the dilaton $`\mathrm{\Phi }`$ and the gauge field $`A`$. The Green-Schwarz anomaly-cancellation mechanism requires that the three-form Bianchi identity receive an $`\alpha ^{}`$ correction of the form

$$dH=\frac{\alpha ^{}}{4}\left(p_1(M)p_1(E)\right)+O(\alpha ^2),$$

where $`p_1(M)`$, $`p_1(E)`$ are the first Pontrjagin forms of spacetime $`M`$ and of the vector bundle $`E`$ with connection $`A`$, respectively. In the $`\alpha ^{}`$ expansion for $`H`$, $`H=T+\alpha ^{}f+O(\alpha ^2)`$, the lowest-order term $`T`$ should be a closed three-form, i.e. $`dT=0`$. This stems from the fact that at tree-level in the sigma model, the string couples to a two-form gauge potential $`b`$, where $`T=db`$. On the other hand, if $`p_1(M)p_1(E)`$, then $`df0`$ and so $`dH0`$. Global anomaly cancellation requires in addition that $`dH`$ be exact, i.e. that $`H`$ be globally defined.

A class of heterotic-string backgrounds for which the Bianchi identity of the three-form $`H`$ receives a correction of the type (1) are those with (2,0) world-volume supersymmetry. Such models were considered in . The target-space geometry of (2,0)-supersymmetric sigma models has been extensively investigated in . Recently, there is revived interest in these models  as string backgrounds and in connection to heterotic-string compactifications with fluxes .

In this paper we investigate the $`\alpha ^{}`$ corrections to heterotic-string backgrounds with (2,0)-world-sheet supersymmetry. We take spacetime to be $`M=\text{}^{102n}\times X_n`$ and demand that the background preserve $`2^{1n}`$ of spacetime supersymmetry. The $`n=2`$ case was examined in . The manifold $`X_n`$ is Hermitian equipped with a compatible connection $`^{(+)}`$ with skew-symmetric torsion $`H`$, i.e. $`X_n`$ is Kähler with torsion (KT). At first order in $`\alpha ^{}`$, the holonomy of the connection $`^{(+)}`$ is contained in $`SU(n)`$ and $`X_n`$ is conformally balanced, see appendix A.

We show that at linear order in $`\alpha ^{}`$ such spacetime-supersymmetric backgrounds satisfy the anomaly-cancellation condition and the field equations. In the proof, we make use of the results of  summarised in appendix A of the present paper. We find that the corrections to the other fields are determined by the corrections to the metric. We stress that consistency of the anomaly cancellation condition with the field equations requires that in the latter we include the two-loop contribution. A sufficient condition for the consistency of spacetime supersymmetry with the anomaly cancellation and the field equations, is the applicability of the $`\overline{}`$-lemma111The $`\overline{}`$-lemma is not valid on all non-Kähler Hermitian manifolds. on $`X_n`$.

We also consider the Donaldson equations on a non-Kähler Hermitian manifold. These are related to the gaugino Killing-spinor equation. For generic Hermitian manifolds, it is not apparent that the Donaldson equations are associated with a second-order equation for the gauge connection, i.e. a field equation. We find that they are, however, if the underlying Hermitian manifold is conformally balanced.

It has been shown in  that if $`X_n`$ is compact, nonsingular and all fields are smooth, then $`T`$ vanishes and to zeroth order in the $`\alpha ^{}`$ expansion $`X_n`$ is a Calabi-Yau $`n`$-fold. We shall take this to be the starting point of the $`\alpha ^{}`$ expansion. Proceeding to first order in $`\alpha ^{}`$, $`X_n`$ is deformed to a conformally-balanced KT manifold with $`\mathrm{hol}(^{(+)})SU(n)`$. We determine the deformations of the fields using Hodge theory. Moreover, we compute the dimension of the moduli space and we find it to be the same as that of the moduli space of the underlying Calabi-Yau manifold. We therefore conclude that at this order in $`\alpha ^{}`$, there is no lifting of moduli in (2,0) compactifications with $`T=0`$. As particular examples of the general theory mentioned above, we compute the $`𝒪(\alpha ^{})`$ corrections to the conifold  and to the $`U(n)`$-invariant Calabi-Yau metric found in . We find that the singularity of the conifold persists to first order in $`\alpha ^{}`$. For other $`\alpha ^{}`$ corrections to conifold geometry see .

This paper is organised as follows: In section two, we establish our notation and write down the field and the Killing-spinor equations for the heterotic string, up to two loops in sigma-model perturbation theory (order $`𝒪(\alpha ^{})`$). In section three, we give the conditions on the deformations of the metric required by spacetime supersymmetry, and express the deformations of the NS three-form and the dilaton in terms of those of the metric. We then show that the Killing-spinor equations for the aforementioned set of fields imply the field equations at this order in $`\alpha ^{}`$, provided the anomalous Bianchi identity of the $`H`$ field is satisfied. In section four, we show that the gaugino Killing-spinor equation, which is equivalent to the Donaldson equations on a Hermitian manifold, implies the field equation for the gauge connection. In section five, we compute the $`𝒪(\alpha ^{})`$ corrections to the fields and show that the dimension of the moduli space is the same as that of the moduli space of the Calabi-Yau space we started with at zeroth order in $`\alpha ^{}`$. In section six and seven, we compute the $`𝒪(\alpha ^{})`$ corrections to the conifold and to the Calabi metric, respectively. In section eight, we discuss the consequences of our results in the context of compactifications with fluxes and we comment on $`\alpha ^{}`$ corrections beyond two-loops. In appendix A, we summarise some of the properties of KT geometry. In appendix B, we explain the relation between the Lichnerowicz and Laplace operators. Finally, in appendix C we give a solution to the field equations at linear order in $`\alpha ^{}`$ without the use of the Killing-spinor equations.

## 2 Field and Killing-spinor equations

The bosonic fields of the ten-dimensional supergravity which arises as low energy effective theory of the heterotic string are the spacetime metric $`G`$, the NS three-form field strength $`H`$, the dilaton $`\mathrm{\Phi }`$ and the gauge connection $`A`$. We define the connections

$$_M^{(\pm )}Y^N=_MY^N\pm \frac{1}{2}H^N{}_{MR}{}^{}Y_{}^{R},$$

where $``$ is the Levi-Civita connection of the metric $`G`$ and $`M,N,R=0,1\mathrm{},9`$ are spacetime indices. The three form $`H`$ has an expansion in $`\alpha ^{}`$ of the form222 Our form conventions are $`\omega _k=\frac{1}{k!}\omega _{i_1,\mathrm{},i_k}dx^{i_1}\mathrm{}dx^{i_k}`$.

$`H=T{\displaystyle \frac{\alpha ^{}}{4}}\left(Q_3(\mathrm{\Gamma }^{()})Q_3(A)\right)+O(\alpha ^2),`$ (2.1)
where $`T`$ is a closed three-form, $`dT=0`$ and $`Q_3`$ are Chern-Simons three-forms. We have

$$dH\alpha ^{}P+O(\alpha ^2),P=\frac{1}{4}[\mathrm{tr}(R^{()}R^{()})\mathrm{tr}(FF)],$$
(2.2)
where the trace on the gauge indices is taken as

$$\mathrm{tr}FF=F^a{}_{b}{}^{}F^b{}_{a}{}^{},F=dA+A^2.$$

Similarly for the trace of $`R^{()}`$, where $`R^{()}`$ is the curvature of the connection $`^{()}`$. The four-form $`P`$ is proportional to the difference of the Pontrjagin forms of the tangent bundle of spacetime and Yang-Mills bundle of the heterotic string.

The string frame field equations of the heterotic string up to two-loops  in sigma model perturbation theory are

$`R_{MN}+{\displaystyle \frac{1}{4}}H^R{}_{ML}{}^{}H_{}^{L}{}_{NR}{}^{}+2_M_N\mathrm{\Phi }`$ (2.3)
$`+{\displaystyle \frac{\alpha ^{}}{4}}[R^{()}{}_{MPQR}{}^{}R_{}^{()}{}_{N}{}^{}{}_{}{}^{PQR}F_{MPab}F_N{}_{}{}^{Pab}]+O(\alpha ^2)`$ $`=`$ $`0`$
$`_M(e^{2\mathrm{\Phi }}H^M{}_{RL}{}^{})+O(\alpha ^2)`$ $`=`$ $`0`$
$`^{(+)}{}_{}{}^{M}(e^{2\mathrm{\Phi }}F_{MN})+O(\alpha ^2)`$ $`=`$ $`0,`$ (2.4)
where we have suppressed the gauge indices. The field equation of the dilaton $`\mathrm{\Phi }`$ is implied from the first two equations above. Our curvature conventions are given in appendix A.

Let $`\{\mathrm{\Gamma }^M;M=0,\mathrm{},9\}`$ be a basis of the Clifford algebra Cliff($`\text{}^{1,9}`$), i.e. $`\mathrm{\Gamma }^M\mathrm{\Gamma }^N+\mathrm{\Gamma }^N\mathrm{\Gamma }^M=2G^{MN}`$. Then the string frame Killing-spinor equations333We have used the notation $`\mathrm{\Gamma }^{M_1\mathrm{}M_k}=\mathrm{\Gamma }^{[M_1}\mathrm{}\mathrm{\Gamma }^{M_k]}`$. are

$`^{(+)}ϵ+O(\alpha ^2)`$ $`=`$ $`0`$
$`\left(\mathrm{\Gamma }^M_M\mathrm{\Phi }{\displaystyle \frac{1}{12}}H_{MNR}\mathrm{\Gamma }^{MNR}\right)ϵ+O(\alpha ^2)`$ $`=`$ $`0`$
$`F_{MN}\mathrm{\Gamma }^{MN}ϵ+O(\alpha ^2)`$ $`=`$ $`0,`$ (2.5)
where $`ϵ`$ is a section of the spin bundle $`S_+`$.444 The spin group $`Spin(1,9)`$ has two inequivalent irreducible sixteen-dimensional spinor representations and $`S_\pm `$ are the associated bundles. It is clear that the first Killing spinor equation is a parallel transport equation for the connection $`^{(+)}`$. Since the connection of the spin bundle $`S_+`$ is induced from the tangent bundle of spacetime, the investigation of this Killing-spinor equation is greatly simplified. The first, second and third Killing-spinor equations are associated with the supersymmetry transformations of the gravitino, dilatino and gaugino, respectively. We shall use this terminology in what follows to distinguish between them.

It is clear from the field equations that the two-loop contribution to the Einstein equations is at the same order as the modification of the torsion $`H`$ due to the cancellation of the heterotic anomaly. Consistency then requires that both should be taken into account. The various field and Killing-spinor equations are expected to receive corrections to all orders in $`\alpha ^{}`$. Therefore a solution of the field and/or Killing-spinor equations of the effective supergravity theory can be expanded as

$`G`$ $`=`$ $`g+\alpha ^{}h+O(\alpha ^2)`$
$`H`$ $`=`$ $`T+\alpha ^{}f+O(\alpha ^2)`$
$`\mathrm{\Phi }`$ $`=`$ $`\phi +\alpha ^{}\varphi +O(\alpha ^2)`$
$`A`$ $`=`$ $`B+\alpha ^{}Q+O(\alpha ^2).`$ (2.6)
In this expansion, the fields $`(g,T,\phi ,B)`$ solve the field and the Killing-spinor equations at zeroth-order in $`\alpha ^{}`$. We again remark that $`dT=0`$ although $`dH`$ may not vanish, $`dH0`$. The deformation $`(h,f,\varphi ,Q)`$ linear in $`\alpha ^{}`$ is the first-order correction to the background $`(g,T,\phi ,B)`$. Of course, the fields receive higher-order corrections in $`\alpha ^{}`$. In what follows, we determine the deformations $`(h,f,\varphi ,Q)`$ by requiring that $`(G,H,\mathrm{\Phi },A)`$ in (2.6) solve the field (2.4) and Killing-spinor (2.5) equations.

## 3 The $`\alpha ^{}`$ corrections to backgrounds with torsion

### 3.1  World-sheet and spacetime supersymmetry

We restrict our attention to heterotic string backgrounds of the form

$`ds^2`$ $`=`$ $`ds^2(\text{}^{102n})+ds^2(X_n)`$
$`T`$ $`=`$ $`{\displaystyle \frac{1}{3!}}T_{ijk}(y)dy^idy^jdy^k`$
$`\phi `$ $`=`$ $`\phi (y)`$
$`B`$ $`=`$ $`B_i(y)dy^i`$ (3.7)
where $`\{y^i;i=1,\mathrm{},2n\}`$ are coordinates on a manifold $`X_n`$, $`n4`$, and $`dT=0`$ as we have explained in the introduction.

In addition, we require that the background $`(g,T,\phi ,B)`$ be compatible with (2,0) world-sheet supersymmetry. This means that the light-cone gauged fixed string world-sheet action is (2,0)-supersymmetric. In particular this implies that $`X_n`$ is a hermitian manifold, $`(X_n,J,g)`$, with complex structure $`J`$ which is parallel with respect to $`^{(+)}`$ connection, i.e. $`(X_n,J,g)`$ is a KT manifold. The torsion $`T`$ of KT manifolds is specified by the metric $`g`$ and the complex structure $`J`$, see appendix A.

The background (3.7) is expected to receive $`\alpha ^{}`$ corrections because the supergravity field equations are modified by two- and higher-loop contributions in sigma model perturbation theory and in particular by the heterotic anomaly-cancellation mechanism. After these corrections are included, the background is expected to be of the form

$`ds^2`$ $`=`$ $`ds^2(\text{}^{10n})+d\stackrel{~}{s}^2(X_n)`$
$`H`$ $`=`$ $`{\displaystyle \frac{1}{3!}}H_{ijk}(y)dy^idy^jdy^k`$
$`\mathrm{\Phi }`$ $`=`$ $`\mathrm{\Phi }(y)`$
$`A`$ $`=`$ $`A_i(y)dy^i,`$ (3.8)
where $`d\stackrel{~}{s}^2(X_n)=G_{ij}(y)dy^idy^j`$. The three-form $`H`$ is not necessarily closed, because of (2.2).

As we have seen, sigma model loop effects and the heterotic anomaly cancellation mechanism alter the geometry of the manifold $`X_n`$. Nevertheless, it is expected that if the original manifold $`(X_n,J,g)`$ has a KT structure, the geometry, after the corrections are taken into account, remains KT. So the manifold $`(X_n,J,G)`$ has a KT structure as well but now the torsion $`H`$ is not closed. This is because it is expected that there is a scheme which preserves the (2,0) world-volume supersymmetry in sigma model perturbation theory .

A solution $`(g,T,\phi ,B)`$ of the zeroth order in $`\alpha ^{}`$ field equations associated with KT manifold $`(X_n,J,g)`$ does not necessarily satisfy the Killing-spinor equations (2.5) of supergravity theory. The conditions for $`(g,T,\phi ,B)`$ to satisfy the gravitino, dilatino and gaugino Killing-spinor equations  are

$`\mathrm{hol}(^{(+)})SU(n)`$ , $`\theta =2d\phi `$ (3.9)
$`F(B)_{2,0}=F(B)_{0,2}=0`$ , $`\mathrm{\Omega }^{ij}F(B)_{ij}=0,`$ (3.10)
where $`\mathrm{hol}(^{(+)})`$ is the holonomy of the connection $`^{(+)}`$, $`\mathrm{\Omega }_{ij}=g_{jk}J^k_j`$ is the Kähler form and $`\theta `$ is the Lee form of the Hermitian geometry. (The Lee-form has been given in appendix A). KT manifolds for which the Lee-form is exact are called conformally balanced. The conditions on the curvature $`F(B)`$ of the gauge connection $`B`$ required by the gaugino Killing-spinor equations imply that $`F`$ is a (1,1)-form with respect to the complex structure $`J`$ and its trace with $`\mathrm{\Omega }`$ vanishes. I.e. considered as a two-form $`F(B)`$ takes values in the Lie algebra of $`SU(n)`$. These conditions are the analogue of the Donaldson equations for Hermitian manifolds. It can be shown that the backgrounds of (3.10) preserve $`2^{1n}`$ of spacetime supersymmetry.

Conversely if $`(g,T,\phi ,B)`$ in (3.7) satisfies the Killing-spinor equations (2.5) preserving $`2^{1n}`$ of spacetime supersymmetry, then $`X_n`$ is a conformally balanced KT manifold and the holonomy of $`^{(+)}`$ is contained in $`SU(n)`$.

As we have explained, the geometry of the background $`(G,H,\mathrm{\Phi },A)`$ (3.8) is expected to be KT. However, it is not apparent that if the $`(g,T,\phi ,B)`$ background is spacetime supersymmetric, then $`(G,H,\mathrm{\Phi },A)`$ will also be spacetime supersymmetric. The corrections to Killing-spinor equations of supergravity (3.10) at order $`𝒪(\alpha ^{})`$ are determined by the corrections to the metric and the torsion but otherwise their dependence on the metric and the torsion remains the same 555It is not expected that this property of the Killing spinor equations persists to all orders in sigma model perturbation theory. The dependence of the Killing-spinor equations on the metric and the torsion will change at higher orders .. This has the consequence that if we insist that the corrected background $`(G,H,\mathrm{\Phi },A)`$ preserve the same number of supersymmetries as $`(g,T,\phi ,B)`$, then $`(X_n,J,G)`$ is again a KT manifold for which $`\mathrm{hol}^{(+)}SU(n)`$, $`\theta =2d\mathrm{\Phi }`$ and $`F(A)_{2,0}=F(A)_{0,2}=0`$, $`\mathrm{\Omega }^{ij}F_{ij}=0`$. In this case, $`^{(+)},\theta `$ and $`\mathrm{\Omega }`$ are the connection, Lee form and Kähler form of the metric $`G`$, respectively.

We conclude that at linear order in $`\alpha ^{}`$, the corrections to the geometry of $`X_n`$ are deformations which preserve the following two properties:

* $`X_n`$ is a conformally balanced KT manifold and
* the holonomy $`^{(+)}`$ is contained in $`SU(n)`$.

In what follows, we derive the conditions on the deformations of the geometry which preserve the above properties and we solve the field and Killing-spinor equations to first order in $`\alpha ^{}`$. We also present a similar analysis for the conditions on the gauge connection.

### 3.2 Gravitino and dilatino Killing-spinor equations

As we have mentioned, in order to solve the gravitino and dilatino Killing-spinor equations, we have to specify the deformations $`(G,H)=(g+\alpha ^{}h,T+\alpha ^{}f)`$ which preserve the properties that $`(X_n,J,g)`$ is conformally balanced KT manifold and $`\mathrm{hol}(^{(+)})SU(n)`$.

First, we consider deformations which preserve the hermiticity of the metric with respect to the complex structure $`J`$. This means that $`h_{\alpha \beta }=0`$, where $`\alpha ,\beta =1,\mathrm{},n`$ are labels for the holomorphic coordinates on $`X_n`$. It can then be easily shown that $`\mathrm{hol}(^{(+)})U(n)`$ provided that the deformation for the torsion is

$$f_{\alpha \beta \overline{\gamma }}=_\alpha h_{\beta \overline{\gamma }}+_\beta h_{\alpha \overline{\gamma }},$$
(3.11)
where $``$ is the Levi-Civita connection of the metric $`g`$, $`f_{\overline{\alpha }\overline{\beta }\gamma }=(f_{\alpha \beta \overline{\gamma }})^{}`$ and the rest of the components vanish. The latter is required because the torsion of a KT geometry is a (2,1)- and (1,2)-form.

Furthermore, the deformation of the connection of the canonical bundle666This is the diagonal $`U(1)`$ part of a $`U(n)`$ connection on the tangent bundle. of $`X_n`$ associated with $`^{(+)}`$ is

$`\omega _\alpha (G)`$ $`=`$ $`\omega (g)_\alpha +\alpha ^{}[2i_\beta h_\alpha {}_{}{}^{\beta }i_\alpha h^\beta _\beta `$ (3.12)
$`+`$ $`iT_{\overline{\delta }}{}_{\beta \overline{\gamma }}{}^{}g_{}^{\beta \overline{\gamma }}h_{\alpha \overline{\delta }}iT_{\alpha \beta \overline{\gamma }}h^{\beta \overline{\gamma }}]+O(\alpha ^2)`$ (3.13)
where $`\omega (g)`$ is the connection of the canonical bundle associated with the connection777To avoid confusion, sometimes we use the notation $`^{(+)}(g)`$ to denote the connection $`^{(+)}`$ with respect to the metric $`g`$. $`^{(+)}(g)`$ and $`\omega _{\overline{\alpha }}=(\omega _\alpha )^{}`$. A necessary and sufficient condition for $`\mathrm{hol}(^{(+)})SU(n)`$ is that the curvature of the canonical bundle vanishes. For the connection (3.13), a sufficient condition is

$$2i_\beta h_\alpha {}_{}{}^{\beta }i_\alpha h^\beta {}_{\beta }{}^{}+iT_{\overline{\delta }}{}_{\beta \overline{\gamma }}{}^{}g_{}^{\beta \overline{\gamma }}h_{\alpha \overline{\delta }}iT_{\alpha \beta \overline{\gamma }}h^{\beta \overline{\gamma }}=0,$$
(3.14)
where $`=(g)`$.

It remains to find the condition required for $`X_n`$ to remain conformally balanced after the deformation. For this, we compute the first-order deformation of the Lee form to find

$$\theta _\alpha =\theta (g)_\alpha +\alpha ^{}[_\alpha (g^{\beta \overline{\gamma }}h_{\beta \overline{\gamma }})_\beta h_{\alpha \overline{\gamma }}g^{\beta \overline{\gamma }}+\frac{1}{2}T_{\alpha \beta \overline{\gamma }}h^{\beta \overline{\gamma }}\frac{1}{2}H^{\overline{\delta }}{}_{\beta \overline{\gamma }}{}^{}g_{}^{\beta \overline{\gamma }}h_{\alpha \overline{\delta }},$$
(3.15)
where $`\theta (g)`$ is the Lee-form of the $`(g,J)`$ geometry. Substituting (3.14) in (3.15), we find that

$$\theta _\alpha =\theta (g)_\alpha +\frac{\alpha ^{}}{2}_\alpha (g^{\beta \overline{\gamma }}h_{\beta \overline{\gamma }})$$
(3.16)
The dilatino Killing-spinor equation can be solved by setting

$$\varphi =\frac{1}{4}g^{\beta \overline{\gamma }}h_{\beta \overline{\gamma }}.$$
(3.17)
Therefore the dilaton is deformed to

$$\mathrm{\Phi }=\phi +\frac{\alpha ^{}}{4}g^{\beta \overline{\gamma }}h_{\beta \overline{\gamma }}+O(\alpha ^2).$$

The equations that remain to be solved are those in (3.14). Observe that these equations are $`2n`$ in number, i.e. as many as the diffeomorphisms of $`X_n`$. Since there is some redundancy in specifying the deformation $`h`$ up to an infinitesimal diffeomorphism generated by the vector field $`v`$, i.e. $`h_{\alpha \overline{\beta }}^{}=h_{\alpha \overline{\beta }}+_\alpha v_{\overline{\beta }}+_{\overline{\beta }}v_\alpha `$, it is expected on physical grounds that it is always possible to choose an $`h`$ so that (3.14) is satisfied. Therefore (3.14) can be viewed as a choice of gauge fixing for diffeomorphisms of $`X_n`$. In the following, we provide more evidence that this is a good gauge choice.

It remains to examine the conditions on the gauge connection. We postpone this for after the investigation of the field equations of the metric and the two-form gauge potential.

### 3.3 The solutions of field equations

Having derived the conditions for the deformations to satisfy the gravitino and dilatino Killing-spinor equations, we now focus on the solutions of the field equations for the metric and the NS two-form potential. In particular we show that at order $`\alpha ^{}`$ both these field equations are satisfied provided that the heterotic anomaly-cancellation condition holds.

Assuming that the background $`(g,T,\phi )`$ satisfies the field equations at zeroth order in $`\alpha ^{}`$, substituting (2.6) in the field equation for the metric $`(\text{2.4})`$ and collecting the terms linear in $`\alpha ^{}`$, we find

$`\mathrm{\Delta }_Lh_{ij}`$ $``$ $`{\displaystyle \frac{1}{4}}T_{imn}f_j{}_{}{}^{mn}{\displaystyle \frac{1}{4}}T_{jmn}f_i{}_{}{}^{mn}+{\displaystyle \frac{1}{2}}h^{mn}g^{kl}T_{imk}T_{jnl}`$ (3.18)
$`+`$ $`2_i_j\varphi g^{kl}(_ih_{jk}+_jh_{ik}_kh_{ij})_l\varphi _0+S_{ij}=0,`$ (3.19)
where $`\mathrm{\Delta }_L`$ is the Lichnerowicz operator with respect to the metric $`g`$ (see appendix B) and

$$S_{ij}=\frac{1}{4}[R^{()}{}_{iklm}{}^{}R_{}^{()}{}_{j}{}^{}{}_{}{}^{klm}F_{ikab}F_j{}_{}{}^{kab}]$$

is the two loop contribution to the beta function. The curvature $`R^{()}`$ is with respect to $`(g,T)`$ and $`F=F(B)`$.

Clearly, (3.19) is rather involved. To proceed, we take the original background $`(g,T,`$ $`\phi ,B)`$ to be spacetime supersymmetric in the sense described in the previous section. In addition we assume that after the deformation the background remains supersymmetric. As we have seen this is equivalent to requiring that the KT geometry $`(X_n,J,G)`$ be conformally balanced and $`\mathrm{hol}((G)^{(+)})SU(n)`$. Substituting the deformation (2.6) in (A.4) of appendix A and collecting the terms linear in $`\alpha ^{}`$, we find that

$`\mathrm{\Delta }_Lh_{ij}`$ $``$ $`{\displaystyle \frac{1}{4}}T_{imn}f_j{}_{}{}^{mn}{\displaystyle \frac{1}{4}}T_{jmn}f_i{}_{}{}^{mn}+{\displaystyle \frac{1}{2}}h^{mn}g^{kl}T_{imk}T_{jnl}`$ (3.20)
$`+`$ $`2_i_j\varphi g^{kl}(_ih_{jk}+_jh_{ik}_kh_{ij})_l\varphi _0={\displaystyle \frac{1}{4}}J^k{}_{i}{}^{}df_{kjmn}\mathrm{\Omega }^{mn}`$ (3.21)
Observe that there is no explicit contribution of the metric deformation on the right-hand-side of (A.4). This is because at zeroth order the torsion is closed, $`dT=0`$. Using (3.19) and (3.21), we find that

$$\frac{1}{4}J^k{}_{i}{}^{}df_{kjmn}\mathrm{\Omega }^{mn}+S_{ij}=0.$$
(3.22)
Next consider the anomaly-cancellation condition (2.2) which to linear order in $`\alpha ^{}`$ can be written as

$$df=P,$$
(3.23)
where $`P`$ depends on $`(g,T,B)`$. Since we have assumed that the background $`(g,T,\phi ,B)`$ is supersymmetric, $`R^{()}`$ and $`F`$ satisfy the conditions

$`R_{mn}^{()}{}_{}{}^{i}{}_{j}{}^{}J_{}^{m}{}_{k}{}^{}J_{}^{n}_l`$ $`=`$ $`R_{kl}^{()}{}_{}{}^{i}{}_{j}{}^{},\mathrm{\Omega }^{mn}R_{mn}^{()}{}_{}{}^{i}{}_{j}{}^{}=0`$ (3.24)
$`F_{mn}{}_{}{}^{a}{}_{b}{}^{}J_{}^{m}{}_{k}{}^{}J_{}^{n}_l`$ $`=`$ $`F_{kl}{}_{}{}^{a}{}_{b}{}^{},\mathrm{\Omega }^{mn}F_{mn}{}_{}{}^{a}{}_{b}{}^{}=0.`$ (3.25)
These conditions on $`R^{()}`$ can be easily deduced from the fact that the holonomy of $`^{(+)}`$ is contained in $`SU(n)`$ and $`R^{()}{}_{ij,kl}{}^{}=R^{(+)}_{kl,ij}`$ provided that the torsion is closed ($`dT=0`$). The conditions on $`F`$ can be deduced from the Killing-spinor equations of the gaugino. Contracting the anomaly-cancellation condition888This derivation of (3.22) from (3.23) is sensitive to the relative numerical coefficient of the two-loop contribution to the metric field equation and that of the anomaly-cancellation condition. (3.23) with the Kähler form $`\mathrm{\Omega }`$ and using (3.25), it is easy to see that the field equation for the metric (3.22) is satisfied.

In order to solve the field equations for the metric, it is sufficient to solve the anomaly-cancellation condition (3.23). Substituting (3.11) in (3.23), we find that

$$P=2i\overline{}Y$$
(3.26)
where $`Y_{ij}=h_{ik}J^k_j`$. The global anomaly-cancellation condition requires that $`P`$ be exact. Since $`P`$ is an exact, real (2,2)-form, if the $`\overline{}`$-lemma is valid on $`X_n`$, then there is a real (1,1)-form $`Y`$ globally defined on $`X_n`$ such that (3.26) is satisfied. On Hermitian manifolds which are not Kähler, the $`\overline{}`$-lemma is not valid in general. Therefore a sufficient condition for the existence of spacetime supersymmetric solutions in backgrounds with non-vanishing torsion, $`T0`$, is the validity of the $`\overline{}`$-lemma.

The solution to the anomaly-cancellation condition (3.26) is not unique. Indeed, if $`Y`$ satisfies (3.26), then

$$Y^{}=Y+\overline{w}+\overline{}w$$
(3.27)
where $`w`$ is a (1,0)-form, is also a solution. This gauge freedom in $`Y`$ is equivalent to specifying the deformation $`h`$ in the metric up to an infinitesimal diffeomorphism. This can be easily seen by setting $`v=iw`$. Therefore having determined $`Y`$ from (3.26), we still have the gauge freedom to solve the supersymmetry condition (3.14).

The solution of (3.26) up to a gauge transformation (3.27) is not unique. The classes of independent solutions are described by the Aeppli group $`V^{1,1}(X_n)`$ defined by

$$V^{1,1}=\frac{\mathrm{Ker}(i\overline{}:\mathrm{\Lambda }^{1,1}(X_n)\mathrm{\Lambda }^{2,2}(X_n))}{\mathrm{\Lambda }^{0,1}(X_n)+\overline{}\mathrm{\Lambda }^{1,0}(X_n)},$$

see  for a related discussion. The dimension of this group is the dimension of the moduli space of solutions of (3.26). However it is not apparent that all elements of this group are associated with spacetime-supersymmetric deformations. The latter should in addition satisfy (3.14).

It remains to show that the field equations of the NS two-form gauge potential are satisfied as well. The proof of this is based on an identity shown in  (corollary 3.2) which can be stated as follows: Let $`(X_n,J,G)`$ be a conformally balanced KT manifold with torsion $`H`$, $`dH0`$, and $`\mathrm{hol}(^{(+)})SU(n)`$, then

$$^iH_{ijk}=\theta _iH^i{}_{jk}{}^{}.$$
(3.28)
This statement is valid irrespectively of whether or not $`G`$ is a small perturbation of another metric $`g`$.

Both KT structures $`(X_n,J,g)`$ and $`(X_n,G,J)`$ satisfy the aforementioned conditions because they are supersymmetric. Therefore both satisfy (3.28) with their respective torsions and Lee forms. Using (3.28) for the $`\alpha ^{}`$ corrected background $`(G,H,\mathrm{\Phi },A)`$, the field equation (2.4) for the NS two-form

$$2_i\mathrm{\Phi }H^i{}_{jk}{}^{}+^iH_{ijk}+O(\alpha ^2)=0$$
(3.29)
can be written as

$$(\theta _i2_i\mathrm{\Phi })H^i{}_{jk}{}^{}+O(\alpha ^2)=0$$

which vanishes identically because $`(X_n,J,G)`$ is conformally balanced. Since the field equations for the background $`(g,T,\phi ,B)`$ are satisfied by assumption and as we have shown the field equations (3.29) for $`(G,H,\mathrm{\Phi },A)`$ are satisfied as well, the part of (3.29) linear in $`\alpha ^{}`$ vanishes identically. Therefore the field equations for the NS two-form gauge potential are satisfied without additional conditions on the deformation $`h`$ of the metric.

## 4 The gauge field

The main purpose of this section is to show that the Killing-spinor equations of the gaugino imply the field equations of the gauge field before and after the $`\alpha ^{}`$ corrections are taken into account. The simplest way to show this is by investigating the properties of gauge fields on conformally balanced KT manifolds.

### 4.1 Gauge Fields on KT conformally balanced manifolds

We first describe the well-known relation between the Donaldson equations and the field equations of a gauge connection on a Kähler manifold. Let $`E`$ be a vector bundle over a Kähler manifold $`(M,J,G)`$ equipped with a connection $`A`$ with curvature $`F`$. If $`A`$ satisfies the Donaldson equations

$$F_{0,2}=F_{2,0}=0,\mathrm{\Omega }^{ij}F_{ij}=0,$$
(4.30)
then it is straightforward to show that $`A`$ solves the field equations

$$^iF_{ij}=0.$$
(4.31)
The proof makes use of the Jacobi identities for $`F`$. Donaldson has shown that if $`E`$ is a stable bundle over a complex surface $`M`$, then there is a unique connection which solves (4.30).

Next suppose that $`E`$ is a vector bundle over a non-Kähler conformally-balanced KT manifold $`(M,J,G)`$ equipped with a connection $`A`$ with curvature $`F`$. Donaldson equations (4.30) can be easily generalised to KT manifolds by allowing $`\mathrm{\Omega }`$ to be the Kähler form of the Hermitian metric $`G`$. We shall show that the Donaldson equations imply the field equations

$$^{(+)}{}_{}{}^{i}(e^{2\mathrm{\Phi }}F(A)_{ij})=0,$$
(4.32)
where $`^{(+)}`$ is the connection of the KT structure $`(M,J,G)`$ with torsion $`H`$ and Lee form $`\theta =2d\mathrm{\Phi }`$. For this we choose complex coordinates with respect to the complex structure $`J`$ and rewrite (4.32) as

$$2_\gamma G^{\gamma \overline{\beta }}F_{\overline{\beta }\alpha }+G^{\gamma \overline{\beta }}_\gamma F_{\overline{\beta }\alpha }\frac{1}{2}H^{\overline{\delta }}{}_{\gamma \overline{\beta }}{}^{}F_{\overline{\delta }\alpha }^{}G^{\gamma \overline{\beta }}\frac{1}{2}H^\delta {}_{\gamma \alpha }{}^{}F_{\overline{\beta }\delta }^{}G^{\gamma \overline{\beta }}=0$$

The Jacobi identities imply that

$$_\gamma F_{\overline{\beta }\alpha }+_\alpha F_{\gamma \overline{\beta }}=_{\overline{\beta }}F_{\alpha \gamma }$$

where

$$_{\overline{\beta }}F_{\alpha \gamma }=\frac{1}{2}H^{\overline{\delta }}{}_{\overline{\beta }\alpha }{}^{}F_{\overline{\delta }\gamma }^{}+\frac{1}{2}H^{\overline{\delta }}{}_{\overline{\beta }\gamma }{}^{}F_{\alpha \overline{\delta }}^{},$$

and $``$ is the Levi-Civita connection of the metric $`G`$. Collecting the various terms together, we find that

$$(\theta _\gamma 2_\gamma \mathrm{\Phi })G^{\gamma \overline{\beta }}F_{\overline{\beta }\alpha }=0$$

which vanishes identically because $`(M,J,G)`$ is conformally balanced, $`\theta =2d\mathrm{\Phi }`$. Therefore equations (4.30) together with the Jacobi equations imply the field equations (4.32).

### 4.2 The gauge field equations

We shall use the result of the previous section to show that the field equations of the gauge field are satisfied provided that the Killing-spinor equations (2.5) are satisfied.

Assuming that the background $`(g,T,\phi ,B)`$ and its deformation $`(G,H,\mathrm{\Phi },A)`$ satisfy the Killing-spinor equations (2.5), the KT structures $`(X_n,J,g)`$ and $`(X_n,J,G)`$ are conformally balanced and the holonomies of their $`^{(+)}`$ connections are contained in $`SU(n)`$. In addition both gauge connections $`B`$ and its deformation $`A`$ satisfy the conditions (4.30)–the latter up to linear order in $`\alpha ^{}`$.

Applying the theorem proven in the previous section, we conclude that the background $`(g,T,\phi ,B)`$ and its deformation $`(G,H,\mathrm{\Phi },A)`$ satisfy the field equations (4.32)–the latter up to linear order in $`\alpha ^{}`$. Expanding (4.32) in $`\alpha ^{}`$ for the background $`(G,H,\mathrm{\Phi },A)`$ and since (4.32) is satisfied at zeroth order in $`\alpha ^{}`$, the linear term in $`\alpha ^{}`$ will vanish identically. Thus if the background $`(g,T,\phi ,B)`$ and its deformation $`(G,H,\mathrm{\Phi },A)`$ satisfy the Killing-spinor equations, then the field equations (2.4) for the gauge potential are satisfied without additional conditions on the deformations. The conditions on the deformation $`Q`$ of the gauge connection $`B`$ are

$`_\alpha Q_\beta _\beta Q_\alpha =_{\overline{\alpha }}Q_{\overline{\beta }}_{\overline{\beta }}Q_{\overline{\alpha }}`$ $`=`$ $`0`$ (4.33)
$`h^{\alpha \overline{\beta }}F(B)_{\alpha \overline{\beta }}+g^{\alpha \overline{\beta }}\left(_\alpha Q_{\overline{\beta }}_{\overline{\beta }}Q_\alpha \right)`$ $`=`$ $`0,`$ (4.34)
where the covariant derivative $``$ is with respect to the gauge connection $`B`$. We have derived these by substituting the deformation $`(G,H,\mathrm{\Phi },A)`$ of $`(g,T,\phi ,B)`$ in the Killing-spinor equations (4.30) and by collecting the terms linear in $`\alpha ^{}`$.

It remains to find whether the Killing-spinor equations for the gaugino or equivalently (4.30) have solutions on a general conformally balanced KT manifold. It is easy to investigate the case where $`A`$ is an abelian connection. However, the non-abelian case is more involved and so we shall not pursue this further.

## 5 (2,0) heterotic compactifications

The compactification ansätze for the heterotic string which preserve (2,0) world-volume supersymmetry and are spacetime supersymmetric, are given in (3.7) with the additional assumption that the internal space $`X_n`$ is compact 999The ansatz (3.7) was considered in  where it was shown that no warp factor is allowed for the non-compact part of the metric. Therefore, as is easy to see using sigma-model perturbation theory, there can be no such warp factor in (3.8) either.. As we have discussed, such backgrounds are expected to receive $`\alpha ^{}`$ corrections. Using the machinery developed in the previous sections, we shall investigate the deformations of these backgrounds due to $`\alpha ^{}`$ corrections.

### 5.1 The zeroth-order solution

As we have explained the requirement for a compactification to preserve (2,0) world-sheet supersymmetry and $`2^{1n}`$ of spacetime supersymmetry in $`(102n)`$-dimensions leads to an internal manifold $`X_n`$ with a conformally balanced KT structure and $`\mathrm{hol}(^{(+)})SU(n)`$.

The additional requirement that $`X_n`$ is compact101010This assumption is sufficient for the spectrum in $`(102n)`$ dimensions to be discrete., the implicit assumption that all the fields $`(g,T,\phi )`$ are smooth on $`X_n`$ and the fact that at zeroth order in $`\alpha ^{}`$ $`dT=0`$, impose strong restrictions on the geometry of $`X_n`$. It has been shown in  under the above assumptions111111 In fact in  it was shown that $`X_n`$ is Calabi-Yau even if $`dT0`$ provided a certain inequality holds. that $`X_n`$ is Calabi-Yau , $`T=0`$ and the dilaton $`\phi `$ is constant. In addition at zeroth order in $`\alpha ^{}`$ the gauge connection $`B`$ satisfies the Donaldson equations (4.30) on the Calabi-Yau manifold $`X_n`$. These data are the starting point of our $`\alpha ^{}`$ expansion.

The Calabi-Yau background $`(g,\phi ,B)`$ receives $`\alpha ^{}`$ corrections. The deformation $`(G,H,`$ $`\mathrm{\Phi },A)`$ of $`(g,\phi ,B)`$ has non-vanishing torsion $`H`$ which is not closed, $`dH0`$, as required by the anomaly-cancellation mechanism. Note that the zeroth-order term in $`H`$ vanishes and so $`H`$ is purely first-order in $`\alpha ^{}`$, $`H=\alpha ^{}f+O(\alpha ^2)`$.

### 5.2 The first-order solution

To find the correction $`(G,H,\mathrm{\Phi },A)`$ to the Calabi-Yau geometry $`(g,\phi ,B)`$, we have to solve equations (3.14), (4.34) for the first-order deformations $`(h,f,\varphi ,Q)`$. The deformation $`\varphi `$ to the dilaton is given in (3.17), $`\varphi =\frac{1}{4}g^{\beta \overline{\gamma }}h_{\beta \overline{\gamma }}`$. Similarly, the deformation $`f`$ of the torsion is given in (3.11). The remaining field and Killing-spinor equations are satisfied without further conditions.

Since for this background the torsion vanishes at zeroth order in $`\alpha ^{}`$, condition (3.14) arising from the requirement that $`\mathrm{hol}(^{(+)})SU(n)`$, can be rewritten as

$$^{\overline{\beta }}h_{\alpha \overline{\beta }}\frac{1}{2}_\alpha (g^{\gamma \overline{\beta }}h_{\gamma \overline{\beta }})=0.$$
(5.35)
The above equation can be thought of as a gauge-fixing condition for the deformations associated with infinitesimal diffeomorphisms of the underlying manifold. Condition (5.35) can always be attained. To see this, first write (5.35) in real coordinates

$$^jh_{ji}\frac{1}{4}_ih^j{}_{j}{}^{}=0.$$
(5.36)
Suppose that $`h`$ does not solve (5.36). We shall show that there is a $`v`$ such that $`h^{}`$ given by $`h_{ij}^{}=h_{ij}+_iv_j+_jv_i`$ satisfies (5.36). $`v`$ is determined by

$$^k_kv_i+\frac{1}{2}_i^kv_k=^jh_{ji}\frac{1}{4}_ih^j{}_{j}{}^{}.$$
(5.37)
First note that the Kernel of the operator on the left-hand-side of the equation above is zero on an irreducible Calabi-Yau manifold. Indeed let $`v`$ be in the Kernel. Then

$$_{X_n}(v^i^k_kv_i+\frac{1}{2}v^i_i^kv_k)𝑑\mathrm{vol}=_M\left(_kv_i^kv^i+\frac{1}{2}(^kv_k)^2\right)𝑑\mathrm{vol}=0.$$

Thus $`v`$ is parallel with respect to the Levi-Civita connection. Since $`X_n`$ is irreducible, there are no parallel one-forms on $`X_n`$ and so the Kernel vanishes. Therefore equation (5.37) can be solved for $`v`$ since the right-hand-side does not vanish, by assumption.

We can also determine the metric moduli of (2,0) compactifications. Since the $`\overline{}`$-lemma applies for Calabi-Yau manifolds, the Aeppli group $`V^{1,1}(X_n)`$ is isomorphic to the the Hodge group $`H^{1,1}(X_n)`$. Thus the dimension of the moduli space is the Hodge number $`h^{1,1}`$ which is the same as the number of metric moduli of Calabi-Yau manifolds. Of course one can also take into account the moduli associated with including in the theory NS two-form gauge potentials. The latter are harmonic (1,1)-forms. This leads to a complex moduli space of real dimension $`2h^{1,1}`$. One concludes that the metric moduli of Calabi-Yau (2,0)-compactifications, which are associated with NS fluxes induced by the heterotic anomaly, are not lifted. An effect of the heterotic anomaly-cancellation mechanism is a shift in the origin of the moduli space.

The moduli of the theory associated with deformations of the complex structure of the underlying Calabi-Yau manifold is not lifted either. The analysis that we have done using the complex structure $`J`$ can be repeated with any other complex structure on the Calabi-Yau manifold. Therefore, we conclude that the presence of NS flux associated with the heterotic anomaly cancellation mechanism does not lift the Calabi-Yau moduli at this order in $`\alpha ^{}`$ perturbation theory.

## 6 The $`\alpha ^{}`$-corrected conifold

The conifold is a singular non-compact Calabi-Yau threefold . Here we apply the machinery of the previous sections to compute the $`\alpha ^{}`$ corrections explicitly.

The conifold can be thought of as a Ricci-flat cone over a $`T^{1,1}`$ space, where the latter is a particular $`U(1)`$ fibration over $`S^2\times S^2`$ . Let $`0\varphi _i2\pi ,0\theta _i\pi ,i=1,2`$ be angular coordinates parametrising the two spheres $`S^2`$, $`0\psi 4\pi `$ be the coordinate on the $`U(1)`$ fibre and $`\rho 0`$ be the radial coordinate. The line element of the conifold is

$`ds^2=g_{mn}dx^mdx^n`$ $`=`$ $`d\rho ^2+{\displaystyle \frac{\rho ^2}{9}}(d\psi +cos\theta _1d\varphi _1+cos\theta _2d\varphi _2)^2`$ (6.38)
$`+`$ $`{\displaystyle \frac{\rho ^2}{6}}(sin^2\theta _1d\varphi _1^2+d\theta _1^2)+{\displaystyle \frac{\rho ^2}{6}}(sin^2\theta _2d\varphi _2^2+d\theta _2^2).`$
The second term on the right-hand-side is the vertical displacement along the $`U(1)`$ fibre whereas the last two terms represent the line element of $`S^2\times S^2`$. There is a conical singularity at $`\rho =0`$, where the $`T^{1,1}`$ base of the cone shrinks to zero size. It is useful to note that $`T^{1,1}`$ is topologically $`S^2\times S^3`$.

Let us now consider a deformation $`g_{mn}g_{mn}+\alpha ^{}h_{mn}`$, where $`h_{mn}`$ is hermitian,

$$h_{kl}J^\kappa {}_{m}{}^{}J_{}^{l}{}_{n}{}^{}=h_{mn}.$$
(6.39)
The complex structure $`J`$ of the conifold is

$`J^{\theta _1}{}_{\varphi _1}{}^{}=sin\theta _1`$ , $`J^\rho {}_{\varphi _1}{}^{}={\displaystyle \frac{\rho }{3}}cos\theta _1,`$
$`J^{\theta _2}{}_{\varphi _2}{}^{}=sin\theta _2`$ , $`J^\rho {}_{\varphi _2}{}^{}={\displaystyle \frac{\rho }{3}}cos\theta _2,`$
$`J^{\varphi _1}{}_{\theta _1}{}^{}={\displaystyle \frac{1}{sin\theta _1}}`$ , $`J^\psi {}_{\theta _1}{}^{}=cot\theta _1,`$
$`J^{\varphi _2}{}_{\theta _2}{}^{}={\displaystyle \frac{1}{sin\theta _2}}`$ , $`J^\psi {}_{\theta _2}{}^{}=cot\theta _2,`$
$`J^\rho {}_{\psi }{}^{}={\displaystyle \frac{\rho }{3}}`$ , $`J^\psi {}_{\rho }{}^{}={\displaystyle \frac{3}{\rho }},`$
and the rest of the components vanish. Condition (6.39) implies that $`h_{mn}`$ is of the form,

$`h_{mn}dx^mdx^n`$ $`=`$ $`D[d\rho ^2+{\displaystyle \frac{\rho ^2}{9}}(d\psi +cos\theta _1d\varphi _1+cos\theta _2d\varphi _2)^2]`$ (6.40)
$`+`$ $`A(sin^2\theta _1d\varphi _1^2+d\theta _1^2)+C(sin^2\theta _2d\varphi _2^2+d\theta _2^2)`$
$`+`$ $`2Bsin\psi (sin\theta _1d\varphi _1d\theta _2sin\theta _2d\varphi _2d\theta _1)`$
$`+`$ $`2Bcos\psi (d\theta _1d\theta _2+sin\theta _1sin\theta _2d\varphi _1d\varphi _2).`$
We take $`A,B,C,D`$ to be functions of the radial coordinate alone. With this assumption, it can be seen from the form of most general $`T^{1,1}`$ metric given in , that (6.40) is a foliation of $`T^{1,1}`$ spaces.

The gauge-fixing condition (5.36) is equivalent to

$`0`$ $`=`$ $`A+C+{\displaystyle \frac{3}{2}}\rho (A+C)^{}{\displaystyle \frac{1}{12}}\rho ^3{\displaystyle \frac{2}{3}}\rho ^2F`$
$`0`$ $`=`$ $`B`$ (6.41)
In order to solve the Einstein equation, we need to find

$$S_{mn}:=\frac{1}{4}R_m{}_{}{}^{kls}R_{nkls}^{}.$$

After some computation, we get

$$S_{\varphi _1\varphi _1}=S_{\varphi _2\varphi _2}=\frac{sin^2\theta }{\rho ^2},S_{\theta _1\theta _1}=S_{\theta _2\theta _2}=\frac{1}{\rho ^2}.$$

The Einstein equation (3.19) (or its gauged-fixed version (C.4) of appendix C) is then equivalent to the following set of conditions,

$`0`$ $`=`$ $`B`$
$`0`$ $`=`$ $`A+C+{\displaystyle \frac{\rho ^2}{24}}(8D+5\rho D^{}+\rho ^2D^{\prime \prime })`$
$`0`$ $`=`$ $`6\rho A^{}+6\rho ^2A^{\prime \prime }+\rho ^2(4D+5\rho D^{}+\rho ^2D^{\prime \prime })3`$
$`0`$ $`=`$ $`A^{}+\rho A^{\prime \prime }C^{}\rho C^{\prime \prime }`$ (6.42)
Demanding that the total metric be asymptotic to the conifold in the region $`\rho /\sqrt{\alpha ^{}}\mathrm{}`$, the general solution to order $`𝒪(\alpha ^{})`$ reads

$`A`$ $`=`$ $`{\displaystyle \frac{1}{16}}({\displaystyle \frac{3}{2}}c_1c_2log{\displaystyle \frac{\rho }{\rho _0}})`$
$`B`$ $`=`$ $`0`$
$`C`$ $`=`$ $`{\displaystyle \frac{1}{16}}({\displaystyle \frac{3}{2}}+c_1+c_2log{\displaystyle \frac{\rho }{\rho _0}})`$
$`D`$ $`=`$ $`{\displaystyle \frac{3}{8\rho ^2}}`$ (6.43)
where $`\rho _0`$ is a dimensionful constant introduced to make the constants $`c_1,c_2`$ dimensionless. Note that the gauge-fixing condition (6.41) is automatically satisfied by the solution (6.43). Therefore the solution is spacetime supersymmetric.

To summarise, the $`𝒪(\alpha ^{})`$-perturbed metric is

$`ds^2`$ $`=`$ $`(1{\displaystyle \frac{3\alpha ^{}}{8\rho ^2}})[d\rho ^2+{\displaystyle \frac{\rho ^2}{9}}(d\psi +cos\theta _1d\varphi _1+cos\theta _2d\varphi _2)^2]`$ (6.44)
$`+`$ $`{\displaystyle \frac{\rho ^2}{6}}[1{\displaystyle \frac{3\alpha ^{}}{8\rho ^2}}({\displaystyle \frac{3}{2}}c_1c_2log{\displaystyle \frac{\rho }{\rho _0}})](sin^2\theta _1d\varphi _1^2+d\theta _1^2)`$
$`+`$ $`{\displaystyle \frac{\rho ^2}{6}}[1{\displaystyle \frac{3\alpha ^{}}{8\rho ^2}}({\displaystyle \frac{3}{2}}+c_1+c_2log{\displaystyle \frac{\rho }{\rho _0}})](sin^2\theta _2d\varphi _2^2+d\theta _2^2).`$
The perturbation is valid in the regime $`\rho /\sqrt{\alpha ^{}}>>1`$. In order to be able to extract any information about the behavior of the metric near the apex ($`\rho =0`$), the full tower of $`\alpha ^{}`$ corrections would have to be taken into account as these become important in the sub-stringy regime $`\rho /\sqrt{\alpha ^{}}1`$. This is clearly beyond the validity of our analysis. Nevertheless, we can attempt to extrapolate our result to the region $`\rho /\sqrt{\alpha ^{}}1`$. An analysis then reveals that at a radial distance of the order of $`\sqrt{\alpha ^{}}`$, an $`S^2`$ in the $`T^{1,1}`$ base shrinks to zero volume. We therefore find that the singularity of the conifold persists, although it becomes milder in the sense that not the entire base shrinks to zero.

## 7 The $`\alpha ^{}`$-corrected $`U(n)`$-invariant Calabi-Yau metric

To describe the $`U(n)`$-invariant Calabi-Yau metric , we introduce complex coordinates $`\{z^\alpha ;\alpha =1,\mathrm{},n\}`$ and consider the $`U(n)`$ invariant Hermitian metric

$$ds^2=A(r^2)dzd\overline{z}+B(r^2)\overline{z}dzzd\overline{z},$$

where $`r^2=\delta _{\alpha \overline{\beta }}z^\alpha z^{\overline{\beta }}`$, $`dzd\overline{z}=\delta _{\alpha \overline{\beta }}dz^\alpha dz^{\overline{\beta }}`$ and similarly for the rest. The metric is Kähler if

$$B=A^{}$$

where the prime denotes differentiation with respect to $`r^2`$. The Levi-Civita connection one-form is

$$\mathrm{\Gamma }^\alpha {}_{\beta }{}^{}=A^1A^{}(\delta ^\alpha {}_{\beta }{}^{}\overline{z}dz+\overline{z}_\beta dz^\alpha )+\frac{A^{\prime \prime }2A^1(A^{})^2}{A+r^2A^{}}z^\alpha \overline{z}_\beta \overline{z}dz$$

The holonomy of the above connection is contained $`U(n)`$. The metric is Calabi-Yau if and only if the holonomy of the above connection is in $`SU(n)`$. The connection of canonical bundle is

$$\omega _\alpha =i_\alpha \mathrm{ln}\text{det}(g_{\alpha \overline{\beta }}),$$

where $`\text{det}(g_{\alpha \overline{\beta }})=A^{n1}(A+r^2A^{})`$. The curvature of canonical bundle vanishes iff

$$A^n+\frac{r^2}{n}(A^n)^{}=\lambda ,$$

where $`\lambda `$ is a constant. The most general solution of this equation is

$$A^n=\lambda +\frac{c}{r^{2n}},$$

where $`c`$ is constant. This metric is the Calabi-Yau metric on the orbifold $`\text{}^n/\text{}_n`$ after resolving the singularity at the origin by replacing with a $`\text{}P^2`$. Next we compute $`P=\frac{1}{4}\mathrm{tr}R^2`$ to find

$$P=\frac{1}{4}C(dzd\overline{z})(dzd\overline{z})+\frac{1}{4}C^{}\overline{z}dzzd\overline{z}(dzd\overline{z}),$$

where

$$C=(n+1)A^2(A^{})^2+2A^1A^{}r^2\frac{A^{\prime \prime }2A^1(A^{})^2}{A+r^2A^{}}+r^4\left(\frac{A^{\prime \prime }2A^1(A^{})^2}{A+r^2A^{}}\right)^2$$

and $`(dzd\overline{z})=\delta _{\alpha \overline{\beta }}dz^\alpha dz^{\overline{\beta }}`$. After some computation, we find that

$$C=n(n+1)\left(\frac{c}{\lambda r^{2n+2}+cr^2}\right)^2$$

In addition setting

$$h=D(r^2)dzd\overline{z}+E(r^2)\overline{z}dzzd\overline{z},$$

and $`Y_{\alpha \overline{\beta }}=ih_{\alpha \overline{\beta }}`$, we find that $`P=2i\overline{}Y`$ implies

$$D^{}E=\frac{1}{8}C.$$
(7.45)
Condition (5.35) for $`h`$, gives

$$2(n1)A^1E(n1)A^1D^{}(n1)A^2A^{}D+\frac{1}{\lambda }[A^{n1}(D+r^2E)]^{}=0.$$
(7.46)
The supersymmetric deformation can be computed by solving (7.45) and (7.46). Substituting for $`E`$ in (7.46), we find after some algebra that

$`0=`$ $``$ $`{\displaystyle \frac{c^2n(n+1)}{8\lambda r^{4n+4}}}{\displaystyle \frac{3\lambda +\frac{nc}{r^{2n}}}{(\lambda +\frac{c}{r^{2n}})^2}}{\displaystyle \frac{c^2(n1)}{\lambda r^{4n+2}}}{\displaystyle \frac{1}{(\lambda +\frac{c}{r^{2n}})}}D`$ (7.47)
$`+`$ $`[{\displaystyle \frac{n1}{\lambda }}(\lambda {\displaystyle \frac{c}{r^{2n}}})+2(\lambda +{\displaystyle \frac{c}{r^{2n}}})]D^{}+{\displaystyle \frac{r^2}{\lambda }}(\lambda +{\displaystyle \frac{c}{r^{2n}}})D^{\prime \prime }.`$
We have not been able to obtain a closed form for $`D`$. But we can solve the equation perturbatively in a large distance expansion. The result reads,

$`E`$ $`=`$ $`{\displaystyle \frac{n(c/\lambda )^2}{8r^{4n+4}}}\left(n2+{\displaystyle \frac{5n^2+8n+1}{2n+1}}{\displaystyle \frac{(c/\lambda )}{r^{2n}}}+\mathrm{}\right)`$
$`D`$ $`=`$ $`{\displaystyle \frac{n(c/\lambda )^2}{8r^{4n+2}}}\left({\displaystyle \frac{3}{2n+1}}+{\displaystyle \frac{n^214n3}{(2n+1)(3n+1)}}{\displaystyle \frac{(c/\lambda )}{r^{2n}}}+\mathrm{}\right)`$ (7.48)
Note that the leading correction to the metric behaves like $`r^{4n2}`$.

## 8 Concluding Remarks

Compactifications with fluxes lead to lower-dimensional effective theories which exhibit potentials lifting some of the moduli. The relevant flux for (2,0) heterotic-string compactifications is the NS three-form $`H`$. There are two possibilities. One is to allow for a non-vanishing flux at zeroth order in $`\alpha ^{}`$. Then the internal manifold is either non-compact or/and some of the fields are singular. We have extensively investigated the case of Calabi-Yau compactifications where the NS flux vanishes at zeroth order in $`\alpha ^{}`$. As we have shown such compactifications develop a non-vanishing flux $`H`$ and a non-constant dilaton at first order in $`\alpha ^{}`$. In addition, at this order in $`\alpha ^{}`$, the compactifications have the same dimension of moduli space as that of the moduli space of the Calabi-Yau manifolds at zeroth order in $`\alpha ^{}`$ and so there is no lifting of moduli.

The effective lower-dimensional theories which arise in standard Calabi-Yau compactifications, i.e. without NS flux, may be different from those with flux. If there is no NS flux induced by the heterotic anomaly-cancellation mechanism, then it is consistent to take the lower-dimensional effective action to be the standard ten-dimensional N=1 supergravity action. Of course there will be higher-order $`\alpha ^{}`$ corrections. Nevertheless it is consistent to consider only the zeroth order in $`\alpha ^{}`$. On the other hand, if one wishes to consider the NS fluxes induced by the heterotic anomaly-cancellation mechanism, consistency requires that curvature square terms in the field equations and their supersymmetric completion should be considered as well. These will contribute to the lower-dimensional effective theories.

The other possibility is to introduce a non-vanishing $`H`$ flux at zeroth order in $`\alpha ^{}`$ and to allow for some fields to be singular or/and for the internal manifold to be non-compact. In the case that the manifold or the fields are singular, one may expect that these singularities can be resolved by taking into account $`\alpha ^{}`$ corrections. We have seen, for example, that after taking into account the linear order $`\alpha ^{}`$ correction to the conifold, the metric is less singular but the singularity is not completely resolved. In a scenario where the singularities are removed and the internal manifold remains compact, some moduli may be lifted and potentials of the type given in  may be generated in the effective theory in lower dimensions.

Similar conclusions can be drawn for compactifications of other theories with fluxes in the presence of an anomaly-cancellation mechanism. Such an example is M-theory . To investigate the consistency of the anomaly cancellation with spacetime supersymmetry as we have done for the heterotic string, one needs to know the higher-order derivative corrections to $`D=11`$ supergravity and their supersymmetric completions.

It is of interest to speculate on the geometry of the background (3.7) after all $`\alpha ^{}`$ corrections are taken into account. It is expected that such a background is a Hermitian manifold, based on the assumption that (2,0) world-sheet supersymmetry is preserved in sigma-model perturbation theory. It is unlikely that the supergravity Killing-spinor equations will remain of the form (2.5). The dependence on the metric and the torsion will change and higher-curvature terms are expected to appear . So the conditions for preserving spacetime supersymmetry will not be simply expressed as conditions on the holonomy of the $`^{(+)}`$ connection and on the Lee form $`\theta `$ of the Hermitian geometry. However, some properties of the underlying manifold may be preserved. It is plausible to assume that the manifold satisfies the $`\overline{}`$-lemma and the canonical bundle is holomorphically trivial. It has been shown in  that Moishezon manifolds with these properties admit a connection with skew-symmetric torsion and holonomy contained in $`SU(n)`$. However, it is not apparent that the associated metric is that which arises after taking into account all $`\alpha ^{}`$ corrections. In addition, on such non-Kähler Moishezon manifolds there is no KT structure for which the associated three-form field strength is closed . Therefore such manifolds cannot be used as the starting point of the sigma-model perturbation theory.

## Acknowledgements

We would like to thank P. Howe for stimulating discussions. This work was partially supported by PPARC grants PPA/G/S/1998/00613 and PPA/G/O/2000/00451 and by EU grant HPRN-2000-00122.

## Appendix A  Useful Formulae for KT Geometry

Let $`(X_n,J,G)`$ be a KT manifold, i.e. $`X_n`$ is a hermitian manifold of complex dimension $`n`$ with metric $`G`$ and complex structure $`J`$ such that $`^{(+)}J=0`$, where $`^{(+)}`$ has skew-symmetric torsion $`H`$. In the mathematics literature $`^{(+)}`$ is called the Bismut connection. The holonomy of $`^{(+)}`$ is contained in $`U(n)`$. In complex coordinates, the holonomy condition requires $`\mathrm{\Gamma }_i^{(+)}{}_{}{}^{\alpha }{}_{\overline{\beta }}{}^{}=0`$ which in turn gives

$$H_{\alpha \beta \overline{\gamma }}=_\alpha G_{\beta \overline{\gamma }}+_\beta G_{\alpha \overline{\gamma }}.$$
(A.1)
The rest of the components of the torsion are determined by complex conjugation. The (3,0) and (0,3) components of $`H`$ vanish as it can be seen from the integrability of the complex structure. So $`H`$ is determined uniquely in terms of the metric and complex structure of $`(X_n,J,G)`$. The Lee form of the KT geometry is

$$\theta _i=\frac{1}{2}J^j{}_{i}{}^{}H_{jkl}^{}\mathrm{\Omega }^{kl},$$

where $`\mathrm{\Omega }_{ij}=G_{ik}J^k_j`$ is the Kähler form. In complex coordinates, the Lee form can be written as

$$\theta _\alpha =_\alpha \mathrm{ln}\text{det}(G_{\beta \overline{\gamma }})G^{\beta \overline{\gamma }}_\beta G_{\alpha \overline{\gamma }}$$
(A.2)
and $`\theta _{\overline{\alpha }}=(\theta _\alpha )^{}`$.

The connection of the canonical bundle induced by $`^{(+)}`$ is

$$\omega _\alpha =i\mathrm{\Gamma }^{(+)}{}_{\alpha }{}^{\beta }{}_{\beta }{}^{}i\mathrm{\Gamma }^{(+)}{}_{\alpha }{}^{\overline{\beta }}{}_{\overline{\beta }}{}^{}=2iG^{\beta \overline{\gamma }}_\beta G_{\alpha \overline{\gamma }}iG^{\beta \overline{\gamma }}_\alpha G_{\beta \overline{\gamma }}$$
(A.3)
and $`\omega _{\overline{\alpha }}=(\omega _\alpha )^{}`$. Let $`\rho =d\omega `$ be the curvature of the $`U(1)`$ connection $`\omega `$. The holonomy of the connection $`^{(+)}`$ is contained in $`SU(n)`$, iff $`\rho =0`$.

A KT manifold is conformally balanced iff there is a function $`\mathrm{\Phi }`$ on $`X_n`$ such that $`\theta =2d\mathrm{\Phi }`$, i.e. the Lee form is exact. It has been shown in  that if $`(X_n,J,G)`$ is a conformally balanced KT manifold and the holonomy of $`^{(+)}`$ is contained in $`SU(n)`$ ($`\rho =0`$), then

$$R_{ij}+\frac{1}{4}H^k{}_{il}{}^{}H_{}^{l}{}_{jk}{}^{}+2_i_j\mathrm{\Phi }=\frac{1}{4}J^k{}_{i}{}^{}(dH)_{kjmn}^{}\mathrm{\Omega }^{mn},$$
(A.4)
where $``$ is the Levi-Civita connection of the metric $`G`$. Note that we do not require $`dH=0`$ in the above expression.

Our conventions for the curvature of a connection $`\mathrm{\Gamma }`$ are

$$R_{ij}{}_{}{}^{k}{}_{l}{}^{}=_i\mathrm{\Gamma }_{jl}^k_j\mathrm{\Gamma }_{il}^k+\mathrm{\Gamma }_{im}^k\mathrm{\Gamma }_{jl}^m\mathrm{\Gamma }_{jm}^k\mathrm{\Gamma }_{il}^m$$

and the Ricci tensor is $`R_{ij}=R_{mi}{}_{}{}^{m}_j`$.

## Appendix B  Lichnerowicz and Laplace operators

Let $`(M,g)`$ be a Riemannian manifold with associated Levi-Civita connection $``$. The Lichnerowicz operator $`\mathrm{\Delta }_L`$ is defined by

$$R_{ij}(g+ϵh)=R_{ij}+ϵ\mathrm{\Delta }_Lh_{ij}+O(ϵ^2).$$

So $`\mathrm{\Delta }_L`$ is the first-order deformation of the Ricci tensor. A calculation reveals that

$`\mathrm{\Delta }_Lh_{ij}=`$ $``$ $`{\displaystyle \frac{1}{2}}^2h_{ij}R_{ikjl}h^{kl}+{\displaystyle \frac{1}{2}}_i^kh_{kj}+{\displaystyle \frac{1}{2}}_j^kh_{ki}`$ (B.1)
$``$ $`{\displaystyle \frac{1}{2}}_i_jh^k{}_{k}{}^{}+{\displaystyle \frac{1}{2}}R_{ki}h^k{}_{j}{}^{}+{\displaystyle \frac{1}{2}}R_{kj}h^k_i`$ (B.2)
The Laplacian operator $`\mathrm{\Delta }`$ on a two form $`Y`$ is

$$\mathrm{\Delta }Y_{ij}=\frac{1}{2}^k_kY_{ij}R_{ikj\mathrm{}}Y^k\mathrm{}+\frac{1}{2}R_{ik}Y^k{}_{j}{}^{}\frac{1}{2}R_{jk}Y^k{}_{i}{}^{}.$$

On Ricci-flat Kähler manifolds, we can relate the Lichnerowicz operator to the Laplace operator on two-forms by choosing the gauge fixing condition

$$^jh_{ji}\frac{1}{2}_ih^j{}_{j}{}^{}=0$$

for infinitesimal diffeomorphisms and by using the relation $`Y_{ij}=h_{ik}J^k_i`$ between symmetric (1,1)-tensors and (1,1)-forms. The Hermiticity condition for the metric implies that the deformations $`h`$ of the metric are (1,1) tensors.

Note that the above gauge can always be attained. Suppose that $`h`$ does not satisfy the gauge. Assume that there is an infinitesimal diffeomorphism $`v`$ such that $`h_{ij}^{}=h_{ij}+_iv_j+_jv_i`$ satisfies the gauge. Then $`v`$ is determined by the equation

$$^k_kv_i=^jh_{ji}\frac{1}{2}_ih^j{}_{j}{}^{}.$$

To show that there is always such a $`v`$, we must invert the above equation. This can be achieved iff $`^jh_{ji}\frac{1}{2}_ih^k_k`$ is orthogonal to the kernel of the elliptic operator $`^k_k`$. We rewrite the above equation as

$$(d\delta +\delta d)V=^jY_{ji}+\frac{1}{2}J^k{}_{i}{}^{}_{k}^{}h^j{}_{j}{}^{},$$

where $`V_i=v_kJ^k_i`$ and $`\delta `$ is the adjoint of $`d`$. Of course this equation can be inverted iff the right-hand-side is orthogonal to harmonic one-forms. Indeed let $`Z`$ be a harmonic one-form, then

$$_MZ^i(^jY_{ji}+\frac{1}{2}\mathrm{\Omega }_{ki}^kh^j{}_{j}{}^{})d\mathrm{vol}=_M(_iZ_jY^{ij}+\frac{1}{2}_iZ_j\mathrm{\Omega }^{ij}h^k{}_{k}{}^{})d\mathrm{vol}=0$$

because $`Z`$ is closed.

## Appendix C  Another derivation of the field equations for (2,0) compactifications

The first-order corrections $`(h,f,\varphi )`$ to the background of a Calabi-Yau compactification $`(g,\phi )`$, $`T=0`$, can be determined by the field equations without using the conditions for spacetime supersymmetry. To show this, we substitute (2.6) in the field equation (2.4) and collect the linear terms in $`\alpha ^{}`$. Using the fact that at zeroth order in $`\alpha ^{}`$ the geometry is Calabi-Yau, the equation for the metric gives

$$\mathrm{\Delta }_Lh_{ij}+S_{ij}+2_i_j\varphi =0,$$
(C.1)
where $`\mathrm{\Delta }_L`$ is the Lichnerowicz operator (see appendix B). In this case, we have

$$\mathrm{\Delta }_Lh_{ij}=\frac{1}{2}^2h_{ij}R_{ikjl}h^{kl}+\frac{1}{2}_i^kh_{kj}+\frac{1}{2}_j^kh_{ki}\frac{1}{2}_i_jh^k_k$$
(C.2)
because $`X_n`$ is Calabi-Yau and $`R_{ij}=0`$, and

$$S_{ij}=\frac{1}{4}[R_{iklm}R_j{}_{}{}^{klm}F_{ikab}F_j{}_{}{}^{kab}]$$
(C.3)
The covariant derivative $``$ in (C.1) and (C.2) and the curvature $`R`$ are with respect to the Calabi-Yau metric $`g`$.

To solve equation (C.1) with respect to $`h`$, we shall exploit the well-known relation between the Lichnerowicz and Laplace operators on Calabi-Yau manifolds. There are two ways to do this. One is to use the scheme dependence of the two-loop beta function and the other is to impose a gauge fixing condition on the deformations $`h`$ of the metric $`g`$. The latter is common in moduli problems in order for the deformation $`h`$ to be orthogonal to the orbits of infinitesimal diffeomorphisms. Using the scheme dependence of the two-loop beta function, we can arrange so that the term

$$\frac{1}{2}_i^kh_{kj}+\frac{1}{2}_j^kh_{ki}+\frac{1}{2}r_i_jh^k_k$$

is cancelled by a wave function renormalization, where $`r`$ is a real number. Alternatively, one can impose the gauge fixing condition

$$^kh_{ki}+\frac{r}{2}_ih^k{}_{k}{}^{}=0.$$

Provided that we set for the deformation of the dilaton

$$\varphi =\frac{1}{4}(r+1)h^k{}_{k}{}^{},$$

the remaining equation is

$$\frac{1}{2}^2h_{ij}R_{ikjl}h^{kl}+S_{ij}=0.$$
(C.4)
To solve this equation observe that $`S`$ is a (1,1) symmetric tensor with respect to the complex structure. This allows us to consider deformations of the metric which are (1,1) as well, i.e. to take $`h`$ to be a (1,1) symmetric tensor. It is well known that on Kähler manifolds there is a 1-1 correspondence between symmetric (1,1) tensors and (1,1) two-forms. Indeed define the forms $`Y_{ij}=h_{ik}J^k_j`$ and $`Z_{ij}=S_{ik}J^k_j`$ associated to $`T`$ and $`S`$. Equation (C.4) becomes

$$\mathrm{\Delta }Y+Z=0$$
(C.5)
where

$$\mathrm{\Delta }Y_{ij}=\frac{1}{2}^k_kY_{ij}R_{ikj\mathrm{}}Y^k\mathrm{}$$

is the standard Laplace operator on $`Y`$ (see appendix B). We have taken into account that Calabi-Yau manifolds are Ricci-flat, $`R_{ij}=0`$. So it remains to invert the Laplace operator to determine $`Y`$ in terms of $`Z`$.

To solve the equation (C.5) in terms of $`Y`$, we have to show that $`Z`$ is orthogonal to the harmonic two-forms of $`X_n`$ in the Hodge decomposition with respect to the Calabi-Yau metric $`g`$. This can be achieved by relating the two-loop contribution $`Z`$ to the beta function of the metric, to the heterotic anomaly $`P`$. Using

$$\mathrm{\Omega }^{ij}R_{ijkl}=\mathrm{\Omega }^{ij}F_{ijab}=0,$$

we can show that

$$Z_{ij}=\frac{1}{4}P_{ijmn}\mathrm{\Omega }^{mn}.$$

Now suppose that $`n=3`$. After some computation, we find that

$$Z_{ij}=\frac{1}{2}{}_{}{}^{}P_{ij}^{}+\frac{1}{16}\mathrm{\Omega }_{ij}P_{mnpq}\mathrm{\Omega }^{mn}\mathrm{\Omega }^{pq}.$$

The cancellation of the global anomaly implies that $`P`$ is exact. As a consequence the dual two-form $`{}_{}{}^{}P`$ is co-exact and so it is orthogonal to harmonic two-forms. It remains to show that $`P_{mnpq}\mathrm{\Omega }^{mn}\mathrm{\Omega }^{pq}`$ is not harmonic. Observe that a harmonic function on $`X_3`$ is a non-vanishing constant. Integrating the identity

$$P\mathrm{\Omega }=\frac{1}{8}P_{mnpq}\mathrm{\Omega }^{mn}\mathrm{\Omega }^{pq}d\mathrm{vol}$$

over the compact manifold $`X_3`$ and using that $`P`$ is exact, it is easy to see that $`P_{mnpq}\mathrm{\Omega }^{mn}\mathrm{\Omega }^{pq}`$ is not harmonic.

This result can be easily extended to four- and eight-dimensional internal manifolds. The $`n=2`$ case has been investigated in . For $`n=4`$, the computation is similar to $`n=3`$. The only difference is the relation between the two-loop counterterm and the anomaly.

Next we investigate the field equation of the three-form field strength. Again substituting (2.6) in (2.4) and collecting the terms linear in $`\alpha ^{}`$, we find

$$^if_{ijk}=0$$

or equivalently

$$d^{}f=0,$$

where $`d^{}`$ is the adjoint operator of $`d`$. To derive this, we have used the fact that $`H`$ vanishes at zeroth order in $`\alpha ^{}`$. In addition, we have that $`df=P`$; $`f`$ is well-defined because $`P`$ is exact. Using the Hodge decomposition, we can write

$$f=f_h+dX+d^{}W$$

where $`f_h`$ is harmonic and $`W`$ is a four-form. Adding the counterterm

$$b=\alpha ^{}X,$$

the exact three-form $`dX`$ can be eliminated as follows

$$H=\alpha ^{}dX+\alpha ^{}f=\alpha ^{}f_h+\alpha ^{}d^{}W.$$

Thus the field equation is satisfied and $`dH=P`$. Alternatively, one can choose $`f`$ such that $`f=f_h+d^{}W`$.


text:
# (submitted to Appl. Phys. A) Oxide formation at the surface of late 𝟒𝒅 transition metals: Insights from first-principles atomistic thermodynamics

## I Introduction

Rhodium and palladium exhibit a high reactivity for the CO oxidation reaction, which has led to their widespread use in catalytic car exhaust converters taylor93 . The degree of oxidation of these materials in the reactive environment has been a frequent object of speculation in the experimental catalysis literature (see e.g. refs. oh83, ; kellog85, ; peden88, ; turner81, ; bondzie96, ; ziauddin97, ; veser99, ), with oxide formation at the surface of the metal particles potentially having either beneficial or detrimental effects on the overall activity. Lacking microscopic in-situ data to really resolve this issue a possibly beneficial role has e.g. been suspected for PdO at Pd ziauddin97 , whereas Rhodium oxides have predominantly been viewed as poisoning the catalytic reaction oh83 ; kellog85 ; peden88 .

While the atomic-scale techniques of Ultra High Vacuum (UHV) surface-science would in principle be able to provide additional insight into this subject matter, formation of oxides in particular of the more noble metals was often neglected in corresponding works, partly due to the fact that these oxides form only at rather high oxygen pressures and elevated temperatures. This emphasis on metallic substrates has changed over the last years, bringing oxide surfaces now also on the agenda of surface-science studies attempting to bridge the pressure gap between UHV and technological oxidation catalysis stampfl02 . Concomitantly, on Ru(0001) over00 ; kim01b , Pd(100) hendriksen03a ; hendriksen03b , and Ag(111) carlisle00b ; li03  oxygen-rich environmental conditions were reported to lead to oxide (or “surface oxide”) formation, in all cases connected with a significant increase in catalytic activity.

This new focus on the effect of the environment on surface structure and reactivity is intertwined with corresponding theoretical efforts. In particular the concept of first-principles atomistic thermodynamics weinert86 ; scheffler88 ; kaxiras87 ; qian88  has recently proven to be most valuable for the study of oxide surfaces (see e.g. refs. wang98, ; wang00, ; reuter02a, ; reuter03a, ; reuter03b, ). In this branch of thermodynamics density-functional theory (DFT) is employed to compute free energies, in order to identify the lowest-energy atomic structure for a given condition of thermodynamic reservoirs representing the surrounding gas phase, and possibly combining this with constraints to facilitate the analysis reuter03a ; reuter03b . In the following we will use and describe this formalism to discuss the stability of bulk and surface oxides of the late $`4d`$ transition metals (TMs) Ru, Rh, Pd, and Ag. The results of these very basic thermodynamic considerations are found to nicely embrace the aforedescribed existing experimental data, e.g. pointing at the relevance of thin surface oxide layers on Pd under the conditions of high-pressure CO oxidation catalysis.

## II “Constrained thermodynamics”

The question we like to ask in this context is, given a certain gas phase environment composed of O2 and CO, does a bulk or surface oxide of the late $`4d`$ TMs form a stable phase? In a thermodynamic description we then resort to some form of equilibrium that exists between various components $`i`$ in the system, all of which are present in sufficient quantities. Under conditions of constant temperature, $`T`$, and pressures, $`\{p_i\}`$, this allows to discuss relations between the respective reservoirs, characterized by their chemical potentials $`\mu _i(T,p_i)`$ or Gibbs free energies $`g_i(T,p_i)`$. For a gas phase composed of CO and O2 a forthright assumption of full equilibrium does, however, not yield a description suitable for our interest in oxidation catalysis: From energy considerations alone, CO2 would then result as the most stable gas phase molecule for almost all temperature and pressure conditions. On the other hand, because of the large free energy barrier for the gas phase reaction CO + 1/2 O$`{}_{2}{}^{}`$ CO2, such a full equilibrium will not be attained on time scales relevant to us. Instead, we may ignore CO2 formation in the gas phase and consider the presence of two separate, independent reservoirs for O2 and CO in the environment. While both components are therefore not in equilibrium with each other, each one is individually assumed in equilibrium with either the metal (M) or the oxide ($`\mathrm{M}_\mathrm{x}\mathrm{O}_\mathrm{y}`$) phase.

As a consequence the chemical potentials of both oxygen and CO in the whole system are then determined by the surrounding gas phase reservoirs, i.e. their temperature and pressure dependence is given by reuter02a ; reuter03b

$$\mu _\mathrm{O}(T,p_{\mathrm{O}_2})=\frac{1}{2}\left[E_{\mathrm{O}_2}^{\mathrm{total}}+\stackrel{~}{\mu }_{\mathrm{O}_2}(T,p^0)+k_\mathrm{B}Tln\left(\frac{p_{\mathrm{O}_2}}{p^0}\right)\right],$$
(1)
and

$$\mu _{\mathrm{CO}}(T,p_{\mathrm{CO}})=E_{\mathrm{CO}}^{\mathrm{total}}+\stackrel{~}{\mu }_{\mathrm{CO}}(T,p^0)+k_\mathrm{B}Tln\left(\frac{p_{\mathrm{CO}}}{p^0}\right),$$
(2)
where the temperature dependence of $`\stackrel{~}{\mu }_{\mathrm{O}_2}(T,p^0)`$ and $`\stackrel{~}{\mu }_{\mathrm{CO}}(T,p^0)`$ includes the contributions from vibrations and rotations of the molecules, as well as the ideal gas entropy at $`p^0=1`$ atmosphere. The latter quantities can be computed from first principles, yielding results that are at the temperature range of interest to us virtually indistinguishable from the experimental values listed in thermodynamic tables reuter03b ; JANAF . Via eqs. (1) and (2) our results obtained as a function of the chemical potentials, i.e. in $`(\mu _\mathrm{O},\mu _{\mathrm{CO}})`$-space, can then be converted into pressure scales at any specific temperature. Roughly representing the temperature range relevant to our study, this will be illustrated with specific scales at $`T=300`$ K and $`T=600`$ K in all figures below.

In the resulting “constrained equilibrium” situation reuter03a ; reuter03b  the only pathway to CO2 formation is due to a reduction of the oxide or due to the catalytic CO oxidation at the substrate surface. In a flow reactor this constant build-up of CO2 is counteracted by the continuous stream (and thus removal) of gases over the catalyst surface, yielding a CO2 concentration gradient under stationary operation conditions. Although formed CO2 molecules may in principle readsorb at the surface (dissociatively or as a molecule), the probability of this event is very low compared to the much more frequent O2 and CO (re)adsorption. The surface is therefore unlikely to equilibrate with the surrounding CO2 gas phase, and a proper description would have to involve a dynamical treatment of the CO2 gas flow close to the catalyst surface. Such treatment will be published elsewhere reuter03c . Here we use a very simple estimate for the CO2 free energy, namely the internal energy of a free CO2 molecule. The error introduced by this estimate will vary from material to material, but in our preliminary kinetic Monte Carlo simulations for RuO2(110) we find it to be small.reuter03c

Although crude, this approximation is appropriate for the present trend study aiming only at a first assessment of oxide stability, and an uncertainty of some tenths of eV does not change the nature of our conclusions. In this respect we stress that the whole concept of a “constrained equilibrium” is not designed to yield precise answers to the microscopic state and reactivity of the catalyst surface. For that, the very dynamic behavior must be modeled by statistical mechanics. Yet, with atomistic thermodynamics one can trace out the large scale behavior and identify those conditions where such a more refined treatment is necessary.

## III Bulk oxide stability

If there is a pure oxygen environment, the condition for the stability of the bulk oxide is

$$g_{\mathrm{M}_x\mathrm{O}_y}^{\mathrm{bulk}}<xg_\mathrm{M}^{\mathrm{bulk}}+y\mu _\mathrm{O},$$
(3)
i.e.

$$\mathrm{\Delta }\mu _\mathrm{O}>\frac{1}{y}\left[g_{\mathrm{M}_x\mathrm{O}_y}^{\mathrm{bulk}}xg_\mathrm{M}^{\mathrm{bulk}}\frac{y}{2}E_{\mathrm{O}_2}^{\mathrm{total}}\right].$$
(4)
Here $`\mathrm{\Delta }\mu _\mathrm{O}`$ is defined as $`\mu _\mathrm{O}(1/2)E_{\mathrm{O}_2}^{\mathrm{total}}`$. For $`T=0`$ K the bracket on the right hand side equals half of the low temperature limit of the heat of formation, $`H_f(T=0\mathrm{K},p=0)`$. Even for higher temperatures this will not change substantially as for bulk phases the $`(T,p)`$-dependence of their Gibbs free energies is rather small, i.e. the right hand side will still be rather close to the $`H_f(T=0\mathrm{K},p=0)`$-value and not follow the pronounced variation of $`H_f(T,p)`$ (which is primarily due to the $`(T,p)`$-dependence of the $`\mu _{\mathrm{O}_2}`$-term, while only $`E_{\mathrm{O}_2}^{\mathrm{total}}`$ enters the right hand side of eq. (4)). We therefore replace the bracket in eq. (4) by $`(1/y)H_f(T=0\mathrm{K})`$ and arrive at our first stability condition

$$\mathrm{\Delta }\mu _\mathrm{O}\stackrel{>}{}\frac{1}{y}H_f(T=0\mathrm{K}).$$
(5)
Additionally, the oxide can also be destroyed (reduced) by carbon monoxide. In a pure CO environment, the stability condition for the oxide is

$$g_{\mathrm{M}_x\mathrm{O}_y}^{\mathrm{bulk}}+y\mu _{\mathrm{CO}}<xg_\mathrm{M}^{\mathrm{bulk}}+y\mu _{\mathrm{CO}_2}.$$
(6)
Following the discussion above we will crudely approximate $`\mu _{\mathrm{CO}_2}`$ in the present study by the internal energy of a free CO2 molecule. In a similar fashion as for the pure oxygen environment one can then simplify the stability condition to

$$\mathrm{\Delta }\mu _{\mathrm{CO}}\stackrel{<}{}\frac{1}{y}H_f(T=0\mathrm{K})+\mathrm{\Delta }E^{\mathrm{mol}.},$$
(7)
introducing $`\mathrm{\Delta }\mu _{\mathrm{CO}}=\mu _{\mathrm{CO}}E_{\mathrm{CO}}^{\mathrm{total}}`$ and using the short hand $`\mathrm{\Delta }E^{\mathrm{mol}.}=(E_{\mathrm{CO}_2}^{\mathrm{bind}}E_{\mathrm{CO}}^{\mathrm{bind}}1/2E_{\mathrm{O}_2}^{\mathrm{bind}})`$ for the difference in binding energies of the three gas phase molecules. As described in detail in a previous publication reuter03b  our DFT computations including zero-point vibrations give $`\mathrm{\Delta }E^{\mathrm{mol}.}=3.2`$ eV, which agrees well with the experimental value of $`2.93`$ eV JANAF . Although state-of-the-art DFT total energies of the O2 molecule are subject to a noticeable error, some cancelation apparently occurs for the composite quantity $`\mathrm{\Delta }E^{\mathrm{mol}.}`$, rendering it rather unimportant on the scale of the present study whether the experimental or theoretical value for $`\mathrm{\Delta }E^{\mathrm{mol}.}`$ is used.

Finally, if O2 and CO are both present in the gas phase in “constrained equilibrium” with the oxide, then the general stability condition is simply obtained by combining eqs. (5) and (7) for the separate cases:

$$\mathrm{\Delta }\mu _{\mathrm{CO}}\mathrm{\Delta }\mu _\mathrm{O}\stackrel{<}{}\frac{2}{y}H_f(T=0\mathrm{K})+\mathrm{\Delta }E^{\mathrm{mol}.},$$
(8)
while eq. (5) still applies for very low CO concentrations. Hence, in both conditions for the stability of the bulk oxide, eqs. (5) and (8), the only quantity left to determine is $`\mathrm{\Delta }H_f(T=0\mathrm{K})`$. This value has been computed in previous works li03 ; reuter02a ; grillo03 ; rogal03  and we content ourselves here with simply listing the DFT values for the most stable oxides of the four late $`4d`$ TMs in Table 1, again comparing with the low-temperature limit of the experimental heat of formation CRC . Keeping the sizable error in the O2 DFT total energy in mind, we notice in all cases a fortuitous error cancelation, leading again to rather small differences when evaluating the stability conditions with either experimental or theoretical numbers. Only in the case of silver oxide has $`\mathrm{\Delta }H_f(T=0\mathrm{K})`$ become so small that this error becomes somewhat disturbing (in particular for the stability condition in eq. (8)). More refined treatments for approximating the stability conditions, e.g. including entropic contributions to $`\mathrm{\Delta }H_f(T,p)`$, can be devised li03 , but for our present purposes it suffices to see that bulk Ag2O has such a low stability that it will not play a role in our further discussion.

The derived $`(T,p)`$-ranges for stability of the $`4d`$ bulk oxides are shown in Fig. 1, exhibiting a pronounced decrease from RuO2 towards the oxides of the metals to its right in the periodic system. We stress that the aforediscussed crude treatment of the CO2 free energy translates into rather large error bars on the diagonal lines running from bottom left to top right in the figure (i.e. the limit due to the stability condition of eq. (8)). The uncertainty in $`\mu _{\mathrm{CO}_2}`$ translates directly into the height of these lines, which with the present error estimate could therefore be shifted up or down by some tenths of an eV.

## IV Surface oxide stability

Defering the discussion of the derived bulk oxide stability to the end of this paper, we proceed to analyze in the stability context a second, only recently emphasized aspect of metal oxidation, namely the formation of thin surface oxides. While traditionally such films were conceived as closely-related thin versions of the corresponding bulk oxides, recent atomic scale characterizations of initial few-atom thick oxide overlayers especially on Pd and Ag surfaces revealed structures that had only little resemblance to their bulk counterparts, and/or were to a large degree influenced by a strong coupling to the underlying metal substrate carlisle00b ; lundgren02 ; todorova03 . Due to this coupling and structures particularly suited for layered configurations, one may expect the stability range for such surface oxides to exceed that of the hitherto discussed bulk oxides.

To determine the range of $`(T,p)`$-conditions in which a surface oxide would represent the thermodynamically most stable state, we follow the approach of Li, Stampfl and Scheffler li03 , i.e. we evaluate the Gibbs free energy of adsorption and compare it to other possible states of the system like on- or sub-surface oxygen phases or the bulk oxide. For the case of a pure O2 environment and using the same approximations as discussed in the last section, we may write this Gibbs free energy of adsorption as

$`\mathrm{\Delta }G(\mathrm{\Delta }\mu _\mathrm{O})`$ (9)
$``$ $`{\displaystyle \frac{1}{A}}\left(E_{\mathrm{O}\mathrm{@}\mathrm{M}}^{\mathrm{total}}E_\mathrm{M}^{\mathrm{total}}N_\mathrm{O}\left({\displaystyle \frac{1}{2}}E_{\mathrm{O}_2}^{\mathrm{total}}+\mathrm{\Delta }\mu _\mathrm{O}\right)\right)`$
$`=`$ $`{\displaystyle \frac{N_\mathrm{O}}{A}}\left(E_{O\mathrm{@}M}^{\mathrm{bind}}+\mathrm{\Delta }\mu _\mathrm{O}\right).`$
Here, $`E_{\mathrm{O}\mathrm{@}\mathrm{M}}^{\mathrm{total}}`$ and $`E_\mathrm{M}^{\mathrm{total}}`$ are the total energies of the surface with and without oxygen coverage of $`N_\mathrm{O}`$ oxygen atoms per surface area $`A`$. In the second line, we have identified the first terms in the brackets with the average binding energy of oxygen in the particular surface configuration and with respect to 1/2 $`E_{\mathrm{O}_2}^{\mathrm{total}}`$.

Obviously, the higher the oxygen content of a considered surface structure, the steeper its $`\mathrm{\Delta }G(\mathrm{\Delta }\mu _\mathrm{O})`$ will decrease with increasing chemical potential. In the limiting case of an infinitely thick bulk oxide on top of the metal substrate, this will result in a vertical line that crosses the zero-axis at the stability condition for the bulk oxide in eq. (5). For any higher $`\mathrm{\Delta }\mu _\mathrm{O}`$ the bulk oxide will be the stable phase, but the interesting question is to see whether there are lower $`\mathrm{\Delta }\mu _\mathrm{O}`$ than this limit, for which the lines of a surface oxide structure turn out lower than e.g. on-surface adsorption or the clean surface corresponding to $`\mathrm{\Delta }G(\mathrm{\Delta }\mu _\mathrm{O})=0`$.

We exemplify this ansatz by first analyzing the stability of a surface oxide on Pd(100). In addition to the well known $`p(2\times 2)`$ and $`c(2\times 2)`$ ordered adlayers with O in fcc sites kolthoff96 ; zheng02 , an ensuing $`(\sqrt{5}\times \sqrt{5})R27^o`$-O surface oxide phase on this surface was recently characterized as a rumpled, but commensurate PdO(101) film with a strong coupling to the underlying Pd(100) substrate todorova03 ; todorova03b . Evaluating the reported binding energies in this study with eq. (9) we obtain the results displayed in Fig. 2. Interestingly, the $`\mathrm{\Delta }\mu _\mathrm{O}`$-range where this surface oxide exhibits the lowest Gibbs free energy of adsorption not only exceeds the one of the aforediscussed PdO bulk oxide, but also the range where the on-surface adsorption phases are more stable than the clean Pd(100) surface. In other words, the latter on-surface phases never correspond to a thermodynamically stable phase, and their frequent observation in UHV experiments kolthoff96 ; zheng02  appears to be a mere outcome of the limited O supply offered, as well as of kinetic barriers e.g. for O penetration at the low temperatures employed (UHV experiments are typically performed by depositing a finite number of adatoms, rather than by maintaining a given gas pressure).

It is interesting to compare these findings with the equivalent situation on another Pd surface orientation. On Pd(111), a surface oxide not resembling the bulk-structure of PdO at all was recently reported as the product of high oxygen exposure and following the well-studied $`p(2\times 2)`$ on-surface adsorption phase lundgren02 . Using the DFT binding energies provided in this study to evaluate eq. (9), we again obtain a range of $`(T,p)`$-conditions outside of the bulk oxide stability range, for which this surface oxide phase is most stable as shown in Fig. 3. This time, however, this range extends only within -1.2 eV $`\stackrel{>}{}\mathrm{\Delta }\mu _\mathrm{O}\stackrel{>}{}0.9`$ eV, below which first the on-surface adsorption phase and then the clean Pd(111) surface becomes more stable. If we compare this to the results shown in Fig. 2, there are thus environmental conditions, in which a surface oxide may already be thermodynamically stable on Pd(100), while on-surface adsorption still prevails on Pd(111). Knowing that these two surfaces form the predominant surface area of Pd nanoparticles szanyi93 , this may have profound consequences on the oxidation behavior of the latter and we will return to this point below.

While a similar situation with the commensurable $`p(4\times 4)`$ surface oxide carlisle00b  slightly exceeding the stability range of bulk Ag2O was also found for Ag(111) li03 , no $`(T,p)`$-range most favorable for the various intermediate precursors suggested in the oxidation pathway from Ru(0001) to RuO2(110) is obtained when evaluating the DFT binding energies reported in the corresponding refs. reuter02b, ; reuter02c, . Tentatively, we therefore expect surface oxides to play a thermodynamic role more for the $`4d`$ TMs towards the right of the periodic system, where the decreasing thermal stability of the bulk oxides and the lowered bulk modulus of oxide and metal phase enhances the influence of oxide-metal coupling, and thus the tendency to form commensurable, even non-bulk like surface oxide configurations. It is interesting to notice that the extended stability range of the surface oxide phase discussed on Pd(100), cf. Fig. 2, corresponds more or less to the range exhibited by bulk Rh2O3 in Fig. 1, i.e. it comes now rather close to the schematically indicated range of $`(T,p_\mathrm{O},p_{\mathrm{CO}})`$-conditions representative of technological CO oxidation catalysis.

## V Implications for the catalytic CO oxidation

Due to the particular construction of our “constrained equilibrium” approach we could expect the results summarized in Figs. 1 to 3 to give a rough reflection of the state of the catalyst during steady-state CO oxidation, as long as kinetic effects both in the formation of the (surface) oxides themselves, as well as in the ongoing reaction on the surface (e.g. possibly consuming oxygen more rapidly than it is replenished) are negligible reuter03c . Although technological catalysis typically operates well above room temperature, such effects can never be ruled out in general. Clearly, a comprehensive understanding of the full catalytic activity and the microscopic state of the catalyst (i.e. its very dynamic behavior) requires modeling by statistical mechanics, and the results of thermodynamic considerations must consequently be treated with great care. Still, we believe that our results may be employed for a first qualitative assessment of oxide formation on the late $`4d`$ TMs, in particular if supplemented by some already known kinetic constraints.

In this regard we first notice the rather large stability range of bulk RuO2, extending well over the whole range of environmental conditions relevant for technological CO oxidation catalysis, cf. Fig. 1. Rather high temperatures of the order of $`T600`$ K are required to form this bulk oxide over00 ; kim01b , which would explain the recently reported lack of oxide formation at Ru(0001) even under high pressure conditions at temperatures around $`T400`$ K hendriksen03b ; hendriksen03c . Yet, once this bulk oxide is formed, our thermodynamic results imply that the catalytic activity of Ru catalysts might in reality be due to oxides, in line with the results of a number of recent experimental studies stampfl02 ; over00 ; kim01b .

For Rh the stability range of its bulk oxide has already decreased significantly. Even if the catalyst was in a situation close to thermodynamic equilibrium, our results suggest that either metal or bulk oxide could prevail at technologically relevant environmental conditions, depending on the exact partial pressures and temperature in the gas phase, i.e. depending on whether one is below or above the stability line in Fig. 1 (and recall that the present uncertainty in the location of this line is some tenths of eV). Even more intriguing, oscillations between the two phases could result as a consequence of fluctuations, when operating under environmental conditions very close to the stability line of Rh2O3. Similar considerations might also be possible for Pd, yet this time not concerning transitions to bulk PdO (which is already far too unstable), but to thin oxide films limited to the very surface region - as mentioned in section IV the stability of the surface oxide on Pd(100) extends over a similar range to that of bulk Rh2O3 in Fig. 1. In this respect we have also roughly marked in Fig. 1 the $`(T,p)`$-conditions employed in a recent experimental study on Pd(100), where a substantial roughening of the surface with presumed constant formation and reduction of ultra-thin oxide domains during the CO oxidation reaction was reported hendriksen03a ; hendriksen03b . The closeness of these experimental environmental conditions with our rough instability estimate for the surface oxide on Pd(100) is startling, in particular when further recalling the frequent observation of spatio-temporal pattern formation during the CO reaction at other Pd surfaces like Pd(110), which was there also connected to reversible oxide formation and reduction bondzie96 .

At this stage it is worth digressing on the fact that such thin oxide films with possibly even fluctuating conditions at the catalyst surface are tough to describe (even conceptually) within the traditional language of generic reaction mechanisms (see e.g. ref. masel96,  for a review). For metal surfaces mostly a Langmuir-Hinshelwood (LH) type behavior is discussed, where both reactants adsorb at the surface first and react thereafter. For the case of oxidation reactions on oxide surfaces on the other hand, Mars and van Krevelen (MvK) mars54  suggested that the underlying substrate itself might become continually reduced and (re-)oxidized in the on-going reaction, i.e. that oxygen from the oxide lattice is consumed in the reaction and then replenished from the gas phase. Within the framework of macroscopic rate equations, where this approach was made and has ever since been very popular (in the oxide literature), this translates to relaxing the constraint of a fixed number of active surface sites underlying the LH kinetics. The resulting MvK rate equation is then similar, but not identical to the one derived for a LH reaction mechanism, although in actual practice most data can be fitted equally well with both rate equations masel96 .

This only vague distinction between both mechanisms becomes even more blurred when starting to think microscopically and particularly when considering what is now called a surface oxide (a 1-2 layer thick oxide-like film). For the case of a fixed oxide lattice, where certain surface oxygen atoms just take part in the reaction and the resulting vacancies are refilled afterwards, a distinction between LH and MvK is in fact just semantics: One could equally well view the oxide lattice with the created vacancies (thus MvK) as the real substrate, where then oxygen adsorbs into these sites and reacts thereafter (thus LH). Although such a scenario has been advocated as a MvK mechanism for CO oxidation on RuO2(110) over00 , one might even argue that it contradicts the original MvK definition in its strictest sense, which emphasized the non-finite number of active sites (that is certainly fixed by the number of surface oxygen sites in the latter situation).

Other interpretations of MvK have therefore focused more on a diffusional aspect that would arise if oxygen is consumed at one point of the lattice surface but replenished elsewhere, requiring some form of oxygen transport in or at the surface (that might even become rate-limiting and thus yield a new type of kinetics) knoezinger . Nevertheless, a clearcut distinction could even then not always be made. Picturing in particular a possibly only one-layer thick oxide film, that does not necessarily resemble a bulk-like oxide structure at all, or the aforedescribed situation of a surface close to an instability with a continuous formation and destruction of a thin surface oxide (possibly creating mesoscopic roughness due to the etching of metal particles from the oxide framework hendriksen03b ; hendriksen02 ), how would one be able to distinguish what is an oxide vacancy, what the oxide, what an oxygen atom diffusing on or below the metal surface, let alone determine whether this would show up in a unique kinetics that would still be describable by simple macroscopic rate equations?

In this regard, another intriguing result of our thermodynamic considerations is the different stability range of surface oxides on Pd(111) and Pd(100). Again, provided the catalyst is close to thermodynamic equilibrium, this would imply that under certain $`(T,p)`$-conditions the active phase for CO oxidation could be on-surface adphases (i.e. LH) on some facets of nanoparticles and surface oxides (let’s call this MvK) on others. A situation that could make the overall kinetic data (and its modelling) much more complex than hitherto assumed. In this particular sense, an understanding of the data from Pd could be much more difficult than say for Ag, where we would not expect neither bulk nor surface oxides to play a significant role in CO oxidation catalysis on the basis of the present results, and in agreement with the conclusions of a more detailed recent theoretical study li03 .

## VI Summary

In conclusion we have derived simple thermodynamic stability conditions for bulk and surface oxides in contact with an environment formed of CO and O2. Applying these to the late $`4d`$ transition metal series from Ru to Ag, we obtain a progressively smaller stability range for the bulk oxides that extends well into the environmental conditions representative of technological CO oxidation catalysis only in the case of RuO2. In particular for Pd, thin surface oxides could nevertheless still be stable in the more oxygen-rich part of this $`(T,p)`$-range, while for CO containing gas phases neither surface nor bulk oxide will be stable on Ag. Most intriguingly, oscillations between metal and bulk (surface) oxide phase for Rh (Pd) are conceivable under technologically relevant $`(T,p)`$-conditions.

Provided the catalyst is close to the constrained thermodynamic equilibrium forming the basis of our considerations, these results may give first insight into the role of oxide formation played in technological CO oxidation catalysis at these $`4d`$ TMs. A comprehensive understanding of the microscopic state and full catalytic cycle must however be based on statistical mechanics as the next step, i.e. by modelling the very dynamic behavior and interplay of the manyfold of elementary processes.

## Acknowledgments

We acknowledge detailed discussions with Cathy Stampfl and Weixue Li on the Ag/Ag2O system and with Mira Todorova on the Pd/PdO system. K.R. is grateful for financial support from the Deutsche Forschungsgemeinschaft (DFG). We thank Mark Miller for a careful reading of the manuscript.