text:
# Novel Colloidal Crystalline States on Two Dimensional Periodic Substrates

\[

## Abstract

We show using numerical simulations that a rich variety of novel colloidal crystalline states are realized on square and triangular two dimensional periodic substrates which can be experimentally created using crossed laser arrays. When there are more colloids than potential substrate minima, multiple colloids are trapped at each substrate minima and act as a single particle with a rotational degree of freedom, giving rise to a new type of orientational order. We call these states colloidal molecular crystals. A two-step melting can also occur in which individual colloidal molecules initially rotate, destroying the overall orientational order, followed by the onset of inter-well colloidal hopping.

\]

Colloidal particles are an ideal system for studying 2D ordering and melting as the individual particle positions and dynamics can be directly visualized. Colloidal melting has been extensively studied for systems with smooth substrates, where evidence for defect-mediated melting transitions has been found . Another avenue of study has been the examination of colloidal crystallization and melting in the presence of a 1D periodic substrate, which are typically created with laser arrays . These studies have revealed a novel laser-induced freezing, as well as a reentrant laser induced melting as a function of substrate strength . A far less studied case is colloidal crystallization on 2D periodic substrates. Here numerous commensuration effects can be expected when the periodicity of the colloidal lattice matches with the substrate lattice constant. Several recent experimental studies have demonstrated that it is possible to create a 2D substrate for colloids using optical tweezer arrays , templating, and 2D crossed laser arrays . Almost nothing is known, however, about what type of colloidal crystalline states could occur and what types of melting can occur in this system. Although colloids interacting with 1D substrates have been investigated theoretically  and numerically , the case of a 2D substrate has not. The study of colloidal crystals with 2D substrates may also lend insight into other condensed matter systems which can be described as elastic particles on 2D substrates. Examples of such systems include atoms on atomic surfaces  and vortices in superconductors with periodic pinning arrays . It should also be possible to realize entirely new states in the colloidal system, since when there are more colloids than substrate minima, each minima will contain multiple colloids which can have their own internal degrees of freedom. In addition, the control of different types of colloidal crystal geometries can be of technological importance for the construction of certain devices, such as photonic band-gap materials.

In this work we examine colloidal ordering and melting on 2D periodic square and triangular substrates using Langevin simulations. We find that a rich variety of novel colloidal crystalline states can be achieved. We focus on the case of filling fractions at which there are an integer number of colloids per substrate minima. When there are more colloids than potential substrate minima, multiple colloids are trapped at each minima. The colloids within each of these minima can act as a single particle with internal degrees of rotational freedom, forming trimer and dimer states that have an additional long-range orientational order with respect to neighboring minima. These states are similar to molecular crystals; hence, we term them colloidal molecular crystals or CMC’s. These crystalline states also exhibit a novel multi-stage melting where, for low $`T`$, the colloidal molecules possess both orientational and translational order. At higher $`T`$, the orientational order is lost as the colloidal molecules in each minima began to rotate, but individual colloidal diffusion does not occur and the colloids are still confined in each substrate minima. For large enough temperature, individual colloidal diffusion occurs. We map out the phase diagram for temperature vs substrate strength and find that two stage melting only occurs for sufficiently strong substrates, and that the transition temperature from the solid to the disordered solid in the presence of a substrate is lower than the same transition temperature for a sample without a substrate. In addition, for fixed temperature and increasing substrate strength, we observe a transition from the ordered solid phase to a partially ordered solid phase, similar to the reentrant melting seen for colloids interacting with 1D periodic substrates.

We simulate a 2D system of $`N_c`$ colloids with periodic boundary conditions in the $`x`$ and $`y`$ directions, using Langevin dynamics as employed in previous colloidal simulations . The equation of motion for a colloid $`i`$ is:

$$\frac{d𝐫_i}{dt}=𝐟_{ij}+𝐟_s+𝐟_T$$
(1)
Here $`𝐟_{ij}=_{ji}^{N_c}_iV(r_ij)`$ is the interaction force from the other colloids. The colloid-colloid interaction between colloids $`i`$ and $`j`$ is a Yukawa or screened Coulomb potential, $`V(r_{ij})=(Q^2/|𝐫_i𝐫_j|)\mathrm{exp}(\kappa |𝐫_i𝐫_j|)`$, where

$`Q`$ is the charge of the particles, $`1/\kappa `$ is the screening length, and $`𝐫_{i(j)}`$ is the position of particle $`i`$ ($`j`$). The length of the system is measured in units of the lattice constant $`a_0`$ and we take the screening length $`1/\kappa =a_0/2`$. For the force from the 2D substrate, $`𝐟_S`$, we consider both square and triangular substrates with strength $`A`$, period fixed at $`a_0`$, and $`N_m`$ minima. For square substrates, $`𝐟_s=A\mathrm{sin}(2\pi x/a_0)\widehat{𝐱}+A\mathrm{sin}(2\pi y/a_0)\widehat{𝐲}`$, and for triangular substrates, $`𝐟_s=_{i=1}^3A\mathrm{sin}(2\pi p_i/a_0)[\mathrm{cos}(\theta _i)\widehat{𝐱}\mathrm{sin}(\theta _i)\widehat{𝐲}]`$, where $`p_i=x\mathrm{cos}(\theta _i)y\mathrm{sin}(\theta _i)+a_0/2`$, $`\theta _1=\pi /6`$, $`\theta _2=\pi /2`$, and $`\theta _3=5\pi /6`$. The thermal force $`𝐟_T`$ is a randomly fluctuating force from random kicks. We start the system at a temperature where all the colloids are diffusing rapidly and gradually cool to $`T=0.0`$. We define the melting temperature at zero substrate strength as $`T_m^0`$. In this model, we do not take into account hydrodynamic effects or possible long-range attractions between colloids. We have conducted a wide variety of simulations for different system sizes, $`a_0`$ values, and screening lengths $`1/\kappa `$, and find that all qualitative results are robust.

In Fig. 1 we show the colloidal positions for a system with a square substrate. In Fig. 1(a) the colloidal periodicity matches one to one with the substrate periodicity, $`N_c=N_m`$, so that each colloid is located at the center of

the potential minima and a square colloidal crystal forms. In Fig. 1(b), for twice as many colloids $`N_c=2N_m`$, each minima now captures two colloids. Neither colloid is located at the exact minima; instead, they are offset from it due to the colloid-colloid repulsion. The states inside the minima can be regarded as a colloidal dimer with a rotational degree of freedom. Fig. 1(b) also shows that there are two types of ordering occurring: one arising from the square substrate, and the other due to the specific rotational orientation of the colloidal dimers, with neighboring dimers perpendicular to one another. The orientational ordering of the dimers is due to the colloidal repulsion, and allows the distance between the colloids to be maximized under the constraint of the square substrate. If the colloid interaction range is short, such that one dimer pair does not interact with the neighboring pair, the orientational dimer ordering seen in Fig. 1(b) does not occur. In Fig. 1(c), the colloidal configuration for $`N_c=3N_m`$ again shows two types of ordering, with each minima capturing three colloids that form a trimer state. The trimers have a specific orientational order in which trimers in adjacent columns of minima are rotated by 60, due to the repulsion of neighboring trimers. In

Fig. 1(d), $`N_c=4N_m`$ also has an ordered superlattice structure with orientational ordering. The colloidal quadrimer states are all aligned in the same direction. For increasing colloidal densities $`N_c=nN_m`$ one can expect even more orderings with each potential minima capturing $`n`$ colloids. Since the colloids in each minima act as a single object with an internal degree of freedom, similar to a molecular dimer or trimer, and since these states are confined in a lattice, we call these states colloidal molecular crystals (CMC’s).

In Fig. 2 we illustrate the CMC’s on a triangular substrate. For one colloid per minima, $`N_c=N_m`$, shown in Fig. 2(a), the colloids form a commensurate triangular lattice with each colloid located at the center of the potential minima. For $`N_c=2N_m`$, a dimer state occurs in each minima as seen in Fig. 2(b). As in the square pinning case, an additional orientational ordering of the dimers occurs. The dimers in each row have the same orientation, which is rotated 45 with respect to the adjacent rows. For $`N_c=3N_m`$, illustrated in Fig. 2(c), a timer state forms and an orientational ordering occurs in which, unlike the square case \[Fig. 1(c)\], all the trimers have the same orientation. In Fig. 2(d) a superlattice state also occurs with the colloid molecules forming a diamond substructure with a triangular superstructure.

We find that it is also possible to create partially ordered and disordered states at fractional filling fractions, such as 1.5 colloids per minima, $`N_c=1.5N_m`$. In this case, for the square substrates every other minima forms a colloidal dimer state; however, the dimers do not have long range orientational order. Similarly, for the triangular substrates it is not possible to arrange a state such that minima with only one colloid will be between every other dimer, so again dimer ordering is not observed at fractional filling.

In Fig. 3 we show a representative example of the two stage melting of the CMC, in the dimer state for the square substrate \[Fig. 1(b)\]. As illustrated in Fig. 3(a) at low temperatures $`T/T_m^0<0.25`$ (where $`T_m^0`$ is the melting temperature at zero substrate strength), both orientational and translational order are present and the system is frozen. We label this phase the ordered solid. In Fig. 3(b), at $`T/T_m^0=1.5`$, the dimers begin to rotate within the minima; however, diffusion of individual colloids throughout the sample does not occur so the system is still frozen with the dimer orientational order lost. We label this phase the partially ordered solid. For a higher temperature $`T/T_m^0=4.0`$ \[Fig. 3(c)\], the system enters a modulated liquid phase. Here the colloids began to diffuse throughout the system. We have observed this same type of multi-stage melting for the other CMC’s in Figs. 1 and 2.

In Fig. 4 we show the phase diagram of the temperature $`T/T_m^0`$ vs substrate strength $`A`$ for the case of a square substrate and $`N_c=2N_m`$. The melting line is determined from the onset of diffusion, and the solid to disordered solid transition line is determined from the correlation between the dimers as well as the onset of dimer rotation, measured using the average particle displacements. For zero substrate $`A=0`$, the colloids form a triangular lattice and the clean melting temperature $`T_m^0`$ is determined from the onset of particle diffusion. For increasing $`A`$ the melting temperature monotonically increases. The ordered solid melts directly to the liquid for $`A<2.0`$. For $`A>2.0`$ an intermediate rotational melting transition between the ordered solid and partially ordered solid occurs. The rotational melting temperature is always less than the clean melting line, since both these melting temperatures are determined by the elastic properties of the colloids, which is maximum for a triangular lattice in the zero substrate limit. The ordered solid is not triangular and hence should have less elasticity. In addition, the phase diagram shows that for increasing $`A`$ the transition line from the ordered solid to partially ordered solid decreases in temperature. This occurs since, as $`A`$ is increased, the dimer length decreases, the dimers become effectively further apart, and the dimer-dimer interaction strength goes down. This result also implies that at fixed

temperature it is possible to observe a transition from the ordered to partially ordered solid by increasing the strength of the substrate. This is similar to the reentrant melting observed for increasing substrate strength for colloids in 1D periodic substrates . We find qualitatively similar phase diagrams for square and triangular substrates for both the dimer and trimer states. For the trimers the onset of rotational melting occurs at weaker substrate strengths than for the dimers, due to the decreased anisotropy of the trimer state compared to the dimers. In addition for stronger screening the transition from the ordered solid to the partially ordered solid occurs for both lower temperature and substrate strength. An interesting issue is the nature of the melting transitions, which is beyond the scope of this work.

To summarize, we have demonstrated that a rich variety of novel colloidal crystalline states can be achieved with square and triangular two dimensional substrates. We find that when there are more colloids than substrate potential minima, certain colloidal molecular crystals appear in which each minima captures an equal number of colloids. The colloids in these traps can act as a single particle with a rotational degree of freedom, such as a dimer or trimer. We also show that CMC states exhibit a multi-stage melting for sufficiently strong substrates, where the orientational order of the colloidal molecule states is lost first followed by the translational order. We map out the phase diagram and show that the solid to disordered solid transition occurs for temperatures lower than the clean melting temperature. It is also possible to have a transition at fixed temperature for increasing substrate strength from a ordered solid to a partially ordered solid, similar to the reentrant melting observed for colloids on 1D periodic substrates. Since the colloids within a minima can act as a single particle with a rotational degree of freedom, our results also suggest that certain canonical statistical mechanics models, such as Ising, XY, Potts, and frustrated models, may be realized with colloids on two dimensional periodic substrates. The states predicted here should be observable for colloids interacting with crossed laser arrays or optical tweezer arrays, dusty plasmas in 2D with periodic potentials, and vortices in superconductors with periodic substrates.

We thank, C. Bechinger, D.G. Grier, P. Korda, S. Ling, A. Persinidis, and G. Spalding for useful discussions. This work was supported by the US Department of Energy under contract W-7405-ENG-36.


format: text

text:
# Optimal quantum pumps have a vanishing transmission coefficient

## Abstract

PACS numbers: 73.23.-b, 72.10.-d

In a recent Letter, Avron et. al  introduced a notion of optimal quantum pumps. These are adiabatic quantum pumps which work without dissipation. In particular, they produce neither entropy nor noise. In the present Comment we show that in the absence of magnetic field optimal quantum pumps always have a vanishing transmission coefficient. Such ‘quantum pumps’ do not make use of Quantum Mechanics since all tunneling or interference effects are banned by vanishing of the transmission coefficient. We leave it as an outstanding question whether genuine optimal quantum pumps with nonvanishing transmission coefficient can be constructed by making use of the magnetic field.

Recall that a quantum pump is a mesoscopic device attached to two (or more) reservoirs by means of ideal quantum wires. All reservoirs have the same chemical potential $`\mu `$, and when the pump is not at work no charge transfer occurs between reservoirs. In the scattering approach pioneered by Büttiker et al.  and developed in  a quantum pump connected to $`n`$ reservoirs is described by the scattering matrix at the Fermi energy $`S_{kl}`$ where the indices $`k`$ and $`l`$ label the outgoing and incoming channels, respectively. The matrix $`S_{kl}`$ is always unitary, $`S_{kl}^1=S_{lk}^{}`$. As the pump operates, the scattering matrix changes with period $`\tau `$, $`S(t+\tau )=S(t)`$. In practice, this is usually achieved by applying an alternating voltage to some gates inside the mesoscopic device . The net current pumped into the channel $`k`$ at the moment $`t`$ is given by formula (eqn. (3) of ),

$$J_k=\frac{ie}{2\pi }(_tSS^{})_{kk}=\frac{ie}{2\pi }\underset{l=1}{\overset{n}{}}(_tS_{kl})S_{lk}^{}$$
(1)
For the noise production one gets (eqn. (10) of ),

$$N_k=\frac{\beta he^2}{24\pi ^2}\underset{lk}{}|(_tSS^{})_{kl}|^2.$$
(2)
In the absence of magentic field, $`𝐁=\times 𝐀=0`$, one can always choose a gauge in which the vector potential $`𝐀`$ vanishes. Then, the Schrödinger equation which governs the motion of electrons through the pump has real coefficients since all the terms which contain $`i`$ are proportional to $`𝐀`$. This implies that taking a complex conjugate of a solution yields again a solution. Choosing the incoming and outgoing wave functions complex conjugate to each other (this corresponds to turning $`e^{ikx}`$ to $`e^{ikx}`$) one obtains an extra symmetry of the scattering matrix $`S_{kl}^1=S_{kl}^{}`$. Together with unitarity this implies that the scattering matrix is symmetric.

For simplicity, we consider quantum pumps with two external reservoirs. In this case, the general form of a unitary symmetric scattering matrix is given by formula,

$$S=\left(\begin{array}{cc}a& b\\ b& c\end{array}\right),$$

where $`b`$ is the transmission amplitude, and $`a`$ and $`c=a^{}b/b^{}`$ are reflection amplitudes. The matrix $`_tSS^{}`$ is anti-Hemritian,

$$_tSS^{}=\left(\begin{array}{cc}ix_1& y\\ y^{}& ix_2\end{array}\right).$$

The requirement that $`_tS`$ is symmetric yields $`yc+y^{}a=i(x_2x_1)b`$. Formula (2) now reads,

$$N_{1,2}=\frac{\beta he^2}{24\pi ^2}|y|^2\frac{\beta h}{6}\frac{T}{1T}J^2,$$
(3)
where $`T=|b|^2`$ is the transmission coefficient and $`J=(J_1J_2)/2=e(x_2x_1)/4\pi `$ is the net current between the reservoirs. We conclude that in the absence of magnetic field an optimal quantum pump ($`N_{1,2}=0`$) is only possible if $`T=0`$. A surprising denominator $`(1T)`$ in formula (3) accounts for the fact that a transparent quantum pump with $`T=1`$ cannot transfer charge between reservoirs, and in this case $`J=0`$.

Acknowledgements. I am grateful to M. Büttiker, J.-P. Eckmann and G.-M. Graf for the discussion which initiated this work and for their valuable comments. I greatly appreciate remarks by V. Cheianov and L. Sadun.


text:
# Transitions between Inherent Structures in Water

## I Introduction

It is believed that the properties of liquids can be understood as motion of the system in a high-dimensional complex potential energy surface (PES) . As a liquid is cooled toward the glassy state, the system is increasingly found near local potential energy minima, called inherent structure (IS) configurations . As temperature decreases, the description of the dynamics in terms of motion on the PES becomes increasingly appropriate. In this description, in the glassy state, the system is localized in one of the potential energy basins .

While such a picture of liquid dynamics is difficult to verify experimentally, computer simulation offers an excellent opportunity to explore these ideas. For a pre-defined liquid potential, a liquid trajectory can be generated via molecular dynamics simulation and the local potential energy minima can be evaluated by an energy minimization method . With this procedure, the motion in phase space is converted into a minimum-to-minimum trajectory, or IS trajectory. A general picture of the system moving among a set of basins surrounding the multitude of local minima has evolved. More specifically, simulations have shown that both the depth of the minima sampled by the system, as well as the number of these minima, decrease on cooling . Simulations have also shown that below a crossover temperature $`T_\times `$, only rare fluctuations bring the system to a saddle point and hence activated processes become important for relaxation of the liquid . For the system we study, $`T_\times `$ coincides numerically  with the critical temperature identified by mode coupling theory (MCT), which has been widely used to understand the dynamics of liquids on “weak” supercooling (the $`T`$ range where characteristic relaxation times approach $`10^8`$ s) .

The description of the real motion of the system as an IS trajectory becomes a powerful way of separating the vibrational contribution, responsible for the thermal broadening of instantaneous measurements from the slow structural component. Such an approach becomes even more powerful below $`T_\times `$, since most of the instantaneous configurations are far from saddles, making correlation functions calculated from the IS trajectory fully account for the $`\alpha `$-relaxation dynamics.

Here we study the IS trajectory below $`T_\times `$ for the extended simple point charge (SPC/E) potential, a well-studied model for water. The dynamics of the SPC/E model have been shown to be consistent with the predictions of MCT . Additionally, the PES of SPC/E has been studied in detail above $`T_\times `$ and a thermodynamic description of the supercooled states based on the PES has been presented. Here we focus on the geometrical properties of the motion, once the vibrational component is subtracted. The possibility of performing such a study below $`T_\times `$, with a very fine time coarse graining, allows us to examine the structural changes that accompany the basin transitions and to describe an elementary step of the diffusive process in terms of hydrogen bond network rearrangement.

This work is organized as follows. In Sec. II we provide the simulation details. In Sec. III we analyze the displacement of the molecules in these IS-transitions and in Sec. IV we study the corresponding changes in the hydrogen-bond (HB) network. Finally, in Sec. V we present a brief summary.

## II Simulation

Our results are based on molecular dynamics simulations of the SPC/E model  of water for 216 molecules, at fixed density $`\rho =1`$ g/cm3 . The numerical procedure is described in Ref.. The integration time step $`\delta t`$ is $`2`$ fs. The mode coupling temperature for this density is $`T_{MCT}194K`$ . We analyze trajectories at $`T=180`$ K, so that the system is in the deep supercooled liquid state. At this temperature, the diffusion coefficient is more than four orders of magnitude smaller than its value at $`T=300`$ K and only a few molecules move significantly (with displacements larger than $`0.025`$ nm) at each simulation time step. Our system is started from equilibrated configurations at $`190`$ K, which relax for nearly 920 ns at $`180`$ K before we record and analyze the trajectory. At such a low temperature, a slow aging in the trajectory could be present, however, the aging should not affect the qualitative picture we present.

We have generated one trajectory of $`30`$ ns, sampling configurations at each $`1`$ ps. For each configuration we find the corresponding IS using conjugate gradient minimization. In this way, we obtain $`30,000`$ configurations with the corresponding IS. Since we could miss some IS transitions with $`1`$ ps sampling, we also ran four independent $`20`$ ps simulations sampling the IS at $`4`$ fs. In this way, we obtain another 20,000 configurations with the corresponding IS.

## III Inherent Structure Trajectories

Figure 1 shows an example of the potential energy of the IS, $`E_{IS}(t)`$, and the mean square displacement of the oxygen atoms $`r^2(t)`$ starting from a single arbitrary starting time. At $`T=180`$ K, the slowest collective relaxation time $`\tau _\alpha >200`$ ns . The IS trajectory in Fig. 1 has a mesh of $`1`$ ps and covers a total time of $`30`$ ns. In this time interval, $`r^2(t)`$ is about $`1\AA ^2`$, i.e. much less than the corresponding value of the average nearest neighbor distance of $`2.8\AA `$. Figure 2 shows an enlargement of the IS trajectory using a much smaller time mesh ($`4`$ fs, two times the simulation time step). Fig. 2 shows that changes occur via discrete transitions, with an average duration of $`0.2`$ ps. The transitions are characterized by an energy change of $`1020`$ kJ/mol and an oxygen atom square displacement of the order of $`0.01\AA ^2`$; they appear to constitute the elementary step underlying the diffusional process in the system.

We note that it is impossible to identify the transition unless the quenching time step is of the order of the simulation time step. This is in distinct contrast to a Lennard-Jones liquid, where such small continuous changes are not present . The difference, we will show, is attributable to the hydrogen bonds. This time scale for IS transitions is in accord with other work on the TIPS2 water model, at $`T=298`$ K .

In Fig. 2, we see the sharp changes in $`E_{IS}(t)`$ coincide with the sharp changes in $`r^2(t)`$. This confirms that the system is repeatedly visiting specific configurations, since $`r^2(t)`$ and $`E_{IS}(t)`$ take on discrete values. The results shown in Fig. 2 imply that the system often returns to the original basin because of both the difference in energy and the displacement approach zero at the end of the time interval.

To aid in understanding the distribution of the displacements during the IS changes (such as those between the two IS labeled A and B in Fig. 2(b)), Fig. 3 shows the displacements $`u`$ of all 216 individual molecules from IS-A to IS-B. We see that there is a relatively small set of molecules with a large displacement. A snapshot of the eight molecules with the largest displacement is shown in Fig. 4. Interestingly, we find that this set of molecules forms a cluster of bonded molecules. Indeed, for all cases studied, we found that the set of molecules which displace most form a cluster of bonded molecules. The observed clustering phenomenon characterizes the IS transitions in water and can be interpreted as the analog of the string-like motion observed in simple atomistic liquids  and connected to the presence of dynamical heterogeneities. Similar results were found by Ohmine et al. using the TIP4P and TIPS2 models for water .

To characterize the distribution of individual molecular displacements between different IS more carefully, we show the distribution of displacements $`u`$ of the oxygen atoms $`P(u,\delta t=4\text{fs})`$ in Fig. 5. The time difference $`\delta t`$ is two times the integration time step. We collected data from all transitions in four independent $`10`$ ps trajectories for the results reported in Fig. 5. Note that $`P(u)`$ was previously studied by Schrøder et al. for a binary Lennard-Jones (LJ) mixture .

We find that the distribution of displacements is monotonic and does not allow us to detect a characteristic length which could help in distinguishing between diffusive and non-diffusive basin changes. $`P(u,t)`$ for $`t=\delta t`$ shows an apparent power-law with a negative slope of about $`2.8\pm 0.2`$, followed by an exponential tail. To highlight the exponential tail, we present the data in a linear-log plot Fig. 5 (upper panel), showing that the tail in $`P(u,\delta t=4\text{fs})`$ is mostly due to these highly “mobile molecules”. The characteristic length of the exponential tail is $`0.2\AA `$, about 15 times smaller than the nearest neighbor oxygen distance of $`2.8\AA `$ and in agreement with the finding of Schrøder et al. for the LJ case, where the characteristic length was about $`1/8`$ of the nearest neighbor distance.

Schrøder et al. interpreted the power-law contribution to $`P(u,\delta t)`$ as a response of the system to the diffusing molecules. In elasticity theory, a local displacement at the origin produces a distribution of displacements which scales with the distance $`R`$ from the origin as $`R^2`$. Hence the distribution of displacements $`u`$ scales as $`u^{2.5}`$. In contrast with the LJ case, the exponent we find is slightly larger than $`2.5`$, a discrepancy which may be related to the application of a continuum theory at a length scale where molecular details are still relevant. In the spirit of elasticity theory, the deviation of the distribution at small $`u`$ values from the power law arises from the cutoff introduced by the finite size of the simulation. Indeed, small $`u`$ values are produced at large $`R`$ and hence are missing in a finite simulation box.

Although a subset of “highly mobile” molecules is identifiable using a pre-defined threshold value in a single basin change, there is no unambiguous general criterion for identifying the molecules responsible for a single basin transition.

An important open question is the relation between the displacement distribution functions for $`t=\delta t`$ (Fig. 5) and the same distribution evaluated for an arbitrary time interval $`t`$. A full knowledge of such relation may shed light on the elementary stochastic process which better describes the dynamics of the deep supercooled state. This calculation requires a significant computational investment due to the very large number of IS configurations which need to be evaluated. Despite such difficulties, it is a promising research line for the near future.

## IV HB network restructuring

Liquid water is an interesting system for studying the physical processes that accompany basin transitions. The unusual dynamic and thermodynamic properties of water are believed to be connected to the microscopic behavior of hydrogen bonding. Many experiments suggest that this tetrahedral HB network has defects, such as an extra (fifth) molecule in the first coordination shell. Indeed, such 5-coordinated molecules have been directly identified in simulations and the defects were found to be a catalyst for motion in the system, making an obvious possible connection between network defects promoting diffusion and the basin transitions that give rise to diffusive motion of that system.

To obtain a physical picture of the IS transitions for water and to hopefully better understand the source of these transitions, we focus on the small changes in the HB network along a minimum to minimum trajectory. Analysis of the HB network based on IS configurations has shown that local PES minima are characterized by both linear bonds (LB) and bifurcated bonds (BB)  whose fraction is both temperature and density dependent. The HB network tends toward a perfect random tetrahedral network on cooling, or on lowering the pressure. Here we emphasize the changes in the network associated with IS-transitions.

To quantify the bonding changes, it is necessary to employ an arbitrary bond definition. Previous works have indicated that several definitions provide physically reasonable results. Here we use the definition that two molecules are bonded if their oxygen-oxygen distance is less than 3.5Å and their mutual potential energy is negative . Using this definition, we obtain the equilibrium distribution of the potential energy for the LB and BB, shown in Fig. 6.

These results agree with previous findings, based on different models. The distribution of BB energies is bimodal with peaks at roughly $`6`$ kJ/mol or $`22.5`$ kJ/mol, while the LB energy distribution is unimodal with a peak at roughly $`24`$ kJ/mol. Therefore, the energy associated with a change in the HB network due to losing one LB and creating two BB ranges roughly from $`21`$ kJ/mol to $`12`$ kJ/mol, depending on which of the two possible BB are created. The relative intensities of the peaks of the BB energy distribution suggest that such a mechanism would more likely lead to an increase in the overall energy. The comparison of the HB-energy changes with those found in Fig. 1 suggest that interchanges between LB and BB can explain the existence of a multitude of IS separated by very small energy barriers. More specifically, we hypothetize that changes increasing $`E_{IS}`$ found in Fig. 1 are due to processes LB$``$BB, while the changes decreasing $`E_{IS}`$ are due to the processes BB$``$LB. To confirm or reject this hypothesis, we study the distributions of LB and BB for IS just before and just after positive and negative “jumps” in the potential energy (Fig. 1b) with energy larger than 9 kJ/mol . These IS are schematically shown in Fig. 7(a). The corresponding distributions for LB and BB are shown in Fig. 7(b) and 7(c). We see that during PE increases, the average number of LB decreases while the number of BB increases; the opposite situation occurs when the potential energy decreases. The distribution for BB has peaks at even numbers of BB, which we expect since for each LB lost, two BB appear, also implying that the distribution should be zero for odd numbers of BB . The anti-correlation of the BB and LB changes is a strong indicator that a mechanism whereby the system accesses higher energy states is via LB$``$BB transitions.

To reinforce the hypothesis that the basin change is associated with a restructuring of the local connectivity, Fig. 8 shows the number of molecules with a coordination number equal to 3, 4 or 5 as a function of time for a characteristic time interval and contrasts this data with the time dependence of $`r^2(t)`$. A clear anti-correlation is observed between the time dependence of the number of 3 and 5-coordinated molecules compared to the time dependence of the 4-coordinated molecules, supporting the proposed interchange mechanism. The fact that increases in the fraction of BB coincides with changes in $`r^2(t)`$ supports the expectation that motion is a result of network imperfections.

## V Summary

We have presented a detailed analysis of the motion on the PES of a 216 water molecule system interacting via the SPC/E potential in a deeply supercooled state, below the MCT temperature. At this temperature, the system populates basins of the local minima. At these conditions, the analysis of the IS trajectories provides a very clean description of the slow alpha relaxation process filtering nearly all vibrational motions.

We have shown that an inherent structure transition is observed about every 0.2 ps. It is the collection of these numerous small transitions that gives rise to the structural relaxation of the system. These fast transitions are characterized by a broad distribution of individual molecule displacements, without a clear characteristic length. Future work must address the issue of the prediction of $`P(u,t)`$ from the knowledge of $`P(u,\delta t)`$.

We perform an analysis of the geometry of the individual event and find that the most mobile molecules are clustered. The analysis of the changes in HB connectivity associated with IS changes reveals that these transitions are associated with the breaking and reformation of HB. This result is in accord with work of Ohmine and colleagues  for TIP4P. We have shown that the transitions associated with an increase in the energy correspond to the breaking of linear bonds and to the simultaneous formation of bifurcated bonds. Similarly, the transitions associated with a decrease in the energy correspond to the breaking of bifurcated bonds and to the simultaneous formation of linear bonds.

This result supports the hypothesis that the linear to bifurcated transition can be considered as an elementary step in the rearrangement of the HB network.

## VI Acknowledgments

We thank T.B. Schrøder, S. Sastry and S.C. Glotzer for interesting discussions. N.G. wants to thanks I. Ohmine for fruitful discussions and suggestions. F.S. acknowledges support from INFM-PRA-HOP and Initiaziva Calcolo Parallelo and MURST COFIN2000. This work was supported by the NSF Chemistry Program.


text:
# Relativistic Causality and Conservation of Energy in Classical Electromagnetic Theory

## I INTRODUCTION

Starting from Einstein’s work on special relativity Eins  it became clear that classical electromagnetic theory is consistent with relativity, and no true paradoxes can be found. However, several apparent paradoxes have been extensively discussed and these discussions enriched our understanding of the electromagnetic theory. Some of these controversial topics are: hidden momentum ShJa , Feynman’s disk FD , Trouton-Noble ExperimentTN , and the 4/3 factor for the self energy of an electron.43  Here we present another situation which, analyzed in a naive way, leads to paradoxical conclusions. The paradoxes are relevant to recent discussions of covariance in the electromagnetic theoryJe99 ; Hn98 ; Co00 ; Hn00 ; Go00 .

Let us start with the paradox which is simplest to present; its resolution will be shown at the end of the paper.

Paradox I

There are two particles of charge $`q`$ initially separated by distance $`l`$. We consider two ways to bring the particles, initially and finally at rest, to a shorter distance $`lx`$, see Fig. 1.

(i) We move one particle the distance $`x`$ toward the other particle. The work required for this is:

$$W^\mathrm{i}=U_{NEW}U_{OLD}=\frac{q^2}{lx}\frac{q^2}{l}.$$
(1)
(ii) We move both particles toward each other for the distance $`x/2`$. We do it simultaneously and fast enough such that the motion of each particle ends before the signal about this motion can reach the location of the other particle. In this case, the work should be the sum of the amounts of work performed by external forces exerted on the two particles calculated as if the other particle has not moved:

$$W^{\mathrm{ii}}=W_1+W_2=2\left(\frac{q^2}{l\frac{x}{2}}\frac{q^2}{l}\right).$$
(2)
Fig. 1. Space-time diagram of the motion in the two processes: (i) one particle moves, (ii) two particles move.

After the procedure is ended, we obtain the same situation in both cases, but we applied less work when we moved both particles: $`W^{\mathrm{ii}}<W^\mathrm{i}`$.

We can get the energy equal to the work $`W^\mathrm{i}`$ back from the system when we reverse the process (i), moving one of the charges to the original distance $`l`$.

We can repeat the cycle of process (ii) followed by reversed process (i) gaining every time the amount of energy:

$$W^\mathrm{i}W^{\mathrm{ii}}\frac{q^2x^2}{2l^3}.$$
(3)
Of course, there must be an error in the above argument. We have not taken all relevant effects into account. However, before explaining this paradox we present and resolve a few other apparent paradoxes demonstrating the relevance of various effects. In Section II we present and in Section III resolve a paradox based upon part of the process (ii) described above. Instead of starting with particles at rest, accelerating, moving with some velocity, and then bringing the particles to rest, we start with the two particles moving with constant velocity and coming to rest at different times. In Section IV we further analyze the setup of Paradox II obtaining and resolving another paradox. Section V explains the same point using an example of a large number of charged particles. In Section VI we consider remaining part of the processes involved in Paradox I: accelerating a pair of particles from rest. In Section VII we consider acceleration of particles moving in parallel. This setup leads to a paradox the resolution of which is due to yet another surprising effect. In Section VIII we return to the analysis of Paradox I and resolve it in a quantitative way.

## II  PARADOX II: CONSERVATION OF ENERGY FOR TWO STOPPING PARTICLES

Consider two particles of charge $`q`$ and mass $`m`$ located on the $`x`$ axis at the separation $`l`$ and moving in the $`x`$ direction with a constant velocity $`v`$. At time $`t_1=0`$ we stop the first particle and at time $`t_2=t`$ we stop the second particle: see Fig. 2. The time $`t`$ is small enough such that signals about the change of the velocity of one particle cannot reach the location of the other, while it is still moving:

$$\frac{l}{cv}<t<\frac{l}{c+v}.$$
(4)
We also require that $`\tau `$, the time of “stopping” a particle, is small: $`\tau |t|`$.

Let us consider conservation of energy for this process. The initial energy should be equal to the final energy plus the work of the forces which the particles exert on external systems:

$$E_{in}=E_{fin}+W_1+W_2+\stackrel{~}{W},$$
(5)
where $`W_1`$ and $`W_2`$ are the works due to the forces the particles exert during the process of stopping; $`\stackrel{~}{W}`$ is the work performed by the particle moving with velocity $`v`$ during the time that the other particle is at rest (for $`t>0`$, the work $`\stackrel{~}{W}`$ is performed by particle 2 and for $`t<0`$, by particle 1). Of course, no work is performed when both particles are at rest, and, also, the net work vanishes during the time when both particles are moving with velocity $`v`$.

For making relativistic analysis more convenient, we include the rest mass energy. Then, the final energy of the system is

$$E_{fin}=2mc^2+\frac{q^2}{lx},$$
(6)
where $`x`$ is the change in the distance between the charges:

$$x=vt.$$
(7)
The distance might decrease or increase (negative $`t`$ and $`x`$) depending on which particle stopped first.

When a particle moves with constant velocity, the total force exerted on it is zero. Therefore, the force it exerts on an external system is equal to the electromagnetic force the other particle exerts on it. Since, in the laboratory frame, the distance between the particles is $`l`$, in the Lorentz frame at which the charges are at rest, the distance between them is $`\gamma l`$ (where $`\gamma 1/\sqrt{1v^2/c^2}`$). The Lorentz transformation for the force in the $`x`$ direction between the rest frame and the laboratory frame is $`F_x=F_x^{}`$ and, therefore, the forces the particles exert on the external systems are:

$$F_{1}^{}{}_{x}{}^{}=F_{2}^{}{}_{x}{}^{}=\frac{q^2}{(\gamma l)^2}.$$
(8)
Thus, the work $`\stackrel{~}{W}`$ is:

$$\stackrel{~}{W}=\frac{q^2x}{(\gamma l)^2}.$$
(9)
This formula is correct both for $`x>0`$, when the work is done by particle 2, and for $`x<0`$, when the work is done by particle 1. Thus, the equation of conservation of energy (5) becomes

Fig. 2. Space-time diagram of the motion of the two particles.

$$E_{in}=2mc^2+\frac{q^2}{lx}+W_1+W_2\frac{q^2x}{(\gamma l)^2}.$$
(10)
The initial energy $`E_{in}`$ obviously does not depend on $`x`$. Due to causality argument, the works $`W_1`$ and $`W_2`$ do not depend on $`x`$ either. The equation of energy has only two terms depending on $`x`$. Therefore, Eq. (10) represents a paradox: it must be true for all $`x`$ in the interval $`[\frac{lv}{cv},\frac{lv}{c+v}]`$ (corresponding to (4)), but it cannot, since it has only two terms depending on $`x`$ which do not balance each other.

## III RESOLUTION OF PARADOX II: INTERFERENCE OF RADIATION

In Paradox II, according to our naive calculation, the final energy together with the obtained work had two terms depending on $`x`$, the change in the distance between the particles, which do not sum up to a constant. There is cancellation of the $`x`$ dependence in the first order of the parameter $`\frac{x}{l}\frac{v}{c}`$, therefore, the leading term of the unbalanced $`x`$ dependent term is $`\frac{q^2x^2}{l^3}`$. Indeed,

$$\frac{q^2}{lx}\frac{q^2x}{(\gamma l)^2}=\frac{q^2}{l}+\frac{q^2x^2}{l^3}+\mathrm{}$$
(11)
The process of stopping cannot be arbitrarily slow since it had to be finished before the signal about stopping the other particle can arrive. Moreover, we choose $`\tau |t|`$. Therefore, we should expect a significant contribution due to radiation which we have not taken into account. The charges accelerate during the process of stopping and the magnitude of the acceleration is $`a=\frac{v}{\tau }`$ . According to the Larmor formula, the total energy radiated by a single charge during the whole process of stopping is

$$R_1=R_2=\frac{2}{3}\frac{q^2a^2}{c^3}\tau =\frac{2}{3}\frac{q^2v^2}{c^3\tau }.$$
(12)
The $`x`$ dependent term which we have to balance is much smaller than $`R_1`$ and $`R_2`$:

$$\frac{q^2x^2}{l^3}=\frac{q^2(vt)^2}{l^3}\frac{q^2v^2}{c^2l}\frac{q^2v^2}{c^3\tau }.$$
(13)
However, everything that happens at the close vicinity of the charges cannot depend on $`x`$, and, in particular, the radiation which each charge emits does not depend on $`x`$, so how can the radiation energy balance the $`x`$ dependent terms in the equation of conservation of energy? The effect is due to the interference of radiation. The total radiated energy is

$$R_{tot}=R_1+R_2+R_{int}.$$
(14)
The interference term $`R_{int}`$ depends on $`x`$ and restores the balance. Now we will show this in detail.

The radiation of the stopping charge propagates inside a spherical shell of width $`c\tau `$ and the energy flux S is given by: Grif

$$𝐒=\frac{q^2a^2\mathrm{sin}^2\theta }{4\pi c^3r^2}\widehat{𝐫},$$
(15)
where $`r`$ is the radius of the shell and $`\theta `$ specifies the direction relative to the $`x`$ axis in our setup. Since we have two accelerated charges, the radiation field due to the two charges will interfere in the region of the overlap, see Fig. 3. The complete overlap will take place for the angle $`\theta `$ defined by:

$$\mathrm{sin}(\theta \frac{\pi }{2})=\frac{ct}{lvt}=\frac{cx}{v(lx)}.$$
(16)
Since the width of the shells is $`c\tau `$, the overlap will be nullified beyond the deviation $`\delta \theta `$ from the angle $`\theta `$ given by

$$\delta \theta =\frac{c\tau }{(lx)\mathrm{sin}\theta },$$
(17)
which is obtained from

$$c\tau =\delta \left[(lx)\mathrm{sin}(\theta \frac{\pi }{2})\right]=[(lx)\mathrm{sin}\theta ]\delta \theta .$$
(18)
Due to the interference, the total energy radiated in the direction of the overlap is twice as much as if the two charges were radiating separately. At the interval $`[(\theta \delta \theta ),(\theta +\delta \theta )]`$ the overlap increases and then decreases linearly. Therefore, the interference term of the radiation energy is

$$R_{int}=2\frac{q^2a^2\mathrm{sin}^2\theta }{4\pi c^3r^2}2\pi r\mathrm{sin}\theta r\tau _{\delta \theta }^{\delta \theta }\frac{\delta \theta |\varphi |}{\delta \theta }𝑑\varphi =\frac{q^2v^2\mathrm{sin}^2\theta }{c^2(lx)}.$$
(19)
Fig. 3. Electromagnetic radiation of the two stopping particles. The area of constructive interference of the radiation field is painted in black.

After expressing $`\mathrm{sin}^2\theta =1\mathrm{sin}^2(\theta \frac{\pi }{2})`$, using (16), and making an approximation up to the lowest order in the parameter $`\frac{x}{l}\frac{v}{c}`$, we obtain:

$$R_{int}=\frac{q^2v^2}{c^2(lx)}\frac{q^2x^2}{(lx)^3}\frac{q^2v^2}{c^2l}\frac{q^2x^2}{l^3}.$$
(20)
Thus, we have shown that (at least up to a second order in the parameter $`\frac{v}{c}`$, the precision to which we made our calculations) the equation of conservation of energy which takes into account the electromagnetic radiated energy does not have $`x`$ dependence. The corrected equation of conservation of energy (which replaces Eq. 5),

$$E_{in}=E_{fin}+W_1+W_2+\stackrel{~}{W}+R_{tot},$$
(21)
leads, after the approximation, to the expression which does not exhibit $`x`$ dependence:

$$E_{in}=2mc^2+W_1+W_2+R_1+R_2+\frac{q^2}{l}\left(1+\frac{v^2}{c^2}\right).$$
(22)
Thus we have resolved Paradox II with regard to the unbalanced $`x`$ dependence. But can we show that the LHS and the RHS of the equation of conservation of energy (22) are equal? We will analyze this in the next section.

The paradox of non-conservation of energy of the system of two charged particles when radiation is neglected has been considered in another example.scat73  The calculation of the scattering on the basis of the Coulomb forces yields an energy of the charged particles after the collision that is larger than the initial energy. The advantage of the scattering example is that no external forces have to be taken into account. However, the resolution of this paradox by taking into account radiation has been shown only qualitatively.scat76

## IV LORENTZ TRANSFORMATION FOR ELECTROMAGNETIC ENERGY

Without knowing the mass and without knowing the local works $`W_1`$ and $`W_2`$ it seems that we cannot test (22). However, we can test the consistency of this equation of conservation of energy with single-particle conservation of energy equations. We can write down the conservation of energy for each particle assuming that it performs exactly the same motion (stopping from velocity $`v`$ during the time $`\tau `$) in case the other particle is not present. We can argue that the local works $`W_i`$ and the emitted radiations $`R_i`$ are the same as in the original example.

This argument is not as strong as the causality argument, i.e. the independence of $`x`$ of the values of these variables, but it seems that since we can take the time $`\tau `$ of the local processes very small, the effect of the external field can be neglected. In order to reduce any doubt that this is a valid approach, we will consider, in the next section, a similar situation with a large number of charged particles. It exhibits the same problem, but we will not need this assumption.

Our approach to finding the initial energy is finding the total energy of the two charges in their rest frame $`E_0`$ and multiplying it by the factor $`\gamma `$. In the rest frame of the moving particles, the distance between them is $`\gamma l`$. Therefore, the total initial energy of the particles is:

$$E_{in}=\gamma \left(2mc^2+\frac{q^2}{\gamma l}\right).$$
(23)
Thus, the equation of conservation of energy (22) becomes

$$2\gamma mc^2+\frac{q^2}{l}=2mc^2+W_1+W_2+R_1+R_2+\frac{q^2}{l}\left(1+\frac{v^2}{c^2}\right).$$
(24)
We can write two (identical) single-particle equations of conservation of energy:

$`\gamma mc^2=mc^2+W_1+R_1,`$
$`\gamma mc^2=mc^2+W_2+R_2.`$ (25)
But when we subtract these equations from the two-particle conservation of energy equation (24) we see that there is inconsistency: the term $`\frac{q^2v^2}{lc^2}`$ is unbalanced! The inconsistency does not follow from the approximations we made in deriving (22). The algebraic approximations can be made irrelevant if we consider simultaneous stopping of the charges corresponding to $`x=0`$, in which case (22) follows without approximation. We have reached another paradox. There must be another error in our analysis. (In fact, this paradox will appear also for large $`|x|`$ when there is no interference of radiation; such a case will be considered in the next section.)

The paradox arises from the error which we made in Eq. (23). We have claimed that if the total energy of a system of charges in their rest frame is $`E_0`$, then its energy in the Lorentz frame in which the system moves with velocity $`v`$ is

$$E=\gamma E_0.$$
(26)
Equation (26) is, of course, correct when the system is an elementary particle. It is also true when the system is a finite stationary isolated body. But it is, in general, not true for a composite system with external forces such as the system of charged particles we consider here.

In order to obtain the correct transformation of the electromagnetic energy from the rest frame to the moving frame, we consider two charges connected by a rigid rod. The energy of the whole system, charges and the rod, does transform according to (26). Therefore, the anomalous term of the transformation of the electromagnetic energy equals to the negative of the anomalous part of the mechanical energy of the rod. The latter is easier to calculate and we will do it now.

In order to calculate the expression for transformation of energy of the rod, we express it as a volume integral of the energy density $`u`$:

$$E_{in}=u𝑑v,$$
(27)
and use the Lorentz transformation for the energy density, the 00 component of the energy-stress tensor:

$$u=\gamma ^2\left(u^{}+\frac{v}{c^2}S_x^{}\frac{v^2}{c^2}\sigma _{xx}^{}\right),$$
(28)
where $`𝐒`$ is the energy flux and $`\sigma `$ is the stress tensor. The transformation of the energy due to the the first term leads to the usual expression (26): the energy density is multiplied by $`\gamma ^2`$, but due to the Lorentz contraction the volume is multiplied by the factor $`\gamma ^1`$. The second term does not contribute since the energy flux in the rest frame vanishes. Therefore, the last term contributes the anomalous term. The tension in the rod prevents the charges, separated by the distance $`\gamma l`$, from moving, therefore it equals $`\frac{q^2}{\gamma ^2l^2}`$. Thus, in the rest frame of the rod, the stress tensor component is:

$$\sigma _{xx}^{}=\frac{q^2}{s\gamma ^2l^2},$$
(29)
where $`s`$ is the cross-section of the rod. Therefore, the contribution to the energy in the laboratory frame due to the tension of the rod is:

$$\frac{\gamma ^2v^2}{c^2}\sigma _{xx}^{}𝑑v=\frac{\gamma ^2v^2}{c^2}\sigma _{xx}^{}ls=\frac{v^2q^2}{c^2l}.$$
(30)
Thus, the correct expression for the initial energy of the electromagnetic field of the two charges (including the anomalous term of the transformation of the electromagnetic energy which equals to the negative of that of the mechanical energy) is:

$$E_{in}=\gamma \left[2mc^2+\frac{q^2}{\gamma l}\left(1+\frac{v^2}{c^2}\right)\right].$$
(31)
The correction we found for the initial energy of the system of two charges equals exactly the interference term of the radiation energy thus restoring the equation of conservation of energy.

## V  CONSERVATION OF ENERGY FOR $`N`$ STOPPING PARTICLES

In this section we can strengthen the arguments of the previous section by considering a large number of charged particles in a row. In this case, we do not subtract single-particle equations of conservations of energy from the $`N`$-particle equation of conservation of energy. Thus, we do not need the assumption of the previous section that the terms of single-particle equations are equal to the corresponding terms of the $`N`$-particle equation. However, since this section does not describe conceptually new effects, it can be omitted on the first reading.

Consider a chain of a large number $`N`$ of identical particles of charge $`q`$ and mass $`m`$ separated by the distance $`l`$ one from the other, all moving with velocity $`v`$ on the $`x`$ axis. The first particle stops at $`t_1=0`$ during a short time $`\tau `$. The second particle stops in the same manner at $`t_2=t`$, the latest possible moment such that the information about stopping of the first particle cannot reach it. This corresponds to

$$x=vt=\frac{vl}{c+v}.$$
(32)
The third particle stops in the same way at time $`t_3=2t`$ just before the information about the stopping of the first two should arrive, the particle $`n`$ stops at time $`t_n=(n1)t`$, etc. until the stopping of the last particle. This is illustrated in Fig. 4.

One difference from the case of two particles is that, due to the particular choice of $`x`$, we have no interference of radiation from different charges. The overlap of the radiation fields takes place only on the $`x`$ axis where the intensity is zero. Another change from the case of two particles to the case of $`N`$ is reflected in the calculations of the initial and final potential energies, the work $`\stackrel{~}{W}`$ (the work made by particles during motion with constant velocity), and the anomalous energy transformation term: in all these terms appear the factor $`\eta `$:

$$\eta =\underset{n=1}{\overset{N1}{}}\underset{i=1}{\overset{n}{}}\frac{1}{i}.$$
(33)
The appearance of the factor $`\eta `$ is obvious for potential energy, since $`\frac{q^2}{\gamma l}_{i=1}^n\frac{1}{i}`$ is the energy of bringing the particle number $`n+1`$ when there are $`n`$ particles in the row. Let us show that the same factor appears for $`\stackrel{~}{W}`$. When all particles move with velocity $`v`$, no net work is done on the system and, of course, no net work is done when all particles are at rest. Consider forces between particle $`n`$ and all particles $`i`$ to the right of it, (i.e., $`i<n`$). The distance the particle $`n`$ moves while $`i`$ is at rest is $`(ni)x`$, and the force between them is $`\frac{q^2}{(\gamma l(ni))^2}`$. Therefore, the contribution to $`\stackrel{~}{W}`$ due to the interaction between particle $`n`$ and particle $`i`$ is

Fig. 4. Space-time diagram of the motion of $`N`$ particles.

$$\frac{q^2x}{(\gamma l)^2(ni)}.$$
(34)
We obtain that the contribution to the potential energy due to the forces between particle $`n`$ and all particles $`i`$ such that $`i<n`$ is:

$$\underset{i=1}{\overset{n1}{}}\frac{q^2x}{(\gamma l)^2(ni)}=\frac{q^2x}{(\gamma l)^2}\underset{i=1}{\overset{n1}{}}\frac{1}{i}.$$
(35)
The sum of the works made by all particles, starting from the moment when the first particle stops, is:

$$\stackrel{~}{W}=\frac{q^2x}{(\gamma l)^2}\underset{n=2}{\overset{N}{}}\underset{i=1}{\overset{n1}{}}\frac{1}{i}=\eta \frac{q^2x}{(\gamma l)^2}.$$
(36)
Instead of performing a direct calculation of the anomalous transformation term (deviation from (26)), we can make the following observation. The anomalous term can be found by calculation of the contribution due to the tension of the rod (compare with (30)):

$$\frac{\gamma ^2v^2}{c^2}\sigma _{xx}^{}𝑑v=\frac{\gamma ^2v^2}{c^2}\underset{n=1}{\overset{N1}{}}(\sigma _{xx}^{})_nls=\frac{\gamma ^2v^2}{c^2}\underset{n=1}{\overset{N1}{}}T_nl.$$
(37)
Consider a rod with $`N`$ charges separated by distance $`l`$ at rest. We will show that $`_{n=1}^{N1}T_nl`$ is equal to the potential energy of the charges. Since the latter is multiplied by $`\eta `$ in the transition from 2 to $`N`$, the former is multiplied by $`\eta `$ too. Potential energy is equal to the work which electromagnetic forces will do in the process of uniform extension of the length of the rod from $`(N1)l`$ to a very large length, which, in turn, is equal to the negative of the mechanical work made by the tension forces of the rod. When the separation between the charges is $`\stackrel{~}{l}`$, the tension in the parts of the rod can be expressed as

$$T_n(\stackrel{~}{l})=T_n(l)\frac{l^2}{\stackrel{~}{l}^2},$$
(38)
because this tension compensates the Coulomb force proportional to $`\stackrel{~}{l}^2`$. Therefore, the work (equal to the potential energy) can, indeed, be expressed as

$$\underset{n=1}{\overset{N1}{}}_l^{\mathrm{}}T_n(\stackrel{~}{l})𝑑\stackrel{~}{l}=\underset{n=1}{\overset{N1}{}}_l^{\mathrm{}}T_n(l)\frac{l^2}{\stackrel{~}{l}^2}𝑑\stackrel{~}{l}=\underset{n=1}{\overset{N1}{}}T_nl.$$
(39)
Now we can write the equation of conservation of energy for $`N`$ charges including the anomalous transformation term (the LHS is the modification of (31) and the RHS is the modification of the RHS of (10)):

$`N\gamma mc^2+\eta {\displaystyle \frac{q^2}{l}}\left(1+{\displaystyle \frac{v^2}{c^2}}\right)=`$
$`Nmc^2+\eta {\displaystyle \frac{q^2}{lx}}+W_1+W_2+\mathrm{}+W_N\eta {\displaystyle \frac{q^2x}{(\gamma l)^2}}.`$ (40)
In order to estimate $`\eta `$ for large $`N`$ we can replace the sums by the integrals (and $`N1`$ by $`N`$):

$$\eta =\underset{n=1}{\overset{N1}{}}\underset{i=1}{\overset{n}{}}\frac{1}{i}_1^N\left(_1^z\frac{dy}{y}\right)𝑑z_1^N\mathrm{ln}zdzN\mathrm{ln}N.$$
(41)
(We omitted $`N`$, since it is negligible relative to $`N\mathrm{ln}N`$).

Since for large $`N`$ we have $`\eta N`$, all terms in (V) which do not have the factor $`\eta `$ can be neglected. These include all terms $`W_n`$, the amount of work obtained in the process of stopping particle $`n`$. Indeed, for small enough $`\tau `$, these terms will not have strong dependence on $`N`$ and, therefore, their sum will be approximately proportional to $`N`$. After substitution of (32), our choice of $`x`$, we can see that the equation of energy with the anomalous transformation term is balanced in the leading $`\eta `$ proportional terms (and it is not balanced if we use the transformation of energy (26)).

## VI  ACCELERATING PARTICLES FROM REST

In order to prepare ourselves for the analysis of Paradox I presented in the Introduction, let us consider a step which has not been discussed yet: the acceleration of the two charged particles from rest to velocity $`v`$. Of course, in the frame of reference moving with velocity $`v`$, this is deceleration and stopping of particles moving with equal velocities, the process we analyzed above. However, the transformation from one frame to another might be a difficult task and, as in many other examples BK ; Nami , an analysis in a different Lorentz frame allows seeing new physical phenomena; in our case it provides yet another possibility to make an error leading to a paradox.

We accelerate the particles in the same way as in the process of simultaneous deceleration discussed in the preceding paragraph, i.e., we perform simultaneous acceleration from rest to velocity $`v`$ during time $`\tau `$. The radiated energy during the acceleration, then, should be the same as in the process of stopping, see Eq. (20). For simultaneous acceleration $`x=0`$, so the interference term is

$$R_{int}=\frac{q^2v^2}{c^2l}.$$
(42)
Initial energy of the particles is

$$E_{in}=2mc^2+\frac{q^2}{l},$$
(43)
Since the final state of the particles (motion with velocity $`v`$ and separation $`l`$) is identical to the initial state of the particles in the previous example, the expression for the final energy $`E_{fin}`$ is given by the RHS of (31).

Again, for each particle we can write the equation of conservation of energy for the process when the other particle is not present:

$`mc^2=\gamma mc^2+W_1+R_1,`$
$`mc^2=\gamma mc^2+W_2+R_2,`$ (44)
where $`W_1`$, $`W_2`$ are defined as work performed by the particles and are negative in this case.

Since the charges start to move together, it seems that the net work is done only during the acceleration period. Therefore, the equation of conservation of energy is:

$$E_{in}=E_{fin}+W_1+W_2+R_1+R_2+R_{int}.$$
(45)
Substituting all the terms and subtracting the single-particle equations we obtain:

$$\frac{q^2}{l}=\frac{q^2}{l}\left(1+\frac{v^2}{c^2}\right)+\frac{q^2v^2}{lc^2}.$$
(46)
The final energy is larger than the initial energy: contradiction!

The error we made here is more transparent. It appears in the sentence stating that the only net work of the charges is done during the acceleration period. It is true that in a stationary case (particles keep their motion all the time) the net work of charges moving with constant velocity vanishes. However, at the beginning of the motion, the fields at the vicinity of the charges are different from the Coulomb field of the stationary motion: each particle feels the static field of the other particle (i.e., as if it has not moved) until the signal from the motion of the other particle can arrive.

Let us calculate the contribution to the work due to the forces between the particles. Particle 2 moves in the static field of particle 1 during the time $`t=\frac{l}{c+v}`$ after which it feels the stationary field of particle $`1`$ which is $`\frac{q}{\gamma ^2l^2}`$. Similarly, particle 1 moves in the static field of particle 2 during the time $`t^{}=\frac{l}{cv}`$, after which it feels the stationary field of particle 2 of the same strength but in the opposite direction. After time $`t^{}`$, there is no contribution to the net work due to the forces between the two particles. Until this time, particle 1 covers distance $`x^{}=vt^{}`$ in the static field of particle 2. Therefore, the contribution to the work from particle 1 is:

$$\frac{q^2}{l}\frac{q^2}{l+x^{}}=\frac{vq^2}{cl}.$$
(47)
The work performed by particle 2 until time $`t^{}`$ has two parts. Until time $`t`$, it is:

$$\frac{q^2}{l}\frac{q^2}{lx}=\frac{vq^2}{cl}.$$
(48)
Between time $`t`$ and $`t^{}`$ it feels a constant field so the contribution to the work is:

$$\frac{q^2}{\gamma ^2l^2}v(t^{}t)=\frac{2v^2q^2}{c^2l}.$$
(49)
The contributions (47) and (48) cancel each other, so the net contribution is given by (49). The net work performed by the particles during the time of motion with constant velocity is:

$$\stackrel{~}{W}=\frac{2v^2q^2}{c^2l}.$$
(50)
This restores the balance in the equation of conservation of energy canceling the unbalanced terms in (46).

We have resolved the contradiction by taking into account the work performed by charged particles during the transition period from static field to stationary field which lasts $`\frac{l}{cv}`$. But what happens if we skip the intermediate stage? We accelerate the particles to velocity $`v`$ and shortly after (before the particles finished performing the work (50)) stop them in a similar manner. What is the source of the radiation energy (42) in this case? In fact, since we have two processes with the acceleration, it seems that we are missing even more, twice this amount!

No, this is another error. We need not look for the source of the radiation energy, because the radiation field due to the acceleration and the radiation field due to stopping interfere destructively. (Note a more bizarre example of a destructive interference of radiation field from a moving body.nonrad ) We are not going to analyze the destructive interference in a quantitative way in this case. The same effect yields the resolution of Paradox I which is demonstrated in a quantitative way in Section VIII. Before this, in the next section, we present a paradox arising from yet another subtle effect.

## VII  ACCELERATING PARTICLES MOVING IN PARALLEL

Let us consider acceleration of two charged particles lined up in the $`y`$ axis instead of the $`x`$ axis. The particles accelerate simultaneously from rest to velocity $`v`$ in the $`x`$ direction. The expression for the initial energy is again (43). The final energy, however, is different:

$$E_{fin}=\gamma \left(2mc^2+\frac{q^2}{l}\right).$$
(51)
Indeed, in the rest frame of the moving particles the distance between them is $`l`$. In this case the electromagnetic energy is transformed in the usual way (26) because the energy of the composite system of charges and the rod is transformed according to (26) and the energy of the rod with the tension in the $`y`$ direction is transformed according to (26). The anomalous behavior of the rod in the previous case followed from the presence of $`\sigma _{xx}`$ component of the stress tensor which vanishes in the vertical configuration.

The interference term of the radiation energy is modified too. In the $`x`$ axis configuration, the interference is in the $`yz`$ plane and it always has the angle $`\frac{\pi }{2}`$ relative to the direction of the acceleration. In the $`y`$ axis configuration, the interference is in the $`xz`$ plane with varying angle $`\theta `$ relative to the direction of the acceleration. Therefore, the interference is not always in the direction of the maximal intensity. The intensity is proportional to $`\mathrm{sin}^2\theta `$, see (15), and, therefore, averaging on $`\theta `$ reduces the interference term relative to the $`x`$ configuration (42) by the factor of 2:

$$R_{int}=\frac{q^2v^2}{2c^2l}.$$
(52)
Although during the stationary motion the charges do not exert forces in the direction of motion, in the transition period, when the charges move in the static field, there is a small component of the force in the direction of motion. The particles move in the static field during the time $`t`$ which fulfills

$$ct=\sqrt{l^2+t^2v^2}.$$
(53)
Therefore $`ct=\gamma l`$. The total work each particle performs is

$$\stackrel{~}{W}_1=\stackrel{~}{W}_2=\frac{q^2}{l}\frac{q^2}{\gamma l}.$$
(54)
The single-particle equations of conservation of energy, of course, remain the same. Thus, putting together all terms of the conservation of energy equation

$$E_{in}=E_{fin}+W_1+W_2+\stackrel{~}{W}_1+\stackrel{~}{W}_2+R_1+R_2+R_{int},$$
(55)
and subtracting single particle equations (VI), we obtain:

$$\frac{q^2}{l}=\frac{\gamma q^2}{l}+\frac{2q^2}{l}\left(1\frac{1}{\gamma }\right)+\frac{q^2v^2}{2c^2l}.$$
(56)
Contradiction again: The final energy is larger than the initial energy. Calculating up to the second order in the parameter $`\frac{v^2}{c^2}`$ we see three contributions in the units of $`\frac{v^2q^2}{c^2l}`$. The increase in the potential energy contributes $`\frac{1}{2}`$, the work of the static fields during the transition period contributes $`2\frac{1}{2}=1`$, and the interference of radiation contributes $`\frac{1}{2}`$. All terms together contribute $`\frac{2v^2q^2}{c^2l}`$.

The effect we missed here is, probably, the most subtle one. We have not taken into account the work of the radiation field. The electric field at the point $`𝐫`$ (relative to the charge), due to the radiation of the charge $`q`$ moving with acceleration $`a`$, is: Grif

$$𝐄=\frac{q}{c^2r}\widehat{𝐫}\times (\widehat{𝐫}\times a).$$
(57)
For our configuration, the field is:

$$𝐄=\frac{qa}{c^2l}\widehat{x}.$$
(58)
This field exerts force during the time $`\tau `$ during which the particle moves distance $`\tau v`$. Taking into account that $`a=\frac{v}{\tau }`$ we obtain that the force of the radiation field changes the energy of each particle by

$$W_{rad}=\frac{q^2v^2}{c^2l}.$$
(59)
Both particles lose their energy in this way and, therefore, we lose two units of $`\frac{v^2q^2}{c^2l}`$ restoring the equation of conservation of energy.

Note that in the $`x`$ configuration of charges, the work of the radiation field vanishes because in this case the radiation fields at the locations of the particles vanish.

## VIII RESOLUTION OF THE PARADOX I

Now we have learned all the effects necessary for the resolution of Paradox I. In fact, we have seen a few effects which do not play a role in this case, but understanding them increases our confidence that our explanation is the correct one.

The anomalous transformation of the electromagnetic energy is not relevant because the charges are at rest at the beginning and at the end of the process. The subtle effect of the work performed by the radiation field is not present too, since the radiation fields in the locations of the particles vanish. It is the interference of radiation which we have not taken into account that resolves the paradox. The radiation energy (12) is much larger than the term (3) which we have to compensate, see (13). However, we would like to get quantitative resolution of this paradox showing how the missing term (3) arises from the calculation of the radiation energy.

In order to obtain a quantitative result we specify how we perform the process described in Section I. We assume that we perform it exactly as in all other setups described here: we accelerate particles during small time $`\tau `$ until they reach velocity $`v`$. In case (i), the particle moves with constant velocity the distance $`x`$ when it stops in the same manner as it was accelerated. In case (ii), both particles reach velocity $`v`$ (absolute value) and stop at time $`t`$ after passing the distance $`x/2`$. The time $`t`$ is short enough such that each particle cannot receive a signal during its motion about the motion of the other particle. Thus,

$$\tau t=\frac{x}{2v}<\frac{l}{c+v}.$$
(60)
In case (i) the radiation energy is created in the same amount due to the acceleration and due to the stopping of the particle and, therefore, it is twice the amount given by the Larmor formula (12):

$$R^\mathrm{i}=\frac{4}{3}\frac{q^2v^2}{c^3\tau }.$$
(61)
In case (ii) there are four events of changing velocity of a particle by amount $`v`$ and, therefore, there are four spherical shells of radiation field of the width $`\tau c`$, see Fig. 5. The radiation energy is four times the Larmor energy (12) with the correction due to the interference. The correction due to the interference has four terms. The interferences are due to radiation emitted during the acceleration of the two particles, stopping of the two particles, acceleration of the first and stopping of the second, and acceleration of the second and stopping of the first. All these terms can be calculated in the same way as we have calculated the interference of radiation energy of two stopping charged particles in Section IV.

Accelerations and decelerations of the particles are performed simultaneously, therefore, the direction of interference is $`\theta =\frac{\pi }{2}`$. This is the direction of the maximal power of the radiation energy, see (15). The range of the angles for which there is the interference is given by (17) and, thus, similarly to derivation of (20), we obtain that the interference term due to simultaneous acceleration is equal to the term due to simultaneous stopping, and it equals

$$\frac{q^2v^2}{c^2l},$$
(62)
where the minus sign is because particles accelerate in opposite directions and the second term of (20) does not appear since simultaneity corresponds to $`x=0`$ in the notation of Section III.

The interference between acceleration of the first and stopping of the second takes place in the direction $`\widehat{\theta }_1`$ defined by

$$\mathrm{sin}(\theta _1\frac{\pi }{2})=\frac{ct}{lvt}.$$
(63)
For calculating this correction we can use (20) again, taking into account that the particle stops after passing the distance $`vt=\frac{x}{2}`$. Therefore, this contribution is:

$$\frac{q^2v^2}{c^2l}\frac{q^2x^2}{4l^3}.$$
(64)
The contribution to the correction of the radiation energy due to the interference between acceleration of the second and stopping of the first particles takes place in the direction defined by

$$\mathrm{sin}(\theta _2\frac{\pi }{2})=\frac{ct}{l+vt}.$$
(65)
Fig. 5. Electromagnetic radiation of the two charged particles which are simultaneously accelerated toward each other and after time $`t`$ stopped, case (ii). The shadowed area signifies destructive interference and the area painted in black signifies constructive interference.

In our case $`lvt`$, so we can make an approximation $`lvtl+vtl`$ and, therefore, we get the same expression again. Summing up all the expressions, we obtain:

$$R^{\mathrm{ii}}=\frac{8}{3}\frac{q^2v^2}{c^3\tau }\frac{2q^2v^2}{c^2l}+2\left(\frac{q^2v^2}{c^2l}\frac{q^2x^2}{4l^3}\right)=\frac{8}{3}\frac{q^2v^2}{c^3\tau }\frac{q^2x^2}{2l^3}.$$
(66)
Now we are able to analyze the setup of Paradox I taking into account the radiation energy. In case (i) the work performed by the external forces should include the radiation energy (61). Thus, instead of (1) we obtain

$$W^\mathrm{i}=U_{NEW}U_{OLD}+R^\mathrm{i}=\frac{q^2}{lx}\frac{q^2}{l}+\frac{4}{3}\frac{q^2v^2}{c^3\tau }.$$
(67)
In case (ii), following the structure of Paradox I, we have to calculate the work taking into account the causality argument: each particle “does not know” that the other particle moved. Therefore, the work against the field and the radiated energy should be calculated as if the other particle has not moved. The work is twice the amount of work in case (i) with the change of $`x\frac{x}{2}`$. Thus, instead of (2), we obtain

$$W^{\mathrm{ii}}=W_1+W_2=2\left(\frac{q^2}{l\frac{x}{2}}\frac{q^2}{l}+\frac{4}{3}\frac{q^2v^2}{c^3\tau }\right).$$
(68)
Clearly we cannot gain energy from constructing a machine with a cycle of process (ii) and reversed process (i). The work required for reversed process (i) is:

$$W^{\stackrel{~}{\mathrm{i}}}=\frac{q^2}{l}\frac{q^2}{lx}+\frac{4}{3}\frac{q^2v^2}{c^3\tau }.$$
(69)
Thus, the work during the whole cycle is:

$`W_{tot}=W^{\stackrel{~}{\mathrm{i}}}+W^{\mathrm{ii}}={\displaystyle \frac{q^2}{l}}{\displaystyle \frac{q^2}{lx}}+{\displaystyle \frac{4}{3}}{\displaystyle \frac{q^2v^2}{c^3\tau }}+`$
$`2\left({\displaystyle \frac{q^2}{l\frac{x}{2}}}{\displaystyle \frac{q^2}{l}}+{\displaystyle \frac{4}{3}}{\displaystyle \frac{q^2v^2}{c^3\tau }}\right){\displaystyle \frac{q^2x^2}{2l^3}}+{\displaystyle \frac{4q^2v^2}{c^3\tau }}.`$ (70)
This work is greater than zero, since the radiation term is much larger than the gain in the potential energy; it can be seen explicitly using (60). However, even if we collect the radiation energy, we still cannot gain energy. Indeed, the total radiation energy is:

$$R_{tot}=R^\mathrm{i}+R^{\mathrm{ii}}=\frac{4}{3}\frac{q^2v^2}{c^3\tau }+\frac{8}{3}\frac{q^2v^2}{c^3\tau }\frac{q^2x^2}{2l^3}=\frac{4q^2v^2}{c^3\tau }\frac{q^2x^2}{2l^3}.$$
(71)
We obtained exactly the same expression, i.e. our calculations have shown (up to the precision of the order of $`\frac{v^2}{c^2}`$) that during the complete cycle $`W_{tot}=R_{tot}`$. This completes the analysis of the paradox presented at the beginning of this paper.

Is it a simple task to demonstrate conservation of energy to a higher order in $`\frac{v}{c}`$? It is not difficult to expand the algebraic expressions we have to a higher order, but this is not enough. We have used more approximations, in particular, the formulas for the radiation of the charged particles we have used are correct only in the approximation of small acceleration and small velocities. Indeed, Eq. (12) cannot be universally correct, since it says that by reducing $`\tau `$, the time of stopping the charged particle, we can obtain unlimited amount of radiation energy: clearly we cannot get more energy than the particle has. Thus, higher order calculations of the equation of conservation of energy is an elaborate task which goes beyond the scope of this paper.

In this paper we have analyzed some relativistic features of the classical electromagnetic theory. We demonstrated in a quantitative way the relevance of the several effects to the balance of conservation of energy in a system of charges. These effects are: changing of the electromagnetic field according to relativistic causality constraints, anomalous transformation of the electromagnetic energy, energy radiated by accelerated charges, interference of radiation, and work performed by the radiation field. We believe that presenting the subject in the form of “paradoxes” helps to achieve a deeper understanding. Obtaining quantitative resolutions of presented paradoxical situations helps to reach confidence in applying the equation of conservation of energy for indirect calculations of various effects.

ACKNOWLEDGMENTS

It is a pleasure to thank Shmuel Nussinov, and Philip Pearle for helpful discussions. This research was supported in part by the EPSRC grant GR/N33058.