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# Contents

## 1 Introduction

Grand Unified Theories in four dimensions have had impressive successes, in accounting for the quantum numbers of fermions , in predicting – with the aid of supersymmetry – a value of $`\mathrm{sin}^2\theta _W`$ that is in excellent agreement with experiment , and in pointing twenty years in advance of decisive measurements to the right order of magnitude of neutrino masses . GUT theories also make the exciting prediction that the proton may decay with a lifetime close to present experimental bounds.

With supersymmetry, even if one assumes an $`R`$-parity symmetry to avoid catastrophic proton decay at low energies, there actually are two different GUT-based mechanisms for proton decay. The proton may decay due to dimension five operators of the form $`d^2\theta Q^3L`$, where $`Q`$ and $`L`$ are quark and lepton superfields. Or it may decay by dimension six operators of the form $`d^4\theta Q^2\stackrel{~}{Q}^{}\stackrel{~}{L}^{}`$ coming from gauge boson exchange; this effect is similar to proton decay in GUT’s without supersymmetry, but is significantly slower because supersymmetry raises the GUT scale. In the simplest models, proton decay by dimension five operators dominates, and in fact present experimental bounds make life difficult for these models  (see, however, ). This suggests the possibility that some mechanism suppresses the dimension five operators and that gauge boson exchange may after all be the dominant mechanism. Various methods to suppress the dimension five operators while preserving the successes of GUT’s are known, though they tend to be somewhat technical. For example, one construction based on discrete symmetries  is fairly natural in the class of models that we will consider in this paper.

Most GUT-like string-based models of particle physics do not precisely lead to four-dimensional GUT’s, since unification takes place only in higher dimensions (for an early review, see , chapters 15 and 16), leading among other things to possibilities for GUT symmetry breaking by discrete Wilson lines  and to a higher-dimensional mechanism for doublet-triplet splitting . Generally, models such as the heterotic string on a Calabi-Yau manifold lead to qualitatively similar issues concerning proton decay to those in GUT’s, though the details are somewhat different. One important reason that the details are different is that because of the higher-dimensional structure, there is generally in these models no precise answer to the question, “Which color triplet gauge boson is the $`SU(5)`$ partner of the standard model gauge bosons?” There is a lightest color triplet gauge boson, whose wave-function in the compact dimensions depends on the details of the model, and its exchange may, depending on the model, give the right order of magnitude though not the correct numerical value of the dimension six part of the proton decay amplitude.

Recently , these issues were reconsidered in another class of models – $`M`$-theory on a $`G_2`$ manifold. (Actually, in many cases these models give dual descriptions, useful in a different region of the parameter space, of the same models that can be studied via the heterotic string on a Calabi-Yau manifold.) The GUT threshold correction to proton decay was computed in this class of models and was seen to give a potential enhancement of the proton decay rate. It was also shown that in this type of model, because of the way quarks and leptons are localized, exchange of the lightest color triplet gauge boson does not dominate the proton decay amplitude. On the contrary, a field theoretic attempt to compute a proton decay amplitude by summing over Kaluza-Klein harmonics runs into an ultraviolet divergence, and consequently the correct answer depends on the cutoff provided by $`M`$-theory. Formally, this UV divergence enhances the proton decay amplitude by a factor of $`\alpha _{GUT}^{1/3}`$ compared to what it would be in a four-dimensional model. (This factor must be combined with the threshold factor, of course.) The coefficient of $`\alpha _{GUT}^{1/3}`$ is universal and independent of the details of the model (such as how the GUT symmetry is broken) – in fact, the dominant four-fermi operator is local and invariant under the full GUT symmetry, in contrast to the usual situation in four-dimensional GUT’s. However, present knowledge of $`M`$-theory does not make it possible to compute the numerical coefficient of this operator.

As an alternative, we will in the present paper consider another dual class of models in which the calculation can be done. These models fall in the general class of intersecting brane worlds  – Type IIA superstrings with gauge bosons supported on $`D6`$-branes and chiral matter multiplets at intersections of the $`D6`$-branes. Many supersymmetric GUT-like models have been constructed along these lines , though so far none with the mechanism of symmetry breaking by Wilson lines on the $`D6`$-brane that we will assume in the present paper to justify borrowing various above-cited results.111 In the dual context of M-theory on $`G_2`$ manifolds, some examples of symmetry breaking by Wilson lines were considered in . (In actual model-building, one typically considers branes in an orbifold of a six-torus, but more generally one may start with any Calabi-Yau manifold: see, for example, .) Threshold corrections in intersecting D6-brane GUT-like models were calculated in . These models are dual to $`M`$-theory on a manifold of $`G_2`$ holonomy as $`g_s`$, the Type IIA string coupling constant, becomes large. The chiral matter fields are localized (at brane intersections) in a similar way to what happens in $`M`$-theory on a $`G_2`$ manifold, and accordingly we will find the same anomalous factor of $`\alpha _{GUT}^{1/3}`$ in the proton decay amplitude. The difference is that in perturbative Type IIA string theory, everything is explicitly calculable, and hence we will be able, at least for $`g_s1`$, to be precise about the numerical factors. Regrettably, the numerical factors accompanying $`\alpha _{GUT}^{1/3}`$ are such that even assuming a plausible enhancement from the threshold factors, the proton decay rate is comparable to or only slightly greater than that in standard SUSY-GUT’s. Of course, the precise factors that appear in the corresponding $`M`$-theory (or large $`g_s`$) limit are still unknown.

In this paper we will not be concerned with any specific model, but will rather try to incorporate universal features of the GUT-like intersecting D-brane models relevant to calculation of the proton decay rate. Typically one needs a stack of D6-branes intersecting an orientifold fixed sixplane along $`3+1`$ dimensions. On the covering space we then have a stack of D6-branes intersecting an image set of D$`6^{}`$-branes. If there are 5 D6-branes in the stack, then on the covering space we find gauge group $`SU(5)\times SU(5)`$, with open strings localized at the intersection transforming in the bifundamental representations $`(\mathrm{𝟓},\overline{\mathrm{𝟓}})+(\overline{\mathrm{𝟓}},\mathrm{𝟓})`$. After the orientifold projection we find $`SU(5)`$ gauge theory with matter in $`\mathrm{𝟏𝟎}+\overline{\mathrm{𝟏𝟎}}`$. Our goal is to calculate the 4-fermion contact term whose $`SU(5)`$ structure is $`\mathrm{𝟏𝟎}^2\overline{\mathrm{𝟏𝟎}}^2`$. Such an interaction mediates proton decay processes such as $`p\pi ^0e_L^+`$ (and, depending on the assumed flavor structure, other modes with $`e_L^+`$ replaced by $`\mu _L^+`$ and/or $`\pi ^0`$ by $`K^0`$). The calculation is conveniently carried out on the covering space where we need the 4-point function for two $`(\mathrm{𝟓},\overline{\mathrm{𝟓}})`$ states and two $`(\overline{\mathrm{𝟓}},\mathrm{𝟓})`$ states. The calculation is sensitive to the local structure of the intersection, and is insensitive to how the D6-branes are wrapped around the compact space, as long as its size is somewhat greater than the string scale so that worldsheet instantons are suppressed.

Four-dimensional GUT’s also have dimension six operators $`\mathrm{𝟏𝟎}\overline{\mathrm{𝟏𝟎}}\mathbf{\hspace{0.17em}5}\overline{\mathrm{𝟓}}`$ which lead to proton decay modes such as $`p\pi ^0e_R^+`$ and $`p\pi ^+\nu `$; as observed in  in the analogous $`M`$-theory case, such interactions do not arise generically in a model of this type. To get such an interaction, we need two stacks of branes that are not mirror images to meet on an orientifold plane; in general, this would be a coincidence. Both four-dimensional GUT’s and the brane worlds have additional $`\mathrm{𝟓}^2\overline{\mathrm{𝟓}}^2`$ interactions (which in the brane worlds arise from brane intersections away from the orientifold planes), but these do not violate baryon number.

## 2 Vertex Operators

Without a loss of generality we may assume that the D6-branes are oriented in the $`0123468`$ directions. The D$`6^{}`$-branes intersect them along the $`0123`$ directions that will have the interpretation of a $`3+1`$ dimensional ‘intersecting brane world.’ To specify its orientation in the six transverse directions, we define the complex coordinates

$$z_1=x^4+ix^5,z_2=x^6+ix^7,z_3=x^8+ix^9.$$
(1)
In order to preserve $`𝒩=1`$ supersymmetry in $`3+1`$ dimensions, the rotation must act as an $`SU(3)`$ matrix on the three complex coordinates . Choosing the matrix to be diagonal, we see that the rotation that turns the D6-branes into the D$`6^{}`$-brane acts as

$$z_1\mathrm{exp}(\pi i\theta _1)z_1,z_2\mathrm{exp}(\pi i\theta _2)z_2,z_3\mathrm{exp}(\pi i\theta _3)z_3,$$
(2)
where

$$\theta _1+\theta _2+\theta _3=2\mathrm{mod}2𝐙.$$
(3)
We need to construct the vertex operators for the $`66^{}`$ and $`6^{}6`$ open strings. Such operators, when inserted on the boundary of the disk, create discontinuities in the boundary conditions for the transverse coordinates and their fermionic partners . A standard method for studying correlators on the upper half-plane is the doubling trick where the half-plane is replaced by the entire plane, but with only the holomorphic part of the field on it (for a review, see ). If we consider complex fields $`X^i`$ corresponding to the transverse coordinates $`z^i`$, then their Laurent expansion around the insertion of the vertex operator has mode numbers shifted by $`\theta _i`$ . This is analogous to what happens near a twist field introduced in orbifold theories and we can use similar methods for calculating the correlation functions.

Consider a bosonic twist field $`\sigma _+`$ which creates a discontinuity in a complex coordinate $`X`$. Then we have the OPE

$$X(z)\sigma _+(w)(zw)^{\theta 1}\tau _+,\overline{X}(z)\sigma _+(w)(zw)^\theta \tau _+^{}.$$
(4)
The dimension of $`\sigma _+`$ is $`\mathrm{\Delta }_\sigma =\theta (1\theta )/2`$, and we will assume that $`\theta `$ lies between $`0`$ and $`1`$. Now consider the complex fermion $`\psi `$, which is a worldsheet superpartner of $`X`$. By worldsheet supersymmetry, its mode numbers are also shifted by $`\theta `$. In the Ramond sector, $`\sigma _+`$ must be accompanied by the fermionic twist $`s_+`$ such that

$$\psi (z)s_+(w)(zw)^{\theta 1/2}t_+,\overline{\psi }(z)s_+(w)(zw)^{1/2\theta }t_+^{}.$$
(5)
If we bosonize $`\psi `$ into a real scalar $`H`$, whose Green’s function is

$$H(z)H(w)=\mathrm{log}(zw),$$
(6)
then

$$\psi =\mathrm{exp}(iH),\overline{\psi }=\mathrm{exp}(iH),s_+=\mathrm{exp}[i(\theta 1/2)H].$$
(7)
This means that the dimension of $`s_+`$ is

$$\mathrm{\Delta }_s=\frac{1}{2}\left(\theta \frac{1}{2}\right)^2.$$
(8)
Therefore,

$$\mathrm{\Delta }_s+\mathrm{\Delta }_\sigma =1/8,$$
(9)
independent of the rotation angle $`\theta `$.

The complete vertex operator that creates a massless $`66^{}`$ string in the R sector is

$$V_+=\lambda _I^iu_\alpha e^{\varphi /2}S^\alpha e^{ik_\mu X^\mu }\underset{i=1}{\overset{3}{}}(\sigma _+^is_+^i)$$
(10)
where $`\varphi `$ is the bosonized ghost field. If we bosonize the fermions $`\psi ^\mu `$, $`\mu =0,1,2,3`$, into scalars $`h_1`$ and $`h_2`$, then the $`3+1`$ dimensional spinor $`S^\alpha \mathrm{exp}[i(s_1h_1+s_2h_2)/2]`$, where $`s_1,s_2=\pm 1`$. The GSO projection for $`66^{}`$ strings requires that $`s_1s_2=1`$, which restricts us to a spinor of definite chirality. $`\lambda _I^i`$ is a Chan-Paton factor with an index $`i`$ in the fundamental of the first $`SU(5)`$, and an index $`I`$ in the antifundamental of the second $`SU(5)`$. Since $`h(e^{\varphi /2})=3/8`$ and $`h(S^\alpha )=1/4`$, we see that the requirement that the dimension of $`V_+`$ is $`1`$ gives the 4-d massless dispersion relation $`k^2=0`$.

The vertex operator $`V_{}`$ for $`6^{}6`$ strings is constructed similarly, except we need to replace the $`\sigma _+`$ and $`s_+`$ twists by $`\sigma _{}`$ and $`s_{}`$. The latter are defined by sending $`\theta 1\theta `$ in the OPE. The GSO projection now requires that $`s_1s_2=1`$; this corresponds to 4-d spinor chirality opposite to that of the $`66^{}`$ string. Thus, we have the vertex operator

$$V_{}=\stackrel{~}{\lambda }_i^I\overline{u}_{\dot{\alpha }}e^{\varphi /2}S^{\dot{\alpha }}e^{ik_\mu X^\mu }\underset{i=1}{\overset{3}{}}(\sigma _{}^is_{}^i).$$
(11)
## 3 The 4-fermion Amplitude in String Theory

Our goal is to calculate the 4-fermion amplitude

$$_0^1𝑑xV_{}(0)V_+(x)V_{}(1)V_+(\mathrm{}).$$
(12)
The crucial ingredient in this calculation is the knowledge of the correlator of the bosonic twist fields $`\sigma `$. In the orbifold theories, these were calculated in . We will take the square root of their result to account for the fact that we have the boundary twist fields rather than the bulk ones. (This intuitively plausible result has been derived in  and, up to normalization, in ; see also  for a treatment of cases where the intersecting D-branes have different dimensionalities.) This gives

$$\sigma _{}(0)\sigma _+(x)\sigma _{}(1)\sigma _+(\mathrm{})\sqrt{\mathrm{sin}(\pi \theta )}[x(1x)]^{2\mathrm{\Delta }_\sigma }[F(x)F(1x)]^{1/2},$$
(13)
where

$$F(x)F(\theta ,1\theta ;1;x)$$
(14)
is the hypergeometric function and $``$ represents a numerical constant.

On the other hand, the correlator of the fermionic twists is simply

$$s_{}(0)s_+(x)s_{}(1)s_+(\mathrm{})[x(1x)]^{2\mathrm{\Delta }_s},$$
(15)
while the ghost factor contributes

$$e^{\varphi /2}(0)e^{\varphi /2}(x)e^{\varphi /2}(1)e^{\varphi /2}(\mathrm{})[x(1x)]^{1/4}.$$
(16)
The correlator of the 4-d spin fields multiplied by spinor polarizations gives an $`x`$-independent factor $`\overline{u}_1\gamma ^\mu u_2\overline{u}_3\gamma _\mu u_4`$. This $`x`$-independence is evident from the form of the bosonized correlator

$$\mathrm{exp}[i(h_1h_2)/2](0)\mathrm{exp}[i(h_1+h_2)/2](x)\mathrm{exp}[i(h_1h_2)/2](1)\mathrm{exp}[i(h_1+h_2)/2](\mathrm{}).$$
(17)
Putting together all the parts of the vertex operators, defining as usual

$$s=(k_1+k_2)^2,t=(k_2+k_3)^2,$$
(18)
and including both $`s`$\- and $`t`$-channel diagrams, we find the amplitude

$`A_4`$ $`(k_1,k_2,k_3,k_4)=iC(2\pi )^4\delta ^4({\displaystyle \underset{i=1}{\overset{4}{}}}k_i)\overline{u}_1\gamma ^\mu u_2\overline{u}_3\gamma _\mu u_4Tr\left(\stackrel{~}{\lambda }_1\lambda _2\stackrel{~}{\lambda }_3\lambda _4+\stackrel{~}{\lambda }_1\lambda _4\stackrel{~}{\lambda }_3\lambda _2\right)`$   $`{\displaystyle _0^1}dxx^{1\alpha ^{}s}(1x)^{1\alpha ^{}t}{\displaystyle \underset{i=1}{\overset{3}{}}}\sqrt{\mathrm{sin}(\pi \theta _i)}[F(\theta _i,1\theta _i;1;x)F(\theta _i,1\theta _i;1;1x)]^{1/2},`$   (19)
where $`C`$ is a normalization that we will fix later, while the $`\lambda `$’s and $`\stackrel{~}{\lambda }`$’s are Chan-Paton matrices of $`66^{}`$ and $`6^{}6`$ strings. In four dimensions, with $`\overline{u}_1,\overline{u}_3`$ having one chirality and $`u_2,u_4`$ the other, we have $`\overline{u}_1\gamma _\mu u_2\overline{u}_3\gamma ^\mu u_4=\overline{u}_1\gamma _\mu u_4\overline{u}_3\gamma ^\mu u_2`$. This insures the antisymmetry of the amplitude under permutation of particles $`2`$ and $`4`$ (or of particles $`1`$ and $`3`$).

We note that the hypergeometric functions are crucial for the convergence of the integral at the endpoints of the integration region for vanishing momenta $`k_i`$. As $`x0`$,

$$F(x)1,F(1x)\frac{\mathrm{sin}(\pi \theta )}{\pi }\mathrm{ln}(\delta /x),$$
(20)
where

$$\mathrm{ln}\delta (\theta )=2\psi (1)\psi (\theta )\psi (1\theta ).$$
(21)
Therefore, even with $`s=t=0`$, we find a convergent integral. Its behavior near $`x=0`$ is

$$\pi ^{3/2}_0\frac{dx}{x}[\mathrm{ln}(1/x)]^{3/2}$$
(22)
The physical reason for the absence of an IR divergence at vanishing momentum is the following. Even though there is a massless intermediate state from the untwisted sector, the special kinematics of this problem gives no IR divergence. For example, if the $`s`$-channel intermediate state is a massless $`6^{}6^{}`$ string, which is a gauge boson, then it can carry arbitrary momentum $`q`$ along the directions of the $`D6^{}`$-brane orthogonal to the intersection. These three components of momentum have to be integrated over:

$$d^3q_0𝑑xx^{\alpha ^{}q^2\alpha ^{}s1}=\pi ^{3/2}(\alpha ^{})^{3/2}_0𝑑xx^{1\alpha ^{}s}[\mathrm{ln}(1/x)]^{3/2},$$
(23)
which converges near $`x=0`$ even for $`s=0`$. Thus, going from the effective field theory to the form of the string integrand near $`x=0`$, we find the replacement

$$\frac{d^3q}{q^2s}\pi ^{3/2}(\alpha ^{})^{1/2}_0𝑑xx^{1\alpha ^{}s}[\mathrm{ln}(1/x)]^{3/2}.$$
(24)
This observation also allows us to normalize the 4-fermion amplitude. If we consider the $`s`$-channel factorization on the $`6^{}6^{}`$ gauge boson, which is the leading term as $`x0`$, then we should find

$$A_4(k_1,k_2,k_3,k_4)i\frac{d^7k}{(2\pi )^7}\frac{\underset{IJ\mu }{}A_J^{I\mu }(k_1,k_2,k)A_{I\mu }^J(k_3,k_4,k)}{k^2iϵ},$$
(25)
where the 3-point function for emission of a gauge boson of Chan-Paton indices $`J,I`$ is

$$A_J^{I\mu }(k_1,k_2,k_3)=iK\sqrt{g_s}(\alpha ^{})^{3/4}(2\pi )^4\delta ^4(\underset{i=1}{\overset{3}{}}k_i)\overline{u}_1\gamma ^\mu u_2\left(\stackrel{~}{\lambda }_1\lambda _2\right)^I{}_{J}{}^{}.$$
(26)
The index $`\mu `$ corresponds to the polarization of the intermediate vector state. Since the gauge coupling on D6-branes is given (according to , eqn. 13.3.25) by $`g_{D6}^2=(2\pi )^4g_s(\alpha ^{})^{3/2}`$, we have

$$K^2=(2\pi )^4.$$
(27)
Performing the integral on the RHS of (25) with the replacement (24), we find

$$iTr(\stackrel{~}{\lambda }_1\lambda _2\stackrel{~}{\lambda }_3\lambda _4)K^2g_s(\alpha ^{})(2\pi )\delta ^4(\underset{i=1}{\overset{4}{}}k_i)\overline{u}_1\gamma ^\mu u_2\overline{u}_3\gamma _\mu u_4\pi ^{3/2}_0x^{1\alpha ^{}s}[\mathrm{ln}(1/x)]^{3/2}.$$
(28)
Equating this to the contribution to $`A_4`$, given in eqn. (19), from the $`s`$-channel $`6^{}6^{}`$ massless intermediate state,

$$iTr(\stackrel{~}{\lambda }_1\lambda _2\stackrel{~}{\lambda }_3\lambda _4)C(2\pi )^4\delta ^4(\underset{i=1}{\overset{4}{}}k_i)\overline{u}_1\gamma ^\mu u_2\overline{u}_3\gamma _\mu u_4\pi ^{3/2}_0x^{1\alpha ^{}s}[\mathrm{ln}(1/x)]^{3/2},$$
(29)
we find that

$$C=(2\pi )^3K^2g_s\alpha ^{}=2\pi g_s\alpha ^{}.$$
(30)
The low-energy limit of the 4-fermion amplitude is hence,

$`A_4(k_1,k_2,k_3,k_4)=`$ $`i(2\pi g_s\alpha ^{})I(\theta _1,\theta _2,\theta _3)(2\pi )^4\delta ^4({\displaystyle \underset{i=1}{\overset{4}{}}}k_i)\overline{u}_1\gamma ^\mu u_2\overline{u}_3\gamma _\mu u_4`$   $`Tr\left(\stackrel{~}{\lambda }_1\lambda _2\stackrel{~}{\lambda }_3\lambda _4+\stackrel{~}{\lambda }_1\lambda _4\stackrel{~}{\lambda }_3\lambda _2\right),`$   (31)
where

$$I(\theta _1,\theta _2,\theta _3)=_0^1\frac{dx}{x(1x)}\underset{i=1}{\overset{3}{}}\sqrt{\mathrm{sin}(\pi \theta _i)}[F(\theta _i,1\theta _i;1;x)F(\theta _i,1\theta _i;1;1x)]^{1/2}.$$
(32)
This has been derived for intersections of two stacks of branes without any orientifolding. Thus, in an intersection of a stack of $`N`$ $`D6`$-branes with a stack of $`M`$ $`D6^{}`$-branes, we would have a $`U(N)\times U(M)`$ gauge theory with the fermions supported at the intersection points transforming as bifundamentals, and the above four-fermi interactions. To get an $`SU(5)`$ theory with fields transforming in the $`\mathrm{𝟏𝟎}`$, we should consider the case that $`N=M=5`$ and the two stacks are exchanged by an orientifolding operation $`\mathrm{\Omega }R`$ and intersect on the orientifold plane ($`\mathrm{\Omega }`$ is the worldsheet parity; $`R`$ acts by complex conjugating all three complex coordinates: $`z_i\overline{z}_i`$, $`i=1,2,3`$). Moreover, we pick an orientifolding operation that projects onto fermions whose wavefunctions $`\lambda _i`$ and $`\stackrel{~}{\lambda }_j`$ transform as antisymmetric, rather than symmetric, tensors of $`SU(5)`$. Tree level amplitudes in the orientifold theory are obtained by computing tree level amplitudes on the covering space for states that are invariant under the orientifolding projection, and then dividing by 2. The $`\mathrm{𝟏𝟎}^2\overline{\mathrm{𝟏𝟎}}^2`$ interaction in an orientifold theory is thus derived from

$`A_4(k_1,k_2,k_3,k_4)=`$ $`i(\pi g_s\alpha ^{})I(\theta _1,\theta _2,\theta _3)(2\pi )^4\delta ^4({\displaystyle \underset{i=1}{\overset{4}{}}}k_i)\overline{u}_1\gamma ^\mu u_2\overline{u}_3\gamma _\mu u_4`$   $`Tr\left(\stackrel{~}{\lambda }_1\lambda _2\stackrel{~}{\lambda }_3\lambda _4+\stackrel{~}{\lambda }_1\lambda _4\stackrel{~}{\lambda }_3\lambda _2\right).`$   (33)
Evaluation Of $`I`$

Now let us discuss the numerical evaluation of the integral $`I`$. After writing

$$\frac{1}{x(1x)}=\frac{1}{x}+\frac{1}{1x},$$
(34)
noting that the two terms contribute equally, and setting $`x=e^t`$ to evaluate the contribution of the first term, we can write $`I`$ as

$$I(\theta _1,\theta _2,\theta _3)=2_0^{\mathrm{}}𝑑t\underset{i=1}{\overset{3}{}}\sqrt{\mathrm{sin}(\pi \theta _i)}[F(\theta _i,1\theta _i;1;e^t)F(\theta _i,1\theta _i;1;1e^t)]^{1/2}.$$
(35)
Let us try to evaluate the integral on the RHS numerically for the most symmetric choice of rotation angles: $`\theta _1=\theta _2=\theta _3=2/3`$. It turns out that for sufficiently large $`t`$, it is hard to maintain numerical precision in evaluating the hypergeometric functions. To deal with this problem, we will break up the integral into the range from $`0`$ to $`T`$ and from $`T`$ to $`\mathrm{}`$. In the first region we use Mathematica to evaluate it numerically, while in the second we may use the asymptotics (20) to replace the integral by

$$2\pi ^{3/2}_T^{\mathrm{}}𝑑t(t+3\mathrm{ln}3)^{3/2}=4\pi ^{3/2}(T+3\mathrm{ln}3)^{1/2},$$
(36)
where we used $`\mathrm{ln}\delta (2/3)=3\mathrm{ln}3`$. In practice, the sum of the two is insensitive to $`T`$ in a certain range; we have checked this for $`T`$ between 15 and 25. We find

$$I(2/3,2/3,2/3)11.52.$$
(37)
It is interesting that a large number $`11.52`$ emerges from an explicit string calculation.

Now cosider a generalization to $`\theta _1=\theta _2=\theta `$ and $`\theta _3=22\theta `$. For the purpose of numerical evaluation, we approximate $`I(\theta ,\theta ,22\theta )`$ by

$$2\mathrm{sin}(\pi \theta )\sqrt{\mathrm{sin}(2\pi \theta )}_0^T𝑑t\frac{[F(22\theta ,2\theta 1;1;e^t)F(22\theta ,2\theta 1;1;1e^t)]^{1/2}}{F(\theta ,1\theta ;1;e^t)F(\theta ,1\theta ;1;1e^t)}$$
(38)
$$+2\pi ^{3/2}_T^{\mathrm{}}\frac{dt}{(t+\mathrm{ln}\delta (\theta ))\sqrt{t+\mathrm{ln}\delta (22\theta )}}.$$

It is interesting to ask how $`I`$ behaves when one of the rotation angles becomes small. This can be determined from (38) by letting $`\theta `$ approach $`1/2`$ from above, so that $`\theta _3=22\theta `$ corresponds to rotation by close to $`\pi `$. It turns out that $`I`$ decreases rather slowly from its maximum value at $`\theta =2/3`$. For example, $`I(0.55,0.55,0.9)9.89`$ and $`I(0.51,0.51,0.98)6.69`$. Even when all three rotation angles become effectively small, $`I`$ does not fall off very rapidly. Using (38), we find $`I(0.9,0.9,0.2)7.675`$; $`I(0.95,0.95,0.1)5.505`$; $`I(0.99,0.99,0.02)2.47`$. We conclude that for a broad range of angles the quantity $`I`$ lies in the range $`711.5`$.

## 4 Comparison To Four-Dimensional GUT’s

According to , eqns. (12.1.10b) and (13.3.24), the gravitational action for Type IIA superstrings is

$$\frac{1}{(2\pi )^7\alpha ^4}d^{10}x\sqrt{G}e^{2\mathrm{\Phi }}R.$$
(39)
The string coupling constant is $`g_s=e^\mathrm{\Phi }`$. After reduction to four dimensions on a six-manifold $`X`$ of volume $`V_6`$, the gravitational action in four dimensions is

$$\frac{V_6}{(2\pi )^7g_s^2\alpha ^4}\sqrt{g}R.$$
(40)
As the coefficient of $`R`$ in four-dimensional General Relativity is conventionally $`(16\pi G_N)^1`$, with $`G_N`$ Newton’s constant, we have

$$g_s^2\alpha ^4=\frac{8V_6G_N}{(2\pi )^6}.$$
(41)
The gauge coupling $`g_{D6}`$ of gauge fields on a $`D6`$-brane is defined by saying that the effective action for the gauge fields is

$$\frac{1}{4g_{D6}^2}d^7x\sqrt{g_7}TrF_{ij}F^{ij},$$
(42)
where $`F_{ij}`$ is the Yang-Mills field strength and $`Tr`$ is the trace in the fundamental representation of $`U(N)`$. If we take the $`D6`$-brane worldvolume to be $`𝐑^4\times Q`$, where $`Q`$ is a compact three-manifold of volume $`V_Q`$, then the action in four dimensions becomes

$$\frac{V_Q}{4g_{D6}^2}d^4xTrF_{ij}F^{ij}.$$
(43)
However, before comparing to four-dimensional GUT’s, we must recall that it is conventional to expand the gauge fields as $`A_i=_aQ_aA_i^a`$, where $`TrQ_aQ_b=\frac{1}{2}\delta _{ab}`$. Similarly, one conventionally expands $`F_{ij}=_aF_{ij}^aQ_a`$. If this is done, the action becomes

$$\frac{V_Q}{8g_{D6}^2}d^4x\underset{a}{}F_{ij}^aF^{ija}.$$
(44)
The GUT action is conventionally written

$$\frac{1}{4g_{GUT}^2}d^4x\underset{a}{}F_{ij}^aF^{ija},$$
(45)
where $`g_{GUT}`$ is the GUT coupling. Hence, we have $`g_{GUT}^2=2g_{D6}^2/V_Q`$. Since $`g_{D6}^2=(2\pi )^4g_s\alpha _{}^{}{}_{}{}^{3/2}`$ according to eqn. (13.3.25) of , we have

$$g_{GUT}^2=\frac{2(2\pi )^4g_s\alpha _{}^{}{}_{}{}^{3/2}}{V_Q}.$$
(46)
The volume $`V_Q`$ enters in the running of $`SU(3)\times SU(2)\times U(1)`$ standard model gauge couplings from very high energies down to the energies of accelerators. Roughly speaking, $`V_Q^{1/3}`$ plays the role of $`M_{GUT}`$, the mass scale of unification, in a four-dimensional $`GUT`$ theory. To find the precise relation between them, one must compute the one-loop threshold corrections to gauge couplings. This was done in  for $`M`$-theory on a manifold of $`G_2`$ holonomy. The one-loop threshold corrections are the same in Type IIA as in $`M`$-theory, since they come from Kaluza-Klein harmonics on $`Q`$ that are the same in the two theories. So we can borrow the result of . According to that result (see eqn. (3.30) of ), the precise relation between $`M_{GUT}`$ understood as the mass at which the low energy coupling constants appear to unify and $`V_Q`$ is

$$V_Q=\frac{L(Q)}{M_{GUT}^3},$$
(47)
where $`L(Q)`$ is a certain topological invariant of $`Q`$ (together with Wilson lines on $`Q`$ that break the GUT symmetry to the standard model) that is known as the Reidemeister or Ray-Singer torsion. $`L(Q)`$ depends on a model, but is readily computable in a given model. For example, in a model considered in  in which $`Q`$ is a lens space $`𝐒^3/𝐙_q`$ for some positive integer $`q`$ (which must be prime to 5 if we want an $`SU(5)`$ model), and the Wilson line on $`Q`$ has eigenvalues $`\mathrm{exp}(2\pi i\delta _i/q)`$ with $`\delta _i=(2w,2w,2w,3w,3w)`$ for some integer $`w`$ prime to $`q`$, one has

$$L(Q)=4q\mathrm{sin}^2(5\pi w/q).$$
(48)
For a slightly more general lens space, also described in , whose definition depends on another integer $`j`$, this is replaced by $`L(Q)=4q|\mathrm{sin}(5\pi w/q)\mathrm{sin}(5\pi jw/q)|`$. The factor $`L(Q)`$ can be important in determining the proton lifetime, as will become clear. For example, for the minimal choice that leads to the standard model gauge symmetry, which is $`q=2`$, $`w=1`$, we have $`L(Q)=8`$, and the threshold correction will prove to enhance the proton decay rate significantly. It is possible for lens spaces to make $`L(Q)<1`$, but only if $`q`$ is extremely large.

Using (48), we can express (46) in the form

$$\alpha _{GUT}=(2\pi )^3L(Q)^1g_s\alpha _{}^{}{}_{}{}^{3/2}M_{GUT}^3,$$
(49)
where as usual $`\alpha _{GUT}=g_{GUT}^2/4\pi `$. Alternatively,

$$g_s^2\alpha _{}^{}{}_{}{}^{3}=\frac{\alpha _{GUT}^2L(Q)^2}{(2\pi )^6M_{GUT}^6}.$$
(50)
Ideally, we would like to compute all of the parameters in the string compactification in terms of the quantities $`G_N=1/M_{Pl}^2`$, $`M_{GUT}`$, and $`\alpha _{GUT}`$, about which we have at least some experimental knowledge. The Planck mass is well-known ($`M_{Pl}1.2\times 10^{19}`$ GeV), but $`M_{GUT}`$ and $`\alpha _{GUT}`$ are somewhat model-dependent. The most commonly cited values based on extrapolation from low energy data are $`M_{GUT}2\times 10^{16}`$ GeV, $`\alpha _{GUT}.04`$. Unfortunately, the string theory really depends on four unknowns $`V_6`$, $`V_Q`$, $`g_s`$, and $`\alpha ^{}`$.

To parametrize our ignorance, we may introduce the dimensionless quantity

$$\lambda =\frac{V_6}{V_Q^2},$$
(51)
which is of order one if $`X`$ is fairly isotropic, and solve for the other stringy parameters in terms of $`G_N`$, $`M_{GUT}`$, $`\alpha _{GUT}`$, and $`\lambda `$. For $`V_Q`$, this has already been done in (47). Dividing (41) by (50), we get

$$\alpha ^{}=\frac{8\lambda G_N}{\alpha _{GUT}^2}.$$
(52)
We can similarly solve for $`g_s`$,

$$g_s=\frac{\alpha _{GUT}^4L(Q)}{2^{9/2}(2\pi )^3M_{GUT}^3G_N^{3/2}\lambda ^{3/2}}.$$
(53)
The factor about which we have the least intuition is $`\lambda `$, which comes from a ratio of volumes. To try to get some intuition about the possible values of $`\lambda `$, and also about whether the model makes sense, let us examine quantitatively the formula (53) for $`g_s`$:

$$g_s=0.1\left(\frac{\alpha _{GUT}}{.04}\right)^4\left(\frac{2\times 10^{16}\mathrm{GeV}}{M_{GUT}}\right)^3\frac{L(Q)}{\lambda ^{3/2}}.$$
(54)
Our calculation does not make much sense if $`g_s1`$, since then we should do the computation in $`M`$-theory (leading back to the discussion in section 5 of ) rather than in Type IIA superstring theory. If $`g_s1`$, our computation makes sense, but it is implausible for the vacuum to be stabilized after supersymmetry breaking in a way that would enable the world as we see it to exist. So the discussion makes most sense if $`g_s`$ is relatively close to 1. We note that happily (54) is compatible with having $`g_s`$ near 1 while the GUT parameters have their usual values, $`L(Q)=8`$, and $`\lambda `$ is not too far from 1.

In view of the preceding discussion, it is perhaps more useful to use (54) to solve for $`\lambda `$, parametrizing our ignorance via the unknown value of $`g_s`$, which we expect to be near 1:

$$\lambda =\alpha _{GUT}^{8/3}\frac{M_{Pl}^2}{M_{GUT}^2}\frac{L(Q)^{2/3}}{8(2\pi )^2g_s^{2/3}}.$$
(55)
Now (52) becomes

$$\alpha ^{}=\frac{\alpha _{GUT}^{2/3}L(Q)^{2/3}}{(2\pi )^2g_s^{2/3}M_{GUT}^2}.$$
(56)
Finally, the amplitude for proton decay is, from (33),

$$A_{st}=\pi \alpha ^{}g_sI(\theta _1,\theta _2,\theta _3)=\frac{\alpha _{GUT}^{2/3}L(Q)^{2/3}g_s^{1/3}I(\theta _1,\theta _2,\theta _3)}{4\pi M_{GUT}^2},$$
(57)
where $`I`$ is the integral discussed in the last section. It is interesting to compare this result with the M-theory estimate of :

$$A_M\frac{\alpha _{GUT}^{2/3}L(Q)^{2/3}}{M_{GUT}^2}.$$
(58)
We find the same scaling with $`\alpha _{GUT}`$, $`L(Q)`$ and $`M_{GUT}`$ as in M-theory. If we keep these parameters and the rotation angles $`\theta _i`$ fixed, then we may study the amplitude as a function of $`g_s`$. String theory indicates that this function behaves as $`g_s^{1/3}`$ for small $`g_s`$; M-theory tells us that it approaches a constant for large $`g_s`$. Strictly speaking, (57) is reliable for small $`g_s`$, but we will take it as a rough approximation for $`g_s`$ of order $`1`$.

Analogous Field Theory Amplitude

Let us compare this to the analogous four-fermion amplitude in four-dimensional GUT’s. For simplicity, we will assume that (as in $`SU(5)`$ models) all superheavy gauge bosons have the same mass $`M_X`$. $`M_X`$ is comparable to the unification scale $`M_{GUT}`$ inferred from the running of the low energy gauge couplings, but differs from it, in general, by model-dependent factors. Exchange of superheavy gauge bosons of mass $`X`$ gives an amplitude

$$\frac{g_{GUT}^2}{M_X^2}\underset{a}{}A_1|J_{\mu a}|A_2A_3|J_a^\mu |A_4,$$
(59)
where we have labeled initial and final fermion states as $`A_1,A_2,A_3`$, and $`A_4`$. The sum runs over the superheavy gauge bosons, but since the standard model gauge bosons contribute baryon-number conserving interactions anyway and taking the sum over all generators of the gauge group will lead to a simpler formula, we will do this. (Standard model gauge boson masses are near zero, not near $`M_X`$, so (59) is not a good approximation to their contribution.) Note that, ignoring worldsheet instantons, the string theory four-fermion amplitude is $`SU(5)`$-invariant, since it comes from a local contribution that does not see the symmetry breaking by Wilson lines, while the four-fermion operator in GUT’s is of course not $`SU(5)`$-invariant.

We first consider the case that the fermions transform as $`\mathrm{𝟓}`$’s of $`SU(5)`$, though the resulting $`\mathrm{𝟓}^2\overline{\mathrm{𝟓}}^2`$ amplitude is actually baryon number conserving. To get baryon nonconservation, we need to incorporate $`\mathrm{𝟏𝟎}`$’s as well, as we will do presently. Also, to get a better match to the local string theory construction with Chan-Paton factors, we take the gauge group to be $`U(5)`$ instead of $`SU(5)`$; the extra $`U(1)`$ gauge field does not violate baryon number anyway. (In string theory, the local construction at a particular brane intersection point has $`U(5)`$ gauge symmetry, but globally in realistic models the extra $`U(1)`$ is Higgsed by absorbing an RR mode.)

Let us work out the group theory part of the matrix element in eqn. (59). For this, we introduce column and row vectors $`\alpha _i`$ and $`\overline{\alpha }_j`$ for states transforming in the $`\mathrm{𝟓}`$ or $`\overline{\mathrm{𝟓}}`$; the group theory factor of the current-current matrix element becomes

$$\underset{a}{}\overline{\alpha }_1T_a\alpha _2\overline{\alpha }_3T^a\alpha _4,$$
(60)
where the $`T_a`$ are traceless $`5\times 5`$ matrices that generate $`U(5)`$. As we noted earlier, the $`T_a`$ are conventionally normalized so that $`TrT_aT_b=\frac{1}{2}\delta _{ab}`$. It is straightforward to show that

$$\underset{a}{}(\overline{\alpha }_1T_a\alpha _2)(\overline{\alpha }_3T^a\alpha _4)=\frac{1}{2}(\overline{\alpha }_1\alpha _4)(\overline{\alpha }_3\alpha _2).$$
(61)
The $`\mathrm{𝟓}^2\overline{\mathrm{𝟓}}^2`$ interaction in GUT’s is hence

$$\frac{g_{GUT}^2}{2M_X^2}\left[(\overline{\alpha }_1\alpha _4)(\overline{\alpha }_3\alpha _2)+(\overline{\alpha }_1\alpha _2)(\overline{\alpha }_3\alpha _4)\right],$$
(62)
where we sum over the two channels in which the gauge boson can be exchanged.

Now we move on to the $`\mathrm{𝟏𝟎}^2\overline{\mathrm{𝟏𝟎}}^2`$ interaction. In order to make clear the origin of a certain factor of 2, we will introduce the $`\mathrm{𝟏𝟎}`$ by a field theory version of the orientifold that we used in string theory. The gauge group is $`U(5)\times U(5)`$, with gauge fields $`A`$, $`A^{}`$ and the fermions consist of fields $`\psi ,\psi ^{}`$ transforming as $`(\mathrm{𝟓},\mathrm{𝟏})+(\mathrm{𝟏},\overline{\mathrm{𝟓}})`$ plus a field $`S`$ transforming as $`(\mathrm{𝟓},\overline{\mathrm{𝟓}})`$. The Lagrangian is invariant under an “orientifolding” symmetry $`\mathrm{\Theta }`$ that exchanges $`A`$ with $`(A^{})^T`$, where $`(A^{})^T`$ is the transpose (or equivalently, as $`A^{}`$ is hermitian, the complex conjugate) of $`A^{}`$, breaking $`U(5)\times U(5)`$ to a diagonal $`U(5)`$. $`\mathrm{\Theta }`$ exchanges $`\psi `$ and $`\psi ^{}`$, leaving a $`\mathrm{𝟓}`$ of the unbroken $`U(5)`$, and we take it to act on $`S`$ with a suitable sign such that the invariant modes in $`S`$ transform as the $`\mathrm{𝟏𝟎}`$ of the diagonal $`U(5)`$, corresponding to an antisymmetric $`5\times 5`$ matrix $`S^{ij}`$.

The kinetic energy is taken to be a general $`\mathrm{\Theta }`$-invariant expression:

$$I=\frac{1}{4g_{GUT}^2}Tr(F(A)^2+F(A^{})^2)+\overline{\psi }i\gamma D\psi +\overline{\psi }^{}i\gamma D\psi ^{}+\overline{S}i\gamma DS.$$
(63)
where sums over all indices of $`\psi ,`$ $`\psi ^{}`$, and $`S`$ are understood. Let us work out the $`S^2\overline{S}^2`$ interaction prior to orientifolding. It comes from exchanges of gauge bosons in the two $`U(5)`$ groups. In working out the contribution from exchange of a gauge boson in either $`U(5)`$ factor, the indices of $`S`$ that transform under the other $`U(5)`$ are spectators. The amplitude due to exchange of either $`U(5)`$ is thus just like (62), except that when we include the spectator index, the wavefunctions all are $`5\times 5`$ matrices $`\stackrel{~}{\lambda }_i`$ and $`\lambda _j`$ rather than row and column vectors, and the pairing of row and column vectors is replaced by a trace. The amplitude due to exchange of either $`U(5)`$ is hence

$$\frac{g_{GUT}^2}{2M_{GUT}^2}\overline{u}_1\gamma ^\mu u_2\overline{u}_3\gamma _\mu u_4Tr(\stackrel{~}{\lambda }_1\lambda _2\stackrel{~}{\lambda }_3\lambda _4+\stackrel{~}{\lambda }_1\lambda _4\stackrel{~}{\lambda }_3\lambda _2).$$
(64)
The total amplitude due to exchange of a gauge boson in one or the other $`U(5)`$ is hence

$$\frac{g_{GUT}^2}{M_{GUT}^2}\overline{u}_1\gamma ^\mu u_2\overline{u}_3\gamma _\mu u_4Tr(\stackrel{~}{\lambda }_1\lambda _2\stackrel{~}{\lambda }_3\lambda _4+\stackrel{~}{\lambda }_1\lambda _4\stackrel{~}{\lambda }_3\lambda _2).$$
(65)
Orientifolding is carried out by restricting to $`\mathrm{\Theta }`$-invariant states and dividing the action by 2. As a result, we can drop $`A^{}`$ and $`\psi ^{}`$, but we must divide the $`S`$ kinetic energy by 2. The resulting kinetic energy is then

$$I^{}=\frac{1}{4g_{GUT}^2}F(A)^2+\overline{\psi }i\gamma D\psi +\frac{1}{2}\underset{ij}{}\overline{S}_{ij}i\gamma DS^{ij}.$$
(66)
The $`S`$ kinetic energy has been divided by $`2`$, but is still canonically normalized in the following sense. $`S`$ is an antisymmetric matrix, so for example has a $`2\times 2`$ block looking like

$$\left(\begin{array}{cc}0& e^+\\ e^+& 0\end{array}\right).$$
(67)
The kinetic energy is canonically normalized for fields like $`e^+`$ appearing above the diagonal in $`S`$.

As for the $`\mathrm{𝟏𝟎}^2\overline{\mathrm{𝟏𝟎}}^2`$ interaction in the orientifold theory, we can borrow it from (65). We merely have to take the wavefunctions $`\lambda _i`$ and $`\stackrel{~}{\lambda }_j`$ to be invariant under $`\mathrm{\Theta }`$, which means that they are $`5\times 5`$ antisymmetric matrices. Also, we have to divide by 2, just as we divided the $`\mathrm{\Theta }`$-invariant part of the classical action by 2 to get (66). So the $`\mathrm{𝟏𝟎}^2\overline{\mathrm{𝟏𝟎}}^2`$ interaction is finally

$$\frac{g_{GUT}^2}{2M_{GUT}^2}\overline{u}_1\gamma ^\mu u_2\overline{u}_3\gamma _\mu u_4Tr(\stackrel{~}{\lambda }_1\lambda _2\stackrel{~}{\lambda }_3\lambda _4+\stackrel{~}{\lambda }_1\lambda _4\stackrel{~}{\lambda }_3\lambda _2).$$
(68)
Of course, we could have derived this directly starting with the kinetic energy (66).

Comparison

To compare string theory to four-dimensional gauge theory, we therefore need merely compare the string theory amplitude $`\pi g_s\alpha ^{}I`$ from (33) to the field theory amplitude $`g_{GUT}^2/2M_X^2=2\pi \alpha _{GUT}/M_X^2`$ from (68). The comparison is thus

$$\pi g_s\alpha ^{}I2\pi \frac{\alpha _{GUT}}{M_X^2}.$$
(69)
We call the left hand side the string amplitude $`A_{st}`$, and the right hand side the corresponding GUT amplitude $`A_{GUT}`$. Using (57), we find the ratio to be

$$\frac{A_{st}}{A_{GUT}}=\frac{L(Q)^{2/3}I}{8\pi ^2}\frac{g_s^{1/3}}{\alpha _{GUT}^{1/3}}\frac{M_X^2}{M_{GUT}^2}$$
(70)
For other parameters fixed, this ratio scales as $`1/\alpha _{GUT}^{1/3}`$, which is the same as in the M-theory calculation of . The negative power of $`\alpha _{GUT}`$ reflects the fact that in this type of model, proton decay is a stringy effect, rather than being dominated by exchange of a single Kaluza-Klein mode. Exploring a possible enhancement due to this factor was the motivation for the present paper, but the factor of $`8\pi ^2`$ in the denominator is clearly unfavorable. We can rewrite (70) as

$$\frac{A_{st}}{A_{GUT}}0.037L(Q)^{2/3}Ig_s^{1/3}\left(\frac{.04}{\alpha _{GUT}}\right)^{1/3}\frac{M_X^2}{M_{GUT}^2}.$$
(71)
Happily, $`g_s`$, of which we can only say that we expect it to be more or less close to 1, is here raised to a relatively small power, helping to reduce the uncertainty.

Using the most commonly cited values $`M_{GUT}2\times 10^{16}`$ GeV, $`\alpha _{GUT}.04`$, a recent evaluation of the proton lifetime in four-dimensional SUSY $`SU(5)`$ due to gauge boson exchange gave the value $`1.6\times 10^{36}`$ years if $`M_X=M_{GUT}`$  (we have taken eqn. (17) of this paper with $`M_X=2\times 10^{16}`$ GeV). If $`M_X`$ or $`\alpha _{GUT}`$ is changed, the proton lifetime scales as:

$$\tau _p=1.6\times 10^{36}\mathrm{years}\left(\frac{.04}{\alpha _{GUT}}\right)^2\left(\frac{M_X}{2\times 10^{16}\mathrm{GeV}}\right)^4.$$
(72)
Using modified values of $`\alpha _{GUT}`$ and $`M_{GUT}`$ is natural in the present discussion if doublet-triplet splitting is accomplished with discrete symmetries as in , since this necessitates extra matter fields (in complete $`SU(5)`$ multiplets) surviving to energies below the GUT scale. For example, in , in models with such additional multiplets, it was found plausible to have values such as $`\alpha _{GUT}=.2`$, $`M_{GUT}=8\times 10^{16}`$ GeV. The net effect of these changes is to roughly double the proton lifetime.

To obtain the proton lifetime $`\tau _{p,st}`$ in this class of string theories from (72), we multiply by $`(A_{GUT}/A_{st})^2`$ and replace the prefactor 1.6 by 2 for a reason explained below. Thus:

$$\tau _{p,st}=2\times 10^{36}\mathrm{years}\left(.037L(Q)^{2/3}Ig_s^{1/3}\right)^2\left(\frac{.04}{\alpha _{GUT}}\right)^{4/3}\left(\frac{M_{GUT}}{2\times 10^{16}\mathrm{GeV}}\right)^4.$$
(73)
A proton lifetime of order $`10^{36}`$ years due to gauge boson exchange is considered unobservably small for the foreseeable future; the present experimental bound on $`p\pi ^0e^+`$ is about $`4.4\times 10^{33}`$ years (for example, see ), while a next generation detector (described for example in ) may reach a limit close to $`10^{35}`$ years. However, it is clear that a relatively modest enhancement in the proton decay amplitude might save the day. Looking at (71), we see a few large and small factors that tend to cancel. This formula contains the small overall factor $`0.037`$, along with the factor $`I`$, which we have found to be roughly $`711`$ for plausible values of the angles, and the threshold factor $`L(Q)^{2/3}`$, where $`L(Q)`$ need not be large but is in fact equal to 8 for the minimal lens space with fundamental group $`𝐙_2`$, and a little larger for many of the lens spaces with other small fundamental groups. Combining these factors, the best we can say is that in a model based on intersecting $`D6`$-branes, rather as in four-dimensional GUT’s, the proton lifetime due to dimension six operators is likely to be close to $`10^{36}`$ years.

Note that one major source of uncertainty in GUT’s is absent here: the proton lifetime directly involves the scale $`M_{GUT}`$ that can be probed using low energy data, rather than the heavy gauge boson mass $`M_X`$ whose relation to $`M_{GUT}`$ is model-dependent.

What we have evaluated in this paper is a local, stringy contribution to proton decay in a certain class of models based on intersecting Type II $`D6`$-branes. If the compactification volume is even slightly larger than the string scale, so that worldsheet instanton effects are at least slightly suppressed, what we have computed is likely to be the dominant contribution (from dimension six operators) in this class of models. The result we have obtained has an anomalous power of $`\alpha _{GUT}`$ because it is a short distance stringy effect. As in , this contribution yields only a $`\mathrm{𝟏𝟎}^2\overline{\mathrm{𝟏𝟎}}^2`$ interaction, which contributes to $`p\pi ^0e_L^+`$. In four-dimensional GUT’s, there is also a $`\mathrm{𝟏𝟎}\overline{\mathrm{𝟏𝟎}}\mathbf{\hspace{0.17em}5}\overline{\mathrm{𝟓}}`$ contribution, leading to $`p\pi ^0e_R^+`$. With the assumptions made in , the ratio of $`p\pi ^0e_R^+`$ to the total is $`y=1/(1+(1+|V_{ud}|^2)^2)`$, where $`V_{ud}1`$ is a CKM matrix element. Hence in comparing the stringy proton decay rate to that in field theory, we should include a factor of $`1/(1y)`$ in the proton lifetime in the string model to account for the missing $`p\pi ^0e_L^+`$. We included this factor in taking the prefactor in (73) to be 2.

The last paragraph has been formulated loosely; with different assumptions about the flavor structure at the GUT scale, the $`\pi ^0`$ could be a $`K^0`$ and the $`e^+`$ could be a $`\mu ^+`$ (in which case the lepton polarization in the final state would be measurable). In either the GUT theory or the string model, the proton lifetime could be increased further by unfavorable assumptions about flavor structure (mixing with the third generation, for instance, or mixing with new GUT-scale fermions). At any rate, the assertion of this class of models that proton decay is caused mainly by $`\mathrm{𝟏𝟎}^2\overline{\mathrm{𝟏𝟎}}^2`$ interactions is testable in principle.

## Acknowledgments

We thank M. Cvetic and S. Raby for useful discussions. I.R.K. gratefully acknowledges the hospitality of the George P. & Cynthia W. Mitchell Institute for Fundamental Physics at Texas A& M University, where some of this work was carried out. This material is based upon work supported in part by the National Science Foundation Grants No. PHY-9802484 and PHY-0070928. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the National Science Foundation.


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# Reverse Monte Carlo Simulations, Raman Scattering and Thermal studies of an Amorphous Ge30Se70 Alloy Produced by Mechanical Alloying

## I Introduction

Amorphous semiconductor materials like chalcogenide glasses present a great potential for application in technological devices, such as optical fibers, memory materials and switching devices, but their use is limited due to several factors. One of them is the difficulty in obtaining information about atomic structures, which define the short-range order (SRO) of the alloy. In this context, the structures of amorphous GexSe1-x (a-GexSe1-x) and liquid GexSe1-x (l-GexSe1-x), in particular Ge33Se67 (GeSe2), have been extensively studied by several experimental techniques, like neutron diffraction (ND) Rao et al. (1998); Penfold and Salmon (1991); Salmon and Petri (2003); Petri et al. (2000), x-ray diffraction (XRD) Tani et al. (2001), extended x-ray absorption fine structure (EXAFS) Gulbrandsen et al. (1999); Zhou et al. (1991) and Raman spectroscopy (RS) Takeuchi et al. (1998); Sugai (1987). On the theoretical side, molecular dynamics simulations (MD) Vashishta et al. (1989a, b); Massobrio et al. (1998, 2001); Cobb et al. (1996); Cobb and Drabold (1997); Zhang and Drabold (2000) have been carried out to understand the SRO in these liquids and glasses in terms of two possible and distinct models. In the first one the distribution of bonds in the structure is purely randomic and determined by the local coordination numbers and composition. In the second one, there is a strong SRO and the structure is formed by well defined structural units, e.g., corner-sharing GeSe4/2 (CS) tetrahedral and edge-sharing Ge2Se8/2 (ES) bitetrahedral units. The distribution of these units gives raise to a medium, or intermediate, range order (IRO), whose signature is the appearance of a first sharp diffraction peak (FSDP) in the neutron Petri et al. (2000); Rao et al. (1998); Salmon and Petri (2003) or x-ray structure factors Tani et al. (2001) at many compositions. In particular, ND experiments performed on melt-quenched Petri et al. (2000); Salmon and Petri (2003) (MQ) GeSe2 (MQ-GeSe2) showed a FSDP in the total structure factor $`𝒮(K)`$ which was associated with correlations in the range of 5–6 Å. As described in Ref. Petri et al., 2000, this alloy is formed by CS and ES units with heteropolar bonds but there are homopolar bonds in very small quantities. These results are reproduced by MD simulations in l-GeSe2 Massobrio et al. (1998, 2001); Cobb and Drabold (1997) and a-GeSe2 Vashishta et al. (1989a, b); Cobb et al. (1996); Zhang and Drabold (2000), except the FSDP in the Bathia-Thorton (BT) Bathia and Thornton (1970) concentration-concentration structure factor $`𝒮_{\text{CC}}(K)`$. It should be noted, however, that almost all available data about a-GexSe1-x alloys were determined for MQ samples, and the preparation method can affect the SRO and IRO, as it was reported by Takeuchi et al. Takeuchi et al. (1998) by comparing the structures of a-Ge30Se70 produced by MQ and by vacuum evaporation (VE) techniques. Tani et al. Tani et al. (2001) studied the a-GeSe2 produced by Mechanical Grinding (MG) of its crystalline counterpart and also found some structural differences. These differences are important because some physicochemical properties can be altered and improved as desired by choosing an appropriate method of preparation.

It is well known that the Mechanical Alloying technique (MA) Suryanarayana (2001) introduces a high quantity of disorder and defects in the structure of the materials produced using this process. Thus, in this paper, we investigated the SRO and IRO of an amorphous Ge30Se70 alloy produced by MA (MA-a-Ge30Se70) starting from the elemental powders of Ge and Se using Raman spectroscopy, Differential Scanning Calorimetry (DSC), X-ray diffraction and reverse Monte Carlo (RMC) simulations McGreevy and Pusztai (1988); McGreevy (1995); RMC ; McGreevy (2001) of its XRD $`𝒮(K)`$. We were interested in studying two main points. Since it is not obvious that starting from the powders of Ge and Se and submitting them to a milling process we would obtain an alloy formed by (ordered) structural units like CS or ES units, first of all we would like to know if the alloy produced by MA contains these units. Besides that, even if these units are formed the SRO and the IRO of the alloy can be significantly altered by the high quantity of defects and disorder introduced by the MA process when compared to MQ samples, for instance. Therefore, the second point is to determine the local structure of the alloy itself, finding coordination numbers and interatomic distances. At our knowledge, this is the first time that such study is reported concerning an a-Ge30Se70 alloy produced by MA.

## II Theoretical Background

### II.1 Structure Factors

#### II.1.1 Faber and Ziman structure factors

According to Faber and Ziman Faber and Ziman (1965), the total structure factor $`𝒮(K)`$ is obtained from the scattered intensity per atom $`I_a(K)`$ through

$`𝒮(K)`$ $`=`$ $`{\displaystyle \frac{I_a(K)\left[f^2(K)f(K)^2\right]}{f(K)^2}},`$
$`=`$ $`{\displaystyle \underset{i=1}{\overset{n}{}}}{\displaystyle \underset{j=1}{\overset{n}{}}}w_{ij}(K)𝒮_{ij}(K),`$
where $`K`$ is the transferred momentum, $`𝒮_{ij}(K)`$ are the partial structure factors and $`w_{ij}(K)`$ are given by

$$w_{ij}(K)=\frac{c_ic_jf_i(K)f_j(K)}{f(K)^2},$$

and

$`f^2(K)`$ $`=`$ $`{\displaystyle \underset{i}{}}c_if_i^2(K),`$
$`f(K)^2`$ $`=`$ $`\left[{\displaystyle \underset{i}{}}c_if_i(K)\right]^2.`$
Here, $`f_i(K)=f_{0_i}(K)+f_i^{}(\lambda )+if_i^{\prime \prime }(\lambda )`$ is the atomic scattering factor, $`f_i^{}(\lambda )`$ and $`f_i^{\prime \prime }(\lambda )`$ are the anomalous dispersion terms and $`c_i`$ is the concentration of atoms of type $`i`$ ($`\lambda `$ is the radiation wavelength). The partial reduced distribution functions $`G_{ij}(r)`$ are related to $`𝒮_{ij}(K)`$ through

$$G_{ij}(r)=\frac{2}{\pi }_0^{\mathrm{}}K\left[𝒮_{ij}(K)1\right]\mathrm{sin}(Kr)𝑑K.$$

From the $`G_{ij}(r)`$ functions the partial radial distribution function $`\text{RDF}_{ij}(r)`$ can be calculated by

$$\text{RDF}_{ij}(r)=4\pi \rho _0c_jr^2+rG_{ij}(r).$$

where $`\rho _0`$ is the density of the alloy (in atoms/Å3). Interatomic distances are obtained from the maxima of $`G_{ij}(r)`$ and coordination numbers are calculated by integrating the peaks of $`\text{RDF}_{ij}(r)`$.

#### II.1.2 Bathia and Thornton structure factors

The BT structure factors can be related to the FZ ones Bathia and Thornton (1970). For a binary alloy the BT number-number structure factor $`𝒮_{\text{NN}}(K)`$ is given by

$$𝒮_{\text{NN}}(K)=c_1^2𝒮_{11}(K)+c_2^2𝒮_{22}(K)+2c_1c_2𝒮_{12}(K),$$
(1)
where $`𝒮_{ij}(K)`$ are the FZ partial structure factors and $`c_i`$ is the concentration of element $`i`$. The BT number-concentration structure factor $`𝒮_{\text{NC}}(K)`$ is

$$𝒮_{\text{NC}}(K)=c_1c_2\left\{c_1\left[𝒮_{11}(K)𝒮_{12}(K)\right]c_2\left[𝒮_{22}(K)𝒮_{12}(K)\right]\right\},$$
(2)
and the BT concentration-concentration structure factor $`𝒮_{\text{CC}}(K)`$ is found through

$$𝒮_{\text{CC}}(K)=c_1c_2\left\{1+c_1c_2\left[𝒮_{11}(K)+𝒮_{22}(K)2𝒮_{12}(K)\right]\right\}.$$
(3)
### II.2 RMC Method

The basic idea and the algorithm of the standard RMC method are described elsewhereMcGreevy and Pusztai (1988); McGreevy (1995); RMC ; McGreevy (2001) and its application to different materials is reported in the literature Rosi-Schwartz and Mitchell (1994); Mellergard and McGreevy (1999); Karlsson et al. (2000); Jóvári and Pusztai (2001); Keen and McGreevy (1990); Wang et al. (1997); Bionducci et al. (1999); Wicks and McGreevy (1995); Cicco et al. (2000); Machado et al. (2002); de Lima et al. (2003); Tengroth et al. (2001); Iparraguirre et al. (1993); Ohkubo et al. (2001); Pusztai and Sváb (1993). In the RMC procedure, a three-dimensional arrangement of atoms with the same density and chemical composition of the alloy is placed into a cell (usually cubic) with periodic boundary conditions and the $`G_{ij}^{\text{RMC}}(r)`$ functions corresponding to it are directly calculated through

$$G_{ij}^{\text{RMC}}(r)=\frac{n_{ij}^{\text{RMC}}(r)}{4\pi \rho _0r^2\mathrm{\Delta }r},$$

where $`n_{ij}^{\text{RMC}}(r)`$ is the number of atoms at a distance between $`r`$ and $`r+\mathrm{\Delta }r`$ from the central atom, averaged over all atoms. By allowing the atoms to move (one at each time) inside the cell, the $`G_{ij}^{\text{RMC}}(r)`$ functions can be changed and, as a consequence, $`𝒮_{ij}^{\text{RMC}}(K)`$ and $`𝒮^{\text{RMC}}(K)`$ are changed. Thus, $`𝒮^{\text{RMC}}(K)`$ is compared to the $`𝒮(K)`$ factor in order to minimize the differences between them. The function to be minimized is

$$\psi ^2=\frac{1}{\delta }\underset{i=1}{\overset{m}{}}\left[𝒮(K_i)𝒮^{\text{RMC}}(K_i)\right]^2,$$
(4)
where the sum is over $`m`$ experimental points and $`\delta `$ is related to the experimental error in $`𝒮(K)`$. If the movement decreases $`\psi ^2`$, it is always accepted. If it increases $`\psi ^2`$, it is accepted with a probability given by $`\mathrm{exp}(\mathrm{\Delta }\psi ^2/2)`$; otherwise it is rejected. As this process is iterated $`\psi ^2`$ decreases until it reaches an equilibrium value. Thus, the atomic configuration corresponding to equilibrium should be consistent with the experimental total structure factor within the experimental error. By using the $`G_{ij}^{\text{RMC}}(r)`$ functions the coordination numbers and interatomic distances can be calculated. In addition, the bond-angle distributions $`\mathrm{\Theta }_{ijl}(\mathrm{cos}\theta )`$ can also be determined.

## III Experimental Procedure

The MA-a-Ge30Se70 alloy was produced by considering a binary mixture of high-purity elemental powders of germanium (Alfa Aesar 99.999% purity, particle size $`<`$ 150 $`\mu `$m) and selenium (Alfa Aesar 99.999% purity, particle size $`<`$ 150 $`\mu `$m) that was sealed together with several steel balls into a cylindrical steel vial under an argon atmosphere. The ball-to-powder weight ratio was 5:1. A Spex Mixer/Mill model 8000 was used to perform MA at room temperature. The mixture was continuously milled for 40 h. A ventilation system was used to keep the vial temperature close to room temperature. The XRD pattern was recorded in a powder Siemens diffractometer equipped with a graphite monochromator, using the CuKα line ($`\lambda =1.5418`$ Å). The total structure factor $`𝒮(K)`$ was computed from the XRD pattern after corrections for polarization, absorption, and inelastic scattering, following the procedure described by Wagner Wagner (1972). The $`f^{}`$ and $`f^{\prime \prime }`$ values were taken from a table compiled by Sasaki Sasaki (1984). Raman measurements were performed with a T64000 Jobin-Yvon triple monochromator coupled to a cooled CCD detector and a conventional photon counting system. The 5145 Å line of an argon ion laser was used as exciting light, always in backscattering geometry. The output power of the laser was kept at about 200 mW to avoid overheating the samples. All Raman measurements were performed at room temperature. DSC measurements were taken with a heating rate of 10C/min using a TA 2010 DSC cell in a flowing argon atmosphere.

## IV Results and Discussion

### IV.1 Raman Scattering

Figure 1 shows the RS spectra of MA-a-Ge30Se70, c-Se and c-Ge. The alloy has bands at around 195, 215, 237 and 255 cm-1. The band at 195 cm-1 is associated with the $`A_1`$ breathing mode of CS units and the 215 cm-1 band is related to the $`A_1^c`$ breathinglike motions (companion peak) of Se in the ES units Sugai (1987); Wang et al. (1998); Popovic et al. (1998). The difference in the intensities of these peaks indicates that the alloy is formed basically by CS tetrahedra and ES tetrahedra are found in a small quantity. The shoulder around 237 cm-1 is associated with $`A_1`$ and $`E`$ modes of Se chains, and they are also seen in the c-Se (see Fig. 1). The broad band at 255 cm-1 is related to $`A_1`$ and $`E_2`$ modes of Sen rings Wang et al. (1998); Popovic et al. (1998); Takeuchi et al. (1998); Gulbrandsen et al. (1999); Kohara et al. (1998). It is important to note that the band at around 165 cm-1, which is associated with Ge-Ge pairs vibrations in ethanlike units, is not seen in the spectrum of the alloy (as well as the other bands of c-Ge), indicating that the quantity of Ge-Ge pairs is very low in the alloy. In addition, the bands related to Se-Se pairs are not seen in the spectra of the alloys produced by MQ Wang et al. (1998) or VE Takeuchi et al. (1998) techniques at this composition, but they exist in the alloy produced by MA, and their intensities suggest that their quantities may be relevant. These results indicate that the tetrahedral units are formed during the MA process and there is a preference for CS units.

### IV.2 DSC measurement

Figure 2 shows the DSC measurement of the alloy, and it displays only two exothermic peaks at about 200C and 360C, which are associated with crystallization temperatures of MA-a-Ge30Se70. There are no peaks associated with melting of c-Se, which should appear around 217C, nor with glass transition or crystallization of a-Se, which should occur at about 45C and 90C, respectively Tani et al. (2001); Lima et al. (2002). These data indicate that the Raman lines associated with Se chains and rings are not due to the presence of some quantity of unreacted a-Se or c-Se and reinforce the existence of a high number of Se-Se pairs in the alloy, indicating that the local structure of MA-a-Ge30Se70 probably is different from that found in MQ, VE and even in MG samples, since now there are Se-Se pairs in a higher quantity.

### IV.3 X-ray Diffraction and RMC Simulations

Figure 3 shows the experimental XRD $`𝒮(K)`$ (full line) for our alloy and the experimental ND $`𝒮(K)`$ (dashed line) given in Refs. Petri et al., 2000 or Salmon and Petri, 2003 for a-GeSe2. The FSDP is seen at around 1.1 Å-1. It is lower than those shown in Refs. Salmon and Petri, 2003 and Rao et al., 1998, indicating that the IRO in the alloy produced by MA is less pronounced than in the MQ-GeSe2 samples Petri et al. (2000); Rao et al. (1998); Salmon and Petri (2003). The FSDP is known to be much dependent on Ge-Ge and, to a lesser extent, on Ge-Se correlations Fuoss et al. (1981); Moss (1974); Vashishta et al. (1989b); Salmon and Petri (2003). Therefore these correlations have a different behavior in MA-a-Ge30Se70.

$`𝒮(K)`$ was simulated using the RMC program available on the Internet RMC . To perform the simulations we have considered a cubic cell with 16000 atoms (4800 Ge and 11200 Se), $`\delta =0.002`$, and a mean atomic number density $`\rho _0=0.03868\pm 0.0005`$ atoms/Å3. This value was found from the slope of the straight line ($`4\pi \rho _0r`$) fitting the initial part (until the first minimum) of the total $`G(r)`$ function Waseda (1980). The minimum distances between atoms were fixed at the beginning of the simulations at $`r_{\text{Ge-Ge}}=1.8`$ Å, $`r_{\text{Ge-Se}}=1.8`$ Å and $`r_{\text{Se-Se}}=1.75`$ Å. The $`𝒮^{\text{RMC}}(K)`$ obtained from the simulations (squares) is also shown in Fig. 3 and there is a very good agreement with the experimental $`𝒮(K)`$.

First hard sphere simulations without experimental data were carried out to avoid possible memory effects of the initial configurations in the results. Then unconstrained runs (i.e. when only hard sphere diameters and experimental data were used during the simulation) were carried out. These runs led to essentially identical $`G_{ij}^{\text{RMC}}(r)`$ functions, because of the proximity of the atomic numbers and scattering factors of Ge and Se. In the next series of simulations we tried to fit the experimental $`𝒮(K)`$ using the ND coordination numbers reported in Refs. Petri et al., 2000 or Salmon and Petri, 2003 as coordination constraints. In this case we reached a poor agreement between the experimental and the simulated structure factor, indicating that the local structure of MA-a-Ge30Se70 is really different from that found in the MQ-GeSe2 alloy, in agreement with Raman results. Thus, based on Raman results (small number of Ge-Ge pairs, presence of CS and ES-like units and a high number of Se-Se pairs) we used as starting coordination constraints the values $`N_{\text{Ge-Ge}}=0.2`$, $`N_{\text{Ge-Se}}=3.7`$ and $`N_{\text{Se-Se}}=1.0`$, which were then allowed to vary freely. The results obtained from the best simulation achieved are shown in Fig. 3 and they are discussed below. As a final test, we also tried to make simulations forcing the Se-Se coordination to be two, as it is in a-Se, but again the simulations did not show a good convergence. When this constraint is released, the Se-Se coordination number decreases until it reaches the number we found for the previous case ($`N_{\text{Se-Se}}=1.25`$, see text below), in agreement with Raman and DSC results.

#### IV.3.1 Pair Distribution Functions

Figure 4 shows the $`G_{ij}^{\text{RMC}}(r)`$ functions obtained from the RMC simulations of MA-a-Ge30Se70 compared to those found for MQ-GeSe2 Salmon and Petri (2003). There are important differences among these functions and those obtained by ND measurements Petri et al. (2000); Salmon and Petri (2003) and also by MD simulations Vashishta et al. (1989a, b); Cobb et al. (1996); Zhang and Drabold (2000). First of all, we should note that the densities of the alloys are very different ($`\rho _{\text{MQ-GeSe}\text{2}}=0.0334`$ atoms/Å-3 Azoulay et al. (1975)), so the heights of the peaks in $`G_{ij}(r)`$ cannot be easily compared. The intensity of the first peak in $`G_{\text{Se-Se}}^{\text{RMC}}`$ is higher, confirming their existence in a larger quantity in the first coordination shell, as indicated by the RS measurement. The two first peaks of the $`G_{\text{Ge-Ge}}^{\text{RMC}}(r)`$ function, which correspond to Ge-Ge first and second neighbors, show up around 2.33 and 3.83 Å. The first peak occurs at a distance a little shorter than that found in the MQ sample Petri et al. (2000); Salmon and Petri (2003), but the second is displaced towards higher-r values by 0.26 Å. Besides that, a minimum occurs at around 3.0 Å. Remembering that the distance between two Ge atoms in adjacent ES and CS units are found at 3.02 Å and 3.60 Å, respectively Cobb et al. (1996); Vashishta et al. (1989b), it can be seen that the fraction of ES units in MA-a-Ge30Se70 is low, in agreement with the results obtained by RS. If we consider that in c-GeSe2 each ES or CS Ge atom has, respectively, three and four nearest-neighbor Ge atoms and there are equal numbers of ES and CS units giving $`N_{\text{Ge-Ge}}=3.5`$ we find that, for a value of $`N_{\text{Ge-Ge}}=3.85`$ (see Table 1), we should have about 85% of the tetrahedral units as CS units and 15% as ES units. Since the intensity of the FSDP in $`𝒮(K)`$ seems to be related to the quantity of ES tetrahedra Vashishta et al. (1989a, b); Cobb et al. (1996); Cobb and Drabold (1997), the low quantity of ES units in our alloy could explain the low intensity of the FSDP.

The first peak of $`G_{\text{Ge-Se}}^{\text{RMC}}(r)`$ function is located at 2.35 Å, as it happens to the MQ-GeSe2 samples Petri et al. (2000); Salmon and Petri (2003); Vashishta et al. (1989b). This shell in our alloy is lower and broader than in MQ-GeSe2 but, due to the difference in densities, Ge-Se coordination numbers are almost the same in both alloys. The next peak appears at 3.84 Å, and it is higher than that at 4.96 Å. In the MQ-GeSe2 samples, there is a peak around 3.02 Å which is not seen, or at least not resolved, in MA-a-Ge30Se70, and there are peaks at 3.78 Å (smaller) and 4.66 Å (higher). In c-GeSe2 an ES Ge atom has Se neighbors in the range $`4.6r5.3`$ Å, and a CS Ge atom has Se neighbors in the range $`4.0r4.8`$ Å. Penfold and Salmon (1991); Rao et al. (1998) Then, we have associated the peak at 3.84 Å with CS units and that at 4.96 Å with CS and ES units.

The first peak of $`G_{\text{Se-Se}}^{\text{RMC}}(r)`$ function is located at 2.33 Å, and it corresponds to a coordination number $`N_{\text{Se-Se}}=1.25`$, which is much higher than that obtained for the MQ-GeSe2 samples ($`N_{\text{Se-Se}}=0.20`$) Petri et al. (2000); Salmon and Petri (2003). This suggests that some of the tetrahedral units are connected by Se “bridges”, forming sequences such as Ge-Se-Se-Se-Ge. As a consequence, Ge-Ge pairs should be found at higher distance values. This agrees with the results obtained from the $`G_{\text{Ge-Ge}}^{\text{RMC}}(r)`$ function. The next peak appears at 3.75 Å, which gives a ratio of Ge-Se:Se-Se distances of 0.627. The value expected for ideal tetrahedral coordination is $`\sqrt{3/8}=0.612`$, indicating that the tetrahedral (CS or ES) units are distorted in our alloy. It is interesting to note that in MQ-GeSe2 samples no peaks are found from $`4.5`$ Å to $`5.9`$ Å either considering ND results Petri et al. (2000); Salmon and Petri (2003) or MD simulations Vashishta et al. (1989b); Zhang and Drabold (2000). On the other hand, in MA-a-Ge30Se70 there are peaks at 4.95 and 5.75 Å, and we believe these peaks are related to the distances between Se atoms in the “bridges” and Se atoms in tetrahedral units. The peaks at around 6.6 and 7.4 Å, which are also seen in MQ-GeSe2 samples, can be associated, following Ref. Vashishta et al., 1989b, to distances between Se atoms belonging to two adjacent tetrahedral units.

The coordination numbers show in Table 1 were calculated considering the RDF$`{}_{ij}{}^{\text{RMC}}(r)`$ functions shown in Fig. 5. The integrations were made using the following ranges: from 1.7 Å to 2.95 Å to the first peak and from 2.95 Å to 4.5 Å to the second peak, for all RDF$`{}_{ij}{}^{\text{RMC}}(r)`$ functions. The interatomic distances are also shown in Table 1.

#### IV.3.2 Partial Structure Factors

The partial $`𝒮_{ij}^{\text{RMC}}(K)`$ are shown in Fig. 6, together with the $`𝒮_{ij}^{\text{ND}}(K)`$ found in Ref. Salmon and Petri, 2003. $`𝒮_{\text{Ge-Ge}}^{\text{RMC}}(K)`$ has its first three peaks at about 1.1, 2.0 and 3.6 Å-1 and two minima at 1.3 and 2.8 Å-1. Their positions agree reasonably well with those found for MQ-GeSe2 studied by ND Petri et al. (2000); Salmon and Petri (2003), but intensities are very different. The first peak is much lower in MA-a-Ge30Se70 than it is in the MQ-GeSe2 sample. This peak is associated with the FSDP in the $`𝒮(K)`$ shown in Fig. 3 and, since the FSDP is known to be strongly dependent on the Ge-Ge correlations and, to a lesser extent, on the Ge-Se correlations Fuoss et al. (1981); Moss (1974); Vashishta et al. (1989b), the low intensity FSDP experimentally observed in Fig. 3 could be caused by weak Ge-Ge and Ge-Se correlations at its position. In addition, the heights of the second and third peaks are almost the same, and in MQ samples the height of the second peak is twice of that of the third peak. It is interesting to note that the first peak obtained from the MD simulations Vashishta et al. (1989a, b) was found only at 1.3 Å-1, where our $`𝒮_{\text{Ge-Ge}}^{\text{RMC}}(K)`$ has a minimum.

$`𝒮_{\text{Ge-Se}}^{\text{RMC}}(K)`$ has two maxima at 1.02 and 3.58 Å-1 and a minimum at 1.7 Å-1. Again, the first peak of MA-a-Ge30Se70 is lower than that found in MQ-GeSe2 samples, but its position is the same, and it is also associated with the FSDP in $`𝒮(K)`$. The second peak and the first minimum in MQ samples are found at 3.5 Å-1 and 2.1 Å-1, respectively, indicating that in our alloy they are dislocated to higher (the maxima) and lower-$`K`$ (the minimum) values. These facts can be explained by the important differences between the $`G_{\text{Ge-Se}}^{\text{RMC}}(r)`$ function and that of the MQ samples for $`r>4`$ Å.

$`𝒮_{\text{Se-Se}}^{\text{RMC}}(K)`$ has two peaks at around 2.0 and 3.6 Å-1, and there is a minimum at 2.8 Å-1. At about 1.2 Å-1 there is a small peak associated with the FSDP in $`𝒮(K)`$. In MQ-GeSe2 samples the peaks are seen at 0.95, 2.05 and 3.55 Å-1, and there is a minimum at 2.75 Å-1. These data indicate that $`𝒮_{\text{Se-Se}}^{\text{RMC}}(K)`$ is similar to that of MQ-GeSe2 samples, at least in the low-$`K`$ region, concerning peak positions. However, we should note that their heights are different, in particular the intensity of the peak at 2.0 Å-1.

It is important to compare our results considering the BT formalism. Figure 7 shows the $`𝒮_{\text{NN}}^{\text{RMC}}(K)`$, $`𝒮_{\text{NC}}^{\text{RMC}}(K)`$ and $`𝒮_{\text{CC}}^{\text{RMC}}(K)`$ factors obtained using Eqs. 1, 2 and 3, together with those factors found by ND and shown in Ref. Salmon and Petri, 2003. As expected, $`𝒮_{\text{NN}}^{\text{RMC}}(K)`$ resembles the XRD $`𝒮(K)`$ because the scattering lengths of Ge and Se are almost the same, and it is very similar to the $`𝒮_{\text{NN}}^{\text{ND}}(K)`$ found for MQ-GeSe2, except for the FSDP intensity at 1.0 Å-1. Although there are differences in the peak intensities, $`𝒮_{\text{NC}}^{\text{RMC}}(K)`$ resembles that found for l-GeSe2 Penfold and Salmon (1991); Massobrio et al. (1998, 2001); Salmon (1992) and for MQ-GeSe2 Salmon and Petri (2003), including the sharp minimum at 2.0 Å-1. $`𝒮_{\text{CC}}(K)`$ also behaves like that obtained for l-GeSe2 Penfold and Salmon (1991); Salmon (1992) and MQ-GeSe2 Salmon and Petri (2003). In l-GeSe2 a sharp FSDP is clearly seen in $`𝒮_{\text{CC}}(K)`$ at around 1.0 Å-1, and this fact also occurs in MQ-GeSe2 samples. MD simulations of l-GeSe2 Massobrio et al. (1998, 2001) and MQ-GeSe2 Zhang and Drabold (2000) could not reproduce well this peak. In our case, a very weak FSDP can be seen at 1.1 Å-1 as a shoulder of the high peak at 2.0 Å-1. Remembering that the FSDP in $`𝒮(K)`$ (see Fig. 3) has a low intensity and considering all the results discussed above, we should not expect that the FSDP in $`𝒮_{\text{CC}}(K)`$ was as high and well defined as it is in l\- or MQ-GeSe2 samples. The IRO in MA-a-Ge30Se70 is different mainly because of the introduction of Se-Se first neighbor pairs as “bridges” between the tetrahedral units, thus decreasing the number of ES units and increasing the number of CS units. This affects the short and medium range order, which, in its turn, changes the concentration-concentration BT factor.

#### IV.3.3 Bond-Angle Distribution Functions

By defining the partial bond-angle distribution functions $`\mathrm{\Theta }_{ijl}(\mathrm{cos}\theta )`$ where $`j`$ is the atom in the corner we calculated the angular distribution of the bonds between first neighbor atoms. The six $`\mathrm{\Theta }_{ijl}(\mathrm{cos}\theta )`$ functions are shown in Fig. 8. All these functions were calculated considering as $`r_{\text{max}}`$ the position of the first minimum after the peak of the first shell ($`r_{\text{max}}3.0`$ Å).

The $`\mathrm{\Theta }_{\text{Ge-Ge-Ge}}(\mathrm{cos}\theta )`$ function is very noisy because of the very small number of Ge-Ge pairs in the first shell, but it shows a tendency for angles around 100. The $`\mathrm{\Theta }_{\text{Se-Se-Se}}(\mathrm{cos}\theta )`$ function has peaks at 55–61 and a broad distribution from 99 to 118, with a maximum at 103. The internal Se-Se-Se angles in perfect tetrahedra are found at $`60^{}`$, the Se-Se-Se angle in trigonal Se is seen at 103 and the angles in small Se chains and rings Kohara et al. (1998) can be found at 90–116. Thus, the $`\mathrm{\Theta }_{\text{Se-Se-Se}}(\mathrm{cos}\theta )`$ function indicates that the tetrahedra in MA-a-Ge30Se70 are slightly distorted and Se chains and rings are formed, in agreement with RS results and with the previous analyses of the $`G_{ij}(r)`$ functions. The $`\mathrm{\Theta }_{\text{Se-Ge-Se}}(\mathrm{cos}\theta )`$ function is very similar to the $`\mathrm{\Theta }_{\text{Se-Se-Se}}(\mathrm{cos}\theta )`$ function, showing peaks at 58 and 105, which is close to the ideal tetrahedral angle of 109.

The $`\mathrm{\Theta }_{\text{Ge-Se-Ge}}(\mathrm{cos}\theta )`$ function peaks at about 58 and 106. The Ge-Se-Ge sequence in ES units has angles around 80 that are not seen in this function, reinforcing the small quantity of these units. On the other hand, this sequence in CS units has angles around 100, and $`n`$-fold rings have angles ranging from 92 to 125.Cobb et al. (1996); Kohara et al. (1998) The $`\mathrm{\Theta }_{\text{Se-Ge-Ge}}(\mathrm{cos}\theta )`$ and $`\mathrm{\Theta }_{\text{Ge-Se-Se}}(\mathrm{cos}\theta )`$ functions are similar to the others, having peaks at 58, associated with threefold rings, and at 116 (Se-Ge-Ge) and 109 (Ge-Se-Se), which are related to tetrahedral angles and $`n`$-fold rings. The $`\mathrm{\Theta }_{ijl}(\mathrm{cos}\theta )`$ functions above confirm that distorted tetrahedral units are formed in MA-a-Ge30Se70, with a clear preference for CS units. These units seem to be connected by Se-Se bridges, forming small chains and rings, as pointed out by the RS data.

## V Conclusion

To summarize, we can conclude that the amorphous Ge30Se70 alloy can be produced by MA starting from the elemental powders of Ge and Se, but the structure of the alloy is different from that found in MQ-, VE- or MG-GeSe2 samples, making clear the importance of the preparation technique. Structural units similar to distorted CS and ES tetrahedra are formed, with a preference for CS tetrahedra, as indicated by Raman spectroscopy. These units seem to be connected by Se-Se bridges, as suggested by the high number of these pairs in the first shell, by the increase in the distance between Ge-Ge second neighbors, by the $`\mathrm{\Theta }_{ijl}(\mathrm{cos}\theta )`$ functions and also by RS vibrational data. These differences in the SRO affect the IRO of the alloy, and this causes the low intensity of the FSDP in $`𝒮(K)`$ of MA-a-Ge30Se70 when compared to the MQ-GeSe2 alloy Petri et al. (2000); Salmon and Petri (2003). The low intensity of the FSDP in $`𝒮(K)`$ can be traced back to the partial $`𝒮_{\text{Ge-Ge}}(K)`$ factor, whose FSDP is related to the ES units, which are found in a small quantity in the alloy. $`𝒮_{\text{CC}}(K)`$ reflects these features and shows a very weak FSDP when compared to the factor found for l-GeSe2 Massobrio et al. (1998, 2001); Penfold and Salmon (1991) or MQ-GeSe2 Salmon and Petri (2003).

As a second remark, this study reinforces the relevance of using and combining RMC simulations with other techniques to model amorphous structures, since all features described above were obtained considering directly the experimental $`𝒮(K)`$ in the simulations.

###### Acknowledgements.

We would like to thank the Brazilian agencies CNPq, CAPES and FAPESP for financial support. We wish to thank Dr. Pál Jóvári (HASYLAB) for helpful suggestions about the RMC simulations. We are indebted to Dr. Philip Salmon (University of Bath) for sending the data on MQ-GeSe2.