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# Consistency of Microcanonical and Canonical Finite-Size Scaling

## 1 Introduction

Investigations of critical phenomena are focused on the properties of systems of infinite size. The application of computer simulational methods, however, supplies data for systems of finite size, and hence the need arises to have an extrapolation method which allows to extract information about the critical behaviour of the infinite system from finite system data. A prominent example of such an extrapolation method is Finite-Size Scaling as introduced by Fisher and Barber. This method allows to determine critical exponents of the infinite system from the system-size dependence of certain canonical quantities of finite systems, and is therefore referred to as Canonical Finite-Size Scaling (CFSS) in the following.

Conventionally, the canonical approach is favoured for the investigation of phase transitions. Recent results, however, reveal advantages of the microcanonical ensemble, at least for the detection and classification of phase transitions as well as for the localization of critical points from finite system data. It is, inter alia, this fact which motivated the investigation of critical phenomena in the microcanonical ensemble and, to this purpose, the development of a Microcanonical Finite-Size Scaling (MFSS) theory.

The existing papers on MFSS of various authors, although quite similar in their titles, are somewhat difficult to compare, which is in particular due to the fact that the naming “microcanonical” is used for different scenarios.222Bruce and Wilding, for example, define their so-called “microcanonical entropy density” via a second order differential equation (!) from the reduced microcanonical partition function (24). Typically, in analogy to CFSS, an assumption is taken as a starting point to derive MFSS laws which enable the determination of critical exponents of the infinite system from the system-size dependence of certain microcanonical quantities of finite systems. In this paper, it is shown that the MFSS Assumption as discussed in refs.  is consistent with its canonical counterpart in the sense that validity of MFSS implies validity of CFSS.

## 2 Notation

We consider classical statistical systems of hypercubic geometry in $`d`$ spatial dimensions with volume $`L^d`$, where $`L`$ is the linear size of the system. Our interest is focused on systems which undergo a continuous equilibrium phase transition in the thermodynamic limit.

For notational simplicity, we restrict ourselves to Hamiltonians $``$ of the form

$$:\mathrm{\Gamma },xL^d\left[\epsilon (x)hm(x)\right]$$
(1)
where $`\mathrm{\Gamma }`$ is the configuration space of the system and $`h`$ is an external magnetic field. $`\epsilon :\mathrm{\Gamma }`$ and $`m:\mathrm{\Gamma }`$ map elements from configuration space onto their intensive interaction energy and magnetization value, respectively. We consider partition functions which depend on 2+1 variables,333The extension to more variables is straightforward. The reduction of the results to 1+1 variables is explicitely demonstrated in the Appendix. whereof one is the inverse linear system size $`L^1`$. The microcanonical partition function or density of states

$$\mathrm{\Omega }=\mathrm{\Omega }(\epsilon ^{},m,L^1)$$
(2)
is written as a function of the intensive magnetization $`m`$ and of the reduced interaction energy

$$\epsilon ^{}:=\epsilon \epsilon _c$$
(3)
where $`\epsilon _c`$ is the critical interaction energy. From the microcanonical partition function $`\mathrm{\Omega }`$, the microcanonical entropy

$$s^{mic}(\epsilon ^{},m,L^1):=L^d\mathrm{ln}\mathrm{\Omega }(\epsilon ^{},m,L^1)$$
(4)
is obtained. The canonical partition function

$$Z(t,h,L^1):=L^{2d}d\epsilon ^{}dm\mathrm{\Omega }(\epsilon ^{},m,L^1)\mathrm{exp}\left\{\frac{L^d(hm\epsilon ^{}\epsilon _c)}{T_c(1+t)}\right\}$$
(5)
is a Laplace transform of $`\mathrm{\Omega }`$ where the range of integration is $`^2`$. The canonical partition function is written as a function of the external magnetic field $`h`$ and of the reduced temperature

$$t:=\frac{TT_c}{T_c}$$
(6)
where $`T`$ is the temperature. For convenience, here and in the following we set Boltzmann’s constant $`k_B1`$. From the canonical partition function, the canonical Gibbs free energy

$$g^{can}(t,h,L^1):=T_c(1+t)L^d\mathrm{ln}Z(t,h,L^1)$$
(7)
is obtained.

In the following, we assume spin inversion symmetry such that the critical magnetization $`m_c0`$ and the critical external magnetic field $`h_c0`$. If this is not the case, $`m`$ and $`h`$ have to be substituted by appropriate reduced variables in the homogeneity relations of the next section.

## 3 Finite-Size Scaling and Homogeneous Functions

Homogeneity relations can be taken as convenient starting points to obtain finite-size scaling laws.

Let us consider the standard case of CFSS first. From renormalization group arguments it can be substantiated444Although recent results of Chen and Dohm question the general validity of Brézin’s arguments. that the canonical Gibbs free energy can be split into a regular and a singular part

$$g^{can}(t,h,L^1)=g_{reg}^{can}(t,h,L^1)+g_{sing}^{can}(t,h,L^1),$$
(8)
where the second term in is subject to the homogeneity relation

$$\overline{)g_{sing}^{can}(t,h,L^1)\lambda ^1g_{sing}^{can}(\lambda ^{a_t}t,\lambda ^{a_h}h,\lambda ^{1/d}L^1),}$$
(9)
valid asymptotically in the vicinity of the critical point $`(t,h,L^1)=(0,0,0)`$ for arbitrary positive values of the parameter $`\lambda `$. The exponents $`a_t`$ and $`a_h`$ determine the static universality class of the corresponding infinite system. The homogeneity relation (9) will be referred to as the CFSS Assumption in the following, as it can serve as a starting point to derive scaling laws which describe the finite-size scaling behaviour of various canonical quantities (see e.g. ref. ).

In contrast to CFSS, its microcanonical counterpart is not a standard textbook formalism. To obtain a starting point for MFSS, it is argued that similar relations as in the canonical case should hold for microcanonical quantities. In analogy to Eqs. (8) and (9), we choose the following formulation which will be referred to as the MFSS Assumption: The microcanonical entropy can be split into a regular and a singular part

$$s^{mic}(\epsilon ^{},m,L^1)=s_{reg}^{mic}(\epsilon ^{},m,L^1)+s_{sing}^{mic}(\epsilon ^{},m,L^1),$$
(10)
where the second term is subject to the homogeneity relation

$$\overline{)s_{sing}^{mic}(\epsilon ^{},m,L^1)\lambda ^1s_{sing}^{mic}(\lambda ^{a_\epsilon }\epsilon ^{},\lambda ^{a_m}m,\lambda ^{1/d}L^1),}$$
(11)
valid asymptotically in the vicinity of the critical point $`(\epsilon ^{},m,L^1)=(0,0,0)`$ for arbitrary positive values of the parameter $`\lambda `$. Analogously to the canonical case, the exponents $`a_\epsilon `$ and $`a_m`$ determine the static universality class of the corresponding infinite system. Scaling laws which describe the finite-size scaling behaviour of various microcanonical quantities can be derived from the MFSS Assumption.

## 4 Consistency of Microcanonical and Canonical Finite-Size Scaling Assumptions

In this section it is shown that the CFSS assumption (9) is a direct consequence of the validity of the MFSS assumption (11), and the latter is therefore consistent with the commonly accepted CFSS assumption.

The relation between the microcanonical entropy and the Gibbs free energy can be established from definitions (4), (5), and (7):

$`g^{can}(t,h,L^1)=\epsilon _cT_c(1+t)L^d\mathrm{ln}\{L^{2d}\times `$
$`\times `$ $`{\displaystyle }\mathrm{d}\epsilon ^{}\mathrm{d}m\mathrm{exp}\left\{L^d[s^{mic}(\epsilon ^{},m,L^1)+{\displaystyle \frac{hm\epsilon ^{}}{T_c(1+t)}}]\right\}\}.`$
As in Eq. (10), the microcanonical entropy is split into a singular and a regular part. To be able to deal with the latter, we make a short excursion to its infinite system analogue. In the thermodynamic limit, $`s_{reg}`$ per definitionem does not determine the critical behaviour of the system. In order to take this into account, an expansion of $`s_{reg}`$ in powers of $`\epsilon ^{}`$ and $`m`$ has to be of the form

$$s_{reg}(\epsilon ^{},m)=\frac{\epsilon ^{}}{T_c}+s_{}(\epsilon ^{},m)$$
(13)
where odd powers of $`m`$ vanish due to the spin inversion symmetry (see Sec. 2) and the thermodynamically irrelevant constant term of the expansion was set to zero. The linear term $`\frac{\epsilon ^{}}{T_c}`$ fixes the value of the critical temperature

$$\frac{1}{T_c}=\frac{s(\epsilon ^{},m)}{\epsilon ^{}}|_{\epsilon ^{},m=0}.$$
(14)
The leading orders in $`\epsilon ^{}`$ and $`m`$ of the remainder $`s_{}`$ have to be such as not to contribute to the leading asymptotic behaviour of thermodynamic quantities in the vicinity of the critical point $`(\epsilon ^{},m)=(0,0)`$, which implies

$$\underset{m0}{lim}\underset{\epsilon ^{}0}{lim}\frac{s_{}(\epsilon ^{},m)}{s_{sing}(\epsilon ^{},m)}=\mathrm{\hspace{0.17em}0}.$$
(15)
Now we go back to the case of finite system sizes. Analogously to the infinite system case, for large but finite system sizes $`L`$ the microcanonical entropy is split into three parts

$$s^{mic}(\epsilon ^{},m,L^1)=\frac{\epsilon ^{}}{T_c}+s_{sing}^{mic}(\epsilon ^{},m,L^1)+s_{}^{mic}(\epsilon ^{},m,L^1).$$
(16)
Now we define $`s_{sing}^{mic}`$ as the part of $`s^{mic}`$ which, apart from the additive term $`\frac{\epsilon ^{}}{T_c}`$, contains the asymptotically leading terms in $`\epsilon ^{}`$ and $`m`$ in the vicinity of the critical point $`(\epsilon ^{},m)=(0,0)`$, i.e.,

$$\underset{m0}{lim}\underset{\epsilon ^{}0}{lim}\frac{s_{}^{mic}(\epsilon ^{},m,L^1)}{s_{sing}^{mic}(\epsilon ^{},m,L^1)}=\mathrm{\hspace{0.17em}0}.$$
(17)
As it is the thus defined $`s_{sing}^{mic}`$ for which we will obtain a homogeneity relation later on, contact is made to Eq. (10) and the naming “singular part” is justified a posteriori. It is worth noting that $`\frac{\epsilon ^{}}{T_c}`$ is not necessarily the only term in Eq. (16) which is linear in $`\epsilon ^{}`$. The coefficient of the linear term is a function $`f`$ of the system size $`L`$ such that it converges towards $`\frac{1}{T_c}`$ in the limit $`L^10`$. Thus, for large but finite system sizes we write the term of $`s^{mic}`$ which is linear in $`\epsilon ^{}`$ as

$$\epsilon ^{}f(L^1)\epsilon ^{}\left(\frac{1}{T_c}+bL^q\right)$$
(18)
where $`q^+`$ and $`b`$. The term $`\frac{\epsilon ^{}}{T_c}`$ is treated separately as indicated in (16), whereas $`\epsilon ^{}bL^q`$, in accordance with Eq. (17), is included in the singular part $`s_{sing}^{mic}`$ of the microcanonical entropy. The exponent $`q`$, which describes the scaling of the transition temperature with the system size, is determined by the homogeneity relation obtained for $`s_{sing}^{mic}`$ later on.

We continue our consideration of the canonical Gibbs free energy by inserting (16) in Eq. (4) and making use of the geometric series. This yields

$`g^{can}(t,h,L^1)=\epsilon _cT_c(1+t)L^d\mathrm{ln}\{L^{2d}\times `$
$`\times {\displaystyle }\mathrm{d}\epsilon ^{}\mathrm{d}m\mathrm{exp}\left\{L^d[s_{}^{mic}+s_{sing}^{mic}+{\displaystyle \frac{1}{T_c}}(hm+t\epsilon ^{}){\displaystyle \underset{k=0}{\overset{\mathrm{}}{}}}(t)^k]\right\}\}`$
where, for notational convenience, some functional dependencies have been omitted. The radius of convergence of the geometric series restricts the validity of (4) to values of $`|t|<1`$. Since our intention is to show consistency of finite-size scaling assumptions which hold asymptotically in the vicinity of the critical point, our further proceeding will be to approximate Eq. (4) for small $`t`$, $`h`$, and $`L^1`$, well within the interval of convergence. To this purpose, higher orders in $`t`$ and $`h`$ are dropped to obtain an asymptotic expression for the singular part of the canonical Gibbs free energy

$$g_{sing}^{can}(t,h,L^1)T_cL^d\mathrm{ln}d\epsilon ^{}dm\mathrm{exp}\left\{L^d\left[s_{}^{mic}+s_{sing}^{mic}+\frac{hm+t\epsilon ^{}}{T_c}\right]\right\}$$
(20)
for $`t,h0`$, where the physically irrelevant additive terms constant in $`t`$ and $`h`$ have been omitted. For large enough system sizes $`L`$, we argue that the maximum of the integrand is located close enough to the critical point $`(\epsilon ^{},m)=(0,0)`$ such that Laplace’s method allows to drop higher orders in $`\epsilon ^{}`$ and $`m`$ in the integrand of (20). Equation (17) implies that this is achieved by neglecting $`s_{}^{mic}`$ in the integrand of (20). Thus we obtain

$`g_{sing}^{can}(t,h,L^1)`$
$``$ $`T_cL^d\mathrm{ln}{\displaystyle d\epsilon ^{}dm\mathrm{exp}\left\{L^d\left[s_{sing}^{mic}(\epsilon ^{},m,L^1)+\frac{1}{T_c}(hm+t\epsilon ^{})\right]\right\}}`$
for $`t,h,L^10`$.

Our next step will be to write down a similar asymptotic equality for $`\lambda ^1g_{sing}^{can}(\lambda ^{a_t}t,\lambda ^{a_h}h,\lambda ^{1/d}L^1)`$ in such a way that we can deduce a condition on $`s_{sing}^{mic}`$ which leads to asymptotic equality of this expression with Eq. (4) and which therefore implies validity of the CFSS assumption (9). From (4) we can write

$`\lambda ^1g_{sing}^{can}(\lambda ^{a_t}t,\lambda ^{a_h}h,\lambda ^{1/d}L^1)T_cL^d\mathrm{ln}{\displaystyle }\mathrm{d}\epsilon ^{}\mathrm{d}m\times `$
$`\times `$ $`\mathrm{exp}\left\{L^d\left[\lambda ^1s_{sing}^{mic}(\epsilon ^{},m,\lambda ^{1/d}L^1)+{\displaystyle \frac{1}{T_c}}\left(h\lambda ^{a_h1}m+t\lambda ^{a_t1}\epsilon ^{}\right)\right]\right\}.`$
Substitution of the integration variables $`\epsilon ^{}\lambda ^{1a_t}\epsilon ^{}`$ and $`m\lambda ^{1a_h}m`$ yields

$`\lambda ^1g_{sing}^{can}(\lambda ^{a_t}t,\lambda ^{a_h}h,\lambda ^{1/d}L^1)T_cL^d\mathrm{ln}{\displaystyle }\mathrm{d}\epsilon ^{}\mathrm{d}m\times `$
$`\times `$ $`\mathrm{exp}\left\{L^d\left[\lambda ^1s_{sing}^{mic}(\lambda ^{1a_t}\epsilon ^{},\lambda ^{1a_h}m,\lambda ^{1/d}L^1)+{\displaystyle \frac{1}{T_c}}(hm+t\epsilon ^{})\right]\right\}.`$
where an additive term $`T_cL^d\mathrm{ln}\lambda ^{2a_ta_h}`$ was dropped, since constants in $`t`$ and $`h`$ are not included in the singular part $`g_{sing}^{can}`$ of the Gibbs free energy. Equating (4) and (4) shows that validity of the MFSS assumption (11) implies validity of the CFSS assumption (9), by which the proof is completed.

## 5 Conclusion

In this paper, we have shown consistency of the MFSS Assumption (11) and the CFSS Assumption (9), which puts previous papers on MFSS on a firmer footing. As the consistency is shown in an asymptotic sense for large system sizes $`L`$, the result does not necessarily imply that both Finite-Size Scaling theories work equally well for given finite system-sizes. In fact, it might be the case that in one ensemble or the other, the Finite-Size Scaling region may be reached for smaller system sizes and the quantities under investigation may converge faster towards their infinite system value.

It is worth noting that the MFSS Assumption (11) also includes the case where $`s_{sing}^{mic}`$ is independent of one or more of the variables indicated. This leads to the astonishing observation that even for a microcanonical entropy which is independent of the system size, canonical quantities show system size dependence according to the CFSS laws (see ref.  for a detailed discussion). This, however, does not seem to be the relevant case for the investigation of critical phenomena.

## Acknowledgement

We would like to thank Alfred Hüller for many valuable discussions.

## Appendix A Reduced Microcanonical or Constant Energy Ensemble

In contrast to the above, in the vast majority of papers on the investigation of phase transitions of magnetic systems in the microcanonical ensemble (see references in  for a detailed list), the reduced microcanonical partition function

$$\mathrm{\Omega }^{red}(\epsilon ^{},L^1):=dm\mathrm{\Omega }(\epsilon ^{},m,L^1)$$
(24)
is considered, where the range of integration is $``$. From $`\mathrm{\Omega }^{red}`$, the reduced microcanonical entropy

$$s^{red}(\epsilon ^{},L^1):=L^d\mathrm{ln}\mathrm{\Omega }^{red}(\epsilon ^{},L^1)$$
(25)
can be derived, which, of course, contains less information than $`s^{mic}`$. An extrapolation $`L\mathrm{}`$ of $`s^{red}`$ towards the thermodynamic limit allows merely for an estimation of the zero-field properties of the infinite system under consideration. This becomes obvious from

$`\underset{L\mathrm{}}{lim}s^{red}(\epsilon ^{},L^1)=\underset{L\mathrm{}}{lim}L^d\mathrm{ln}{\displaystyle dm\mathrm{exp}\left\{L^ds^{mic}(\epsilon ^{},m,L^1)\right\}}=`$ (26)
$`=`$ $`\underset{m}{sup}s(\epsilon ^{},m)=\underset{m}{sup}\left\{s(\epsilon ^{},m){\displaystyle \frac{hm}{T_c(1+t)}}\right\}|_{\frac{h}{T_c(1+t)}=0}=:`$
$`=:`$ $`\widehat{s}(\epsilon ^{},\frac{h}{T_c(1+t)})|_{\frac{h}{T_c(1+t)}=0}`$
where

$$s(\epsilon ^{},m):=\underset{L\mathrm{}}{lim}s^{mic}(\epsilon ^{},m,L^1)$$
(27)
is the entropy of the infinite system and $`\widehat{s}`$ is a so-called Massieu function.

In order to make contact with papers like ref. , we want to explicitely transfer our main result to the reduced microcanonical entropy by showing consistency of the homogeneity relation

$$s^{red}(\epsilon ^{},L^1)\lambda ^1s^{red}(\lambda ^{a_\epsilon }\epsilon ^{},\lambda ^{1/d}L^1)$$
(28)
with the CFSS Assumption (9). This can be achieved by showing that (28) is a direct consequence of the MFSS Assumption (11).

From (4), (16), (24), and (25), we obtain

$$s^{red}(\epsilon ^{},L^1)=\epsilon ^{}+L^d\mathrm{ln}dm\mathrm{exp}\left\{L^d\left[s_{}^{mic}+s_{sing}^{mic}\right]\right\}.$$
(29)
Due to Eq. (17), for large system sizes $`L`$, Laplace’s method allows to drop the term $`s_{}^{mic}`$ in the exponent, and the asymptotic relation

$$s^{red}(\epsilon ^{},L^1)\epsilon ^{}+L^d\mathrm{ln}dm\mathrm{exp}\left\{L^ds_{sing}^{mic}(\epsilon ^{},m,L^1)\right\}$$
(30)
is obtained for $`\epsilon ^{},L^10`$. Making use of the MFSS Assumption (11) yields

$$s^{red}(\epsilon ^{},L^1)\epsilon ^{}+L^d\mathrm{ln}\lambda ^{a_m}dm\mathrm{exp}\left\{\lambda ^1L^ds_{sing}^{mic}(\lambda ^{a_\epsilon }\epsilon ^{},m,\lambda ^{1/d}L^1)\right\}$$
(31)
where a substitution of the integral variable $`m\lambda ^{a_m}m`$ was performed. Neglecting the terms constant in $`\epsilon ^{}`$, a homogeneity relation for the singular part of the reduced microcanonical entropy

$`s_{sing}^{red}(\epsilon ^{},L^1)`$ (32)
$``$ $`\lambda ^1\left(\lambda ^{1/d}L^1\right)^d\mathrm{ln}{\displaystyle dm\mathrm{exp}\left\{\left(\lambda ^{1/d}L^1\right)^ds_{sing}^{mic}(\lambda ^{a_\epsilon }\epsilon ^{},m,\lambda ^{1/d}L^1)\right\}}`$
$``$ $`\lambda ^1s_{sing}^{red}(\lambda ^{a_\epsilon }\epsilon ^{},\lambda ^{1/d}L^1)`$
valid for $`\epsilon ^{},L^10`$, is obtained as a direct consequence of the MFSS Assumption (11).


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# Pairing evidence of 8CB molecules adsorbed on MoS2: Influence of 2D commensurability on the intralamellar structure

## I Introduction

Since the last decade, various interfaces between organic films and crystals have been described as well ordered in 2D, whereas the organic bulk is obviously liquid or liquid crystal. This is even true on chemically inert crystals, such as graphite or MoS2 where molecules are only physisorbed, as probed by a number of Scanning Tunneling Microscopy (STM) measurements . These interfaces are interesting in particular for two reasons. First, they can be studied very precisely at ambient temperature, as presented in the present article, which has led to the possibility of connecting the microscopic structure of the first adsorbed molecules to the relevant surface interactions; second, the structure is studied under the organic film which can lead in a second step to studies of the propagation of interfacial ordering into the organic bulk. In case of liquid crystal phases (8CB bulk is smectic at ambient temperature), this phenomenum is called anchoring . In the case of physisorbed rare gas atoms or simple molecules on the same substrates, isotropic structures are formed, so that equilibrium structures can be exactly calculated . They are described as commensurate or incommensurate with respect to the substrate. These structures can be generally described with one or two molecules in the crystallographic cell, such that the structure is completely determined by its commensurability. Organic molecules are more complex and exact calculations are already extremely more difficult to perform. However their study in the adsorbed configuration can be considered as a first step towards even more complex adsorbed molecules as for example biological molecules.

On graphite or MoS2 substrates, organic molecules are usually organized in lamellae which can be straight or regularly kinked . Until now, the molecule-substrate interactions have been considered in some numerical calculations  or through a phenomenological Landau de Gennes-type model . This mean-field model describes the monolayer structure as lamellae, which periodicity is imposed by the substrate, ignoring the intra-lamella structure. Structures are described as commensurate (straight lamellae) or incommensurate (kinked lamellae) with respect to the substrate, depending mainly on the ratio between the substrate-molecule and molecule-molecule interactions and on the mismatch between the natural periodicity of the lamellae and the one imposed by the substrate. This model allows a global interpretation of the STM results and leads to a commensurate description of various structures which are naively expected to be incommensurate on such substrates since the molecules-substrate interactions are expected to be weak, in particular weaker than on metallic substrates . In order to confirm such results, we have studied a straight lamellae interface, which is “a priori” commensurate, as probed by STM : 4-8-alkyl-4’-cyanobiphenyl (8CB) molecules adsorbed on molybdenum disulphide (MoS2) substrate. STM images of 8CB on MoS2  reveal that the molecules are flat on the substrate, organized in straight lamellae, with a head to tail geometry. By combining two techniques, STM and X-ray diffraction at grazing incidence (GIXD), we have verified the commensurability of the interfacial structure and we have also precisely determined the intralamellar structure, allowing to go beyond the phenomenological model and to propose a study of the relationship between microscopic structures and interface interactions in physisorbed molecules.

The combination of STM and GIXD experiments appeared particularly useful for the determination of such adsorbed structures. Single monolayers only are often studied in case of adsorbed organic molecules . They can be observed by combining LEED and Auger experiments. In the case of an interface between a substrate and a thick organic film, these LEED and AUGER measurements are unoperating due to the presence of the bulk and mainly two techniques remain available, STM and GIXD. However it is difficult to image simultaneously the substrate and the adsorbed molecules by STM, especially in case of a semi-conducting substrate as MoS2 (by contrast to graphite as substrate ). Another limitation of STM techniques is due to drift phenomena of the piezoelectric materials used for scanning the sample surface, preventing a precise estimation of absolute distance values. Finally, as the contrast in STM images is not perfectly understood, the precise molecular structure is difficult to infer from the images. On the other hand the Bragg peaks coming from the monolayer and from the substrate structures can be simultaneously obtained from GIXD experiments. This allows a precise determination of the relative orientation of the two structures as well as of the lattice constants and of the molecule localizations which can be extracted with a precision as good as 0.5 $`\AA `$. The major disadvantage of this latter technique remains the complexity of the experiment mainly due to the small amount of matter contained in physisorbed organic monolayers which imposes the use of synchrotron sources. This complexity justifies that up to now mainly STM experiments have been performed on such interfaces. However the refinement of X-ray data can be strongly simplified if one introduces constraints on the molecule position parameters. These constraints can be obtained from STM images, leading then to a fruitful combination of the two techniques. To our knowledge the only physisorbed organic film studied by combined STM and GIXD has been the 10CB/graphite system, showing metastable commensurate structure, coexisting with the a priori more stable incommensurate one. In the first part of this article, we describe the experimental details; in a second part, the X-Ray diffraction results; in a third part, we analyse the peak intensities trough a model of the molecules localization in the monolayer crystallographic cell. Finally in a fourth part, we discuss the energetic balance between molecule-molecule and molecule substrate interactions by developing an unilamellar model of the monolayer structure.

## II Experimental

The 8CB film has been prepared by melting the organic material on top of a freshly cleaved MoS2 substrate, at 80oC. The 8CB is a BDH product used without any purification. MoS2 natural single crystal comes from Australia (Queensland) through the Wards’ company. This lamellar compound can be easily cleaved, giving a surface parallel to the basal planes. The surface plane is composed of sulphur atoms organized with an hexagonal symmetry (3.16$`\AA `$ as cell parameter), with less than 0.02o mosaicity, as checked by X-Ray diffraction. Grazing incidence X-Ray diffraction experiments have been performed on beam-lines BM32 at ESRF and D41 at LURE. The incident beam (8 keV) reaches the interface through the 8CB bulk at an incidence of 0.5o, comparable to the MoS2 critical angle and larger than the 8CB bulk one. The diffracted intensity is scanned parallel to the plane by a linear detector covering an angle of 13o (PSD) perpendicular to the surface at LURE-D41 and a solid state detector at ESRF-BM32. The in-plane resolution is of the order of 1 mrad. The beam size width is about 500 $`\mu `$m and its intensity is monitored by a diode. The STM and GIXD experiments have been performed on many different samples. Always reproducible results have been obtained, but only the most intense Bragg peaks of the monolayer structure were observed at LURE-D41.

## III Results

31 in-plane diffraction peaks (Table I, fig. 1) of the adsorbed molecules have been measured. They can be indexed in a (4x8) superstructure position, indicating that the monolayer structure is indeed commensurate with the MoS2 lattice. However such a unit cell contains only one lamella, and a close inspection of the STM images indicates that the number of non equivalent lamellae is 4. Considering this constraint, the basic unit corresponds to a (4x32) superstructure and each peak has been indexed in this (4x32) superstructure (fig. 1). The low index Bragg peaks of such a superstructure can not be observed since they are very close to the direct beam. An example of diffraction peak, (4,-48), is presented on the figure 2. The rocking curve (fig. 2a) indicates that the in-plane mosaicity (0.02o) mimics the substrate one, showing that the adsorbed monolayer is constituted of well-ordered single crystallized domains. The observed radial scan width (fig.2b) is limited by the experimental resolution, revealing a correlation length at least larger than 1000 $`\AA `$.

The experimental intensities measured on a given sample (BM32 experiment) are indicated on Table 1. They have been obtained by a gaussian adjustment to the peak shapes. The reciprocal space have been explored along the twelve high symmetry directions and four main commensurate positions have been unambiguously assigned to a nul intensity after careful investigations. Since the $`\theta `$-range is rather small ($`\mathrm{\Delta }\theta `$$``$13o), we neglected any geometrical correction. We used these intensity values to perform a refinement of the molecular structure: we start with an an eight-molecule cell, built in order to form lamellae parallel to the MoS2  direction, with a head to tail geometry. The cell parameters are fixed to the (4x32) MoS2 superstructure. Calculated intensities are adjusted to the measured ones with a least square criterium. Molecules are considered as flat on the substrate, therefore only 2D calculations are performed. They are divided in two rigid parts: the alkyl chain in trans configuration and the cyanobiphenyl part also flat on the substrate. The degrees of freedom of the model are the length of the alkyl chain and of the cyanobiphenyl group (considered as equal for all molecules), the angles between the alkyl chain and the cyanobiphenyl group (with an equal value for the molecules of same lamella), the location and the overall rotation of molecules. Considering the STM observations, and in order to limit the number of parameters, we divide the crystallographic cell in two blocks of four molecules, which can be translated one from each other, the value of the displacement being an adjustable parameter.

We consider two other fit parameters, anisotropic Debye-Waller terms and the monolayer 3-fold degeneracy. Indeed, due to the hexagonal symmetry of the MoS2, three different directions (at $`\pm `$60o) are equivalent for the adsorbed 2D crystal. They can coexist on the sample, and their relative weight must be adjusted. Note that since the commensurabilities along the two high symmetry directions of the MoS2 substrate are multiples from each other, Bragg peaks originating from two coexisting domains can be superimposed.

The best result ($`\chi ^2`$ = 3.19) is presented on the figure 3a. The corresponding calculated Bragg peaks intensities, compared to the measured ones, are presented on the table I. The alkyl chain length is 0.866 nm, the cyanobiphenyl length 0.901 nm and the angles between them are 34.5o for one lamella and 35.2o for the other one. The displacement between the two four molecules blocks has been obtained as half the cell parameter. The crystallographic cell is then a ”centered” c(4x32) superstructure of the MoS2. Considering that the 8CB cell is eight times longer along the k direction than along the h direction, an STM images can be normalized in order to avoid the deformations connected to the drift of the piezoelectric materials and superimposed to the fit solution. Such a comparison, presented on the figure 3b, shows that the refinement result is in very good agreement with the STM observations, in particular the different orientations and locations of the eight molecules in the cell.

## IV Discussion

### A Molecular conformation

We have allowed independent values for the angles between the alkyl chain and the cyanobiphenyl group of the molecules of two successive lamellae. Values very close from each other are finally obtained, also similar to the one calculated for an isolated flat molecule, 35.5o. This indicates that the adsorbed 8CB molecules on MoS2 are essentially not distorted, which is coherent with the numerical calculation of 8CB molecules adsorbed on graphite , but differs from the recent observations on organic molecules covalently bonded onto Ag(111) . The obtained lengths of the alkyl chain and of the cyanobiphenyl group are close (about 10$`\%`$ larger) to the ones estimated for an isolated flat molecule in a completely trans conformation. This confirms that the adsorbed molecules are lying flat on the substrate, with the alkyl chain, completely elongated, in all trans conformation. This indicates that, in their isotropic phase, the molecules are mobile enough to find their 2D-crystallized equilibrium conformation, with only very few gauche defects . Due to the number of measured Bragg peaks, we could not consider the possibility of rotation of the phenyl groups, but the good agreement between the measured and calculated Bragg intensities indicates that, if such a rotation occurs, it remains small. The observed flat conformation of the molecules is clearly related to a strong molecule-substrate interaction.

### B Unilamellar model

The observation of a pair association in one lamella over two is probably the most spectacular result of these X-ray measurements (fig. 3). We underline that such a non-equivalence of two successive lamellae, with the presence of pair-associations in one lamella and equidistant molecules in the neighboring one, is a particularly robust result which appears almost systematically in the fit solutions. Avoiding pair association lead to very high $`\chi ^2`$ values. It demonstrates that, whatever organized in a commensurate network, the adsorbed molecules do not lie on identical adsorption sites. The origin of such a feature is probably connected to the microscopic interactions between molecules as well as between molecules and the substrate, which can not be described in a mean field model. In order to check this assumption, we have built a simple model for a single lamella. We consider a commensurate model, with two dipoles which can be displaced anywhere in the cell, with an antiferroelectric alignment. The knowledge of the 8CB characteristics (dipole (D = 4.9 D) , polarizability ($`\alpha `$ = (40 10-30 4$`\pi `$$`ϵ`$o) m3) , ionization potential (I = 8.7eV, derived from the diphenyl one by analogy with the hydrocarbons case)  allows the calculation of the energy per molecule as a function of the distance, r, between the molecule and its first neighbours :

$`E`$ $`=E_D+E_{VdW}+E_S`$ (5)
$`={\displaystyle \frac{D^2}{4\pi ϵ_o}}\left({\displaystyle \frac{1}{r^3}}+{\displaystyle \frac{1}{(4ar)^3}}\right)`$
$`{\displaystyle \frac{3\alpha ^2I}{(4(4\pi ϵ_o)^2)}}\left({\displaystyle \frac{1}{r^6}}+{\displaystyle \frac{1}{(4ar)^6}}\right)`$
$`+C\left({\displaystyle \frac{1}{r^{12}}}+{\displaystyle \frac{1}{(4ar)^{12}}}\right)`$
$`+E_oB\mathrm{cos}2\pi \left({\displaystyle \frac{2ar}{2a}}\right)`$
with r in $`\AA `$ and the energy in J. ED is the term of dipolar interactions between adjacent molecules. EVdW is the term of Van der Waals interactions between adjacent molecules which includes the dispersion forces as well as a steric repulsion where C is a phenomenological value as usual. The attractive dispersion interactions appear to be about three to four times larger than the attractive dipolar ones, by varying the distances between molecules from 4.3 to 6.32$`\AA `$, as already pointed out by Tildesley et al.  \[note1\]. ES is the molecule-substrate potential which is described by a constant term Eo for the adsorption energy, and an oscillating term, the potential corrugations, which period is fixed to the MoS2 cell parameter a = 3.16$`\AA `$.

Plotting the energy as a function of r leads to two types of configuration, depending on the substrate corrugations parameter, B (fig. 4). If B is strong, one minimum minimorum appears, corresponding to a location of the molecules in the substrate potential wells (fig. 4c). The intermolecular distance is then r1 = 2a = 6.32$`\AA `$. If B is weak, two r values give equal energy minima and pair associations are formed (fig. 4a). The molecules are located out of the potential wells and the intermolecular distance is mainly imposed by the balance between attractive dipolar, dispersion interactions and steric repulsion. One can then calculate C by neglecting B $`\mathrm{cos}`$ 2$`\pi `$(2a-r/2a): we have determined through our X-ray refinement a pair intermolecular distance of 4.3$`\AA `$ (r2) which leads to C = 5.088 10-12J $`\AA `$12.
A first order transition between the two configurations occurs for a critical value Bc (Bc = 7.45 10-20J) which can be calculated by equating the two energy minima at r1 and r2 (fig. 4b):

$`B_c`$ $`={\displaystyle \frac{1}{1\mathrm{cos}2\pi \left({\displaystyle \frac{2ar_2}{2a}}\right)}}`$ (6)
$`[`$ $`{\displaystyle \frac{D^2}{4\pi ϵ_o}}\left({\displaystyle \frac{2}{r_1^3}}{\displaystyle \frac{1}{r_2^3}}{\displaystyle \frac{1}{(4ar_2)^3}}\right)`$ (9)
$`{\displaystyle \frac{3\alpha ^2I}{(4(4\pi ϵ_o)^2)}}\left({\displaystyle \frac{2}{r_1^6}}{\displaystyle \frac{1}{r_2^6}}{\displaystyle \frac{1}{(4ar_2)^6}}\right)`$
$`+C({\displaystyle \frac{2}{r_1^{12}}}{\displaystyle \frac{1}{r_2^{12}}}{\displaystyle \frac{1}{(4ar_2)^{12}}})]`$
The observation of the two kinds of solutions on the same sample, one lamella with pair associations, adjacent to one lamella with equidistant molecules, indicates a variation of the substrate corrugation parameter from B$``$Bc to B$``$Bc between two successive lamellae. This has to be correlated to the refinement results which indicates an average difference in molecular orientations of around 10o for two neighboring lamellae. This directly demonstrates the anisotropic nature of the molecule-substrate corrugations which depend on the orientation of the molecule with respect to the substrate crystallographic directions. We can also conclude that the calculation of Bc gives a minimum value for the substrate corrugation which indeed stabilizes the observed configuration with equidistant molecules: 7.45 10-20J per molecule (i.e. 17 kBT) . We checked that this value is independent of the precise form of the repulsion function and remains identical for different type of repulsive functions (for example varying as C/r9 or C/r15).

### C commensurability of the lamellae

The explanation for the observed alternate solution needs to go beyond the unilamellar model described above. It can be justified by considering the 2D structure associated to a single type of lamella. If one considers a c(4x32) superstructure composed by equidistant molecules only, a limited number of possibilities exists due to the commensurability of the molecules location. It appears then that, in each case, the cyanobiphenyl groups of adjacent lamellae would be located directly in front of each other. Such a c(4x32) superstructure suffers then from strong steric incompatibilities and a c(4x34) superstructure appears to be the smallest superstructure which does not exhibit such a steric repulsion. However in a c(4x34) superstructure the mismatch between the lamellae period imposed by the substrate and the natural lamellae period would jump from 2.5% to 9%. Such a lack of compacity would become unfavorable for the attractive part of the interactions between adjacent lamellae: indeed 11CB molecules on MoS2 with a 10% similar mismatch relax by creating kinks leading to an incommensurate structure perpendicularly to the lamellae . Alternating two intralamellar structures favours the attractive interactions without inducing steric repulsion due to different locations of the cyanobiphenyl groups of adjacent lamellae. On the other hand, a 2D structure composed of pair associations only would correspond to a completely incommensurate structure within the lamellae. Consequently, in our model the postulated commensurability is in fact imposed by the interaction between adjacent lamellae. The observed alternating structure appears as a compromise which allows to preserve the commensurability in both directions, within the lamellae and between the lamellae. The energy gain of the perpendicular commensurability is balanced by the presence of pair associations, a priori less favorable, one lamella over two. It shows how the commensurabilities of these structures in both directions are strongly correlated and cannot be described through a phenomenological model which ignores the intralamellar structures. It justifies to perform now similar X-ray studies on 9CB and 11CB on MoS2, since our result suggests that 9CB and 11CB lamellae on MoS2 which are kinked , should present a single type of lamellae with a commensurate intra-lamellar structure.

### D Molecule-substrate interaction

The obtained value of the substrate corrugations is high, 7.45 10-20J (17 kBT) and such, consistent with the observation of a commensurate structure at ambiant temperature and to its thermal stability \[note2\]. Very few data exist for evaluating it more precisely, especially in case of MoS2. Best of available studies deal with rare gas atoms on graphite. In case of xenon atoms on graphite, the substrate corrugation has been estimated at about 2.78 10-21J , 27 times smaller than our estimated value of 8CB on MoS2.

Substrate-atoms interactions are only of the Van der Waals type in the Xe/graphite system. Calculating the homogeneous Van der Waals part of the molecule-substrate interactions through a continuous model , one obtains a value 15 times smaller for the Xe/graphite system  than for the 8CB/MoS2 one  instead of the 27 times for the substrate potential corrugations ((0.25 $`\alpha `$Xe)/D3J compare to (0.38 $`\alpha `$8CB)/D3J, with D the distance in $`\AA `$ between the Xe or the 8CB and the substrate and $`\alpha `$ the polarizability) . However the 8CB/MoS2-Xe/graphite corrugations ratio is expected to be smaller than the 8CB/MoS2-Xe/graphite homogeneous potentials ratio, due to the large and anisotropic size of the 8CB which should average and such diminish the substrate corrugations compare to the Xe atoms. In the way to explain the calculated increasing, one can assume that the previous lamellar model overestimate the corrugation parameter, B. Calculating the dipolar interaction for two 8CB molecules, as they are located in the structure, one obtains only a 1.06% increase with respect to the model result. However, Van der Waals interactions between the molecules may have been overestimated due to the far location of the more polarizable cyanobiphenyl groups in the antiferroelectric alignment. Another possibility is that the 8CB/MoS2 corrugation potential is not only related to pure Van der Waals interactions. This is supported by the presence of a strong dipolar momentum, 4.9D, located on the cyanobiphenyl group in 8CB molecules possibly inducing special molecule-substrate interactions, apart the pure Van der Waals ones. Dipole-induced dipole interactions have a negligible influence compare to Van der Waals ones, as shown by continuous calculations (8.10-20/D3 J compare to 2.43 10-18/D3 J). However one should consider that MoS2 is composed of two types of atoms, which differences in polarizabilities could play a role. Numerical calculations could test such an hypothesis. Clearly such an effect should be absent on graphite, as shown in the study of polar molecules as CH2Cl2 adsorbed on graphite . This result on MoS2 suggests that the location of the cyanobiphenyl groups with respect to this substrate should play a predominant role as it is generally assumed that the alkyl chains determine the structure on the graphite substrate.

## V Conclusion

We have precisely determined, through a combination of scanning tunneling microscopy and grazing incidence X-rays diffraction, the 2D network of 8CB molecules adsorbed on MoS2 which anchor along the  MoS2 direction. The crystallographic cell has been determined, as well as the intracell fine structure. The X-ray diffraction spectra refinement lead a molecular structure very close to the STM images. Introduction of constraints in the refinement method allows a reduction of the a priori large number of fit parameters, connected to the size of the molecules and to the number of molecules in the unit cell. The constraints being directly defined by the STM results, this demonstrates how the combination between the two techniques (STM and GIXD) is fruitful. In the reverse way, the X-ray results evidence the fine structures within the lamellae, which are not straightforward in the STM images.

The structure appears to be commensurate, perpendicularly to the lamellae as predicted by a phenomenological model , but moreover within the lamellae. The 8CB crystallographic cell is a centered c(4x32) MoS2 superstructure

The determination of the crystallographic parameters is clearly not sufficient to describe correctly the adsorbed network. The description of the intracell structure evidences complex intralamellar structures that we have interpreted through an unilamellar model of the microscopic interactions. Pair associations in one lamella over two correspond to lamellae with molecules out of the molecule-substrate potential wells adjacent to lamellae with molecules inside the wells. This alternating series reflect the connection between the commensurabilities along and perpendicularly to the lamellae. The critical value of the molecule-substrate potential corrugations which impose the observed commensurate lamellae has been calculated to be 7.45 10-20J per molecule. This particularly high value with respect to the Xe/graphite system could be connected to the presence of a high dipolar momentum in the 8CB molecules. The anisotropy of these corrugations is already demonstrated, directly connected to the orientation of the molecules with respect to the substrate crystallographic directions. Numerical simulations as well as similar measurements on slightly different systems could now be very usefully compared to such a study, in order to go towards the complete understanding of the complex interactions substrate-organic molecules. This could allow, in the future, of directly forecasting adsorbed structures of molecules, at least in case of physisorption.

$`\mathit{Note1}`$:

This observation justifies the occurrence of two different structures for only slightly different molecules on the same substrate: a ”single layer” one for 8CB on MoS2, which lamellae are characterized by an antiferroelectric alignment, a priori favorable for dipolar interactions; a ”double layer” one for 10CB on MoS2 , which lamellae are characterized by a ferroelectric alignment, unfavorable for dipolar interactions . The relative lost of dipolar energy is even smaller for larger molecules (10CB compare to 8CB) and could be partly compensated by a win in Van der Waals interaction connected to the proximity of the more polarizable cyanobiphenyl groups in the second structure. So the win in molecule-substrate interactions necessary for imposing a ”double layer” structure can be only small and indeed correlated to some odd-even effect due to the position of the end of the alkyl chain on the underlying substrate, as recently proposed . This remark also justifies the observation that in 10CB/graphite case the two types of structure have been evidenced, also through the association of STM and GIXD experiments .

$`\mathit{Note2}`$:

The 8CB adsorbed layer Bragg peaks starts to disappear at 120oC only, whereas the 8CB bulk already starts to evaporate around 100oC.


text:
# Final State Interaction in Exclusive (𝑒,𝑒'𝑁𝑁) Reactions

## I Introduction

Exclusive $`(e,e^{}NN)`$ reactions, as well as photoinduced two nucleon knock-out experiments ($`\gamma ,NN`$) experiments, are often considered as very powerful tools to explore correlations in the nuclear many-body wave function, which are beyond the mean field or Hartree-Fock approximation. Using a simple picture for such reactions the real or virtual photon of inelastic electron scattering is absorbed by a pair of nucleons. This pair of nucleons is knocked out from the target nucleus while the residual (A-2) nucleons can be considered as spectators which form the ground state or another well defined bound state of the daughter nucleus. Due to the progress in accelerator and detector technology such triple coincidence experiments with sufficient resolution to identify specific states of the daughter nucleus have become possible and first results have been reported in the literature.

If the mean field approximation, in which the nucleons move independent from each other in the Hartree-Fock field, would be valid for the nuclear wave function, such processes should be strongly suppressed. Therefore the analysis of these reactions may provide detailed information about the correlations between the two nucleons which absorb the photon. Various modern models for the nucleon-nucleon (NN) interaction, which all yield an excellent fit to the NN scattering data below the threshold for pion production, provide different predictions for the short-range and tensor correlations. Therefore one hopes that the analysis of exclusive two-nucleon knock-out experiments will provide additional constraints on the models for the NN interaction.

However, correlations in the ground state wave function of the target nucleus is not the only contribution to the cross section of photoinduced two-nucleon knock-out. One may also think about processes in which the photon is absorbed by one nucleon, which propagates off-shell and then shares the absorbed energy and momentum by scattering on a second nucleon. This process of a final state interaction (FSI) might be as important as the effect of correlations in the initial state. In fact, if we describe the absorption of a photon by a correlated pair of nucleons within Brueckner theory, such processes are represented by the diagrams (a) and (b) in Fig. 1. The processes of the FSI, which we just discussed, can be represented by the diagrams displayed in (c) and (d) of the same Fig. 1. Therefore these effects of correlations and FSI could be interpreted as just two different time orderings of NN interaction and photon absorption.

Of course there are some significant differences between these two contributions. The correlation effect can be described in terms of a Brueckner G-matrix, which is evaluated at a starting energy of two bound nucleons. Therefore the resulting G-matrix is real and the corresponding correlated wave function is bound to heal to the uncorrelated wave function at medium relative distances. The FSI on the other hand must be described in terms of a solution of the Bethe-Goldstone equation at a starting energy for the two nucleons above the Fermi energy. The G-matrix for these starting energies becomes complex and therefore we denote it by $`T`$. This implies that the wave function of the two outgoing nucleons is a scattering wave function which does not show the healing property. Nevertheless, the symmetry of the contributions displayed in (a) - (d) of Fig. 1 suggests that one should try to treat them on the same level of accuracy. This is in fact the main aim of the study presented in this manuscript.

It should be mentioned that there is another important effect of FSI, which is usually considered in terms of an optical potential for the outgoing nucleons. This mean field contribution, which accounts for the fact that the outgoing nucleons will be slowed down, redirected or absorbed in the field of the residual nucleus, must be be considered in addition to the FSI contribution discussed above.

Furthermore it is important to keep in mind that there are additional mechanisms which also contribute to the cross section of two-nucleon knock-out. Beside the contributions due to the pair correlations in the ground state wave function of the target nucleons and the FSI one must also consider the effects of the two-body terms in the operator for the electromagnetic current. These two-body terms include meson exchange currents (MEC) which can be derived from the commutator of the charge density with the nuclear Hamiltonian to obey the continuity equation. These meson exchange current contributions should be evaluated in a way consistent with the NN interaction used to describe correlations and FSI. In the present work we include the MEC effects which are due to the exchange of $`\pi `$ and $`\rho `$ mesons using the same couplings as in the realistic interactions used to determine FSI and correlation effects.

In addition, there are contributions to the two-body current which are of a different origin. Here we, mention the contribution due to the excitation of intermediate $`\mathrm{\Delta }`$ isobar excitations. The contribution of this isobar current (IC) is not constrained by a continuity equation like the MEC and therefore depends on parameters like the meson-nucleon $`\mathrm{\Delta }`$ coupling constants and the propagator of the $`\mathrm{\Delta }`$ in the nuclear medium.

In the present work we want to evaluate the nuclear matrix elements for the absorption of a photon by a correlated pair of nucleons determining the effects of correlations, MEC and FSI in a consistent way from a realistic NN interaction. As a first step we investigate the absorption of photons by a pair of nucleons in nuclear matter. For that purpose the technique, which has been described in , accounting for correlations, MEC and IC effects, is extended to allow the consideration of FSI as well. The investigation of these various effects shall provide a comparison of the relative importance of these different mechanisms and their interference under various kinematical conditions.

It is of course a serious disadvantage of such a study in nuclear matter that it does not provide results for a cross section which can directly be compared with experimental data produced for a specific target nucleus. In particular, it is impossible to take advantage of the fact that reactions leading to specific final states of the residual nucleus can be selective for one of the two-nucleon knock-out mechanisms discussed above. Such a feature has been observed in theoretical studies of ($`e,e^{}pp`$) an ($`e,e^{}pn`$) reactions on $`{}_{}{}^{16}\mathrm{O}`$. On the other hand, however, a study of nuclear matter shall exhibit general features which are independent on the specific target nucleus considered and the corresponding long-range or low-energy correlations. In particular we would like to explore the importance of the FSI effects as compared to correlation and MEC effects in $`pp`$ and $`pn`$ knock-out, if the two nucleons are emitted back to back or in more parallel directions.

After this introduction we will briefly present the extension of the approach described in  to include the effects of final state interaction between the two ejected nucleons. The discussion of results is presented in section 3 and the final section 4 contains some concluding remarks.

## II From the Nuclear Current to the Cross Section

As it has already often been described in the literature the differential cross section for the exclusive $`(e,e^{}NN)`$ reaction can be written

$`{\displaystyle \frac{\mathrm{d}^9\sigma }{\mathrm{d}\stackrel{~}{E_1}\mathrm{d}\stackrel{~}{\mathrm{\Omega }_1}\mathrm{d}\stackrel{~}{E_2}\mathrm{d}\stackrel{~}{\mathrm{\Omega }_2}\mathrm{d}E_e^{}\mathrm{d}\mathrm{\Omega }_e^{}}}`$ $`=`$ $`{\displaystyle \frac{1}{4}}{\displaystyle \frac{1}{(2\pi )^9}}\stackrel{~}{p_1}\stackrel{~}{p_2}\stackrel{~}{E_1}\stackrel{~}{E_2}\sigma _{\mathrm{Mott}}\left\{v_CW_L+v_TW_T+v_SW_{TT}+v_IW_{LT}\right\}`$ (2)
$`\times (2\pi )\delta (E_fE_i)`$
where the nuclear structure functions $`W_i`$ ($`i=L,T,TT,LT`$) contain the matrix elements of the nuclear current operator which consists of contributions for the different absorption processes of the virtual photon carrying momentum $`\stackrel{}{q}`$ and energy $`\omega `$. Here, the kinematical variables are the energies $`\stackrel{~}{E_1},\stackrel{~}{E_2}`$ and the final momenta $`\stackrel{~}{p_1},\stackrel{~}{p_2}`$ of the two ejected nucleons.

These final nucleon momenta, $`\stackrel{~}{p_i}`$, are different from the momenta of the two nucleons after absorption of the photon inside the target, which we denote by $`p_i^{}`$ because of the mean field effect of the final state interaction. This mean field contains the attraction of the outgoing nucleons by the nuclear single-particle potential and essentially reduces the momentum of the outgoing nucleon. In infinite nuclear matter this retardation can simply be parameterised through an effective mass $`m^{}`$ and we obtain

$$\stackrel{~}{E_i}=\frac{\stackrel{~}{p_i}^2}{2m}=\frac{p_{i}^{}{}_{}{}^{2}}{2m^{}}+U.$$
(3)
In  we investigated the influence of correlations (diagrams (a) and (b) of Figure 1), meson exchange currents (MEC, ) arising from pions and $`\rho `$ mesons, and isobaric currents (IC, ) (diagram (e) of Figure 1) on the structure functions of $`(e,e^{}pp)`$ and $`(e,e^{}pn)`$ reactions. As an example we recall the expression for the matrix elements entering the structure functions from the correlation effect displayed in Figure 1(a)

$$\mathrm{d}\stackrel{}{p}_a\stackrel{}{p}_1{}_{}{}^{}|\stackrel{}{\epsilon }\stackrel{}{J}_{\gamma NN}|\stackrel{}{p}_aS_2(\stackrel{}{p}_a,\stackrel{}{p}_2{}_{}{}^{})\stackrel{}{p}_a{}_{}{}^{}\stackrel{}{p}_{2}^{}{}_{}{}^{}|G|\stackrel{}{p}_1\stackrel{}{p}_2.$$
(4)
Here, $`\stackrel{}{J}_{\gamma NN}`$ is the current operator for the absorption of the virtual photon with momentum $`\stackrel{}{q}`$ and energy $`\omega `$ on a single nucleon . The matrix element of $`G`$ is calculated for the starting energy of two bound nucleons with momenta $`\stackrel{}{p}_1`$ and $`\stackrel{}{p}_2`$. Also the two-particle propagator $`S_2`$ contains the energy of these bound states and a Pauli operator which guarantees that the momenta $`\stackrel{}{p}_a`$ and $`\stackrel{}{p}_2^{}`$ are larger than the Fermi momentum. All this ensures that the dynamical correlation function, which is described in terms of $`S_2`$ and $`G`$, exhibits the so-called healing property.

In close analogy to this correlation term, we construct the single-particle current contribution with a re-scattering process taking place after the absorption of a virtual photon on a single bound nucleon. In order to give more insight in the evaluation of the corresponding structure functions entering the cross section in eq.(2), we take diagram (c) of Figure 1 as an example.

The matrix element for the absorption process displayed in Figure 1(c) for initial momenta $`\stackrel{}{p}_1`$ and $`\stackrel{}{p}_2`$ and final momenta $`\stackrel{}{p}_1^{}`$ and $`\stackrel{}{p}_2^{}`$ of the nucleon-nucleon pair reads

$$\mathrm{d}\stackrel{}{p}_c\stackrel{}{p}_1{}_{}{}^{}\stackrel{}{p}_{2}^{}{}_{}{}^{}|T|\stackrel{}{p}_c\stackrel{}{p}_2S_1(\stackrel{}{p}_c)\stackrel{}{p}_c|\stackrel{}{\epsilon }\stackrel{}{J}_{\gamma NN}|\stackrel{}{p}_1.$$
(5)
The one-nucleon propagator $`S_1(\stackrel{}{p}_c)`$ describes the propagation of the nucleon after absorption of the energy and momentum of the photon. It also contains a Pauli operator for the momentum of the intermediate nucleon $`\stackrel{}{p}_c`$. Finally, the re-scattering after the photon absorption is described via the $`T`$ matrix element $`\stackrel{}{p}_1{}_{}{}^{}\stackrel{}{p}_{2}^{}{}_{}{}^{}|T|\stackrel{}{p}_c\stackrel{}{p}_2`$. The $`T`$ matrix entering this calculation of the re-scattering process is derived from the solution of the Bethe-Goldstone equation for starting energies which lie above the threshold of twice the Fermi energy. In contrast to the case of eq.(4) this leads to complex $`T`$ matrix elements.

## III Results and Discussion

The calculations are performed in nuclear matter at saturation density ($`k_F=1.35\mathrm{fm}^1`$). The coupling constants for the $`\pi `$ exchange are $`f_{\pi NN}=1.005`$, $`f_{\pi N\mathrm{\Delta }}=2f_{\pi NN}`$, and $`f_{\gamma N\mathrm{\Delta }}=0.12`$. For the $`\rho `$ exchange, the coupling constants were chosen to be $`g_\rho ^2/4\pi =0.86`$, $`\kappa _\rho =6.1`$. The cutoff masses for the $`\pi `$-nucleon and $`\rho `$-nucleon form factors were fixed at $`\mathrm{\Lambda }_\pi =1.3\mathrm{GeV}`$ and $`\mathrm{\Lambda }_\rho =1.95\mathrm{GeV}`$ respectively. The $`\pi `$-nucleon and the $`\rho `$-nucleon vertices are compatible with the $`\pi `$ and the $`\rho `$ exchange part of the One-Boson-Exchange potential BONN A  we used to determine the $`G`$ and the $`T`$ matrix for calculating the effects of NN correlations and re-scattering processes, respectively. The same potential has also been used to determine the single-particle energies for the nucleons in the nuclear medium which were parametrised according to (3) by $`m^{}=623\mathrm{MeV}`$ and $`U=86.8\mathrm{MeV}`$.

For all presented structure functions, the MEC contributions contain the seagull and meson in-flight currents for the exchange of a $`\pi `$ meson as well as the seagull, pair and in-flight currents for the $`\rho `$ meson. As we reported already in , MEC contributions like the photon absorption on a pair of $`\pi `$ and $`\rho `$ mesons were found to give negligible contributions in all kinematical setups we investigated.

Our earlier investigations showed that the so-called ’super parallel’ kinematical setup is very appropriate to investigate effects of nucleon-nucleon correlations. Therefore we will first present results of calculations including the re-scattering processes for this kinematical situation. For that purpose we chose once again the setup in which one of the two ejected nucleons moves in direction of the momentum of the absorbed photon and the other antiparallel to this direction. In Figures 2 and 3 we show the longitudinal and transverse structure functions for the knock-out of a proton-proton and a proton-neutron pair, respectively. In both cases, the virtual photon carries an energy of $`\omega =215\mathrm{MeV}`$.

For the structure functions of the $`(e,e^{}pp)`$ reaction displayed in Figure 2 we find non-negligible contributions from the FSI re-scattering term. This is true in particular in the case of a very asymmetric splitting of the available energy to the the kinetic energy of the outgoing protons ($`T_{p,1}=156\mathrm{MeV}`$ and $`T_{p,2}=33\mathrm{MeV}`$), which is presented in the left part of the Figure. The contribution from FSI re-scattering is almost as large as the correlation effects. Both are significantly stronger than the contribution of the isobar current. Correlation and FSI effects add up in a rather coherent way to the total cross section.

The values for the structure functions are reduced by almost one order of magnitude if one considers the more symmetric distribution of the available energy among the two emitted protons, which is considered in the right part of the figure ($`T_{p,1}=116\mathrm{MeV}`$ and $`T_{p,2}=73\mathrm{MeV}`$). This shows that correlations as well as FSI effects are not very efficient in redistributing energy and momentum from the proton emerging in direction parallel to the momentum transfer $`\stackrel{}{q}`$ to the second proton, which is emitted antiparallel to $`\stackrel{}{q}`$. In this example the isobar current yields the largest contribution to the transverse structure function. It is worth noting that the FSI re-scattering effect is smaller than the correlation effect. This is true in particular for the longitudinal structure function.

In the case of the knock-out of a proton-neutron pair in Figure 3, the effects of correlations and final state interaction are masked to a large extent by the effects of meson exchange currents (MEC). The large MEC contribution is one reason for the fact that the structure functions of proton-neutron knock-out are almost one order of magnitude larger than the corresponding structure functions for proton-proton emission. In the case of the asymmetric energy splitting (large kinetic energy for the proton emitted parallel to $`\stackrel{}{q}`$), however the dominant contribution to the longitudinal structure function originates from correlation effects. The larger correlation contribution in $`pn`$ knock-out as compared to $`pp`$ reflects the importance of tensor correlations in the case of the $`pn`$ pair. In contrast to the proton-proton knock-out, the influence of the final state interaction is negligible for the more symmetric distribution of the kinetic energies (see right part of Figure 3).

Comparing the absolute values of the contributions arising from re-scattering processes, one finds that these contributions are about twice as large as for the knock-out of a proton-proton pair. This demonstrates that the proton-neutron interaction is in general stronger than the proton-proton interaction. The enhancement of the correlation effect in going from the $`pp`$ case to the $`pn`$ case, however, is much stronger.

Sometimes the argument has been used that the FSI re-scattering effects should be minimal if the two nucleons are emitted back to back, the case which we have considered up to now. It is evident that FSI effects are very important if the two nucleons are emitted parallel or even form a deuteron as in ($`e,e^{}d`$) experiments. How important is the FSI re-scattering contribution in kinematical setups, which are in between antiparallel and parallel emission? To answer this question we consider a kinematical set up, which we also inspected in our earlier investigations of . Here, the two nucleons are ejected in a symmetrical way ($`\theta _{p,1/p}^{}=\theta _{p,2/n}^{}=30^\mathrm{o}`$, on opposite sides of the momentum transfer $`\stackrel{}{q}`$) having the same kinetic energies of $`70\mathrm{MeV}`$. Results for the structure functions of $`pp`$ and $`pn`$ knock-out are displayed in Figures 4 and 5, respectively.

In the longitudinal channel of the $`(e,e^{}pp)`$ reaction (Figure 4) the contribution from final state interaction is clearly the dominating one. Contributions from correlations are only of minor importance. For the transverse channel, however, both effects yield contributions of similar size, which are furthermore of the same order of magnitude as the isobar contribution.

The absolute strength of re-scattering contribution to $`(e,e^{}pn)`$ displayed in Figure 5 is about twice as large as for the corresponding ($`e,e^{}pp`$) case. The cross section for $`pn`$ emission in this setup, however, is by far dominated by the meson exchange currents which are related to the pion exchange.

## IV Summary and Conclusions

The effects of re-scattering processes in the final state interaction of two-nucleon knock-out reactions induced by electron scattering have been investigated. The corresponding matrix elements leading to longitudinal and transverse nuclear structure functions have been calculated for a pair of nucleons in nuclear matter. The contributions from re-scattering are calculated in a way which is consistent with the evaluation of correlation effects and meson exchange current contributions. All contributions are derived from the same realistic meson exchange model of the NN interaction. This allows a systematic study of the relative importance of these effects under various kinematical conditions.

The effects of final state interactions (FSI) are very important if the two nucleons are emitted in directions with small angle in between. As an example we consider the longitudinal structure function for $`(e,e^{}pp)`$ with an angle of $`60^\mathrm{o}`$, between the momenta of the outgoing protons. This example is completely dominated by the FSI effects. FSI contributions are larger by a roughly a factor of two in ($`e,e^{}pn`$) as compared to ($`e,e^{}pp`$) processes. Since other mechanisms, like correlation effects and meson exchange current contributions, are enhanced by a factor larger than two in $`pn`$ as compared to $`pp`$ knock-out, the relative importance of FSI are less pronounced in ($`e,e^{}pn`$) reactions.

FSI effects are non-negligible also in the case of back to back emission of the two nucleons. In this case the FSI effects tend to be smaller than correlation effects. Nevertheless they yield contributions of similar size and therefore should be treated in a way which is consistent with the treatment of correlation effects.

This research project has been supported by the SFB 382 of the Deutsche Forschungsgemeinschaft.


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# 1 1

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Bobroff et al. Reply to the comment of Tallon et al., Cond-mat/0008295: The existence of local moments induced by spinless impurities in cuprates has often been denied by Tallon and coauthors, e.g. . In , they finally accept our interpretation of the 7Li NMR shifts in terms of induced local moments nearby Li in the underdoped and optimally doped regime. In contrast they still maintain that our conclusion is incorrect in the overdoped regime. This issue is certainly important in their scenario for which the abrupt change of physical properties (absence of the pseudo gap) which occurs near $`p=0.19`$ would correspond to the disappearance of magnetic correlations. Their argument is based on the qualitative analogy between the $`T`$ dependences of their 89Y and our 7Li shifts. This leads them to attribute this $`T`$ variation in the overdoped regime to the intrinsic bulk susceptibility $`\chi `$ of the CuO2 planes. In Fig. 1 we show that apart the variation of the Kondo temperature, the $`T`$ dependences of the 7Li NMR shift in the YBa2Cu3O7 and Y1-xCaxBa2Cu3O7 substituted samples of  have similar magnitudes. These data cannot therefore be associated with two totally different physical effects, a local moment in one case and the pure material $`\chi `$ in the other. The failure of this qualitative argument is even more obvious from the following simple quantitative comparison.

7Li and 89Y nuclei are coupled to the CuO2 planes respectively through their 4 and 8 n.n. coppers. Hence, if 7Li and 89Y nuclei probe the uniform $`\chi `$ of the pure material their shifts should be related by

$${}_{}{}^{7}K^7K_0=\frac{1}{2}\frac{{}_{}{}^{7}A_{hf}^{}}{{}_{}{}^{89}A_{hf}^{}}(^{89}K^{89}K_0)$$
(1)
where $`{}_{}{}^{7}A_{hf}^{}=2.45kOe/\mu _B`$ ,$`{}_{}{}^{7}K_{0}^{}=90ppm`$  and $`{}_{}{}^{89}A_{hf}^{}=2kOe/\mu _B`$, $`{}_{}{}^{89}K_{0}^{}=150ppm`$  are the hyperfine couplings between the 7Li and 89Y nuclei and one Cu of the CuO2 planes, and the reference shifts. These parameters do not change significantly over the entire phase diagram and can be safely used in the overdoped regime. From the data of Fig.1 of the comment we compute, using Eq.(1), the expected 7Li shifts in Tallon’s scenario. They exhibit much weaker $`T`$ variations than the actual data even for the largest overdoping given in . The $`T`$ variation of the 7Li shift is thus much too large to be attributed to the bulk $`\chi `$, even for $`p0.19`$, for which the 89Y satellites cannot be resolved. As $`\chi `$ has a large $`T`$ independent component in the pure samples, fitting both the magnitude of the $`T`$ variation and the actual high $`T`$ limiting value for $`{}_{}{}^{7}K`$ is impossible for any value of $`{}_{}{}^{89}A_{hf}^{}/^7A_{hf}`$. Rather, the continuous variation of $`{}_{}{}^{7}K`$ and $`{}_{}{}^{7}T_{1}^{}`$  with hole doping supports our interpretation in terms of induced local moments which are Kondo-screened by the carriers introduced by doping. This implies, contrary to the speculation of , that the magnetic correlations responsible for the existence of such moments still play a role in the overdoped regime.

The other point considered ”less secure” in  concerns the connection between the electronic properties of the impurities and the scattering. We agree that one cannot infer the physical origin of the scattering solely from comparison of the $`T_c`$ variations induced by Ni and Zn (or Li) . However the data taken in our group clearly indicate that these two types of impurities display totally different magnetic properties both of which reveal the occurence of magnetic correlations in the host (the local spin S=1/2 on the Ni site is smaller than the expected S=1 value ). This remarkable difference has been recently confirmed by STM measurements of the local electronic structure . The correlation between the microscopic electronic structure and the scattering is evidently not simple, and thus in  we made no attempt to speculate on this point. However, the anomalously large scattering by the Zn defect has very often been attributed to pure local potential scattering . This is somewhat awkward as Zn2+ and Cu2+ have the same charge. We suggested that it is rather linked with the existence of electronic correlations which result in a Kondo resonance. This is strenghtened by the fact that the charge difference between Zn and Li is not reflected both in their local magnetic properties and the Tc variation.

legend of fig.1 :

J. Bobroff, W.A. MacFarlane, H. Alloul, P. Mendels

Laboratoire de Physique des Solides, UMR 8502, CNRS 91405 Orsay, France