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# Order-disorder layering transitions of a spin-1 Ising model in a variable crystal field.

## 1 Introduction

The Blume-Capel model (BC) was originally proposed to study the first-order magnetic phase transitions in spin$`1`$ Ising systems . This model was generalised to the Blume-Emery-Griffiths (BEG) to study phase separation and superfluity in 3He-4He mixtures . Later it has been applied to describe properties of multicomponent fluids , semiconductor alloys  and electronic conduction models . The (BC) model is not exactly solvable in more than one dimension, but it has been studied over infinite $`d`$-dimensional lattices by means of many different approximate techniques and its phase diagram is well known.
When the theory of surface critical phenomena started developing, some attention has been devoted to the study of the (BC) model over semi-infinite lattices, with modified surface couplings. Benyoussef et al.  have determined the phase diagram in the mean field approximation, reporting four possible topologies at fixed bulk/surface coupling ratios. A similar analysis have also been done using a real space renormalization group transformation . Other works referring to particular regions of the phase space are those using: the mean field approximation , the effective field approximation  and the low temperature expansion . All these works show that it is possible to have a phase with ordered surface and disordered bulk, which is separated from the completely ordered phase by the so-called extraordinary transition and from the completely disordered phase by the surface transition. When such a phase is absent, the transition between the completely ordered and the completely disordered phase is called ordinary. The meeting point of the lines of these three kinds of phase transitions is named special and it is generally a multicrititcal point. As discussed in Ref. , the strong interest in these models arises partly from the unusually rich phase transition behaviour they display as their interaction parameters are varied, and partly from their many possible applications. In most of these cases considered so far the bilinear interaction is ferromagnetic. In the antiferromagnetic case, the spin-$`1`$ Ising systems are used to describe both the order-disorder transition and the crystallisation of the binary allow, and it was solved in the mean field approach . One of the most interesting and elusive features of the mean field phase diagram for the antiferromagnetic spin-$`1`$ Blume-Capel model in an external magnetic field is the decomposition of a line of tricritical points into a line of critical end points and one of double critical points . This model was also studied by transfer-matrix and Monte Carlo finite-size-scaling methods , but such decomposition does not occur in this two dimensional model. On the other hand, ferroelectric films can be described by an Ising model and when the film becomes very thick, its properties are those of the semi-infinite Ising system \[15-17\]. From the experimental point of view, the most commonly studied magnetic multilayers are those of ferromagnetic transition metal such as Fe/Ni, where the coupling can exist between magnetic layers \[18-20\]. The discovery of enormous values of magnetoresistance in magnetic multilayers are far exceeding those found in single layer films and so exceeds the discovery of oscillatory interlayer coupling in transition metal multilayers. These experimental studies have motivated much theoretical works to study magnetic thin films as well as critical phenomena \[21-26\]. This is partly motivated by the development of new growth and characterisation techniques, but perhaps more so by the discovery of many exciting new properties, some quite unanticipated. Using the mean field theory, Benyoussef et al.  and Boccara et al.  have studied the spin-$`1`$ Ising model with a random crystal field.
The effect of the surface and bulk transverse fields on the phase diagrams of a semi infinite spin-$`1`$ ferromagnetic Ising model with a crystal field was investigated in  within a finite cluster approximation with an expansion technique for cluster identities of spin-$`1`$ localised spin systems. On the other hand, the transverse field or crystal field effects of spin-$`1`$ Ising model has been studied by several authors \[30-33\].
The purpose of this paper is to study the effect of a variable crystal field according to the law $`\mathrm{\Delta }_k=\mathrm{\Delta }_s/k^\alpha `$ ($`\mathrm{\Delta }_s`$ being the surface crystal field and $`k`$ the layer number from the surface and $`\alpha `$ a positive constant), on the order-disorder layering transitions of a spin-$`1`$ using the mean field theory. This paper is organised as follows. Section $`2`$ describes the model and the method. In section $`3`$ we present results and discussions.

## 2 Model and method

The experimental measurements of layer-by-layer ordering phenomena have been established on free-standing liquid crystals films such as $`\mathrm{𝑛𝑚}OBC`$ (n-alkyl-4’-n-alkyloxybiphenyl-4-carboxylate)  and $`54COOBC`$ (n-pentyl-4’-n-pentanoyloxy-biphenyl-4-carboxylate)  for several molecular layers. More recently, Lin el al.  have used the three-level Potts model to show the existence of layer-by-layer ordering of ultra thin liquid crystal films of free-standing $`54COOBC`$ films, by adjusting the interlayer and intralayer couplings between nearest-neighbouring molecules.
The system we are studying here is formed with $`N`$ coupled ferromagnetic square layers in the presence of a crystal field. The Hamiltonian governing this system is given by

$$=\underset{}{}J_{ij}S_iS_j+\underset{i}{}\mathrm{\Delta }_i(S_i)^2$$
(1)
where, $`S_l(l=i,j)=1,0,+1`$ are the spin variables. The interactions between different spins are assumed to be constant so that $`J_{ij}=J`$. The crystal field acting on a site $`i`$ is so that $`\mathrm{\Delta }_i=\mathrm{\Delta }_k`$ for all spins of the layer $`k`$ so that: $`\mathrm{\Delta }_1>\mathrm{\Delta }_2>\mathrm{}>\mathrm{\Delta }_N`$.
Using the mean field theory, the quadrupolar moment and the magnetisation of a plane $`k`$ are given, respectively, by :

$$q_k=<(S_k)^2>=\frac{2\mathrm{cosh}(\beta h_k)\mathrm{exp}(\beta \mathrm{\Delta }_k)}{1+2\mathrm{cosh}(\beta h_k)\mathrm{exp}(\beta \mathrm{\Delta }_k)}$$
(2)
$$m_k=<S_k>=\frac{2\mathrm{sinh}(\beta h_k)\mathrm{exp}(\beta \mathrm{\Delta }_k)}{1+2\mathrm{cosh}(\beta h_k)\mathrm{exp}(\beta \mathrm{\Delta }_k)}$$
(3)
where $`h_k=J(4m_k+m_{k+1}+m_{k1})`$, and $`\beta =1/(k_BT)`$, $`k_B`$ the Boltzmann constant ant $`T`$ the temperature.
The model we are studying, in this paper, corresponds to a crystal field distributed according to the law:

$$\mathrm{\Delta }_k=\mathrm{\Delta }_s/k^\alpha $$
(4)
where $`\mathrm{\Delta }_s=\mathrm{\Delta }_1`$ is to the crystal field acting on the surface (first layer $`k=1`$). Values of the parameter $`\alpha `$ will be discussed in the following; in particular $`\alpha =0`$ corresponds to a uniform crystal field $`\mathrm{\Delta }_s`$ applied on each layer of the film.
The free energy of a layer $`k`$, can be expressed as:

$$F_k=\frac{1}{\beta }\mathrm{log}(1+2\mathrm{cosh}(\beta h_k))+\frac{1}{2}m_k(4m_k+m_{k+1}+m_{k1})$$
(5)
the parameters $`h_k`$ and $`\beta `$ still have the definitions given above.
As far as we know there is no natural compounds with decreasing crystal field from the surface to deeper layers. However, there exist a series of single crystals $`R_2Fe_{14}B`$ $`(R=Y,Nd,Gd,Tb,Er,Tm)`$ with a variable crystal field anisotropy. Indeed, by adjusting this anisotropy for each layer so that the amplitude of the crystal field will decrease from a layer $`k`$ to the next layer $`k+1`$. Hence, these materials can be grown layer-by-layer in a thin film with a decreasing crystal field from the surface to deeper layers. This can lead to an experimental realisation of our model. Moreover, the decreasing function considered in this model, i.e. $`k^\alpha `$, is not unique since the order-disorder layering transitions are found for any decreasing function of the crystal field from the surface to deeper layers.

## 3 Results and discussion

We are considering a system formed with $`N`$ ferromagnetic square layers of a simple cubic lattice spin$`1`$ Ising model, with free boundary conditions. The notation $`D^kO^{Nk}`$ will be used to denote that the first $`k`$ layers are disordered while the remaining $`Nk`$ layers are ordered. In particular, $`O^N`$ corresponds to an ordered film whereas $`D^N`$ denotes a totally disordered film. The surface crystal field $`\mathrm{\Delta }_k`$, applied on each layer $`k`$ is distributed according to the law given by Eq. $`(4)`$.
The ground state phase diagram of this system is illustrated by Fig. 1. For very small values of the surface crystal field $`\mathrm{\Delta }_s`$, the system orders in the phase $`O^N`$. When increasing $`\mathrm{\Delta }_s`$ the surface (first layer $`k=1`$) disorders and the phase $`DO^{N1}`$ occurs at $`\mathrm{\Delta }_s/J=3(1)^\alpha `$. Increasing $`\mathrm{\Delta }_s`$ more and more, the second layer $`k=2`$ becomes disordered at $`\mathrm{\Delta }_s/J=3(2)^\alpha `$, and so on. The transition from the phase $`D^kO^{Nk}`$ to the phase $`D^{k+1}O^{N(k+1)}`$ is seen at $`\mathrm{\Delta }_s/J=3(k+1)^\alpha `$ provided that $`k+1N`$. For higher values of the surface crystal field the system is totally disordered and the phase $`D^N`$ occurs.
In particular, it is found that there exist a critical order layer $`k_0`$ corresponding to the transition $`D^{k_0}O^{Nk_0}D^N`$, at a reduced surface crystal field given by:

$$\mathrm{\Delta }_s/J=(3(Nk_0)1)/(\underset{k=k_0+1}{\overset{N}{}}(1/k^\alpha )).$$
(6)
$`k_0`$ is exactly the number of layering transitions existing at $`T=0`$. It is shown that $`k_0`$ depends both on the parameter $`\alpha `$ and the film thickness $`N`$. The special case: $`\alpha =0`$ is a situation with a constant crystal field applied on each layer and there is only a single transition $`O^ND^N`$, occurring at $`\mathrm{\Delta }_s/J=31/N`$ for $`T=0`$.
A preliminary study, for $`N=2`$, $`3`$, $`5`$, $`10`$ and $`20`$ layers, shows that the topology of the phase diagrams is not affected by the increasing film thickness, for a fixed exponent $`\alpha `$ value. Hence, the numerical results established in this work are done for a film with a thickness $`N=10`$ layers.
In order to outline the effect of the parameter $`\alpha `$ at a fixed film thickness, we plot in Figs. 2a, 2b, 2c and 2d the corresponding phase diagrams for several $`\alpha `$ values: $`0.0`$, $`0.5`$, $`1.0`$ and $`2.0`$.
In the case $`\alpha =0.0`$, Fig. 2a, a constant crystal field is applied on each layer and the corresponding transition $`O^ND^N`$ is found at $`\mathrm{\Delta }_s/J=31/N=2.9`$ for very low temperatures. Increasing $`\alpha `$ values, it is seen that large values of $`\mathrm{\Delta }_s/J`$ are needed to disorder the film. This result is summarised in Figs. 2b, 2c and 2d. Indeed, due to the effect of the equation law $`(4)`$, separate layering transitions are found. For non null but very low temperatures, the surface crystal field values found in the phase diagrams are exactly those predicted by the ground state study: $`\mathrm{\Delta }_s/J=3(k)^\alpha `$ for a layer order $`k`$ with $`kk_0`$. For example, in Fig. 2c for $`\alpha =1.0`$, the first transition is found at $`\mathrm{\Delta }_s/J=3.0`$, the second transition at $`\mathrm{\Delta }_s/J=6.0`$, the third transition at $`\mathrm{\Delta }_s/J=9.0`$ and so on. The other numerical values of the surface crystal field corresponding to $`\alpha =0.5`$ in Fig. 2b, and $`\alpha =2.0`$ in Fig. 2d are exactly those predicted by the ground state phase diagram. Furthermore, Figs. 2b, 2c and 2d show that the remaining $`Nk_0`$ transitions, not seen for $`T=0`$, arise for higher temperature values with separate tricritical points. More over, these results ensure the existence of a critical value $`\alpha _c(k)`$ above which a layer $`k`$ disorders at a very low temperature. The reentrant phenomena, seen in these figures for a given layer $`k`$, is caused by the competition of the temperature and an inductor magnetic field created by the deeper layers. Indeed, when the thermal fluctuations become sufficiently important, the magnetisation of some spins, of deeper layers, becomes non null (+1 or -1). This leads to the appearance of an inductor magnetic field. This magnetic field is responsible of the ordered phase seen for the layer $`k`$. This argument can also explain the absence of the reentrant phenomena for the last layer(s), once the magnetisation of the remaining layer(s) $`Nk`$ is not sufficient to create an inductor magnetic field. It is worth to note that the reentrant phenomena is always present for the layers $`k`$, ($`kk_0`$), and the corresponding tricritical points $`C_i`$ are located at a constant temperature. An interesting question arises at this stage: what is the effect of the parameter $`\alpha `$ on the surface of the film ($`k=1`$)? To clarify this point, we illustrate in Fig. 3a the profiles of the critical temperature for several values of $`\alpha `$ as a function of $`\mathrm{\Delta }_s/J`$. It is found that increasing $`\alpha `$ values leads to important reentrants phenomena. Indeed, for large values of $`\alpha `$, the layer with $`k>1`$ needs higher values of the surface crystal field to disorder. It is also found that, except the special case $`\alpha =0.0`$, the tricritical point is not affected by variations in $`\alpha `$ values. This surface tricritical point is located at $`(\mathrm{\Delta }_s/J=3.0,T_c/J=0.78)`$ for $`\alpha 0`$ and $`(\mathrm{\Delta }_s/J=2.9,T_c/J=1.9)`$ for $`\alpha =0`$ for a film with a thickness $`N=10`$ layers. The effect of increasing $`\alpha `$ on a medium layer $`k=N/2=5`$ is illustrated in Fig. 3b. The same topology is found, but higher values of $`\mathrm{\Delta }_s/J`$ are needed to overcome the disorder of this layer.
On the other hand, for $`\alpha \mathrm{}`$ the studied system is equivalent to a configuration with $`\mathrm{\Delta }_s/J(k=1)=cste`$ and $`\mathrm{\Delta }_s/J(k>1)=0.0`$: the applied crystal field is present only at the surface and absent on the bulk. The corresponding phase diagram is illustrated by Fig. 4. Only two transitions are present in this case: $`O^{10}DO^9`$, occurring for low temperatures at $`\mathrm{\Delta }_s/J=3.0`$, and $`DO^9D^{10}`$ occurring at a constant temperature $`T/J=3.899`$ and any non null surface crystal field value. In order to complete this study, we illustrate in Fig. 5, the thermal behaviour of the surface magnetisation for $`\mathrm{\Delta }_s/J=3.2`$ and selected values of $`\alpha `$: 0.0, 0.2, 0.5, 1.0 and 2.0. At this surface crystal field value, the increasing $`\alpha `$ values effect is to increase both the surface magnetisation amplitude and the critical temperature needed to disorder this layer. This is a consequence of the factor $`k^\alpha `$ effect for $`k>1`$, as it has been anticipated in the discussion above.

## 4 Conclusion

We have studied the effect of a variable crystal field according to the law Eq. (4), and found order-disorder layering transitions of the Blume-Capel Ising model using mean field theory. We found a reentrant phenomena for each layer $`k`$ ($`kk_0`$, see text), and a tricritical point at a fixed temperature with a vertical first order line. We established the temperature-crystal field phase diagrams and found that the last layer tricritical point depend strongly on the small values of the exponent $`\alpha `$ for a fixed film thickness. The thermal behaviour of the surface magnetisation has also been investigated.

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Figure Captions

Figure 1.: The ground state phase diagram in the plane $`(J,\mathrm{\Delta }_s)`$ for a film thickness $`N`$. The notations $`D^kO^{Nk}`$ are defined in the body text. The calculations presented in this manuscript correspond to a film thickness $`N=10`$ layers.

Figure 2.: The critical temperature behaviour as a function of the surface crystal field $`\mathrm{\Delta }_s`$ for several values of the exponent $`\alpha `$ : a) $`\alpha =0.0`$, b) $`\alpha =0.5`$, c) $`\alpha =1.0`$ and d) $`\alpha =2.0`$.
The first-order transition lines (dashed line) are connected to the second-order transition lines (continuous line) by a tricritical point.

Figure 3.: The critical temperature behaviour of the first layer $`k=1`$ and the medium layer $`k=5`$, as a function of the surface crystal field $`\mathrm{\Delta }_s`$ for selected values of the parameter $`\alpha `$: $`0.0,0.2,\mathrm{0.51.0}`$ and $`2.0`$. a) First layer $`k=1`$. b) Medium layer $`k=N/2=5`$.

Figure 4.: The dependence of the critical temperature as a function of the surface crystal field $`\mathrm{\Delta }_s`$ for $`\alpha =\mathrm{}`$. Only two transitions are present in this case: $`O^{10}DO^9`$ and $`DO^9D^{10}`$.

Figure 5.: The thermal behaviour of the surface (layer $`k=1`$) magnetisation for selected values of $`\alpha `$: $`0.0,0.2,0.5,1.0`$ and $`2.0`$.


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# Packet Transport on Scale Free Networks

## I Introduction

The Internet has become a central feature of all our lives. This has lead to interest in information packet transport on massive, heterogeneous, random, network geometries.

Many empirical studies of packet transport on the Internet have been carried out . The principal conclusion of these measurements is that the aggregate packet streams are fractal, obeying long-range correlated in time. Of particular interest are studies of packet density at a particular link (or on a node) and ping time statistics , in which the round trip time, or the time it takes a packet to travel to a destination and back to its source, are measured. Analysis of the power spectrum of the packet density and round trip times allows one to distinguish two regimes with free flow and jammed traffic, respectively, depending on the traffic intensity. In  it was shown that the power-law behaviour of the distribution of packet inter-arrival times has a significant effect on packet queuing performance, and consequently on the overall packet transport.

These dynamical transport and queuing processes are taking place on the Internet, the network made up of routers and computers as vertices and cables as edges. Recent studies of the geometry of the Internet, , indicate that the degree distribution has a power-law, scale free behaviour .

Another topological property, the betweenness, or the total number of shortest paths going through each node , was also found to have a power-law distribution with an exponent $`2.2`$ on a scale free graph. In terms of transport processes, this corresponds to the distribution of the number of packets transferred through a node (in a long-time limit), in a system in which the packet transport is dominated by non-interacting packets that always take the shortest route between source and destination.

In reality, the information packet transport is much more complex for the following reasons: (1) no global navigation is technically available; (2) many packets are being transported simultaneously, hindering each others motion, depending on the search algorithm and network structure. In particular, the kinetics of many interacting packets leads to a qualitatively new feature, which is manifested in the queueing  of packets at individual nodes. In the network we have the problem of many interacting queues. Thus a close relationship seems to exist between the kinetic properties of the packet transport, such as the distribution of round trip times, or the number of packets on a node, and the network on which the kinetics takes place. The interplay between network structure and packet kinetics becomes particularly important when one imagines the transport in a network with buffers, which restrict the length of packet queue at each node, or with reduced ability of nodes to handle the packets. In recent studies of traffic on idealized geometries—on a linear chain  and on Cayley trees  and one- and two-dimensional lattices  a sharp transition from a free to congested traffic was found. The smallest buffer along the chain causes jamming in the linear model , while transport through the node at the top of hierarchy is crucial for the onset of congestion on the hierarchical lattice . In a network with scale-free structure of links the multiplicity of potential paths among pairs of nodes may alter the role of buffers in the crossover to jammed traffic. It is expected that the local geometry of the hub nodes, and their buffer sizes, is of critical importance, while the buffer sizes of the majority of other nodes are largely irrelevant. The relative importance of nodes, of course, depends on the search algorithm being used. For practical reasons, search algorithms can only be applied to small sections of the network. An attempt was reported recently  to find optimal topology of the network for a given local algorithm in the presence of congestion.

In this paper we introduce a simple model of packet transport on networks in an attempt to understand which of the elements present in a real system are necessary for the system to display the observed empirical results. In particular, we study the effect of the geometry of the network on the major properties of the packet transport. We develop a model for simultaneous transport of packets and implement this model on scale free and randomly grown networks. Packets are posted by a given input rate $`R`$ and moved according to a local algorithm which uses up to next-neighbour search and the local geometry. In this way the packet queue at each individual node is dynamically formed by packets moving from neighbouring nodes. We measure a number of kinetic quantities that allow us to characterize the nature of the packet transport process on the two networks.

The paper is organized as follows: In Section II we introduce the model by first presenting the algorithm of graph growth and then the search algorithm for packet kinetics on the graphs. In Section III we define precisely the quantities that we determine in the simulations and present the results for the packet time series and power spectra of these quantities. In Section IV we study the distribution of transit times of packets, the queue lengths and the networks’ output rate. In Section V we present a short summary of the results and discuss the main conclusions.

## II The Model

Our model is developed in two separate stages. Firstly the network is grown and then we simulate the motion of packets on the network.

Network Structure

We consider two different tree networks, one of which is scale-free and the second is a grown random network.

The scale free network (SFN) structure  is grown as follows. At each time step one new node is added to the network and is linked to a node of degree $`k`$ with a rate

$$p(k,t)=\frac{k+\alpha }{D(t)+\alpha N(t)}.$$
(1)
Here $`D(t)`$ is the total degree of the network at time $`t`$ and $`N(t)`$ is the total number of nodes in the network, and $`\alpha >0`$ is a tunable parameter. For networks grown in this way, the degree distribution is power-law . More precisely, the number of nodes with degree $`k`$, $`P(k)`$, behaves as $`P(k)k^\tau `$ with $`\tau =2+\alpha `$. Choosing $`\alpha =0.2`$ means that this network has the same in-degree distribution  as that observed on the Internet.

The random network (RGN) is grown by adding one new node at each time step and connecting it to a node of degree $`k`$ with rate $`1/N(t)`$, independent of $`k`$. In this case the degree distribution $`P(k)`$ behaves as $`P(k)2^k`$.

Sending Packets

At each time step, with probability $`R`$, a new information packet is initiated. This is done by randomly selecting a source node and a destination node for that packet.

Packet Transport

At each time step, each node is investigated in turn, and if it has a packet on it then the top packet on the node attempts to move. This is done by searching the nearest and next nearest neighbours of the node for the destination node of that packet. If found, the packet is moved to or towards the its destination node. If the destination node isn’t found, the packet moves to a randomly selected neighbour. Each node has a buffer size of integer $`B`$, the maximum number of packets that can be on a node at any one time. If a packet attempts to move to a full node, it is unable to stay there and moves back to the node it came from. We assume that every node has the same buffer size. Similarly, in order to fully investigate the effect of the geometry of the graph, we assume that all the links have the same capacity. When the packet reaches its destination node, it is removed from the network.

In terms of queuing theory , our nodes can be thought of as single server queues, with buffer size $`B`$, and a deterministic service time distribution. The service discipline is last in first out (LIFO). For single server queues with this discipline some approximations have been developed  for the waiting time distribution. Finally the inter-arrival time distribution is not put in by hand, but arises naturally as a function of the network geometry and the kinetics of the packets at neighbouring nodes on the network. The waiting time distribution has two different contributions: First, a node receives packets with a Poisson distribution as a result of packets being initiated on that node; and, second, the node receives packets from neighbouring nodes with a time series that turns out to have a long range, power-law temporal correlation.

Thus we have packet transport rules which yield paths for the packet which are close to, but longer than, the minimum path between source and target node. We also have networks which are trees containing no loops. We do not believe that the loops present in real networks  play an important role in the observed behavior .

## III Traffic Time Series and Power Spectra

We have performed a number of simulations of the kinetics of the packet transport on both the scale free network and the random grown network of size $`N=10^3`$ nodes. We considered a number of different quantities that characterise the kinetics and allow comparison to be made with real data from the Internet . These were

(a) Activity, $`a(t)`$, the total number of nodes with a packet on at time $`t`$. This gives a measure of the fraction of the network that is busy.

(b) Total Load, $`n(t)`$, the total number of packets in the network at time $`t`$.

(c) Load (or queue length), $`q(t)`$, the number of packets on a node at time $`t`$.

(d) Load on the active nodes at time $`t`$, $`l_a(t)=_{active}q(t)`$. This quantifies the load carried by the active nodes at a particular time step.

(e) Density, $`\rho (t)`$, the total number of packets arriving at the hub node at time $`t`$.

(f) Transit time, $`T_{tr}`$, the time taken by a packet to reach its destination.

The characteristics of these quantities change as a function of the geometry of the network, the buffer size $`B`$ and the input rate $`R`$. In order to examine these changes, we calculated their power-spectra. In general, the power spectrum of a time series $`X(t)`$ is defined by

$$S_X(f)=|\underset{t=1}{\overset{\mathrm{}}{}}X(t)e^{ift}|^2.$$
(2)
For a time series with no temporal correlation, the plot of $`S_X(f)`$ against $`f`$ is independent of $`f`$. If the time series $`X(t)`$ has an auto-correlation function $`r_X(k)k^\varphi `$ then $`S_X(f)f^\varphi `$.

The output rate, or average number of packets leaving the system per time step, is, along with the transit time $`T_{tr}`$, a measure of the efficiency of the system. It is defined by

$$\mu =R\frac{n(t)}{t}.$$
(3)
In general the value of the ratio $`\mu /R`$ allows one to determine  whether the queues in the system are getting longer with time. As it will be shown below, in our model, the queues are growing with time for all values of the parameters.

A comparison of the packet traffic on the scale-free network and the randomly grown network in our simulations is demonstrated by time series for load carried by active nodes and by number of nodes that are active at given time shown in Fig. 1. With identical driving conditions, the random network tends to distribute the activity over many nodes simultaneously, whereas in the scale-free network the activity is localised to the hub, which carries most of the packets, and a few other high degree nodes in the centre of the network.

In Figure 2 we compare the power spectra of the time series for activity, load at active nodes, density at the hub, and number of packets in the network for the two network geometries operating in the identical driving conditions of low input rate $`R=0.01`$ and buffer size $`B=100`$ for network size $`N=1000`$ nodes. For these driving conditions the long-range correlations in the time series are present in certain range of frequencies in both networks. The slopes are generally closer to -1 in the case of SFN ($`1/f`$-noise), whereas in the RGN we measure the slope close to -2, except for the density where it is close to -0.5, and a whiter spectrum (c.f. Fig. 2). These features, however, change with increased input rate and/or decreased buffer size, suggesting that the character of the transport depends on the relative ratio of these parameters.

In particular, when the input rate is increased by a factor of four and the buffer size is unchanged ($`B=100`$, $`R=0.04`$) the power spectrum of the density at the hub in SFN behaves as $`1/f^2`$ (top line in Fig. 3). In the case of RGN the slope becomes approximately -1 and the range of frequencies where the correlation occurs is reduced. Changes in the spectrum of density indicates that the character of packet transport at the hub changed from $`1/f`$ noise in the free-flow regime, to simple diffusive transport.

In Figure 3 we also show the power spectrum of the density measured at a node away from the hub in the free-flow regime for both network geometries. It is interesting to note that, in the SFN, in contrast to the density at hub, the spectrum inside the network for low traffic intensity is a white noise (bottom curve in Fig. 3). In the RGN, however, the correlations similar to the ones at the hub are measured, once again supporting the conclusion that the RGN tends to distribute the activity over the entire graph.

## IV  Packet Transit Times and Queueing Properties

To further investigate how the network performs under dense packet traffic we study transit times for individual packets. Within our algorithm we mark the first $`10^3`$ packets with an additional time label and monitor the time that they spend on the network from posting until arrival at their respective destinations. Packets are still posted probabilistically with rate $`R`$. In the inset to Fig. 4 an example of the time series of transit times against posting time of the packets is shown. It is noticeable that the duration of the journey for each packet is different, both because the difference in distances that they make on the graph and because of the time that they spend waiting in queues at particular nodes. The distribution of transit times is given in main part of Fig. 4 both for SFN and RGN for low packet density ($`R=0.01`$, $`B=100`$).

For the range of values of the transit times $`T_{tr}`$ we find power-law distributions, but with different slopes, indicating the difference in the efficiency of the two network structures. Namely, $`\tau _T=1.25\pm 0.02`$, for SFN, and $`\tau _T=0.53\pm 0.02`$, for RGN. In addition, the transit times larger than approximately $`10^3`$ time steps for SFN, and $`10^4`$ in the case of RGN, contribute to tail of the distribution. Among these are packets that become buried deep in queues at certain nodes in the network. Thus, it is the dynamics of queueing, in addition to the network’s structure, that determines the network’s transport efficiency. Next we study some properties of queues in both networks.

In Figure 5 we show the probability distributions of the queue lengths (loads) measured at individual nodes throughout the network after each time step is completed. Apart from the cut-off which is determined by the maximum buffer size (here $`10^3`$), there is a larger probability to find a queue of given length $`q`$ in the RGN compared to the SFN, in agreement with generally lower efficiency of the randomly grown network. The relative appearance of large queue lengths in the RGN decays with the power-law exponent $`\tau _q=1.4\pm 0.02`$, and with $`\tau _q=0.48\pm 0.02`$ in the SFN. In both cases there is a part of the network in which nodes carry a small load, with a similar power-law decay.

Compared to standard single-queue theories , here we have many interacting queues in which packets hop from one queue to the other along the edges of the graph, as they are directed by the search algorithm. Thus the input rate of packets at each node is different and related to the local connectivity of that node and number of paths that the actual search algorithm selects to pass through that node at a single time step. (As already mentioned in the introduction, we keep the output rate of one packet per time step equal at each node, in order to single out the effects of networks structure more clearly.) Therefore, in the SFN, the kinetics of the queues at the nodes with high connectivity are of primary importance, whereas queues at the majority of other nodes in the network rarely exceed a few packets. This is due to the topology of SFN, in which cluster of nodes linked to the hub increases faster than any other subgraph, and also due to the search algorithm we are using, which is suitable for that topology. In the RGN the same search algorithm is much less effective, because the dominant cluster grows only logarithmically in time making the edges more evenly distributed throughout the network.

Thus, the input rate at the hub varies in time and it is precisely given by the density $`\rho (t)`$ that we determined in Section III. In the SFN $`\rho (t)`$ was found to exhibit long-range correlations of $`1/f`$ type for low intensity of traffic (cf. Fig. 2), that changes to a short-range $`1/f^2`$ correlations when traffic intensity increases. In the RGN within the same conditions, for comparison, the spectrum is much closer to white noise. Next we investigate how the queueing dynamics at the hub affects performance of the network.

We determine the network’s output rate $`\mu `$, defined as the number of packets arriving to their destination per time step. Therefore, the difference of the input and output rate $`R\mu =n(t)/t`$ determines the workload  on the level of the entire network. In main part of Fig. 6 we show the workload in SFN for two input rates $`R`$ and fixed buffer size $`B=100`$. For large input rate (top curve) $`R\mu `$ saturates for large times $`t`$ at a finite average value, indicating that total load in the network $`n(t)=(R\mu )t`$ increases linearly in time. In this case the jamming that first occurs at the hub seems to spread gradually throughout network. For comparison, in the case of low input rate (bottom curve) the workload $`R\mu `$, after a sharp initial increase, decays approximately as $`t^{1/2}`$, indicating that total load $`n(t)`$ increases sub-linearly in this flow regime. Taking the average asymptotic value of $`\mu `$, in the inset to Fig. 6 we show the ratio of the network’s output and input rates $`\mu /R`$ for the SFN and the RGN, which, once again shows the systematically better performance of the scale-free structure for a range of input rates.

## V Conclusions and Discussion

In this paper we have introduced a new model of packet transport on networks and investigated its major properties on both randomly grown and scale free networks. The model incorporates in a natural way three basic elements—network topology, search algorithm, and queueing dynamics—which determine overall efficiency of the transport. By fixing the input rate and using the near and next near neighbour search algorithm, which is fairly efficient on structured graphs, in this work we focused on the effects of networks’ topology on the queueing dynamics. For this purpose we also keep link capacities at a minimal one packet per time step.

We found long-range temporal correlations for many of the important quantities within the system, in particular for the density of arriving packet streams, with non-universal exponents that were dependent on the traffic intensity and the network on which the transport was taking place. The power-law dependences of the transit time distribution with the exponent $`\tau _T<2`$ implies that the average time that a packet spends on the network increases with network size, causing queueing processes on the network. We find the power-law behavior of the queue length distribution reflects the networks’ structural efficiency in the transport. The character of the queueing dynamics in our model is dominated by queues at highly connected nodes, which are driven by fractal packet streams from neighbouring nodes. Measured by the single-queue criteria, the queues in our model are predetermined to increase with time. However, measured on the level of entire network, we find that the networks’ workload may increase sub-linearly for low traffic intensity, and linearly when traffic approaches the congested regime. At the same time the observed long-range correlations and power-law dependences of the distributions are different in two traffic regimes, a transition seems to take place along a line $`R_c(B)`$. A detailed analysis of this transition was not included in this work.

Finally we found that the scale free network was much more efficient, in terms of network output to input ratio, than the randomly grown network. Allied to this was the observation that transport on the scale free network was very dependent on the queuing at a few highly connected nodes, and many of the low-connectivity nodes had very low activity. In contrast, the randomly grown network distributed the activity much more evenly over the graph.

This work is an initial study, in future we intend to investigate a system of this type with (i) different search algorithms and (ii) different queuing disciplines, with a view to investigating their effect on packet transport.

## VI Acknowledgements

We would like to thank NATO for partial financial support through PEST grant PST.CLG.978404. Work of B.T. was supported by the Ministry of Education, Science and Sports of the Republic of Slovenia.


text:
# Solitons in Poly(oxyethylene)

## Abstract

We introduce a soliton model to describe conformational structure of poly(oxyethylene) in aqueous solution. The model is based on former investigations for twistons in polyethylene, and the soliton solution corresponds to stable excitation that locally transforms the gauche conformation of the O-CH2-CH2-O dihedral angle from the positive (negative) configuration to its negative (positive) partner. The conformational deformation in the polymer main chain is mediated by the unstable cis conformation which changes the physical profile of the chain, contributing to trigger important properties of the polymer. For instance, it may activate the process for the capture of metallic ions in aqueous solution and it may also enlarge solubility of the polymer in water. The soliton solution is used to guide a quantum chemistry investigation that examine, and characterize, a chain containing 40 monomeric units, tracing quantitative correlations with the soliton model.

Solitons appear under the direct influence of nonlinearity, and may play important role in several branches of nonlinear science. In particular, they may spring as finite energy excitations in nonlinear polymeric chains. A classic example is polyacethylene (PA): in this chain, single and double bonds alternate, generating Peierls instability that gives rise to solitons, as accounted for in the Su-Schrieffer-Heeger model ssh79 ; see Ref. hks88  for further details. As one knows, the PA chain admits an interesting field theoretical formulation in terms of bosonic and fermionic fields jsc81 ; jac95 . Another example of a nonlinear polymeric chain that supports solitonic excitations is polyethylene (PE): in this case the chain only contains single sigma bonds, which activate degrees of freedom of the torsional type, giving rise to twiston excitations in the polymeric chain mbo78 . The presence of twistons in the PE chain was further explored in Refs. 80 ; zco93 , and more recently in Ref. we  one has shown that these twistons can be seen as topological solitons that appear in a specific model of two real scalar fields.

The work of Ref. we  follows the investigations on topological solitons iniciated in 95 , and further explored more recently in bnr ; bbr00 ; ilg . The main idea is that the presence of topological solitons in a polymeric chain may directly contribute to the conformational characteristics of the polymer, a fact important to the understanding of physical, chemical and biological properties of the substance. A singular example is the poly(oxyethylene) (POE), which has long been the subject of great attention due to its various biotechnical and biomedical applications har92 . In this letter we develop the idea that the POE chain is able to support topological solitons, and that these solitons contribute significantly to the undertanding of important features of this polymer.

We start with the PE chain, which is a very long chain made of CH2 units. It may be seen as the limit for large $`n`$ of the chain family \[(CH2)n-O-\]m. In this family the second member ($`n=2`$) is the POE, which is formed by repetitions of the chain unit CH2-CH2-O-. The POE is a very important polymer in this family, because the peculiar array in the chain provides to this polymer some very impressive features, among them the remarkable ability to entrap metallic ions in aqueous solution and its solubility in water to almost any extent. Besides, one knows that ethylene oxide polymers are amongst the most commonly used substances in pharmaceutical and other industrial formulations har92 ; jpc93 ; jacs1995 ; jpca97 ; tas96 ; tas99 ; peg01 ; mat02 .

Molecular dynamics simulations smi96 ; tas96 ; prl2000  on the conformational structure of the POE and 1,2-dimethoxyethane (DME = CH3-O-CH2-CH2-O-CH3, which is correlated with the POE’s dimer) have shown that the polymeric chain may present a very rich family of conformational possibilities, with preference for $`tgt`$ conformers in condensed media – we are using standard notation, where ‘$`t`$’, ‘$`c`$’ and ‘$`g`$’ represent trans ($`\pi `$), cis ($`0`$) and gauche ($`\pi /3`$) arrangements, respectively. The $`tgt`$ conformer was also observed in POE chains used as hidrophilic moiety of nonionic surfactants, in aqueous solutions, through Raman spectroscopy poe-raman . The stabilization of the $`tgt`$ conformer in the liquid or solid state may be understood in terms of polar intermolecular interactions, because this conformer has an appreciable dipole moment while the $`ttt`$ conformer (all trans conformations) has zero dipole moment jacs1995 . This preference for $`tgt`$ conformation is also predicted for DME by experimental NMR dme-nmr  and infrared dme-ir  spectroscopic studies. The water affinity of POE is directly related to a structural similarity between the POE chain and liquid water, which is not found for other polyethers kf81 ; ngm01 : when substantially hydrated, the POE chain assumes local conformations mostly with the $`tgt`$ arrangement; in this case there is almost perfect match between the distance of the oxygen atoms in the structure of liquid water and the distance between the nearest neighbor oxygen atoms in the polymer chain. Thus, the POE chain may be easily incorporated into the structure of liquid water, with the ether oxygen atoms replacing some of the water molecules, with the hydrophobic ethylene groups being encaged in voids in between water molecules. There are other conformational possibilities in the POE chain; for instance, the $`tgg`$ conformer is considered the second most populated in DME, also based on spectroscopic results both for DME and POE, probably because of the presence of an important intramolecular 1,5-CH$`\mathrm{}`$O interaction that stabilizes this particular conformation. The nomenclature $`ttt`$, $`tgt`$, and so forth, that we are using is valid to represent the three most important dihedral angles in the polymer main chain, namely O-CH2-CH2-O, CH2-CH2-O-CH2, and CH2-O-CH2-CH2, as we illustrate in Fig. 1.

We can visualize topological solitons in the POE chain thinking of the $`tgt`$ conformation, the most stable conformational configuration in the POE chain in liquid water. The symmetry of the chain admits two equivalent possibilities, where the helix can be clockwise, generated by a sequence of $`tg^+t`$ arrangements, or counterclockwise, generated by a sequence of $`tg^{}t`$ orientations. These two gauche conformations (helixes) are degenerate in energy, and they are typically very populated, according to the previous discussion dme-nmr ; dme-ir . They appear to be the most stable of all the conformational possibilities the POE chain may comprise. Thus, although the POE chain may adopt other distinct conformations, our model considers only the two most important set of degrees of freedom, represented by the O-CH2-CH2-O and CH2-CH2-O-CH2 dihedral angles, and the most stable conformation, the gauche and trans arrangements, respectively. For both angles, the cis conformation is unstable, and is seen as a barrier for gauche and trans orientations to tunnel to its symmetric partner. We illustrate this in Fig. 2 for the gauche conformation of the O-CH2-CH2-O dihedral angle.

This reasoning allows introducing a model of two real scalar fields to describe the nonlinear chain. Under this assumption we could establish, a priori, the two most relevant sets of degrees of freedom to describe the transition $`tg^+ttg^{}t`$ that springs as the topological soliton.

The connection between these detailed information at molecular level with the mathematical representation of the polymer is implemented by the field theoretical model that we now develop. The model is described by two real scalar fields, $`\varphi `$ and $`\chi `$, which live in the bidimensional space-time $`(x,t)`$. The Lagrangian density has the form

$$=\frac{1}{2}_\alpha \varphi ^\alpha \varphi +\frac{1}{2}_\alpha \chi ^\alpha \chi V(\varphi ,\chi )$$
(1)
where

$$V(\varphi ,\chi )=\frac{1}{2}W_\varphi ^2\frac{1}{2}W_\chi ^2$$
(2)
Here $`_\alpha \varphi =\varphi /x^\alpha `$, $`W_\varphi =W/\varphi `$, etc. We are using standard notation, with $`x^\alpha =(x^0=t,x^1=x)`$, and $`x_\alpha =(x_0=t,x_1=x)`$, and $`\mathrm{}=c=1`$. The form of the potential is special, because it allows obtaining static solutions of the equations of motion

$`{\displaystyle \frac{d^2\varphi }{dx^2}}`$ $`=`$ $`W_\varphi W_{\varphi \varphi }+W_\chi W_{\chi \varphi }`$ (3)
$`{\displaystyle \frac{d^2\chi }{dx^2}}`$ $`=`$ $`W_\varphi W_{\varphi \chi }+W_\chi W_{\chi \chi }`$ (4)
through the first order differential equations

$`{\displaystyle \frac{d\varphi }{dx}}`$ $`=`$ $`W_\varphi `$ (5)
$`{\displaystyle \frac{d\chi }{dx}}`$ $`=`$ $`W_\chi `$ (6)
Solutions of the first order equations are stable and are minimum energy solutions – see bbr00  and references therein for more details.

The model we consider is defined by the superpotential $`W=W(\varphi ,\chi )`$, which has the specific form

$$W=\lambda a^2\varphi +\nu a^2\chi \frac{1}{3}\lambda \varphi ^3\mu \varphi \chi ^2$$
(7)
We consider $`\lambda ,\mu ,\nu `$ real, and $`a`$ real and positive. This model is new, and reproduces the model first considered in Ref. 95  in the limit $`\nu 0`$. We calculate $`W_{\varphi \varphi }`$ and $`W_{\chi \chi }`$ to see that

$$W_{\varphi \varphi }=2\lambda \varphi ,W_{\chi \chi }=2\mu \varphi $$
(8)
We notice that the superpotential is harmonic for $`\mu +\lambda =0`$, thus the equations of motion can be reduced to a family of first order equations for $`\lambda +\mu =0`$ bms01 .

The potential presents absolute minima at the points $`(\overline{\varphi }_i,\overline{\chi }_i)`$, where $`\overline{\chi }_i/a=\nu a/2\mu \overline{\varphi }_i`$ are given in terms of $`\overline{\varphi }_i`$, which represent the real solutions of

$$\left(\frac{\overline{\varphi }}{a}\right)^2=\frac{1}{2}\pm \frac{1}{2}\sqrt{1\frac{\nu ^2}{\mu \lambda }}$$
(9)
There are two solutions for $`\nu ^2/\lambda \mu <0`$, four solutions for $`0<\nu ^2/\mu \lambda <1`$, two solutions for $`\nu ^2/\lambda \mu =1`$, and no solution for $`\nu ^2/\mu \lambda >1`$. We consider the case $`0<\nu ^2/\mu \lambda <1`$. We write $`\mu =\lambda r`$, and $`\nu =\lambda s`$, to get to $`0<s^2/r<1`$. This implies that $`r>0`$, and we take $`\sqrt{r}<s<\sqrt{r}`$.

The equations of motion for static fields are solved by solutions to the first order differential equations, after changing $`\varphi a\varphi `$, $`\chi a\chi `$, and $`x\lambda ax`$

$`{\displaystyle \frac{d\varphi }{dx}}`$ $`=`$ $`1\varphi ^2r\chi ^2`$ (10)
$`{\displaystyle \frac{d\chi }{dx}}`$ $`=`$ $`s2r\varphi \chi `$ (11)
We notice that this system does not allow one-field solutions for $`s0`$. This peculiar behavior of the model is important, and is in good agreement with the quantum chemistry investigation that we have implemented, as we comment on below. We can find true two-field solutions to the above first order equations. They are described by the field configurations

$`\varphi _s(x)`$ $`=`$ $`a\sqrt{{\displaystyle \frac{1}{2r}}}\mathrm{tanh}(\lambda a\sqrt{2r}x)`$ (12)
$`\chi _s(x)`$ $`=`$ $`\pm a\sqrt{{\displaystyle \frac{1}{r}}{\displaystyle \frac{1}{2r^2}}}\mathrm{tanh}(\lambda a\sqrt{2r}x)`$ (13)
which are valid for $`s=\pm \sqrt{21/r}`$, with $`r>1/2`$. We notice that the limit $`r1/2`$ transforms the above solution back to the one-field solution of the simpler model, where $`s=0`$. We see that the amplitude of $`\varphi `$ is $`A_\varphi =a/\sqrt{2r}`$, and that of $`\chi `$ reads $`A_\chi =|s|A_\varphi `$. Thus, for $`1/2<r<1`$, we get $`0<s^2<1`$, and the amplitude of $`\chi `$ is always smaller then that of $`\varphi `$. For $`r>1`$ we get $`s^2>1`$, and in this case the amplitude of $`\chi `$ is greater then that of $`\varphi `$. A complete investigation of the two-field model will be published elsewhere.

In the POE polymer, the topological soliton represents a conformational distortion in the $`tgt`$ chain: it describes the change from the $`tg^+t`$ conformation to the $`tg^{}t`$ conformation. This modification is done with the chain passing through the unstable cis conformations, in a way such that the topological distortions locally increase the dipole moment in the chain, which are evenly distributed along the entire chain in both the $`tg^+t`$ and $`tg^{}t`$ conformations. The presence of a topological soliton breaks the dipole moment uniformity in the chain, increasing the polar nature of the chain in the soliton core, and this is the mechanism that triggers the process for capturing metallic ions in aqueous solution, or that favors the presence of hidrogen bonds in water solutions.

To make our investigations more quantitative we now examine the connections between the detailed informations obtained in the model described by two real scalar fields and the POE chain at molecular level. This can be obtained through quantum chemistry calculations, with the mathematical representation of the polymer as given by the field theoretical model. We investigate the chain H(-CH2-CH2-O-)40H, a POE chain with 40 monomeric units. We suppose that the topological soliton represents the transition state between the positive and negative helix conformations for the polymer main chain. The transition state between the two most stable conformations of the POE is represented by a polymer that mixes the gauche and the energetically unfavorable cis conformations at the same molecule, in a way such that it makes possible the application of quantum chemistry machinery to do the investigation, since the soliton excitation is a continuum phenomenon that needs an extended molecular representation. In Fig. 3 one depicts the polymer molecules considered as reagent, named positive helix (lower figure), and as transition state, named soliton (upper figure). We established that the dihedral angle C-O-C-C was maintained at configuration trans ($`\pi `$) throughout the entire polymer molecule, and that the other two dihedral angles in the main chain – namely O-CH2-CH2-O and CH2-CH2-O-CH2 – are choosen according to the field theoretical model, in which we are identifying the $`\varphi `$ and $`\chi `$ fields with the two dihedral angles CH2-CH2-O-CH2 and O-CH2-CH2-O, respectively. \[In fact, we have done several other investigations: for instance, if the CH2-CH2-O-CH2 angle is also frozen, the results are very unusual, showing that the polymer main chain visit very energetic configurations, returning along the same chain axis, but reversing its direction; also, if all the three dihedral angles are free, the polymer main chain bends considerably, breaking the unidirecional character of the polymer\].

We use results of the two field model to see that the modification of the two dihedral angles that are correlated with important degrees of freedom of the main chain follow the hyperbolic tangent behavior. We identify the two dihedral configurations O-CH2-CH2-O and CH2-CH2-O-CH2 with the $`\chi `$ and $`\varphi `$ fields, respectively, and so we use the quantitative pattern of the soliton solution (12) and (13) to set the values for dihedral angles through the 40 monomeric unities of the POE molecule. The positive helicity is achieved by setting the O-CH2-CH2-O and CH2-CH2-O-CH2 angles with the values $`+\pi /3`$ and $`\pi `$, respectively, in the entire polymer molecule – see Fig. 3, lower chain. For the soliton, however, we consider the first $`8`$ monomeric units in both extremities of the polymer as positive and negative helicities, respectively, while for the 24 central units the values of the O-CH2-CH2-O and CH2-CH2-O-CH2 dihedral angles vary according to the hyperbolic tangent profile. The O-CH2-CH2-O angle was modified from $`+\pi /3`$ to $`\pi /3`$, while the CH2-CH2-O-CH2 angles was modified from $`\pi `$ to $`+\pi `$, through the curvature of each one of the two hyperbolic tangent solutions that describe the soliton. This identification restrains the parameters $`r`$, $`s`$, and $`a`$ that appear in the field theoretical model to the values $`r=9/17`$, $`s=1/3`$, and $`a=\pi \sqrt{18/17}`$ and the soliton solution can be rewritten as

$`\varphi (x)`$ $`=`$ $`\pi \mathrm{tanh}\left(\sqrt{18/17}x\right)`$ (14)
$`\chi (x)`$ $`=`$ $`(\pi /3)\mathrm{tanh}\left(\sqrt{18/17}x\right)`$ (15)
where we have changed $`\lambda axx`$, to use dimensionless coordinate.

The molecules shown in Fig. 3 represent the final results obtained with semi-empirical molecular orbital calculations that were made by using AM1 AM1  method implemented in the MOPAC 93 version 6.0 package mopac1 . During the geometry optimization procedures used in order to find the stationary point at the potential energy surface (PES) in each case (positive helicity and soliton), all the dihedral angles were maintained frozen, while the normal angles and bond lengths were allowed to relax. In Fig. 3 we notice that the upper chain (which contains the soliton) slightly deviates from its unidirensional character, but the linear configuration is still in good approximation with the field model. The main results for the electronic properties are given in the Table below, which shows the heat of formation and dipole moment ($`\mu `$) for both the soliton (upper line) and the helix (lower line) molecules.

| Heat of Fomation (kJ) | $`\mu `$ (Debye) |
| --- | --- |
| -7621.47 | 11.53 |
| -7719.56 | 1.42 |

The results reveal that the soliton is 98.09 kJ more energetic than the normal gauche conformation, in agreement with the fact that the soliton induces a localized transition between positive and negative helicities of the gauche conformation. This energy difference is explained by the instability of the cis or near-cis conformations in both O-CH2-CH2-O and CH2-CH2-O-CH2 dihedral angles, found in the soliton core. We believe that it can be minimized in condensed media, particularly in polar solvents like water, for example, because of the greater polarity of the soliton molecule ($`\mu =11.53`$ D) in comparison to the positive or negative helicity ($`\mu =1.42`$ D).

The soliton model that we have used seems to be limited, since it does not account for intermolecular interactions between neigbour POE chains. However, this is a good approximation in aqueous solutions, even at high concentrations, since interactions between POE chains via hydrogen bonds are scarce prl2000 . In fact, there are more interactions between oxyethylene units in the same chain prl2000 , mediated by hydrogen bonds via neighbour water molecules, but this we have empirically taken into account by considering the positive and negative helix conformations for the POE main chain as the most populated conformations in aqueous solutions.

We thank A.R. Gomes, R. Longo, and E. Ventura for stimulating discussions, and CAPES, CNPq, PROCAD and PRONEX for partial support.


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# Systematic trends in the electronic structure parameters of 4𝑑 transition metal oxides Sr𝑀O3 (𝑀 = Zr, Mo, Ru, and Rh)

## I Introduction

There have been lots of investigations on 3$`d`$ transition metal oxides (TMO), including cuprates and manganites, because they show a variety of interesting electric and magnetic properties. These behaviors are closely related to the strong electron-electron (el-el) correlation, which originates from the localized 3$`d`$-orbitals. On the other hand, 4$`d`$ TMO have attracted relatively less attention because it was thought that the el-el correlation effects should be small and insignificant due to their more extended $`d`$-orbitals. However, numerous intriguing properties, such as superconductivity, non-Fermi liquid behavior, pseudogap formation, and metal-insulator transitions, have been observed recently in the 4$`d`$ TMO, especially ruthenates and molybdates. These observations have stimulated new attention to the 4$`d`$ TMO.

Because 4$`d`$ TMO are characterized by more extended orbitals than 3$`d`$ TMO, it has been generally believed that electrons in the extended 4$`d`$-orbitals feel rather weak on-site Coulomb repulsion energy $`U`$ and exchange energy $`J`$, and the 4$`d`$-orbitals hybridize more strongly with neighboring orbitals, e.g., O 2$`p`$-orbitals, than 3$`d`$-orbitals. Additional interactions, such as spin-orbit coupling, also become significant. However, these qualitative ideas are not sufficient to understand the intriguing physical phenomena observed in some 4$`d`$ TMO. In 3$`d`$ TMO, systematic investigations on $`U`$ and charge transfer energy $`\mathrm{\Delta }_{pd}`$ provide a basis to elucidate origins of numerous intriguing properties. Unfortunately, there have been few quantitative studies about the electronic structures of 4$`d`$ TMO, except ruthenates, which makes it difficult to understand their physical properties in more depth. Quantitative information on physical parameters related to the electronic structures of TMO will serve as a starting viewpoint in investigating various 4$`d`$ TMO with a potential to discover other new intriguing phenomena. And, they will also allow us to make comparisons with the 3$`d`$ TMO cases, which can provide us a better understanding of physics of both TMO.

Optical spectroscopy is known to be a powerful tool to analyze the electronic structures of TMO by probing the joint density of states between unoccupied and occupied states. In this paper, we report a systematic investigation on the electronic structures of the perovskite-type 4$`d`$ Sr$`M`$O3 ($`M`$ = Zr, Mo, Ru, and Rh) by measuring their optical conductivity spectra $`\sigma (\omega )`$. From these series with the same structure and valency state $`M^{4+}`$, one can investigate how the electronic structures change with $`M`$. As far as we know, our study is the first systematic effort to investigate wide range optical properties of the 4$`d`$ Sr$`M`$O3 series. Based on proper electronic structure diagrams, the interband transitions observed in their $`\sigma (\omega )`$ are assigned properly. From this, we estimate important physical parameters, such as $`\mathrm{\Delta }_{pd}`$, $`U`$, and crystal field splitting energy 10$`Dq`$, which show systematic trends with $`M`$. Compared with the 3$`d`$ cases, the magnitudes of $`\mathrm{\Delta }_{pd}`$ and 10$`Dq`$ are larger and those of $`U`$ are smaller in the 4$`d`$ Sr$`M`$O3 compounds. These behaviors can be understood as the more extended character of the 4$`d`$-orbitals than the 3$`d`$-ones. From our observations, it is found that these 4$`d`$ oxides belong to the Mott-Hubbard regime.

## II Experimental techniques

Polycrystalline SrZrO3, SrMoO3, and SrRhO3 were prepared using the solid state reaction technique. For the SrZrO3 sample, SrCO3 and ZrO2 were used as raw materials. After calcining and grinding repeatedly, the resultant powders were pressed into a pellet under 200 MPa using cold isostatic pressing. The SrZrO3 pellet was sintered at 1700 $`^\text{o}`$C for 5 hours. For the SrMoO3 sample, the fine and pure SrO2, MoO3, and Mo powders were mixed with a composition of SrMoO3. The mixture of approximately 0.2 g was placed into a gold capsule and then compressed at 6 GPa in a high-pressure apparatus. The sample was heated at 1300 $`^\text{o}`$C for 1 hour and quenched to room temperature at the elevated pressure. For the SrRhO3 sample, a preparation procedure similar to that of the SrMoO3 sample was used. The details of this procedure were published elsewhere. The high pressure of sintering technique is effective to provide metastable Mo4+ and Rh4+ states. From x-ray diffraction measurements, it was confirmed that all the samples have a single phase. From dc resistivity and magnetization measurements, it was also found that their electric and magnetic properties are consistent with the previous reports.

Just before optical measurements, we polished the sample surfaces up to 0.3 $`\mu `$m. Then, we measured reflectivity spectra from 5 meV to 30 eV at room temperature. In the energy region between 5 meV and 0.6 eV, we used a conventional Fourier transform spectrophotometer. Between 0.5 eV and 6.0 eV, we used a grating spectrophotometer. And, in the deep ultraviolet region above 6.0 eV, we used synchrotron radiation from the normal incidence monochromator beam line at Pohang Accelerator Laboratory. After the optical measurements, thin gold films were evaporated onto the samples and used for making corrections for light scattering loss from the rough sample surfaces.

In order to obtain $`\sigma (\omega )`$ from the measured reflectivity spectra, we performed the Kramers-Kronig (KK) analysis. It was known that the KK analysis for the highly anisotropic polycrystalline samples could provide incorrect $`\sigma (\omega )`$. However, all of our 4$`d`$ TMO have the slightly distorted perovskite structure and their optical constants should be nearly isotropic, so the KK analysis could be applied without any problem. For the analysis, the reflectivity below 5 meV was extrapolated with the Hagen-Rubens relation for the metallic samples and with a constant value for the insulating SrZrO3 sample. For a high frequency region, the reflectivity value at 30 eV was used for reflectivities up to 40 eV, above which $`\omega ^4`$ dependence was assumed. To check the validity of our KK analysis, we independently determined $`\sigma (\omega )`$ using spectroscopic ellipsometry techniques in the photon energy range of 1.5 - 5.5 eV. The $`\sigma (\omega )`$ data from the spectroscopic ellipsometry agreed quite well with the results from the KK analysis.

## III Results and Discussions

### A Schematic diagrams of the electronic structures

Figure 1 shows schematic diagrams of the electronic structures of the perovskite-type Sr$`M`$O3 compounds, where the 4$`d`$ transition metal $`M`$ is either Zr, Mo, Ru, or Rh. Figure 1(a) shows a typical diagram of electronic structure for a $`d^0`$-insulator. SrZrO3 is known to be a 4$`d^0`$-insulator with a bandgap between the O 2$`p`$\- and the Zr 4$`d`$ $`t_{2g}`$-band. The $`e_g`$-band has a higher energy level by 10$`Dq`$ than the $`t_{2g}`$-band. Usually, the Sr 4$`d`$-band is in a higher energy level than $`M`$ 4$`d`$-bands.  As the atomic number of $`M`$ increases from Zr, extra 4$`d`$ electrons start to fill the $`t_{2g}`$-band partially without any significant change in the overall feature of the band structure. Here, the details of the partially-filled $`t_{2g}`$ orbitals can vary according to the el-el correlation. When the el-el correlation is quite weak, i.e., 4$`d`$ bandwidth $`W`$ $`U`$, the partially-filled band induces a band metallic state, as shown in Fig. 1(b). Since SrMoO3 is a 4$`d^2`$-system and known to be a Pauli paramagnetic band metal, its electronic structure should resemble Fig. 1(b). On the other hand, when the el-el correlation is quite large, i.e., $`U`$ $`W`$, the partially-filled band is split into two Hubbard bands by $`U`$, which induces a Mott insulator. In the intermediate state between two extreme cases, there can occur correlated metals, whose band diagram is shown in Fig. 1(c). In the low-spin configuration, the quasiparticle band is located at $`E_F`$ in addition to the Hubbard bands, and the $`e_g`$-band remains empty. The electronic structure of SrRuO3, a low-spin 4$`d^4`$-system, was investigated by earlier workers, and known to follow Fig. 1(c). It was recently found that a 4$`d^5`$-system SrRhO3 is a paramagnetic correlated metal with the low-spin configuration. Because the $`W`$ of SrRhO3 is narrower than that of SrRuO3, the Hubbard bands induced by the el-el correlation are more dominant in SrRhO3 than in SrRuO3. So, the band diagram of SrRhO3 can be also explained by Fig. 1(c).

According to the Fermi golden rule, the p-d transitions such as O 2$`p`$ $``$ $`M`$ 4$`d`$ $`t_{2g}`$, $`M`$ 4$`d`$ $`e_g`$, and Sr 4$`d`$, should be distinct in $`\sigma (\omega )`$ of the 4$`d`$ Sr$`M`$O3 systems. From such interband transitions, we can estimate some physical parameters; a charge transfer energy $`\mathrm{\Delta }_{pd}`$ from the O 2$`p`$ $``$ $`M`$ 4$`d`$ $`t_{2g}`$ transition, and $`10Dq`$ from the energy difference between O 2$`p`$ $``$ $`M`$ 4$`d`$ $`t_{2g}`$ and $`M`$ 4$`d`$ $`e_g`$ transitions. On the other hand, the $`U`$ value should be estimated from the d-d transition between two Hubbard bands, which should be much weaker than the p-d transitions.

### B Assignment of interband transitions in the Sr$`M`$O3 compounds

Figure 2 shows $`\sigma (\omega )`$ of SrZrO3 up to 20 eV. It is clearly shown that this insulating $`d^0`$-compound has a large optical gap of $``$ 5.6 eV, consistent with the previous reports. This value is larger by $``$ 2 eV than the bandgap of SrTiO3, i.e., 3.4 eV. Distinct interband transitions are observed around 8 eV and 12 eV. To our knowledge, there has been no band calculation report on this compound, so we assigned these interband transitions by referring to the band structure of SrTiO3, which is a 3$`d^0`$ insulator. The dotted line in Fig. 2 represents $`\sigma (\omega )`$ of SrTiO3. Its overall featurea are very similar to that of SrZrO3, but with $``$ 2.5 eV shift to lower energy. K. van Benthem et al. assigned the peaks around 5 eV and 9 eV of SrTiO3 as O 2$`p`$ $``$ Ti 3$`d`$ $`t_{2g}`$ and O 2$`p`$ Ti 3$`d`$ $`e_g`$ transitions, respectively.  \[They also claimed that the higher frequency peak should come from O 2$`p`$ Ti 3$`d`$ $`e_g`$ and/or Sr 4$`d`$.\] Similarly, we can assign the peaks around 8 eV and 13 eV in SrZrO3 as O 2$`p`$ $``$ Zr 4$`d`$ $`t_{2g}`$ and O 2$`p`$ Zr 4$`d`$ $`e_g`$ transitions, respectively. Note that these assignments are consistent with the energy diagram of a band insulator, shown in Fig. 1(a). By using the positions of the strong peaks, we can approximately estimate that $`\mathrm{\Delta }_{pd}8`$ eV and 10$`Dq`$ $``$ 5 eV in SrZrO3, which are larger than the values for SrTiO3 (i.e., $`\mathrm{\Delta }_{pd}`$ 5 eV and 10$`Dq`$ 4 eV).

Figure 3 shows $`\sigma (\omega )`$ of the Sr$`M`$O3 series, with $`M`$ = Zr, Mo, Ru, and Rh, up to 12 eV. The $`\sigma (\omega )`$ of SrRuO3 is quoted from our previous paper. The insulating SrZrO3 has a relatively large optical gap. For other metallic compounds, $`\sigma (\omega )`$ below 1.0 eV have zero-frequency spectral weights, which decrease with the increasing atomic number of $`M`$. The coherent mode of the band metallic SrMoO3 can be fitted well by the Drude model with a plasma frequency of $``$ 2.8 eV and a scattering rate of $``$ 0.3 eV. For other correlated metallic SrRuO3 and SrRhO3, the low frequency $`\sigma (\omega )`$ decreases more slowly than the 1/$`\omega ^2`$-dependence which is predicted by the Drude model. This behavior, which have often been observed in many correlated metals, indicates that the incoherent character in the mid-infrared region might be rather strong.

The observed peaks of the Sr$`M`$O3 compounds can be assigned according to their electronic structures shown in Fig. 1. It is noted that, according to the Fermi golden rule, the $`p`$-$`d`$ transition should be dominant in $`\sigma (\omega )`$. The assignments for the SrZrO3 peaks were already given. For SrMoO3, the 5.0 eV and 8.5 eV peaks are observed clearly, as shown in Fig. 3(b). These two peaks can be assigned as O 2$`p`$ $``$ Mo 4$`d`$ $`t_{2g}`$ and O 2$`p`$ Mo 4$`d`$ $`e_g`$ transitions. For SrRuO3, the 3.0 eV, 6.0 eV, and 10 eV peaks shown in Fig. 3(c) can be assigned as O 2$`p`$ $``$ Ru 4$`d`$ $`t_{2g}`$, O 2$`p`$ Ru 4$`d`$ $`e_g`$, and O 2$`p`$ $``$ Sr 4$`d`$ transitions, respectively, according to our previous report. Note that the d-d transition between the lower and the upper Hubbard bands is located around 1.7 eV, but too weak to be clearly seen in this compound.

The interband transitions in SrRhO3 can be similarly assigned for the case of SrRuO3. However, the lowest interband transition near 2.5 eV is quite asymmetric with a broad tail in the low energy region, compared with the corresponding one in SrRuO3. From the electronic structure shown in Fig. 1(c), we fitted this peak with two Lorentz oscillators, where a lower energy peak with a relatively small strength can be assigned as the d-d transition between the Hubbard bands. The fitting results are represented by the dotted lines in Fig. 3(d). From this fitting, the 1.6 eV, 2.6 eV, 5.2 eV, and 9.0 eV peaks in SrRhO3 can be assigned as the d-d transition between Hubbard bands, O 2$`p`$ $``$ Rh 4$`d`$ $`t_{2g}`$, O 2$`p`$ Rh 4$`d`$ $`e_g`$, and O 2$`p`$ $``$ Sr 4$`d`$ transitions, respectively. The relatively stronger d-d transition in SrRhO3 indicates that the carriers in this compound should be more correlated than those in SrRuO3.

It is interesting to observe systematic trends in the interband transitions of the Sr$`M`$O3 series. As it goes from SrZrO3 to SrRhO3, all of the p-d transitions shift to lower energies. In the photon energy region up to 12 eV, only the O 2$`p`$ $``$ $`M`$ 4$`d`$ $`t_{2g}`$ transition is observed in SrZrO3, but the O 2$`p`$ $``$ $`M`$ 4$`d`$ $`e_g`$ transition is additionally observed in SrMoO3. And, in SrRuO3 and SrRhO3, the O 2$`p`$ $``$ Sr 4$`d`$ transition as well as the O 2$`p`$ $``$ $`M`$ 4$`d`$ transition are observed. Note that as the atomic number of $`M`$ increases, the O 2$`p`$ $``$ $`M`$ 4$`d`$ transitions shift to the lower energy side. In addition, the peak interval between the O 2$`p`$ $``$ $`M`$ 4$`d`$ $`t_{2g}`$ and the O 2$`p`$ $`M`$ 4$`d`$ $`e_g`$ transitions decreases. These interesting trends in peak positions should be originated from the systematic changes of $`\mathrm{\Delta }_{pd}`$ and $`10Dq`$.

### C Systematic trends in $`\mathrm{\Delta }_{pd}`$ and $`10Dq`$

Figure 4(a) shows a systematic trend in the $`\mathrm{\Delta }_{pd}`$ values, which are estimated from the position of the O 2$`p`$ $``$ $`M`$ 4$`d`$ $`t_{2g}`$ transition. As the atomic number increases, $`\mathrm{\Delta }_{pd}`$ decreases. According to J. B. Torrance et al.’s work with the ionic model, the change of $`\mathrm{\Delta }_{pd}`$ with the atomic number of a transition metal is attributed mainly to the change in electronegativity (or ionization energy) of a transition metal; as the electronegativity of a transition metal becomes larger, the $`\mathrm{\Delta }_{pd}`$ decreases. So, the decrease of $`\mathrm{\Delta }_{pd}`$ in 4$`d`$ Sr$`M`$O3 can be explained by the larger electronegativity of $`M`$ with its atomic number increasing.

Figure 4(b) shows a systematic trend in the 10$`Dq`$ values, which are estimated from the peak position difference between the O 2$`p`$ $``$ $`M`$ 4$`d`$ $`t_{2g}`$ and the O 2$`p`$ $`M`$ 4$`d`$ $`e_g`$ transitions. The 10$`Dq`$ of SrZrO3 is approximately estimated to be $``$ 5 eV, as shown in Fig. 2. The $`10Dq`$ value of SrMoO3, $``$ 3.8 eV, is comparable to that in Mo 4$`d`$-bands of double perovskite Sr2FeMoO6, $``$ 4 eV, from x-ray absorption spectroscopy. SrRhO3 is estimated to have 10$`Dq`$ $``$ 2.6 eV, a little smaller than that of SrRuO3, i.e., 3 eV. It is noted that the $`10Dq`$ decreases with the increasing atomic number of $`M`$. It is generally accepted that, as the overlap (or covalency) between the O 2$`p`$\- and the $`d`$-orbital becomes stronger, $`10Dq`$ becomes larger. So, the decrease of the $`10Dq`$ in the 4$`d`$ Sr$`M`$O3 series can be understood as the shrinking of the $`d`$-orbitals, and the resultant weakening of the covalency between the $`M`$ 4$`d`$\- and the O 2$`p`$-orbitals with the increasing atomic number. For a quantitative analysis, we estimate the covalency strength as the p-d matrix element with the $`\sigma `$-bonding, $`V_{pd\sigma }d_r^{1.5}/d_{MO}^{3.5}`$, suggested by W. A. Harrison. Here, $`d_r`$ and $`d_{MO}`$ are the radial size of the $`d`$-orbital and the distance between the $`M`$ and the O ions, respectively. As shown in the inset of Fig. 4(b), the value of $`d_r^{1.5}/d_{MO}^{3.5}`$ in the 4$`d`$ compounds decreases with increasing atomic number of $`M`$, consistent with the decrease of $`10Dq`$. This suggests that the p-d covalency should play a crucial role in determining the $`10Dq`$ value.

### D Comparison with 3$`d`$ transition metal oxides

We also display the reported results on some 3$`d`$ Sr$`M^{}`$O3 with a 3$`d`$ transition metal $`M^{}`$= Ti, V, Mn, and Co in Fig. 4. Most of the displayed results were determined from $`\sigma (\omega )`$ in the same way as was adopted in this paper. Note that we include only the optical results except for the 10$`Dq`$ value of SrCoO3. In Fig. 4(a), the values of $`\mathrm{\Delta }_{pd}`$ in the 3$`d`$ Sr$`M^{}`$O3 series are displayed as the open circles. Similar to the case of the 4$`d`$ TMO, $`\mathrm{\Delta }_{pd}`$ decreases as the atomic number of $`M^{}`$ increases. \[While there are no optical reports on metallic SrFeO3 and SrCoO3, photoelectron spectroscopy (PES) results claimed that their $`\mathrm{\Delta }_{pd}`$ values be nearly zero.\] However, the magnitudes of $`\mathrm{\Delta }_{pd}`$ in 4$`d`$ Sr$`M`$O3 are relatively larger than those of 3$`d`$ Sr$`M^{}`$O3 with the same electron occupancy in $`d`$-orbitals. As mentioned earlier, the systematic change of $`\mathrm{\Delta }_{pd}`$ is attributed to the change in electronegativity. The larger $`\mathrm{\Delta }_{pd}`$ values in the 4$`d`$ Sr$`M`$O3 series than those in the 3$`d`$ Sr$`M^{}`$O3 series can be also explained by the smaller electronegativity for 4$`d`$ transition metals.

In Fig. 4(b), the reported values of $`10Dq`$ in the 3$`d`$ Sr$`M^{}`$O3 series are plotted as the open circles. The general trend of $`10Dq`$ in the 3$`d`$ series is also similar to that in the 4$`d`$ series. It is interesting to see that the $`10Dq`$ of 4$`d`$ Sr$`M`$O3 is larger than that of 3$`d`$ Sr$`M^{}`$O3. This behavior is consistent with the larger values of $`d_r^{1.5}/d_{MO}^{3.5}`$ in 4$`d`$ Sr$`M`$O3 than those in 3$`d`$ Sr$`M^{}`$O3, shown in the inset. It is evident that the more extended 4$`d`$-orbitals induce stronger p-d covalency, which causes the $`10Dq`$ values of the 4$`d`$ oxides to be larger than those of the 3$`d`$ oxides.

While the high-spin configuration is more prevalent in 3$`d`$ TMO, the low-spin configuration can be more easily found in 4$`d`$ Sr$`M`$O3. This behavior should be closely related to the relatively larger $`10Dq`$ values in the 4$`d`$ Sr$`M`$O3 series. The spin-configuration in TMO is determined according to the relative magnitude of $`10Dq`$ and $`J`$: a high-spin configuration for $`10Dq<J`$, and a low-spin configuration for $`10Dq>J`$. It is known that some 3$`d`$ TMO, such as Mn- and Fe-oxides, have the high-spin configuration. For example, the values of $`10Dq`$ and $`J`$ in Mn-oxides are estimated to be 1.1 $``$ 1.8 eV and $``$ 3 eV, respectively. On the other hand, 4$`d`$ TMO favor the low-spin configuration with the relatively larger $`10Dq`$ and smaller $`J`$ due to the more extended 4$`d`$-orbitals. For Ru-oxides, the values of $`10Dq`$ and $`J`$ are estimated to be 3 eV and 0.5 $``$ 0.6 eV, respectively. Although there is no report about $`J`$ in SrRhO3, the large $`10Dq`$ value of $``$ 2.6 eV strongly suggests that this compound should have the low-spin configuration. Because the Rh 4$`d`$-orbitals become more extended in the Rh3+ state than in the Rh4+ state, an insulating 4$`d^6`$ LaRhO3 material with a Ru3+ state is very likely to be a band-insulator which has fully-occupied $`t_{2g}`$ orbitals in the low-spin configuration.

In the 3$`d`$ TMO, the character of the low energy charge excitations has been investigated intensively. According to Zaanen, Sawatzky, and Allen’s picture, the charge excitation should be the $`d`$-$`d`$ transition between the Hubbard bands, if $`U<\mathrm{\Delta }_{pd}`$. This is classified as the Mott-Hubbard regime. If $`U>\mathrm{\Delta }_{pd}`$, the low energy excitation should be a $`p`$-$`d`$ transition, and this regime is classified as the charge transfer regime. While the early 3$`d`$ TMO are classified to be in the Mott-Hubbard regime ($`U<\mathrm{\Delta }_{pd}`$), the late 3$`d`$ TMO mainly fall in the charge-transfer regime ($`U>\mathrm{\Delta }_{pd}`$), implying some kind of crossover between the two regimes. This behavior is related to the increase of $`U`$ and the decrease of $`\mathrm{\Delta }_{pd}`$ as the atomic number of a transition metal increases.

To find the character of the low energy charge excitation in the 4$`d`$ Sr$`M`$O3 series, we estimated the values of $`U`$ from the position of the d-d transition between the Hubbard bands in $`\sigma (\omega )`$. The values of $`U`$ for SrMoO3 and SrRuO3 are estimated from the previous studies.  Note that the $`U`$ value obtained from $`\sigma (\omega )`$ is usually somewhat smaller than that measured from PES, due to the exciton effects, but its difference between optical spectroscopy and PES is usually less than 1.0 eV.

In Fig. 4(a), the values of $`U`$ for the 4$`d`$ Sr$`M`$O3 series are plotted as solid triangles. It appears that the magnitude of $`U`$ in 4$`d`$ Sr$`M`$O3 is relatively smaller than that in 3$`d`$ Sr$`M^{}`$O3. As shown in Fig. 4(a), the value of $`U`$ $``$ 2 eV in SrVO3 ($`d^2`$) is comparable to those of SrRuO3 and SrRhO3, 1.6 - 1.7 eV. Generally, the $`U`$ value increases as the size of the $`d`$-orbitals decreases. Because the $`d`$-orbital shrinks as the the atomic number increases, the late 3$`d`$ Sr$`M^{}`$O3, such as SrFeO3 ($`d^4`$) and SrCoO3 ($`d^5`$), are expected to have larger $`U`$ than the early 3$`d`$ SrVO3, as has been confirmed by many PES studies.  From this, it is clear that the $`U`$ value of SrRuO3 and SrRhO3 should be smaller than those of SrFeO3 and SrCoO3.  So, we can say safely that 4$`d`$ Sr$`M`$O3 have smaller $`U`$ than 3$`d`$ Sr$`M^{}`$O3, which is quite natural due to the more extended nature of the 4$`d`$-orbitals.

The larger value of $`\mathrm{\Delta }_{pd}`$ than $`U`$ indicates that all of the 4$`d`$ Sr$`M`$O3 compounds investigated in this study should belong to the Mott-Hubbard regime. From our studies on SrRuO3 and SrRhO3, the magnitude of $`\mathrm{\Delta }_{pd}`$, 2.6 - 3.0 eV, is larger than that of $`U`$, 1.6 - 1.7 eV, which indicates that even these compounds belong to the Mott-Hubbard regime. This implies that these 4$`d`$ TMO can be used for investigating the Mott-Hubbard transition with the el-el correlation. Indeed, the importance of the el-el correlation has been observed in ruthenates and molybdates, This was rather surprising, since it was thought that the el-el correlation effects should be insignificant in 4$`d`$ TMO due to the extended nature of the 4$`d`$-orbitals. And, due to the small value of $`U`$, the multiplicity of the 4$`d`$ orbitals might play important roles in physical properties of some 4$`d`$ TMO. It is highly desirable to reinvestigate physical properties of some 4$`d`$ TMO in view of the correlation effects.

## IV Summary

We reported quantitative studies on physical parameters such as charge transfer energy $`\mathrm{\Delta }_{pd}`$, on-site Coulomb repulsion energy $`U`$, and crystal field splitting energy 10$`Dq`$ of the perovskite-type of various 4$`d`$ Sr$`M`$O3 ($`M`$ = Zr, Mo, Ru, and Rh) by optical conductivity analyses. While the systematic changes of these parameters with the transition metal are similar to those for the case of 3$`d`$ transition metal oxides, their magnitudes are different; the $`\mathrm{\Delta }_{pd}`$ and the 10$`Dq`$ values are relatively larger, while the $`U`$ value is relatively smaller. These behaviors are explained by the more extended character in 4$`d`$-orbitals than in 3$`d`$-orbitals, which distinguishes the physical properties of the 4$`d`$ compounds from those of the 3$`d`$ ones. The relatively larger $`10Dq`$ is closely related to the low-spin configuration in 4$`d`$ Sr$`M`$O3. Due to the relatively smaller $`U`$ and larger $`\mathrm{\Delta }_{pd}`$, it is very likely that most 4$`d`$ transition metal oxides lie in the Mott-Hubbard regime. Although their $`U`$ values are relatively small, some intriguing physical phenomena with the correlation effects could occur in 4$`d`$ transition metal oxides.

###### Acknowledgements.

We would like to thank Jaejun Yu, S.-J. Oh, and S. D. Bu at SNU and D. Y. Jung at SKKU for useful discussions. This work was supported by the Ministry of Science and Technology through the Creative Research Initiative program, and by KOSEF through the Center for Strongly Correlated Materials Research. The experiments at PLS were supported by MOST and POSCO.