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# Mutagenesis and Metallic DNA

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## Abstract

Positions of protons in DNA hydrogen bonds are fundamental for the fidelity of the replication process. Because the hydrogen bond is partially covalent the electronic structure of DNA plays an important role in the replication process. Current studies of electron transfer in DNA have shown that simple pictures based on independent electron physics are not sufficient to account for the experimental data. In this paper we propose a model for electron-proton interaction in DNA and its relationship to mutagenesis. We argue that mutations will be more frequent in DNA sequences where electron delocalization occurs. To test our theory we calculate the heat capacity of DNA at low temperatures and compare with the available experimental data in hydrated DNA. We find that our model is in good agreement with the data. We also propose new measurements of infrared absorption which would further test our ideas.

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Watson and Crick  pointed out the importance of proton transfer as a possible cause of tautomeric base pairs in DNA and its deep relationship to mutagenesis. Errors in the replication process of DNA can lead to the occurrence of mutations related to genetic diseases and some forms of cancer. Löwdin  argued that proton transfer is a quantum mechanical effect which has purely electrostatic origin. Since then many researchers have calculated the potential energy profiles for proton transfer reactions in isolated base pairs . These studies have shown the importance of the electronic configuration at each base pair as a stabilizing factor of the hydrogen bond (H-bond). Indeed, recent experiments  show the occurrence of proton transfer in excited base pairs. The problem of electron transfer in DNA has been a source of intense debate . Many different experimental studies of electron transfer by chemical reaction have shown that long range electron transfer in DNA may be rather different from the same process in proteins, where single electron processes are dominant . In this paper we propose a model which combines two essential ingredients in the physics of DNA: the electronic degrees of freedom, and the protons in the H-bonds along the double helix. Our model is different from other proposed models for electron-proton interactions in DNA , since we take into account (i) the quantum mechanical character of electron motion, (ii) the charging energy due to electron transfer between different base pairs, and (iii) the specificity of the electron-proton processes due to differences in base pair sequences.

Let us consider a periodic DNA sequence. It is well-known that the electrons in such DNA can move by the overlap of $`\pi `$ orbitals along the DNA helix . In this case DNA can be viewed as an one-dimensional (1D) solid. Because a periodic DNA provides a periodic potential for electron motion, basic quantum mechanics tells us that the quantum states of the system are Bloch waves with wavenumber $`k`$ and band index $`n`$. To each value of $`k`$ we associate a wavelength $`\lambda `$ of the electron ($`k=2\pi /\lambda `$), and for each band we associate a molecular or atomic state. Band structure calculations  indicate that such a DNA sequence should be an insulator with a band gap of order of a few electron volts. In this case the low energy excitations of the DNA are excitons. Recent experiments in Poly(G)-Poly(C) DNA seem to confirm this picture . However, electronic states in biologically relevant DNA (non-periodic) depend considerably on the environmental conditions (such as pH, hydration, etc). Although the study of periodic DNA sequences is very important, it probably does not provide final information on the behavior of electrons in DNA under conditions where mutagenesis is relevant.

Recent experiments on long range electron transfer in DNA indicate that the introduction of Guanine-Citosine (G-C) base pairs enhance electron transfer . This situation is analogous to that in semiconductors where the introduction of electron donors (acceptors) increases the charge conduction by the creation of localized states close to the band edges. When a sufficiently large number of donors or acceptors is introduced into the DNA molecule an impurity band can be formed and conduction is possible. This picture seems to be supported by recent measurements of DNA resistivity . Another possible source of 1D conduction is via non-linear excitations such as solitons . As is well-known, disorder in 1D systems leads to localization of electron wavefunctions . However, when the localization length is large compared with typical electronic scales, electron transfer occurs. Moreover, DNA is aperiodic rather than random, and Anderson localization is a weaker effect.

We assume from the outset that the charge carriers (electrons or solitons) of DNA are delocalized over a region of size $`L`$ such that the energy level spacing $`\mathrm{}v_{F,l}/L`$ (where $`v_{F,l}`$ is the Fermi velocity in the strand $`l`$) is much smaller than the thermal energy $`k_BT`$ (where $`k_B`$ is the Boltzmann constant and $`T`$ is the temperature). The low energy excitations in this case are particle-hole pairs close to the Fermi points at $`\pm k_{F,l}`$. This simple scenario, however, is not enough to describe charge propagation in DNA because the charging energies for electron transfer between different base pairs is of order of electron volts as it is common in organic systems. From this point of view DNA is very close to being a Mott insulator instead of an ordinary band insulator . In 1D, such a conductor is called a Luttinger liquid . In a Luttinger liquid the low lying excitations are bosonic collective modes of spin and charge which have solitonic character.

Long ago Pauling  proposed that H-bonds have important covalent character, which has subsequently been confirmed . Proton states at the H-bonds are very important because they stabilize the double helix. Protons are much heavier than the electrons and therefore much slower. In A-T base pairs there are 2 H-bonds anchoring the two strands of DNA, while in the G-C case there are 3 H-bonds. In principle each proton in the H-bond can occupy one of its sides, and therefore there are 4 (8) possible states for the protons in A-T (C-G) base pairs. These states do not have the same energy because of the electrostatic interaction between the atoms in the base pairs with the protons at the H-bonds. Moreover, the difference in energy between the states is usually much larger than the thermal energy and therefore we only need to consider the ground state and the first excited state. We call the excitation energy between these two states $`ϵ_m`$, where $`m`$ labels the position of the base pair along the DNA backbone. In this case the proton Hamiltonian can be simply written as

$`H_p={\displaystyle \frac{1}{2}}{\displaystyle \underset{m}{}}ϵ_m\sigma _m^z`$ (1)
where $`\sigma ^z`$ is a Pauli matrix. In this representation the ground state of the proton problem is the pseudo-spin state $`|`$ while the excited state is $`|`$. Notice that $`ϵ_m`$ can have only two values corresponding to a A-T or G-C base pair. Thus, strictly speaking $`ϵ_m`$ is the energy required to produce a tautomeric state on an isolated base pair. Because of the large proton mass we disregard proton tunneling and treat the proton as a classical particle. Notice that at temperature $`T`$ the probability of having a local proton configuration in a mutated state is given by the Boltzmann distribution:

$`P_m(T)\mathrm{exp}\left[ϵ_m/(k_BT)\right]`$ (2)
corresponding to a thermal jump over the energy barrier. At room temperature and with $`ϵ_m`$ of the order of tenths of eV this probability is very small and mutation is a rare event.

Let us now consider the coupling between protons and $`\pi `$ electrons. This coupling depends strongly on the degrees of freedom of the H-bonds and the $`\pi `$ orbitals. On the one hand, the protons in the H-bond have their own magnetic spin degrees of freedom and non-magnetic pseudo-spin variables associated with their position in the H-bond. On the other hand, electron states in DNA can be labeled by their momentum $`\mathrm{}k`$, their true spin magnetic quantum number, and by their two possible strand numbers: $`l=\pm 1`$. While the strand and the spin quantum numbers of the electrons couple directly to the pseudo-spin of the proton, the proton spin couples to the electron spin via dipolar forces or contact interactions. If we view the single H-bond problem as an impurity in a chain (or ladder) then the DNA problem is of the so-called multi-channel Kondo type . Since in this paper we are only interested with the stability of the H-bond due to the presence of electrons and not with the magnetic properties of DNA, we neglect completely the dipolar interactions which can be studied separately. Moreover, the symmetry of the coupling between pseudo-spins and electrons is reduced due to the strong anisotropy of the proton positions. Therefore, in the simplest model, the electron-proton problem reduces to a local coupling of value $`\lambda _{m,l}`$ between the electronic charge density and the H-bond at the base pair $`m`$ on the strand $`l`$:

$`H_{ep}={\displaystyle \underset{m,l}{}}\lambda _{m,l}\left[\rho _{m,l}\overline{\rho }_{m,l}\right](\sigma _m^z1)`$ (3)
where $`\overline{\rho }_{m,l}`$ is the average electron density of the $`m`$th base pair in the $`l`$th strand and $`\rho _{m,l}`$ the actual electronic density. The physics of this problem is rather simple. In the absence of electronic coupling the H-bond of a given base pair $`m`$ will find itself in the lowest energy state which is stable at room temperature. Because the proton is coupled to the electrons it can generate electronic displacements along the helix with a gain of electrostatic energy. This gain of electrostatic energy, in turn, can stabilize a tautomeric configuration of the protons leading to mutation. The main question is whether the gain in energy due to the electron-proton interaction is enough to compensate for the loss of electrostatic energy between the proton and the base pair. Moreover, the coupling between H-bonds and electrons also generates an exchange interaction between H-bonds, which oscillates in space with a wavelength of order of the distance $`a`$ between base pairs.

The low energy excitations of this Luttinger liquid can be studied by the bosonization technique in which solitonic modes are bosons with momentum $`\mathrm{}k`$, energy $`\mathrm{}v_{F,l}|k|`$ and strand number $`l=\pm 1`$. In Hamiltonian form it can be written as

$`H_L={\displaystyle \underset{k,l}{}}\mathrm{}\overline{v}_{F,l}|k|b_{k,l}^{}b_{k,l}`$where $`b_{k,l}`$ ($`b_{k,l}^{}`$) is the boson annihilation (creation) operator and $`\overline{v}_{F,l}=v_{F,l}\sqrt{1+2U_l/(\pi v_{F,l})}`$ is the renormalized Fermi velocity due to the electron-electron interaction strength $`U_l`$. In our case the spin degrees of freedom are completely decoupled (unless we introduce a direct coupling between the proton and the electron spin) and do not appear explicitly into the problem. In particular, the density operator which appears in (3) can be written as

$`\rho _{m,l}={\displaystyle \underset{k}{}}k\sqrt{{\displaystyle \frac{L}{2\pi \left|k\right|}}}e^{\theta _l}\left(b_{k,l}e^{ikx_m}+b_{k,l}^{}e^{ikx_m}\right)`$where $`x_m`$ is the position of the $`m`$th pair along the helix and $`e^{\theta _l}=[1+U_l/(\pi v_{F,l})]^{1/4}`$. The main gain in using the bosonization procedure for this problem is that it maps the DNA problem given by the Hamiltonian $`H=H_p+H_L+H_{ep}`$ into an exactly solvable problem in many-body physics called the independent boson model . Our model describes the relaxation of the Luttinger liquid along the helix due to the proton configuration.

The first result of the model is that the excitation energy $`ϵ_m`$ of the H-bond is reduced by an amount $`\mathrm{\Delta }_m`$, where

$`\mathrm{\Delta }_m={\displaystyle \frac{1}{2}}{\displaystyle \underset{l=\pm 1}{}}{\displaystyle \frac{\lambda _{m,l}^2}{\pi v_{F,l}+U_l}}.`$ (4)
Thus, in the presence of a local metallic electron fluid one gets a reduction of the “natural” bias in the system and an increase in the probability (2) of finding the system in a tautomeric state. It is clear from (4) that this can only happen when coupling between H-bonds and electrons is large or when the Coulomb interaction between electrons is weak. In metallic DNA the electron-electron interactions will be screened by the electron motion and therefore $`\mathrm{\Delta }_m`$ can be large enough to induce mutation at room temperature. This mechanism for mutation seems to be consistent with recent findings relating the existence of repetitive sequences in DNA (which tend to delocalize the electrons) and mutagenesis associated with evolution .

In order to test our ideas we have calculated the heat capacity of DNA using the above described model. There are three main contributors to the DNA specific heat at low temperatures: the phonons which give a contribution growing like $`T^3`$, the electrons which contribute with a term proportional to $`T`$, and the protons which contribute with a Schottky term. The total specific heat can be calculated once the DNA sequence is known. We assume that the renormalized bias $`\overline{ϵ}_m=ϵ_m\mathrm{\Delta }_m`$ can be written as a series expansion of the temperature: $`\overline{ϵ}_mA_m+B_mT`$. The temperature dependence of the bias is due to the exchange interaction between the H-bonds propagated by the electron fluid. In a sample of DNA the values of $`A_m`$ and $`B_m`$ are distributed around an average value which is given by the average number of G-C and A-T pairs. For simplicity we assume here a gaussian distribution for both quantities. In Fig. 1 we compare the results of our model with the experiments reported in Ref.. The agreement between our model and the experiments is good. However, there are serious questions about sample quality in experiments dealing with DNA and therefore we have also calculated, as a further check, the infrared (IR) absorption for DNA using many-body techniques. The correlation function of interest is the proton spectral function which is defined as $`S_m(\omega )=2Im[G_m(\omega )]`$ where $`G_m(\omega )`$ is the Green’s function of the proton at base pair $`m`$ as a function of the frequency $`\omega `$. We found that IR absorption at a certain site $`m`$ is controlled by a parameter $`g_m`$ defined as

$`g_m={\displaystyle \frac{a\mathrm{\Delta }_m}{\pi \mathrm{}\overline{v}_F}}.`$ (5)
At zero temperature and $`g_m<1`$, DNA shows an X-ray edge effect with a sharp absorption edge. This effect is a result of the many-body character of DNA electronic conduction. If $`g_m>1`$ or the temperature is finite the IR absorption becomes smooth. For a specific DNA sequence one has to calculate the absorption of the DNA as a whole. In Fig. 2 we show the absorption spectrum for one of the DNA sequences of Fig. 1 at finite temperatures. Observe that no sharp X-ray edge is visible because of the superposition of many X-ray edges coming from individual protons. There is, however, a suppression of the absorption at low frequencies with the formation of a “pseudo-gap”.

In conclusion, we have proposed a model for electron-proton coupling and mutagenesis in DNA based on the idea of charge delocalization. We have shown that the position of the protons in DNA can change, leading to mutations when the $`\pi `$ electrons delocalize. We have compared our results for the specific heat at low temperatures with the available experimental data and found near quantitative agreement. We have also proposed new IR absorption experiments which can further test our model.

We acknowledge partial support from a Los Alamos CULAR grant under the auspices of the U. S. Department of Energy.


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# Influence of solvent granularity on the effective interaction between charged colloidal suspensions

## I Introduction

Most of soft matter systems, as colloids, polymers or biological macromolecules, are dispersed in a molecular solvent . Therefore, a full statistical description of supramolecular solutions should include the solvent explicitly. Such a treatment is highly non-trivial, however, since the length scale separation between the mesoscopic particles and the molecular solvent directly implies that the number of solvent particles which have to be included is enormous. On the other hand, one is interested mainly in properties of the big particles such that a solvent pre-average makes sense. The crudest form of such a course-grained level is to treat solvent properties just by a dielectric background or by some effective parameters which enter in the effective colloidal interactions. This procedure is questionable for polyelectrolytes where the solvent couples directly to the counterions which may affect the effective interaction between the polyelectrolytes via the long-ranged Coulomb coupling of counterions to the polyelectrolytes.

In this paper, we consider the case of two spherical charged colloidal particles (polyions) which are immersed in a bath of the molecular solvent and their oppositely charged counterions plus additional salt ions . Our main focus is the total effective force acting onto the colloidal pair which is the key quantity to understand colloidal stability and which governs colloidal correlations and phase transitions. In almost any theoretical treatment, the discrete structure of the solvent particles was neglected and only the charged constituents were treated explicitly within the so-called “primitive” model (PM) of strongly asymmetric electrolytes. Even this model is non-trivial in the colloidal context due to the large asymmetry between poly- and counterions and bears a rich physics resulting from the strong coupling between the different species. In recent computer simulations , counterionic correlations have been shown to be responsible for effective attractions between the like-charge polyions. The PM, re-formulated in terms of modern density functional theory of the inhomogeneous counterion plasma , can also also used as a starting point to derive simpler theories such as the mean-field nonlinear Poisson-Boltzmann approach or the linearized Debye-Hückel-type screening theory. The latter results in an effective Yukawa pair potential between the colloids as given by the electrostatic part of the celebrated Derjaguin-Landau-Verwey-Overbeek (DLVO) theory . This potential can also be used with renormalized parameters to include parts of the nonlinear screening effects arising from Poisson-Boltzmann theory .

In the present paper, we investigate the influence of solvent granularity on the effective interactions between charged colloids. We model the solvent as a hard sphere fluid at intermediate packing fractions and use computer simulations and the theoretical concept of effective interactions to derive effects due to the discrete solvent. The PM is tested against this more general model. Although the hard sphere model neglects some important solvent properties as its polarizibility  and its permanent multipole moments , it provides a minimal framework to get insight into counterion hydration and screening effects. The hard sphere solvent model (which is sometimes called solvent-primitive model) has been used also in many other investigations of ordinary electrolytes and for electrolytes confined between two parallel charged plates. Most of the approaches invoke additional approximations as different versions of liquid-integral equations , Poisson-Boltzmann theory suitably modified to include the short-ranged solvent depletion effects , or more sophisticated density functional approaches of multicomponent systems . For charged plates  and for small neutral particles  some computer simulations have already been performed including a hard sphere solvent explicitly but there are no results for charged colloidal spheres.

Most of the results in this paper are based on a new “solvent bath” simulation scheme which allows to simulate many neutral spheres together with the charged species. For divalent counterions, we obtain attractive forces due to overscreening of polyions by counterions which are attracted towards the colloidal surfaces via hydration (or solvent depletion) forces. For monovalent counterions and large distances we show that the concept of charge renormalization can be used to extract a Yukawa picture of the effective interaction with a solvent-renormalized polyion charge. We check the trends of this renormalized charge with respect to the colloidal density and the concentration of added salt and find qualitative agreement but quantitative differences as compared to the Poisson-Boltzmann theory. All our results can be reproduced within a solvent-averaged primitive model (SPM) which was extensively used in earlier theoretical studies of electrolytes between plates . This idea originates from McMillan and Mayer  dating back to 1945.

Our paper is organized as follows: In chapter II, we describe our model and define approximations on different levels. The computer simulation method is described in chapter III. We then turn to results for the neutral case in chapter IV and for the salt-free case in chapter V. Parts of the latter have been published elsewhere . The effect of added salt is described in chapter VI and other mechanisms of polyion-polyion attraction are critically discussed in chapter VII. We finally conclude in chapter VIII.

## II Modeling on different levels

In this section we summarize the modeling on different levels. In the following we shall use the most detailed description of the hard sphere solvent model and test the validity of the different inferior levels with respect to our data.

### A The hard sphere solvent model (HSSM)

The hard sphere solvent model (HSSM) involves spherical polyions with diameter $`\sigma _p`$ and homogeneously smeared charge $`q_p`$ together with their counterions of diameter $`\sigma _c`$ and charge $`q_c`$ in a bath of a neutral solvent $`(q_s=0)`$ with diameter $`\sigma _s`$. In the absence of salt, the pair potentials between the particles as a function of their mutual distances $`r`$ are a combination of excluded volume and Coulomb terms

$$V_{ij}(r)=\{\begin{array}{cc}\mathrm{}\hfill & \text{for }r(\sigma _i+\sigma _j)/2\hfill \\ q_iq_j/ϵr\hfill & \text{else}\hfill \end{array}$$
(1)
where $`ϵ`$ is the a smeared background dielectric constant of the solvent and $`(ij)=(pp),(pc),(ps),(cc),(cs),(ss)`$. Further parameters are the thermal energy $`k_BT`$ and the partial number densities $`\rho _i(i=p,c,s)`$ which can be expressed as partial volume fractions $`\varphi _i=\pi \rho _i\sigma _i^3/6(i=p,c,s)`$. Charge neutrality requires $`\rho _p|q_p|=\rho _c|q_c|`$. Additional salt ions can readily be included into the description as further charged hard spheres.

### B The solvent-averaged primitive model (SPM)

For a fixed configuration of charged particles the solvent can be traced out exactly arriving at depletion forces $`\stackrel{}{F}_i^{(d)}`$ acting onto the $`i`$th charged particle. They can be related to a surface integral over the solvent equilibrium density field $`\rho _s(\stackrel{}{r})`$ which depends parametrically on the positions of the fixed charged particles:

$$\stackrel{}{F}_i^{(d)}=k_BT_{𝒮_i}𝑑\stackrel{}{f}\rho _s(\stackrel{}{r})$$
(2)
where $`\stackrel{}{f}`$ is a surface vector pointing towards the center of the $`i`$th charged particle. If one adds these forces to the PM, the resulting model is strictly equivalent to the HSSM. The integrand $`\rho _s(\stackrel{}{r})`$ is affected by the space excluded for the solvent due to the presence of the finite core of the charged particles resulting in inhomogeneous density distributions around the excluded volume. The range of this inhomogeneity is characterized by the hard sphere bulk correlation length $`\xi `$ which depends on the solvent packing fraction $`\varphi _s`$. A further approximation decomposes the forces $`\stackrel{}{F}_i^{(d)}`$ into pairwise parts, i.e. into a superposition of pair contributions coming from neighboring charged particles. This approximation is justified if the average distance between triplets, quadruplets, etc. of charged particles is much larger than the bulk correlation length $`\xi `$. In the salt-free case, this is generally granted except for nearly touching polyions with squeezed counterions. If salt is added, the justification is less clear as ion pairing by counter- and coions near polyions may be an important configuration.

The resulting pairwise interactions define the solvent-averaged model (SPM) where the depletion pair potentials $`V_{ij}^{(d)}(r)`$ ($`(ij)=(pp),(pc),(cc)`$) have to be added to the interactions of the primitive model of the next paragraph. These pairwise depletion forces have been the subject of intense recent research . In particular, we will determine them by computer simulation, and use these results as an input for the SPM.

### C The primitive model (PM)

The primitive model has the same interactions as the HSSM except for the absence of the solvent. Hence the basic interactions are again

$$V_{ij}(r)=\{\begin{array}{cc}\mathrm{}\hfill & \text{for }r(\sigma _i+\sigma _j)/2\hfill \\ q_iq_j/ϵr\hfill & \text{else}\hfill \end{array}$$
(3)
but now for $`(ij)=(pp),(pc),(cc)`$ only.

### D DLVO-theory

In DLVO theory, only the polyions are treated explicitly. The electrostatic part of their interaction is an effective Yukawa pair potential which has the form:

$$V(r)=\frac{q_p^2\mathrm{exp}(\kappa (r\sigma _p))}{(1+\kappa \sigma _p/2)^2ϵr}$$
(4)
with

$$\kappa =\sqrt{4\pi \rho _cq_c^2/ϵk_BT}$$
(5)
### E The PB-renormalized Yukawa model (PBYM)

This approach was suggested by Alexander et al  and is based on Poisson-Boltzmann theory in a spherical cell around a single polyion. The cell radius $`R`$ is fixed by the polyion concentration:

$$R=(4\pi \rho _p/3)^{1/3}$$
(6)
Within Poisson-Boltzmann theory, one calculates the counterion density $`\stackrel{~}{\rho }_c`$ at the cell boundary. Linearizing the nonlinear Poisson-Boltzmann theory at the cell boundary, one obtains again an effective Yukawa potential between the colloids arriving at the PB-renormalized Yukawa model (PBYM). The Yukawa potential has the same form as in Eqn.(4) but contains a renormalized inverse screening length

$$\kappa ^{}=\kappa \sqrt{\frac{\stackrel{~}{\rho }_c}{\rho _c}}$$
(7)
and a renormalized charge

$$q_p^{}=q_p\frac{\stackrel{~}{\rho }_c}{\rho _c}$$
(8)
which is considerably smaller than the bare charge $`q_p`$. Many experimental data for the colloidal structural correlations , the long-time self-diffusion  or the freezing line  have been analyzed using this concept of charge renormalization and in general good agreement was found for monovalent counterions provided the colloids are far away from charged plates .

### F The solvent-renormalized Yukawa model (SYM)

This approach is a generalization of the Poisson-Boltzmann cell modell  to the presence of a granular solvent. Again, one considers a single polyion in a spherical cell, but uses the full HSSM to obtain the counterion density $`\stackrel{~}{\rho }_c`$ at the cell boundary. As in the PBYM, the associated Yukawa pair potential has a solvent-renormalized inverse screening length $`\kappa ^{}`$ and a solvent-renormalized charge $`q_p^{}`$, which, however, differ from that of the PBYM approach.

## III Simulation method

We consider two large spherical polyions in a cubic simulation box of length $`L`$ with periodic boundary conditions, hence $`\rho _p=2/L^3`$. The polyions are fixed along the body diagonal of the cubic box. While the simulation methods for the PM are straightforward and are described elsewhere , a significant volume fraction of solvent particles together with large colloidal particles implies a huge number of solvent spheres in the simulation box.

As the solvent interactions are short ranged and the solvent-averaged interactions are only of range $`\xi `$, one can reduce the number of solvent particles in the simulation box considerably using a “solvent-bath” method. This procedure is sketched in Figure 1 and works as follows: we define a spherocylindrical cell around the colloidal pair such that the minimal distance $`h`$ from the colloidal surface to the spherocylindrical boundary is much larger than the hard sphere bulk correlation length $`\xi `$. The hard sphere solvent is only contained in this spherocylinder. As the cell volume is considerably smaller than the volume $`1/L^3`$ of the whole simulation box, the number of solvent particles for fixed given volume fraction $`\varphi _s`$ is drastically reduced. No restriction is done for the counter- and salt-ions, which can move within the whole simulation cell.

Care has to be taken at the artificial cell boundary. We use the Molecular Dynamics (MD) method calculating the particle trajectories and performing statistical averages over some physical quantities. The hard sphere solvent is treated by the well-known hard sphere collision rules. Once a solvent particle is leaving the spherocylindric cell it is randomly inserted at another place of the cell boundary with the same velocity. The position of its random insertion has a randomly chosen distance from the spherocylindrical boundary up to $`2\sigma _s`$ which avoids unphysical solvent layering there.

Since the width of the cell $`h`$ is much larger than the hard sphere bulk correlation length $`\xi `$, the presence of the boundary has no influence on the inhomogeneous density distribution of the solvent and the counterions near the colloidal surfaces. The counterion motion is implemented as follows: Outside the spherocylindrical cell the counterions interact via a solvent-averaged effective depletion potential. This is justified as the typical distance between the counterions is much larger than the hard sphere bulk correlation length $`\xi `$. Therefore, the correction to $`V_{cc}(r)`$ due to solvent layering is negligibly small anyway for counterions outside the spherocylindrical cell. This is not the case when salt is added as the attraction between co- and counterions may lead to short distances where solvent depletion effects may dominate the interactions. For a counterion approaching the cell boundary, there is an artificial asymmetry between the solvent bath inside the cell and the “vacuum” outside the cell which hinders a counterion to penetrate into the solvent bath. This unphysical effect is repaired in the simulation scheme by switching off the counterion-solvent interaction for a counterion which is penetrating from outside. Once the counterion is fully surrounded by solvent molecules the interaction is turned on again. This leads to a symmetric counterion crossing rate across the spherocylindrical cell boundary.

We have carefully tested the algorithm against simulations of small systems where the whole space was filled with solvent particles. We also tested against a situation of a solvent slab between charged plates. Perfect agreement was found compared to simulations where the whole space was filled with solvent particles.

## IV Results for the neutral case

Let us first discuss the much simpler case of neutral polyions ($`q_p=0`$) under absence of counterions. The resulting system is just a pair of big hard spheres in a sea of small solvent spheres. This simple model for binary mixtures of hard sphere colloids has gained considerable attention during the past ten years. The effective interaction between the large spheres as induced by depletion of the small spheres in the zone intermediate between the nearly touching big spheres has the following characteristic features which were obtained by density functional theory , computer simulation  and experiments : it is attractive for nearly touching spheres, then it oscillates with the bulk correlation length of the hard sphere solvent $`\xi `$. The depletion interactions decays to zero exponentially with the surface-to-surface separation of the big spheres. The characteristic decay length is again the bulk correlation length $`\xi `$.

Our motivation to investigate the neutral case is twofold: First, it is a simple case which allows to test our simulation set-up. There are some computer simulations of the depletion interaction in the literature but the range of parameters examined is far from being complete. Second, for the solvent-averaged primitive model (SPM) it is exactly the solvent depletion term (2) which one has to add to the primitive interactions as given by eqn.(3). Therefore, studies of the SPM require a full knowledge of the neutral case.

Computer simulation results for the total effective depletion force $`F_{pp}^{(d)}(r)`$ acting onto the big spheres are presented in Figure 2 for two size ratios $`\sigma _p/\sigma _s`$ of $`2`$ and $`14`$. The solvent packing fraction was chosen to be $`\varphi _s=0.3`$. The force is projected onto the particle separation vector such that a positive sign means repulsion. We note that a direct evaluation of eqn. (2) is difficult as the solvent density field piles up strongly at the surfaces of the big particles. A much more effective way is to measure the momentum transfer on the fixed big spheres due to colliding small spheres during the Molecular Dynamics simulation. The results are compared with a recently proposed fitting formula of Roth and Evans based on density functional theory . One sees that the contact value of the force and the oscillations are well-described by the theory but there are deviations around the first maximum. This is less apparent if the effective potential is compared as shown in the inset of Figure 2. Obviously, the reason for that is that the force is a derivative which is more sensitive to approximations. In the computer \[

\] simulation, the effective potential $`V_{pp}^{(d)}(r)`$ can be accessed by integrating the distance-resolved computer simulation results of the force

$$V_{pp}^{(d)}(r)=_{\mathrm{}}^r𝑑r^{}F_{pp}^{(d)}(r^{})$$
(9)
Also the whole set of depletion pair potentials $`V_{ij}^{(d)}(r)`$ ($`(ij)=(pp),(pc),(cc)`$) which are the input of a typical SPM simulation are presented in Figure 3. The counterion-counterion interaction is dominated by the Coulomb repulsion also shown as a dashed line in Figure 3c. The bare Coulomb repulsion between the polyions is much larger than the polyion-polyion depletion potential and is not shown in Figure 3a. Finally, the polyion-counterion depletion interaction exhibits a deep attraction near contact of the order of $`k_BT`$ which is of similar order than the Coulomb attraction also shown as a dashed line on Figure 3b. This will have important consequences of counterion adsorption on the colloidal surface. This effect is induced by the granularity of the solvent and is absent in the PM.

## V Results for the salt-free case

### A Nano-sized colloids

Although the amount of solvent which has to be simulated explicitly has been reduced drastically by the solvent-bath scheme, only colloidal sizes which are in the nano-domain can be addressed on present-day computers. We have performed extensive computer simulation in this domain to check carefully the different approaches. We find that the SPM describes the full simulation data of the HSSM very well. Larger colloidal sizes are thus only accessible within the SPM and discussed in chapter V.B.

In our simulations, we fixed $`T=298^oK`$ and $`ϵ=81`$ (water at room temperature) with $`\sigma _s=3\AA `$, $`\varphi _s=0.3`$ such that $`\xi `$ is about $`3\sigma _s`$. We varied the polyion charge and size and the counterion diameter $`\sigma _c`$. The width of the spherocylindrical cell $`h`$ is $`10\sigma _c`$ such that typically $`N_s=25.00030.000`$ solvent hard spheres are simulated.

We have basically calculate two quantities: first, as a reference, we have calculated the spherically averaged counterion density profile $`\rho _c(r)`$ around a single polyion where $`r`$ is the distance from the polyion center. The simulation was done in a cubic box of reduced length $`L/2^{1/3}`$ with periodic boundary conditions in order to reproduce the colloidal packing fraction $`\varphi _p`$. Second, our target quantity is the total force $`F(r)`$ acting onto a polyion for a given colloid-colloid separation $`r`$. This effective force $`F(r)`$ is the sum of four different contributions:
i) the direct Coulomb repulsion as embodied in $`V_{pp}(r)`$ (note that all the periodic images contribute to the total force),
ii) the counterion screening resulting from the averaged Coulomb force of counterions acting onto the polyions,
iii) the counterion depletion term arising from the hard sphere part of $`V_{pc}(r)`$,
iv) the solvent depletion force.

Explicit results for $`F(r)`$ are presented in Figure 4 where the solvent and the counterion diameter were chosen to be equal and the counterion were monovalent.

The force exhibits oscillations for molecular distances due to solvent and counterion layering and is repulsive for larger distances. The SPM yields surprising agreement with the HSSM describing even the molecular oscillations for nearly touching polyions, see the inset of Figure 4, while the PM overestimates the force considerably. This can be attributed to the fact that the SPM incorporates the additional counterion accumulation at the colloidal surface due to the hydration or solvent depletion. This can clearly be seen in the counterionic density profile around a polyion as shown in Figure 5 which piles up near the colloidal surface. While this accumulation is quantitatively described by the SPM it is absent in the ordinary PM. The PBYM and DLVO theory lead to forces which strongly overestimate the HSSM data.

We have further tested the frequently invoked “superposition principle” which approximates the total force as a sum of the PM and the depletion term. Its comparison to the full HSSM data is given in Figure 6a. The first maximum of the total force is semi-quantitatively reproduced but the superposition principle predicts a second maximum which is too sharp as compared to the HSSM data. This becomes even worse for a doubled counterion diameter of $`6\AA `$ where the superposition predicts a secondary maximum which is completely absent in the HSSM data, see Figure 6b. The physical reason for that is that the counterion layering coupled to the solvent degrees of freedom becomes relevant for these distances.

The forces for a doubled counterion diameter $`\sigma _c`$ are presented in Figure 7. For small distances (except for touching), the PM yields larger forces as compared to Figure 4, as the counterion repulsion is stronger which reduces screening. In the HSSM and SPM, on the other hand, also the polyion-counterion depletion attraction is getting stronger, such that the total polyion screening is practically unaffected. Of course, the PBYM and DLVO theory yield results which are insensitive to the counterion diameter.

Furthermore we have investigated the case of stronger Coulomb coupling by considering divalent counterions. Explicit data are shown in Figure 8. There is overscreening of polyions resulting in a mutual attraction between like-charged polyions. We emphasize that it is the electrostatic term of the counterions that produces the attraction but not the counterion or solvent depletion term.

Nearly every counterion is in the presence of the colloidal surfaces, as demonstrated by the counterionic density profile shown in Figure 9 where the piling-up of counterions near the colloidal surface is much stronger. The attractive force has a range of several polyion diameters. Again the SPM perfectly reproduces the forces. The PM (and also the PBYM and DLVO theory), on the other hand, yield repulsion. This demonstrates that a discrete solvent has a profound influence on the effective interactions.

We finally discuss the validity of the solvent-renormalized Yukawa model (SYM). Computer simulations have been performed for a single polyion in a spherical cell and the counterion boundary density was calculated. The boundary of the cell was not hard but counterions leaving the cell were inserted at the opposite side of the cell. Again a smaller spherical solvent bath around the polyions with a width $`h`$ was used, see Figure 10 for the set-up and a projected simulation snapshot. As Figures 4 and 7 show, the SYM is indeed a reasonable description of the forces for large distances. We also remark that the SPM and the HSSM yield the same counterion density at the boundary of the spherical cell needed as an input for the SYM which justifies the usage of the SPM to get the solvent-renormalized Yukawa parameters of the SYM.

The validity of the SYM only holds for the case of monovalent counterions where the remaining “free” counterions are responsible for the screened, repulsive force. For divalent counterions, no free counterions are left, and a linearized screening theory breaks down such that an attraction cannot be encaptured by the SYM.

### B Mesoscopically-sized colloids

Our results for mesoscopically-sized colloids are based on SPM simulations as justified in the previous chapter. Distance-resolved colloidal forces $`F(r)`$ for monovalent counterions, a size asymmetry of $`\sigma _p:\sigma _c:\sigma _s=370:1:1`$ or $`370:2:1`$, and a charge ratio of $`q_p/q_c=280`$ are presented in Figure 11. These forces are repulsive but much smaller than that from PM simulations. Again, this is due to counterion accumulation near the colloidal surface as induced by the additional solvent depletion attraction. As the corresponding potential energy gain is only few $`k_BT`$, this depletion attraction is different from chemisorption of counterions. The solvent-renormalized Yukawa model (SYM) leads to forces which are very similar to the SPM over the whole range of distances explored while the PM overestimates the forces.

The traditional meaning of the “bare” charge $`q_p`$ in the PM is not the full polyion charge but a smaller charge which results from a polyion charge reduction by strongly adsorbed (or condensed) counterions. This picture can also be tested against our results. We first have calculated the average number of counterions in a molecular shell around the colloids of width $`\xi `$. If the polyion charge is reduced by this amount and the PM is used to predict the effective interaction, the resulting force still overestimates the HSSM data, see the open diamonds in Figure 11a. In order to fit these data satisfactorily, one has to assume an unphysically large width of $`5\xi `$ to get a charge reduction that reproduces the SPM data. Hence the PM cannot be justified even with a polyion charge reduction. The reason for that are the weak hydration forces which are quite different from chemisorption providing a strong counterion binding with an energy gain of hundreds or thousands of $`k_BT`$. Furthermore, an arbitrary splitting into a fraction of condensed counterions and “free” counterions described by DLVO, Poisson Boltzmann or any other local density functional theory is not possible: near the colloidal surface the electric double layer is highly correlated such that fixing a fraction of counterions gives a completely different picture. Only if the fraction of free counterions is determined within an approach that includes all these correlations (as in the SYM), a linearized screening theory far away from the colloidal surfaces is justified.

This consideration casts some doubts to some recent theories where such a partitioning of counterions is an input, see e.g. Refs. . Further SPM results for a doubled counterion diameter are presented in Figure 11b. As the counterion depletion force is getting stronger for a large counterion, the force is getting smaller, compare the full and dashed line in Figure 11b. The PM (short-dashed line in Figure 11b), on the other hand, is practically insensitive to a change of the counterion diameter except very close to the colloidal surfaces. This picture gains further support from the counterionic density profiles around a single polyion shown in the inset of Figure 11b for distances very close to the colloidal surface. A layer of condensed but still mobile counterions close to the surfaces is present in the SPM which is absent in the PM. The larger the counterion diameter the more counterions are in this layers as the depletion is getting stronger.

We finally discuss the solvent-renormalized charge $`q_p^{}`$ as a function of the colloid volume fraction $`\varphi _c`$ for fixed bare charge $`q_p`$ and compare with the prediction of the traditional charge renormalization approach within in Poisson Boltzmann cell theory (PBYM) . Simulation data for $`q_p^{}`$ based on the SPM in a spherical cell are shown on the full line in Figure 12. The renormalized charge is smaller than the bare charge and behaves non-monotonic with the particle density. The non-monotonicity is stable with respect to added salt and is related to a non-monotonic counterion density at the cell boundary as a function of density. It can be understood as follows: For extremely high packing fractions the spherical cell accessible for the counterions is a very thin shell across which the polyion-counterion attraction varies slowly. Due to the rapidly decreasing volume accessible for the counterions, the boundary counterion density becomes larger for increasing $`\varphi _p`$, see the volume fraction correction in Refs. . On the other hand, for very small $`\varphi _p`$, entropy of counterions will force them to cover the whole accessible space. The counterion density at the cell boundary will increase for decreasing $`\varphi _p`$ getting close to the average density in the limit $`\varphi _p0`$. We remark, however, that the non-monotonicity occurs at high polyion packing fractions of order $`\varphi _p0.050.2`$ where the approximation of a spherical cell becomes questionable.

The PBYM for a fixed bare charge leads to larger values (long-dashed line in Figure 12) which still correctly describe the trend and the non-monotonicity. If the SPM data for the smallest colloid concentration are taken as a benchmark, a bare charge of $`q_p=269e`$ is necessary to reproduce the same renormalized charge within the Poisson-Boltzmann theory. This procedure is in strong analogy with interpreting an experiment where the charge is a fit parameter to describe the structural data. Starting from this bare charge and changing the colloidal density, the PBYM predicts a similar trend for the renormalized charge (short-dashed line in Figure 12) but the actual numbers are different. This is consistent with experiments on strongly deionized colloidal samples which were successfully interpreted using a Poisson-Boltzmann renormalized colloidal charge .

## VI Effects of added salt

Within the HSSM, the salt ions enter as charged hard spheres. For simplicity, we have considered a situation where the salt ions are monovalent and have the same diameter as the counterions and the solvent. Results for the effective interactions for a case with added salt are presented in Figure 13. As expected, the salt ions provide an additional screening such that the forces are less repulsive than in the salt-free case (compare with Figure 4). The SPM reproduces the full HSSM data for intermediate distances but there are deviations for molecular distances. This is in contrast to the salt-free case where good agreement between the SPM and the HSSM was found even for small distances. The physical reason for this is that the pair potential decomposition which is the basic approximation of the SPM breaks down for nearly touching polyions as important configurations are paired microions squeezed between the polyions. This is a manifest many-body situation beyond the pair level. Still for two well-separated polyions or a single polyion, the SPM and the HSSM yield similar results for the counterion density field or the colloidal forces.

As in the salt-free case, we have tested the PBYM. The solvent-renormalized charge $`q_p^{}`$ as obtained from the SPM is plotted as a solid line in Figure 14 versus salt concentration. It decreases for increasing salt concentration. The PBYM for the same bare charge of $`q_p=280e`$ yields the same trend as obtained in earlier investigations , see the long-dashed line in Figure 14. If scaled by

using the SPM data for the salt-free case as a benchmark (short-dashed line in Figure 14), the trend obtained in the PBYM is almost the same as that in the SPM. This explains the success of fitting experimental data  by using the PBYM for real colloidal samples which typically contain a lot of added salt. If the SPM data for a high concentration of added salt is used as benchmark point, the PBYM predicts much smaller renormalized charge upon deionization (dot-dashed line in Figure 14).

## VII Comments on other mechanisms for polyion-polyion attraction

We finally comment on two other physical mechanism for mutual attraction between like-charge colloids. The first is the counterion depletion mechanism which was found within the PM in salt-free colloidal suspensions with strong Coulomb coupling (as realized by a small dielectric constant) . We have redone the simulation using the same parameters as in Ref.  but now with added salt. The depletion attraction is reduced but still present, see Figure 15. As put forward in Ref. , the range of the attraction is comparable to

$$a=\sqrt{q_c/q_p}\sqrt{4\pi /\sqrt{3}}\sigma _p$$
(10)
which is a typical counterion distance corresponding to the spacing of a triangular lattice on the spherical colloidal surface. This length is also included in Figure 15.

Unfortunately, the polyion radius used in Ref.  is too large to allow for a reasonable number of solvent particles in the solvent bath. Therefore we have slightly reduced the polyion size such that the PM yields the same counterion depletion-mediated attraction. Results based on the HSSM and PM are collected in Figure 16. As can be deduced form this figure, the depletion-mediated attraction is stable with respect to an explicitly added solvent. It is further stable but reduced with respect to added salt. However, an added solvent reduces the attraction a bit. The physical reason for that is that the solvent will prefer to stay in the counterion-free space near the colloidal surfaces such that the solvent depletion cancels part of the counterion depletion force.

Second, we comment on the mechanism of metastable oppositely-ionized colloids leading to long-ranged Coulomb attraction as found in recent salt-free PM simulations by Messina et al . We have confirmed and reproduced this effect in our simulations for the parameters of Figure 16. We found, however, that the opposite ionization of the colloids will be immediately suppressed if salt is added. In Figure 16, it is shown that for large distances the salt-free PM data are close to the long-ranged Coulomb force for an ionization degree by one counterion (compare the dot-dashed and the short-dashed line in the inset of Figure 16). Once salt is added, however, the additional microscopic ions will be attracted directly towards the ionized polyions and the long-ranged Coulomb attraction disappears (see the long-dashed line in the inset of Figure 16). Hence, the mechanism of attraction due to metastable ionized states is not stable with respect to added salt. We also remark that metastable ionized states will disappear for separations shorter than the characteristic depletion zone length $`a`$. For such close configurations, the mutual attractive Coulomb correlations in the counterion cloud around both polyions will lead to a symmetric shearing of counterions by the two neighboring polyions. For such small separations, counterion depletion is responsible for the attraction. As a function of distance, the total force is nonmonotonic. For small distances it is dominated by counterion depletion which decays off rapidly on the scale $`a`$, while for larger distances the electrostatic resulting from the metastable oppositely-ionized colloids leads to a long-ranged attraction.

## VIII Conclusions

In conclusion, based on simulations of an model which contains the granularity of the solvent explicitly, we have shown that hydration forces profoundly influence the colloidal interaction. For divalent counterions, there is solvent-induced attraction which is not contained in the traditional primitive model but can be encaptured within a solvent-averaged primitive model (SPM). For monovalent counterions, the forces can be described by a solvent-induced charge renormalization. This picture is in agreement with experiments on strongly deionized samples where a Yukawa picture can be employed provided the colloidal charge is renormalized towards a value smaller than the bare charge . The trends of the renormalized charge upon increasing the salt concentration is similar in the Poisson-Boltzmann cell model and the SPM which explains why the experimental data could be well-described by using a Yukawa interaction with a Poisson-Boltzmann-renormalized charge . Still, quantitatively, there are differences between the renormalized charges of the Poisson-Boltzmann cell model and the SPM.

Future research should focus on the role of the permanent dipole moment in a polar solvent as modelled by dipolar hard spheres  or a Stockmayer liquid . Also more work has to be done to explore the role of charge regulation and chemisorption of counterions near the colloidal surfaces. Furthermore the dielectric discontinuity at the colloidal surfaces resulting in image charge effects has to be explored in more detail. For all these circumstances the concept of a renormalized polyion charge resulting in a Yukawa picture should be possible provided there are free counterions left which dominate the effective repulsion between the colloids.

We finally point out further possible applications of our simulation technique: If used without the confining solvent-bath shell, our approach starts “ab initio” and even employs the correct microscopic (molecular) dynamics of the solvent. Therefore, it could also be used to address dynamical questions in equilibrium and non-equilibrium. Important examples concern the motion of poly- and counterions under the influence of an external electric field including effects as the electrophoretic mobility , ion migration , electro-kinetic properties  and electrolyte friction . Our approach produces both diffusive motion and hydrodynamic interactions mediated by the solvent as an output. Of course, one will not be able to simulate large time scale separations between the Brownian and the structural relaxation time  but one should try to start with moderate time scale separations in order to test the approximative theories of electrophoresis.

We thank R. Roth, M.Schmidt and T. Palberg for helpful remarks and the DFG for financial support.


text:
# Quantum and classical solutions for a free particle in wedge billiards

## Abstract

We have studied the quantum and classical solutions of a particle constrained to move inside a sector circular billiard with angle $`\theta _w`$ and its pacman complement with angle $`2\pi \theta _w`$. In these billiards rotational invariance is broken and angular momentum is no longer a conserved quantum number. The “fractional” angular momentum quantum solutions are given in terms of Bessel functions of fractional order, with indices $`\lambda _p=\frac{p\pi }{\theta _w}`$, $`p=1,2,\mathrm{}`$ for the sector and $`\mu _q=\frac{q\pi }{2\pi \theta _w}`$, $`q=1,2\mathrm{}`$ for the pacman. We derive a “duality” relation between both fractional indices given by $`\lambda _p=\frac{p\mu _q}{2\mu _qq}`$ and $`\mu _q=\frac{q\lambda _p}{2\lambda _pp}`$. We find that the average of the angular momentum $`\widehat{L}_z`$ is zero but the average of $`\widehat{L}_z^2`$ has as eigenvalues $`\lambda _p^2`$ and $`\mu _q^2`$. We also make a connection of some classical solutions to their quantum wave eigenfunction counterparts.

Pacs 05.45.+b, 03.65.-w,72.20.Ht

Significant progress has been made in the last few years in understanding the connection between classical and quantum solutions for problems that show chaotic behavior. A particularly important role in this progress has been played by studies in billiards with different geometries . The dynamics of a free particle in a circular billiard is completely integrable since energy and angular momentum are conserved. A simple change of the circular billiard to the stadium billiard immediately leads to chaotic particle dynamics . The analysis of these billiards eigenvalue spectra and eigenfunctions have yielded a number of clearly defined quantum manifestations of classically chaotic Hamiltonians . There are also other types of billiards that, although not being explicitly chaotic, can yield interesting novel quantum and classical behavior. A case in point considered in this paper has a free particle that moves inside a boundary defined by a wedge shaped section of a circular billiard. In this case regular $`2\pi `$-rotational invariant angular momentum is no longer conserved. However, fractional quantum angular momentum is well defined. It is this fractional angular momentum that makes this problem interesting. There have been other studies of modified circular billiards, like a wedge sector in the presence of a constant linear field that shows chaotic behavior , and circular chaotic billiards with a straight cut . These billiards are different from the ones we study in this paper. Here we consider sector billiards with angle $`\theta _s=\theta _w`$ and their pacman complement of angle $`\theta _p=2\pi \theta _w`$. These two types of billiards can be considered special cases of simple wedge billiards that have corner discontinuities. For our quantum analysis it is, however, relevant to separate them this way since the angular momentum spectral properties of the sector and its corresponding pacman can be related to each other.

Our original motivation to study this problem actually came from experiments carried out in pacman type mesoscopic billiards . These billiards were studied in the presence of a magnetic field where the breaking of rotational invariance precludes the full rotational closing of Aharonov-Bohm loops. This significantly affects their contribution to the magnetoresistence. As a first step towards understanding the magnetic field problem, we consider in this paper the quantum and classical zero field cases. The quantum problem can be studied to some extent analytically, leading to interesting duality spectral relations. We also make a connection between the quantum and classical solutions that help to understand the quantum results.

The quantum Hamiltonian for a free particle of mass $`M`$ in a wedge billiard is $`\widehat{H}=\frac{\widehat{P}^2}{2M}+V(r)`$, with

$`V(r)=\{\begin{array}{cc}0\hfill & r\epsilon D,\hfill \\ \mathrm{}\hfill & rD.\hfill \end{array}`$

Here $`D`$ is the domain of the wedge billiard. The corresponding time-independent Schrödinger equation is

$$(^2+k^2)\mathrm{\Psi }_D=0,$$
(1)
with boundary condition $`\mathrm{\Psi }_C=\mathrm{\Psi }(rC)=0`$, with $`C`$ the boundary of the domain $`D`$. Here $`k^2=\frac{2ME}{\mathrm{}^2}`$, $`E`$ is the energy and $`2\pi \mathrm{}=h`$ is Planck’s constant. We can immediately write the full set of solutions for the sector and pacman wave-functions that satisfy the radial and angular boundary conditions. The general normalized sector wave function is then given by

$$\mathrm{\Psi }_s=\mathrm{\Sigma }_p^{\mathrm{}}\mathrm{\Sigma }_{n>1}^{\mathrm{}}\frac{J_{\lambda _p}(\frac{\alpha _{\lambda _p,n}}{r_w}\rho )\mathrm{sin}\lambda _p\theta }{\frac{\sqrt{\theta _s}}{2}r_wJ_{\lambda _{p+1}}(\alpha _{\lambda _p,n})}.$$
(2)
Note that this wave function vanishes when $`\theta =0`$ and $`\theta =\theta _s`$, and $`\rho =r_w`$, with $`r_w`$ the sector radius. The angular boundary condition determines the values for the indices $`\lambda _p`$ that are

$$\lambda _p=\frac{p\pi }{\theta _s},p=1,2,3\mathrm{}$$
(3)
Consider, for example, the case where the angular momenta are the integers $`\lambda _p=ap`$ that correspond to the sector angles $`\theta _s=\pi /a`$, with $`a`$ an integer. Depending on the value of $`a`$ we will have a set of integers that will be a subset of the index values for the angular momenta of the full circle. For example, if we take $`\theta _s=\pi /4`$, we get $`\lambda _p=4,8,12,16,\mathrm{}`$ or if $`\theta _s=\pi /3`$ we get $`\lambda _p=3,6,9,12,15,\mathrm{}`$. If the index is even we get a subset of even integer angular momenta while for the odd case we get a subset of even and odd values for the angular momentum. We can instead chose $`\theta _s=\frac{b}{a}\pi `$, which will give $`\lambda _p=p\frac{b}{a}`$, with $`b`$ and $`a`$ prime numbers. In this case $`\lambda _p`$ will generally be fractional and no full circle angular momentum values will be present. In the case where the angle is irrational, say $`\theta _s=\alpha \pi `$, with $`\alpha `$ irrational, the situation radically changes since $`\lambda _p=p/\alpha `$ has no corresponding analog in the angular momenta for the complete circle or for the rational angles.

In the pacman case we can also write the complete wave function as

$$\mathrm{\Psi }_p=\mathrm{\Sigma }_{\mu _q}^{\mathrm{}}\mathrm{\Sigma }_{m>1}^{\mathrm{}}\frac{J_{\mu _q}(\frac{\alpha _{\mu _q,m}}{r_w}\rho )\mathrm{sin}\mu _q\theta }{\frac{\sqrt{2\pi \theta _w}}{2}r_wJ_{\mu _{q+1}}(\alpha _{\mu _q,m})},$$
(4)
where $`\mu _q`$ is the order of the Bessel function and $`m=1,2,3\mathrm{}.`$, with $`\theta _p=2\pi \theta _w`$, and

$$\mu _q=\frac{q\pi }{(2\pi \theta _w)},q=1,2,3\mathrm{},$$
(5)
which is of the same form as in the sector case. Again as in that case this wave function satisfies the imposed angular and radial boundary conditions. Note that if we take the pacman angle equal to $`\pi /4`$, or equivalently as a $`7\pi /4`$ wedge, then $`\mu _q=4/7,8/7,12/7,16/7,\mathrm{}`$ that has even numerators as in the sector case but with a fractional angular momentum index that has no counterpart in the sector nor in the circle cases. For an angle $`\theta _w=\pi /a`$, with $`a`$ an integer, we have $`\mu _q=q/(2a1)`$, $`a1`$. Or, more generally, for $`\theta _w=\frac{b}{a}\pi `$, with $`b`$ and $`a`$ prime numbers, we have $`\mu _q=\frac{q}{(2ab)}`$, and we need to have that $`2ab`$, which is satisfied for prime numbers. This is an interesting result since these fractional angular momentum cases do not correspond to cases previously studied in group theory , at least not to the best of our knowledge. In the irrational case with $`\theta _w=2\pi \alpha \pi `$, we have $`\mu _q=q/\alpha `$, which has the same value as in the sector case. In fact, we show from geometric relations between the sector and the pacman wedges and for the same $`\theta _w`$, the “duality” relations between the corresponding Bessel function fractional angular momentum indices given by

$$\mu _q=\frac{\lambda _p}{2\lambda _pp}q\lambda _p=\frac{\mu _q}{2\mu _qq}p.$$
(6)
We note that, although the energy eigenvalues for the sector and the pacman given by $`E_{\mu {}_{q}{}^{}m}=\frac{\mathrm{}\alpha _{\mu _q,m}^2}{2M}`$ and $`E_{\lambda {}_{p}{}^{}n}=\frac{\mathrm{}\alpha _{\lambda _p,n}^2}{2M}`$, are not the same, this duality relation gives a nontrivial connection between fractional Bessel functions and the corresponding “fractional” angular momenta for the sector and its pacman complement. In the wedge billiards rotational invariant angular momentum is not a good quantum number. We calculate then the average of the $`z`$-component of the angular momentum $`\widehat{L}_z=(\frac{\mathrm{}}{i})\frac{}{\theta }`$, using the wave function given in Eq.(2), and we get

$$<\mathrm{\Psi }_s\widehat{L}_z\mathrm{\Psi }_s>=(\frac{\mathrm{}}{i})\frac{\mathrm{sin}^2\lambda _p\theta _w}{\theta _w}=0,$$
(7)
and also for the pacman

$$<\mathrm{\Psi }_p\widehat{L}_z\mathrm{\Psi }_p>=(\frac{\mathrm{}}{i})\frac{\mathrm{sin}^2\mu _q(2\pi \theta _w)}{(2\pi \theta _w)}=0.$$
(8)
These results can be physically understood from a semi-classical analysis. In a full circle we have that the particle motion completes a full rotation between $`0`$ and $`2\pi `$. For the wedges the angular motion is limited to be between $`\theta [0,\theta _w]`$ for the sectors or $`\theta [\theta _w,2\pi ]`$ for the pacmen. Since in the sector the particle moves from $`0`$ to $`\theta _w`$ and then bounces back to move from $`\theta _w`$ to $`0`$, the motion is librational rather than rotational. One result of this is that for the separable eigenfunctions given above all have zero average $`L_z`$. When the particle bounces off the outer periphery, only $`v_r`$ changes and $`L_z`$ is unchanged. When it bounces off either wedge wall, $`v_\theta `$ changes sign and thus $`L_{z}^{}{}_{}{}^{2}`$ is unchanged. This quantum result comes from our use of a specific coordinate system with origin of rotation at the apex of the billiard. However, in the classical analysis described below we also find internal closed orbits in the billiards where the angular momentum is not zero. To represent the latter ones we need to write a linear combination of the apex centered eigenfunctions and carry out a coordinate transformation to define the new angular momentum with center of rotation away from the apex.

Because of the $`v_r`$ cancellations with the boundary collisions we are led to consider instead $`\widehat{L}_z^2`$ that would take care of these cancellations. Using the full sector and pacman wave-functions we get

$$<\mathrm{\Psi }_s(\widehat{L}_z)^2\mathrm{\Psi }_s>=(\frac{\mathrm{}}{i})^2\lambda _p^2,$$
(9)
and

$$<\mathrm{\Psi }_p(\widehat{L}_z)^2\mathrm{\Psi }_p>=(\frac{\mathrm{}}{i})^2\mu _q^2.$$
(10)
We then see that the square of the Bessel function indices are good quantum numbers. Note that this result applies even in the irrational $`\theta _w`$ angle case. Additionally, we also evaluated the expectation value of the quantum mechanical currents defined by $`JIm[(\mathrm{\Psi })^{}\mathrm{\Psi }]`$. We found that the angular component of the current is zero, contrary to what happens in the circle case, while the radial current component is zero in both billiard types, as in the circular case.

We now make a qualitative connection of these quantum results to their classical counterparts. Consider a wedge cut from a thin disk with radius $`r_w`$. A particle moves freely within the wedge, bouncing elastically from the walls. Define a polar coordinate system $`(\rho ,\theta )`$ with origin at the apex of the wedge billiard and with $`\theta =0`$ pointing along the right hand boundary of the wedge. The particle is constrained to move in the ranges $`0\theta \theta _w`$ and $`0<\rho <r_w`$. The classical motion of the particle is complicated in polar coordinates, but the elastic collisions are simple to describe. Suppose the particle has velocity $`(v_\rho ,v_\theta )`$ when it encounters the maximum radius of the wedge. The outer circle normal vector is perpendicular to $`\widehat{\theta }`$, so $`v_\theta `$ will be unchanged. Because the collisions are elastic, the energy $`\frac{m}{2}(v_\rho ^2+(rv_\theta )^2)`$ must also be constant. This requires that $`v_\rho v_\rho `$. Similarly, for a collision with a wedge radial wall, $`(v_\rho ,v_\theta )(v_\rho ,v_\theta )`$. We can use dimensionless coordinates where $`r_w=1`$ and $`\left|\stackrel{}{v}\right|=1`$, since the geometry of the trajectory is not changed by the scaling of time and radius. In fact, the collisions with the radial walls can be removed by lifting copies of the wedge onto an infinite spiral in $`\theta `$. The wedge copies are connected on the spiral in such a way that the motion of a particle The spiral is then projected onto the wedge by folding it like a fan. The mapping from the spiral to the wedge is done in two stages. First, define $`\sigma \theta mod\mathrm{\hspace{0.17em}2}\theta _w`$. Then

$`\theta =\{\begin{array}{cc}\sigma ,\hfill & 0\sigma \theta _w\hfill \\ 2\theta _w\sigma ,\hfill & \theta _w\sigma <2\theta _w.\hfill \end{array}`$

In order for an orbit to close, the particle must bounce off exactly the same point on the periphery, going in the same direction. This requires that the total angle traversed must be $`b2\theta _w`$, for some positive integer $`b`$. Combining the two, a closed orbit is possible when $`a\theta _c=b2\theta _w`$. It is easy to show that orbits will be closed or open independently of the starting position of the first orbit. Orbits can then be characterized by the pair of positive integers $`(a,b)`$ . The chord angle $`\theta _c`$ is related to the angle of incidence $`\varphi `$ by $`\theta _c=2\varphi `$. In order for the chord to stay within the wedge, $`\theta _c\pi `$, with $`n\frac{2\theta _w}{\pi }b`$. This implies, in particular, that the trajectory will be repeating if and only if $`\theta _w`$ and $`\theta _c`$ are commensurate. The particle makes a series of collisions with the outer perimeter at regular intervals $`a\theta _c`$.

We can now compare the spectra of two wedges to see if they both have orbits for certain common values of $`\theta _c`$. In particular, consider a wedge sector with angle $`\theta _s`$ and its $`\theta _p=2\pi \theta _s`$ complement pacman. In order for an orbit in each to share a common $`\theta _c`$, we need to have $`\theta _c=\frac{b_s2\theta _s}{n_s}=\frac{b_p2\theta _p}{n_p}`$ or $`\frac{n_p}{b_p}=\frac{\theta _p}{\theta _s}\frac{n_s}{b_s}`$. Thus, if the pacman complement angle is an integer multiple $`m`$ of the angle of the sector, any orbit $`(a,b)`$ in the wedge will have an orbit $`(ma,b)`$ in the pacman for exactly the same value of $`\theta _c`$.

In Fig. (1) we show an example of a pacman rational angle case with angle of $`\pi /4`$. In this figure we show the orbit $`(16,3)`$, where the particle strikes the outer circle boundary 16 times before the orbit closes. During such a traversal, the total rotation of the particle on the lifted spiral is equal to $`6\frac{7\pi }{4}`$. We can also generate a whole family of classical orbits for this pacman with indices like $`(7,1)`$, $`(8,1)`$, $`(28,1)`$, $`(28,3)`$, $`(28,5)`$ and so on. In Fig. (2) we show the corresponding eigenfunction for this pacman case. Note that the caustic radius and the number of small and large triangles correlate to the wave function amplitude densities shown in this figure. The eigenfunction calculations were carried out by solving directly the Shr$`\ddot{o}`$dinger equation using the finite element method. In order to make a direct correlation between classical orbits and quantum eigenfunctions we need to consider all the possible allowed classical and quantum solutions for different values of the caustic radius and set of parameter orbits $`(a,b)`$ and their corresponding quantum counterparts. We do not carry out this analysis since we already know the exact quantum solutions and we have described some of the classical solutions to further understand their corresponding quantum counterparts.

In conclusion, we have considered the quantum and classical problems of a free particle in wedge billiards that exhibit fractional angular momentum due to the breaking of rotational invariance. We found a new duality relation between the “fractional” indices for the angular momentum Bessel functions for the sector and its complement pacman billiard. We showed that $`\widehat{L}_z^2`$ becomes a good quantum operator that can be used to characterize the fractional angular momentum eigenvalues of these billiards. We will treat elsewhere the classical and quantum dynamics of a charged particle in wedge billiards in the presence of a constant homogeneous magnetic field. In that case there is a full transition from integrable to chaotic behavior as the magnetic field increases and new states of chaotic whispering gallery modes appear in the large field limit.

The work by AGT has been supported in part by CONACYT 3047P and UNAM sabbatical grants, México. JVJ thanks NSF for partial financial support.


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# A Newly Discovered SU UMa-Type Dwarf Nova, HS 1449+6415

## 1 Introduction

Dwarf novae are a sub-class of the cataclysmic variable stars (CVs), which show quasi-periodic outbursts (for a review, see Warner w95 (1995)). SU UMa-type dwarf novae show two types of outbursts, namely normal outbursts, and so-called superoutbursts. Normal outbursts (typically 2–4 mag) last 3–5 days, and superoutbursts (0.5–1.0 mag brighter than normal outbursts) last about 3–4 times longer than normal outbursts. Between two successive superoutbursts, 3–10 normal outbursts occur. This behavior is now well explained in the thermal-tidal disk instability model (e.g. Osaki o96 (1996)): a normal outburst is caused by a thermal limit-cycle based on the strong dependence of the hydrogen opacity on the ionization state. in the accretion disk. When the disk has enough mass to extend itself radially to the critical tidal radius at the maximum of a normal outburst, efficient removal of angular momentum due to tidal stress induced by the secondary maintains the disk longer in the hot state (superoutburst). The tidal effects force the accretion disk into a slowly precessing eccentric form. The beat phenomenon of this disk precession and the orbital motion yields photometric variations with a period slightly longer than the orbital period $`P_{\mathrm{orb}}`$ (e.g. Whitehurst w88 (1988), w94 (1994)). Such oscillations called superhumps are observed only during superoutbursts.

Some SU UMa-type systems with short orbital periods ($``$ 80–90 min) show various patterns of the outburst and the superhump evolution which are not easily explained in the current disk instability scheme, such as stars of the WZ Sge-subclass (see e.g. Nogami n98 (1998)) and the ER UMa-subclass (see e.g. Kato et al. k98 (1998)). Although several models have been proposed to explain their outburst behaviors, especially that of WZ Sge stars, a common understanding has not yet been reached. This is partly because there are few observations of dwarf novae just before a superoutburst, owing to the difficulty of predicting a superoutburst.

In this Paper, we report photometric observations of HS 1449+6415 (= RX J1450.5+6403), which has been identified as a CV candidate by Bade et al. (b98 (1998)) based on its emission-line spectrum in the Hamburg Quasar Survey (HQS) and on the X-ray emission in the ROSAT All Sky Survey. The CV nature of HS 1449+6415 has been onfirmed by spectroscopic observations (Jiang et al. j00 (2000)). The HQS has lead to discoveries of some interesting dwarf novae, for instance, the eclipsing stars EX Dra (= HS 1804+6753, Fiedler et al. f97 (1997), and references therein) and HS 0907+1902 (Gänsicke et al. g00 (2000)). HS 1449+6415 is also identified with USNO–A2.0 1500–05846206: r\_mag = 16.3, b\_mag = 15.8; $`\alpha `$ = 14h 50m 38$`\stackrel{s}{.}`$3, $`\delta `$ = +64 03 29′′ (J2000.0). Skiff (s00 (2000)) pointed out another identification as FBS 1449+642, a blue stellar object found in the First Byurakan Spectral Sky Survey (Abrahamian & Mickaelian a94 (1994)).

## 2 Observations and Results

In order to measure the orbital period, we carried out time-resolved photometry of HS 1449+6415 using a standard Johnson $`V`$ filter and a TEK CCD attached at the Cassegrain focus of the 1.23-m telescope at the Calar Alto Observatory (CA) on 2000 May 7, 10, and 11, when the star was in quiescence. The exposure time was 60 sec, and the dead time between exposures was 12 sec, adopting the fast read-out mode and limiting the read-out region on the CCD. The journal of our observations is shown in Table 1.

The first outburst of this star was reported to the VSNET by Vanmunster (2000a ), three days after our CA observations. We immediately started a photometric run at the Nicholas Copernicus Observatory (NC) on 2000 May 15. The NC data were obtained through a Kron-Cousins $`R_\mathrm{c}`$-band filter with an SBIG ST-7 camera and a 40cm Newtonian telescope. The exposure time and the dead time were 50 s and typically 5 sec, respectively.

At the Crimean Astrophysical Observatory (CR), we then monitored the behavior of HS 1449+6415 during the late stages of the long outburst. The CR observations were carried out using a 38-cm Cassegrain telescope with an SBIG ST-7 camera and with a Kron-Cousins $`R_\mathrm{c}`$ or no filter, depending on the atmospheric condition and the brightness of the target. The exposure time was also varied between 90 s and 250 s. This outburst proved to be in the final decline during the second run at CR, implying that the outburst lasted $``$12 days.

After the standard reduction of the frames, we measured the magnitudes of the variable using either an aperture photometry routine in MIDAS (CA data), the CCD photometry package Munidos (http://ian.cz/munipack), which is based on DAOPHOT (Stetson s87 (1987)) (NC data), or an aperture photometry package developed by V. P. Goransky (CR data).

To calibrate the magnitudes, we used the local comparison star ‘C’ (= USNO–A2.0 1500–05845729; Fig. 1), whose photometric properties were given by Henden (h00 (2000))111His original BVRI photometry file for this star is available at ftp://ftp.nofs.navy.mil/pub/outgoing/aah/sequence/j1450.dat. as $`V`$ = 13.151(17), $`BV`$ = 0.701(5), and $`VR_\mathrm{c}`$ = 0.384(9). Constancy of the comparison star within 0.02 mag during our run was checked using stars ‘C1’ and ‘C2’.

HS 1449+6415 was in quiescence during the CA observations (Table 1). The light curves in quiescence are shown in Fig. 2; large amplitude flickering seen each night with no hint of an eclipse. After subtraction of nightly averages from the quiescent CA data, a period analysis using the Phase Dispersion Minimization (PDM) method (Stellingwerf s78 (1978)) yields two candidate periods, 0$`\stackrel{d}{.}`$0558(2) (= 17.9 d-1, 80.4 min) and 0$`\stackrel{d}{.}`$0590(2) (= 17.0 d-1, 85.0 min) as shown in Fig. 3, which are one-day aliases of each other. We can not distinguish between these candidates from our CA data alone because of the short coverage.

Time resolved photometry obtained at NC on May 15 (Fig. 4) and 22 during the long outburst clearly revealed the existence of superhumps, proving the SU UMa nature of HS 1449+6415. These superhump data help to determine the true orbital period. After subtraction of nightly averages from the data, we performed a PDM period analysis. The two best candidates for the superhump period $`P_{\mathrm{sh}}`$ are 0$`\stackrel{d}{.}`$06019(2) (= 16.614(5) d-1, 86.67 min) and its 7-day alias, 0$`\stackrel{d}{.}`$05965(2) (= 16.764(5) d-1, 85.90 min). Nevertheless, the latter possibility can be rejected from Vanmunster et al. (vsf00 (2000)), who have much denser coverage of this superoutburst than we have. The superhump period is, therefore, determined to be 0$`\stackrel{d}{.}`$06019(2), which exactly accords with the value in Vanmunster et al. (vsf00 (2000)). The superhump excess $`ϵ`$ (= $`(P_{\mathrm{sh}}P_{\mathrm{orb}})/P_{\mathrm{orb}}`$) is 7.9 % and 2.0 % for the two $`P_{\mathrm{orb}}`$ candidates of 0$`\stackrel{d}{.}`$0558 and 0$`\stackrel{d}{.}`$0590, respectively. Since SU UMa stars with short orbital periods have $`ϵ`$ $``$ 1–3 % (see e.g. Nogami et al. nmk97 (1997)), this well-determined superhump period strongly supports the latter $`P_{\mathrm{orb}}`$ candidate. Moreover, Thorstensen (t00 (2000)) reported two orbital period candidates of 0$`\stackrel{d}{.}`$0588 and 0$`\stackrel{d}{.}`$0599 deduced from radial velocity measurements. The former is in good agreement with our candidate period of 0$`\stackrel{d}{.}`$0590(2). Hence, we can safely regard this period as the orbital period of HS 1449+6415. The lower panel of Fig. 3 shows the light curve obtained by folding all the CA data with the orbital period. The phase was determined to place the large peak at $`\varphi `$ = 0.0.

To check whether our periodogram may be biased by night-to-night variability, we made another period analysis using only the longest continuous observing sequence obtained on May 10. The resultant theta diagram yields two broad peaks around frequencies of $``$18.0 d-1 and $``$38 d-1 with almost the same significance. This may indicate the underlying double-peaked form of the orbital light curve found by Kato et al. (k00 (2000)) in observations obtained during quiescence on 2000 February 24 at the Nyrola Observatory. Their period analysis has yielded two strong peaks at 0$`\stackrel{d}{.}`$0289 and its double. Double-peaked orbital modulations in quiescence are found in WZ Sge (e.g. Warner & Nather wn72 (1972)) and AL Com (see e.g. Szkody et al. s89 (1988)).

Quiescent data was also obtained at CR around JD 2451716. Fig. 5 exhibits the result of a PDM period analysis after subtraction of nightly averages and the folded light curve of the data from JD 2451716 to 2451720. The shape of the orbital modulation is almost the same as in Fig. 3 (for instance, the full amplitude of $``$0.4 mag) but the secondary peak around $`\varphi `$ = 0.4 is stronger.

A PDM period analysis using all our quiescence data obtained at CA and CR yields the refined photometric ephemeris:

$$HJD_{\mathrm{max}}=2451672.047(2)+0.05898(2)\times E.$$
(1)
The superhump maxima in Fig. 4 are around $`\varphi `$ = 0.77 in this ephemeris.

A short outburst lasting only 3 days were caught on JD 2451721 in the course of our monitoring of this star at CR (Fig. 6). This duration is typical for a normal outburst of SU UMa stars. There are no periodic variations but weak flickering in the first and the second night of this outburst. Large flickering of $``$ 0.5 mag can be seen on HJD 2451724, when this variable star was still about 0.5 mag brighter than its quiescence level.

## 3 Discussion

The superhump period we derived is 0$`\stackrel{d}{.}`$0601(6), 1.9 % longer than $`P_{\mathrm{orb}}`$ of 0$`\stackrel{d}{.}`$05898(2). This orbital period is close to the minimum of the period distribution of SU UMa-type dwarf novae (see e.g. Nogami et al. nmk97 (1997)). In general, observations have shown that the amount of time after the maximum of a superoutburst needed for SU UMa stars to evolve superhumps increases towards shorter orbital periods (see e.g. Table 1 in Osaki o96 (1996)). This correlation is also expected on the theoretical grounds: Lubow (l91 (1991)) showed that the growth rate of the eccentricity is proportional to $`q^2`$, where $`q`$ is the mass ratio of the secondary mass to the primary mass (= $`M_2/M_1`$). Thus, if a normal SU UMa star, superhumps in HS 1449+6415 are expected to appear at least 4 days after the supermaximum. In contrast, fully grown superhumps with an amplitude of 0.32 mag were detected less than 2 days after the maximum of the superoutburst detected on 2000 May 14.864 (UT), only 2.7 day after the end of our CA observations (Vanmunster 2000b ; Vanmunster et al. vsf00 (2000)), taking into account the rise time to the supermaximum. A determination of the binary parameters of HS 1449+6415 by spectroscopy may thus be able to test the tidal instability theory.

Kato et al. (k98 (1998)) pointed out that all ER UMa stars, i.e., the most active SU UMa-type dwarf novae, exhibit a peculiar phenomenon: the amplitude of the superhump is largest around the superoutburst maximum and decreases as the time proceeds even though the superhump period remains almost constant (see also Kato et al. k96 (1996)). ER UMa stars also have very short $`P_{\mathrm{orb}}`$ close to that of HS 1449+6415. The early development of the superhump in the present system may be related to the superhump evolution in ER UMa stars which is still theoretically unexplained. To trace the variation of the superhump in HS 1449+6415 throughout a superoutburst is another future work which should be performed.

WZ Sge stars, another extreme subset of SU UMa-type dwarf novae (O’Donoghue et al. o91 (1991), and references therein) also have very short orbital periods, similar to that of HS 1449+6415. However, WZ Sge stars shows only superoutbursts with a very long recurrence time ($``$ 10 yr) and with a very large amplitude ($`\mathrm{\Delta }V7`$), but no normal outbursts. For this behavior, Meyer-Hofmeister et al. (m98 (1998)) proposed a model in which the accretion disk steadily grows during quiescence, and the tidal instability starts before the superoutburst onset. If this model were applicable to HS 1449+6415, we could observe superhumps also before the onset of a superoutburst. However, only modulations with the orbital period were detected in our data. The amplitude variation in our data before the superoutburst may indicate a beat phenomenon of the orbital hump and the superhump, but a much longer photometric pre-outburst observation would be needed to confirm this hypothesis.

Note that the average profile of the orbital modulation is almost the same between just before the superoutburst and before the normal outburst. This implies that the physical status of the accretion disk and the hot spot, which are thought to emit most of the optical light in quiescence, is quite similar in both these periods. Nothing special seemed to occur before the superoutburst, compared to the situation before the normal outburst, although more observations of the orbital modulation with much smaller errors are needed to strictly probe differencies of the accretion disk in different phases.

The brightest magnitude of HS 1449+6415 reported to VSNET is $`m_{\mathrm{vis}}`$ = 14.1 (Kinnunen ki00 (2000)), after calibration using the magnitude of the comparison star (Kinnunen, private communication) given by Henden (h00 (2000)). The amplitude of the superoutburst, thus, is $``$3.5 mag, which is the smallest among SU UMa stars with orbital periods shorter than 90 min, other than ER UMa stars (see e.g. Table 1 in Nogami et al. nmk97 (1997)). As mentioned above, the normal outburst was caught about 40 days after the onset of the superoutburst. If this value is considered as the recurrence cycle of the outbursts, this is typical for an SU UMa star (see e.g. Table 1 in Nogami et al. nmk97 (1997)). The VSNET data222http://www.kusastro.kyoto-u.ac.jp/vsnet/etc/searchobs.html can exclude the possibility of an outburst-recurrence cycle shorter than 14 days. The combination of the outburst amplitude of 3.5 mag and the recurrence cycle of 40 days is almost the same as that in SX LMi, which is regarded as the dwarf nova bridging the gap between ER UMa stars and SU UMa stars (Nogami et al. nmk97 (1997)). The orbital period of 0$`\stackrel{d}{.}`$06717(11) (= 97 min) of SX LMi (Wagner et al. w98 (1998)) is, however, a little out of range of the orbital period distribution of ER UMa stars and WZ Sge stars. Thus, HS 1449+6415 is an intermediate object between ER UMa stars and WZ Sge stars, and might be in the evolutionary transition state between ER UMa and WZ Sge phases. HS 1449+6415 deserves to be monitored over long timescales to measure the accurate recurrence cycles of the normal outburst and the superoutburst and to reveal variations of these cycles and the outburst amplitude.

###### Acknowledgements.

The authors are really thankful to VSNET contributors for their observation reports and discussions on VSNET. Thanks also to T. Kato and F. V. Hessman for their useful comments. DN and BTG were supported by DLR/BMBF grant 50 OR 9903 6. The HQS was supported by the Deutsche Forschungsgemeinschaft through grants Re 353/11 and Re 353/22.