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# In situ photoemission study of the room-temperature ferromagnet ZnGeP2:Mn

## Abstract

The chemical states of the ZnGeP2:Mn interface, which shows ferromagnetism above room-temperature, has been studied by photoemission spectroscopy. Mn deposition on the ZnGeP2 substrate heated to 400C induced Mn substitution for Zn and then the formation of metallic Mn-Ge-P compounds. Depth profile studies have shown that Mn 3$`d`$ electrons changed their character from itinerant to localized along the depth, and in the deep region, dilute divalent Mn species ($`<`$ 5 % Mn) was observed with a coexisting metallic Fermi edge of non-Mn 3$`d`$ character. The possibility of hole doping through Mn substitution for Ge and/or Zn vacancy is discussed.

The successful synthesis of the III-V-based ferromagnetic diluted magnetic semiconductors (DMSs) has opened up a large number of exciting functionalities such as non-volatile memories, spin injection, and the optical control of ferromagnetism in semiconductor devices Ohno . However, the reported Curie temperature ($`T_C`$) to date has been limited to 120 K realized in Ga1-xMnxAs, due to the limited ability of incorporating Mn ions and p-type carriers in the III-V-based DMS. Overcoming this limitation and increasing the $`T_C`$ hopefully above the room temperature (RT) has been a challenging subject.

Recently, there have been several reports on high-$`T_C`$ ferromagnetism in new DMSs RTDMSs . Among them are intriguing reports by Medvedkin et al. on Mn incorporated II-IV-V2 chalcopyrite semiconductors CdGeP2 CGP  and ZnGeP2 ZGP , which show ferromagnetism above RT. A high concentration of Mn ions is incorporated in the semiconductors through deposition of Mn metal and annealing. The use of II-IV-V2 semiconductor as a host material is attracting, since, while it is an average III-V semiconductor, it has two types of cation sites. This distinct property compared to the binary III-V semiconductors allows us to functionalize each cation site in different ways, e.g., magnetic ion doping at the II site and acceptor doping at the IV site. In addition, the chalcopyrite semiconductors have many natural defects, e.g., zinc ion on the germanium site (ZnGe), zinc vacancy (VZn), etc, in ZnGeP2, which may also act as acceptors defect . This rich chemistry stimulated many theoretical calculations on II-IV-V2:Mn Calc . However, there has been little experimental information about the chemical reactions and chemical products in this system.

Photoemission spectroscopy (PES) is a powerful tool to investigate chemical reactions in surface and interfacial regions. Particularly for studying the Mn-doped chalcopyrites, where the Mn density varies as a function of the depth, PES combined with ion sputtering provides us with the depth profile of the interface. At the same time, PES provides insight into the electronic structures of DMSs PES , particularly into the Mn 3$`d`$ partial density of states (PDOS) through resonant PES and through subsequent analyses of the $`p`$-$`d`$ exchange interaction between the Mn $`3d`$ electrons and the host semiconductors.

Ultraviolet photoemission (UPS) and x-ray photoemission (XPS) measurements were performed at BL-18A of Photon Factory. The total energy resolution of the VG CLAM analyzer including temperature broadening was 800 meV for XPS and 200 meV for UPS. Mn metal (99.999 %) was evaporated in situ onto the (001) surface of single crystal ZnGeP2 at 400C ZGP . The deposition rate was 3 Å/min, determined by a quartz thickness monitor. After the Mn deposition, the sample was post-annealed at 400C for 5 min and then cooled to RT. All the spectra were taken at RT. Ar+-ion sputtering at 1.5 kV was used both for cleaning and etching. Sputter-etching rate was $``$ 2 Å/min. Surface cleanliness was checked by core-level XPS. The pressure was below 7 $`\times `$ 10-10 Torr during the measurements. The magnetization was measured ex situ using a SQUID magnetometer. (Quantum Design MPMS). For comparison, polycrystalline MnP ($`T`$C = 290 K MnP ) was also measured.

First, the effect of annealing and sputtering on the ZnGeP2 substrate was studied. The core-level intensities above 300C showed strong Zn deficiency and weak Ge excess. \[See the relative chemical composition at $`d`$ = 0 Å in Fig. 1(b), where the deviation from the stoichiometry of ZnGeP2 is seen for the surface once annealed at 400C.\] At the reported “optimum” substrate temperature 400C, therefore, deposited Mn atoms may easily diffuse into the Zn-deficient surface region. This Zn-deficient region could be removed by 3-min Ar+-ion sputtering (corresponding to $``$ 6 Å thickness). Further sputtering did not change the core-level intensities of the substrate within the accuracy of 3 %. This suggests that selective sputtering of different atomic species can be ignored, and we assumed that the as-sputtered substrate spectra rrepresent the bulk stoichiometry of ZnGeP2.

Next we show a series of spectra for Mn deposition on the 400C-annealed substrate. Each time after having taken a set of spectra for one Mn coverage, the deposited Mn was completely removed by prolonged sputtering and then Mn was newly deposited. Figure 1(a) shows the core-level spectra of the Mn-deposited surface, and Fig. 1(b) shows their intensities normalized to those for the as-sputtered ZnGeP2. The Mn 2$`p`$ intensity has been normalized using the Mn 2$`p`$ and P 2$`p`$ intensity ratio of MnP. In the region of Mn thickness $`d`$ $`<`$ 64 Å, one can see a monotonic increase and decrease of the Mn and Zn signals, respectively, without significant changes in the Ge and P intensities. This behaviour suggests that Mn atoms primarily substituted for Zn and a Zn1-xMnxGeP2-like compound was formed. In the Mn 2$`p`$3/2 spectra below $`d`$ = 16 Å, one can see some signal on the higher binding energy side \[indicated by vertical bars in Fig. 1(a)\] of the dominant metallic peak ($`E_B`$ = 638.7 eV, broken line). This indicates that a portion of the incorporated Mn atoms chemically reacted with the substrate and presumably became Mn2+. In going from $`d`$ = 64 to 130 Å, the Ge and P intensities suddenly changed. The saturation of the Mn intensity with sizable signals of Ge and P above $`d`$ = 130 Å is a signature of atomic diffusion associated with the chemical reaction for such a thick Mn overlayer. The surface region above $`d`$ = 130 Å consisted of Ge-rich, ternary metallic compound(s) of Mn, Ge, and P with possible inhomogeneity and/or phase mixture.

The valence-band spectra taken for photon energies in the Mn 3$`p`$-3$`d`$ core-excitation region are shown in Fig. 2. The spectra have been primarily normalized to the post-focusing Au mirror current and then to the intensities of the $`d`$ = 0 Å spectra at the corresponding photon energies. The Mn 3$`d`$-drived spectra were obtained by subtraction between these normalized on- (51 eV) and off-resonance (48 eV) spectra. In this way, we could virtually eliminate the effect of the photon energy dependence of the host valence band. For $`d`$ = 4 and 16 Å, one can see a peak located $``$ 4 eV below $`E`$F in the difference spectra. This observation is similar to the previous results of the Mn incorporated II-VI- and III-V-based DMSs PES  and thus is attributed to the localized nature of Mn 3$`d`$ electrons. However, above $`d`$ = 32 Å, there was a change in the decay process of the Mn 3$`p`$ core hole and strong Mn M3L45L45 Auger peak replaces the $``$ 4 eV peak, indicating that the Mn 3$`d`$ electrons became itinerant. The disappearance of the $``$ 4 eV peak is in accordance with the Mn 2$`p`$ core-level spectrum \[Fig. 1(a)\], where the divalent Mn signal disappeared above $`d`$ = 32 Å and the highly asymmetric line shape characteristic of a metallic Mn compound appeared. We note that MnP also shows Mn M3L45L45 Auger signals in the valence-band spectra Kakizaki . However, the Mn $`2p_{3/2}`$ core-level peak of MnP was observed at $`E_B`$ = 639.2 eV, different from the peak positions observed above $`d`$ = 32 Å in Fig. 1(a). As for the $`d`$ = 16 Å spectrum, both a clear Fermi edge and the $``$ 4 eV peak is observed. The difference spectrum for $`d`$ = 16 Å is almost a superposition of the $`d`$ = 4 Å and 32 Å spectra, as in the case of the Mn 2$`p`$ core-level spectra \[Fig. 1(a)\].

In order to study the chemical states formed underneath the surface metallic compound(s), ZnGeP2:Mn of the nominal Mn thickness of 150 Å was repeatedly sputter-etched without annealing and studied by PES. Figure 3 (a) shows core-level spectra taken in the sputter-etching series and Fig. 3 (b) shows their intensities \[the same normalization as in Fig. 1 (b)\] as functions of sputtering time. The change in the first 20 min sputtering is attributed to the removal of the metallic Mn-Ge-P layer in the surface region. Subsequently, the Mn 2$`p`$3/2 core level started to show a shoulder structure at $`E`$B = 641.7 eV due to ionic Mn (Mn2+ most likely). The systematic increase of this shoulder and the decrease of the metallic main peak between 20 to 70 min sputtering indicate that these signals are originated from chemically different Mn species. After 100 min sputtering, the relative compositions became Zn:Ge:P $``$ 1:1:2, suggesting that the chalcopyrite-type matrix of Zn, Ge, and P plus dilute Mn was exposed \[Fig. 3 (b)\]. After 230 min sputtering, the Mn signal became totally that of the ionic one \[Fig. 3 (a)\], indicating that a dilute-Mn phase ($`<`$ 5 % Mn) appeared. Since Zn:Ge:P $``$ 1:1:2 and the amount of Mn was small, it was difficult to determine from Fig. 3(b) which element Mn substituted for. Now, since the peak position of the ionic Mn 2$`p`$ signal below $``$ 200 min sputtering (in the intermediate phase) corresponds to that above $``$ 200 min sputtering (dilute Mn phase), the ionic Mn species in the former phase region may be precursors of those in the latter phase.

Figure 4 shows the valence-band spectra in the sputter-etching series for photon energies in the Mn 3$`p`$-3$`d`$ core excitation region. Before 80 min sputtering, the M3L4,5L4,5 Auger process was dominant \[Fig. 4 (a) and (b)\] and after that resonant photoemission became dominant \[Fig. 4 (c) and (d)\]. This indicates again that the Mn 3$`d`$ states changed their character from itinerant to localized along the depth profile. A peak at $`E`$B $``$ 4 eV was seen after 80 min sputtering, and hence Mn was divalent in the deep region. The divalent Mn signal in the recent EPR measurements may come from this region EPR . The Mn 3$`d`$-derived intensity near $`E`$F in the difference spectra is weak compared to that in Fig. 2 (b). This indicates that the Mn 3$`d`$ states are more strongly localized in the deep bulk region than the Zn1-xMnxGeP2-like phase in the early stage of Mn deposition. Inset of Fig. 4 shows valence-band spectra near $`E_F`$ after 230 min sputtering, where Mn had fully reacted with the substrate \[Fig. 3 (a)\]. They clearly show a Fermi edge. Since the Mn 3$`d`$ PDOS is supressed near $`E_F`$, this Fermi edge comes from the valence band of the host semiconductor which was somehow doped with metallic charge carriers. Since isovalent substitution of Mn2+ for Zn2+ cannot produce carriers, Mn2+ may have substituted for the Ge site and/or Mn incorporation simultaneously induced defects such as, e.g., VZn and ZnGe, all of which produce hole carriers. The Fermi edge became obscure after 540 min sputtering, in accordance with the diminishing Mn 2$`p`$ core-level intensity (Fig. 3). In the sputter-etching series, too, no MnP signal was observed.

We have also studied the depth profile of ZnGeP2:Mn of the 200 Å nominal thickness Mn annealed at 200C. Up to 800 min sputtering, Mn signal was observed together with Zn, Ge, and P signals, indicating that diffusive reaction of Mn into the substrate occurred already at 200C. However, the Mn 2$`p`$3/2 signal always appeared at $`E`$B = 638.7 eV without any divalent signal. Correspondingly, only the Mn M3L4,5L4,5 Auger peak was observed in the valence-band spectra. We therefore conclude that the annealing at 200C was insufficient for the Mn atoms to be chemically incorporated in the host semiconductor as divalent ions with localized nature of Mn 3$`d`$ electrons.

Figure 5(a) shows the magnetization of as-prepared ZnGeP2:Mn ($`d`$ = 150 Å at 400C) and that after having removed the surface metallic Mn compound (200 min sputtered). Clear hysterisis was observed between 10 K and 330 K for the 150 Å deposited sample. Surprisingly, one can observe nearly the same magnetization at both 330 K and 10 K even after removing the surface metallic Mn compound, indicating that the divalent Mn phase deep in the substrate ($`<`$ 5 % Mn) was probably a RT ferromagnet. Figure 5(b) clearly shows ferromagnetism up to $``$ 400 K. One can see a kink at $``$ 300 K which may correspond to the $`T_C`$ = 312 K of bulk Zn1-xMnxGeP2 Cho . Another anomaly at 20 - 50 K may also correspond to the 47 K anomaly of bulk Zn1-xMnxGeP2. Therefore, the present sample may contain Zn1-xMnxGeP2 as a minority component. Recently, ZnGeP2:Mn prepared at 550C was studied, and the $`M`$($`T`$) curve showed pronounced singularities at $``$ 318 K and 20 - 50 K and small magnetization tailing above 318 K, the behaviour of which is more similar to bulk Zn1-xMnxGeP2 than the present sample 550C . We note that the bulk Zn1-xMnxGeP2 was reported to be electrically insulating, while the present sample showed a metallic Fermi edge. Further studies are necessary, in particular to understand the relationship between the magnetic behaviour, the carrier density, and the preparation temperature.

In conclusion, we have observed spectral features of localized, most likely divalent Mn 3$`d`$ states incorporated into the host ZnGeP2 in the thin Mn-deposited surface region (probably as a Zn1-xMnxGeP2) and in deep region below the surface metallic Mn compound after thick Mn deposition. A Fermi edge was observed in the deep region, indicating that carrier doping took place in that region of ZnGeP2:Mn. RT ferromagnetism was observed after removing the surface Mn compound. This indicates that ferromagnetism in ZnGeP2:Mn is caused by the dilute Mn ions in the deep region. No signature of MnP was observed in the photoemission spectra.

We thank T. Okuda, A. Harasawa, and T. Kinoshita for their valuable technical help, V.G. Voevodin, K. Ono, T. Komatsubara, and M. Okusawa for sample measurements, and T. Mizokawa for useful discussions and suggestions. This work was supported by a Grant-in-Aid for Scientific Research in Priority Area “Semiconductor Spintronics” (No. 14076209) from the Ministry of Education, Culture, Sports, Science and Technology, Japan. DDS thanks the University of Tokyo for hospitality during a part of this work. The experiment at Photon Factory was approved by the Photon Factory Program Advisory Committee (Proposal No. 01U005).


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# Protein crystals and charged surfaces: interactions and heterogeneous nucleation

## I Introduction

Here we will consider the interaction between charged surfaces and protein crystals. Proteins are themselves charged and so we would expect them to interact strongly with a surface that is charged. Using the Poisson-Boltzmann equation we find that indeed protein crystals are attracted by oppositely charged surfaces and repelled by surfaces with charges of the same sign. In itself this is hardly surprising but with quite simple calculations we quantify this attraction and repulsion. We show that easily accessible surface charge densities of the opposite sign to that of the protein molecules, are able to greatly favour heterogeneous nucleation at the surface by reducing the free energy of a nucleus at the surface by several $`k_\mathrm{B}T`$ per protein molecule at the surface. Controlled heterogeneous nucleation is vital to the production of protein crystals, which are required for structure determination via X-ray crystallography.

At a first-order phase transition, such as the crystallisation of a protein from solution, the transition starts with nucleation debenedetti ; rosenberger96 . Protein crystallisation is the “main bottleneck” chayen02  in the determination of the three-dimensional structure of proteins. Determining this structure is crucial for understanding what a protein does and how it does it. Protein crystallographers wish to: i) induce nucleation in the relatively weakly supersaturated solutions, within which protein crystals grow slowly and so incorporate few defects, and ii) control heterogeneous nucleation, in particular have nucleation occurring only at specific locations on a surface. If crystals only nucleate on widely separated patches on a surface then the growth of one crystal will not interfere with and limit the growth of another crystal.

See for example Refs. mcpherson88 ; chayen01  for experimental work on adding solid surfaces to protein solutions to induce nucleation, and see Refs. sanjoh99 ; sanjoh01  for experimental work on patterned surfaces, which shows that protein crystals can be made to grow preferentially on specified patches of a surface. In Refs. sanjoh99 ; sanjoh01  a patterned surface is used in which patches of the surface are one form of doped Si and the rest is a different form. The protein nucleates preferentially on one of these forms and so by controlling where this form is found in the pattern, the crystals can be made to nucleate and grow far from each other, facilitating the formation of large crystals. Here we show that a pattern of two different surface types of opposite charges can produce sufficiently large differences in surface free energy to make heterogeneous nucleation much easier on one surface than on the other.

We note that here we only consider the effects of charge interactions, screened by a 1:1 electrolyte. Other interactions, such as short-range specific interactions between the protein molecules and surface are known to be important, see the review of Ostuni et al. ostuni99 . When these interactions are important, our calculations, which neglect them, will only yield estimates of the variation with 1:1 salt concentration, of the interaction free energy of a protein crystal or crystalline nucleus with a surface. However, experimental systems do exist with high, variable charges and highly hydrophilic surfaces. These highly hydrophilic surfaces will have only weak non-electrostatic interactions with the proteins, they also has the advantage of minimising the problem of protein denaturation.

One example is a highly charged self-assembled monolayer, such as has been shown to adsorb polyelectrolytes clark97 , another is a membrane containing charged lipids wagner00 ; murray99 . Both of these systems should be well described by the theory presented here. There is a great deal of work on the association of proteins and DNA with oppositely charged lipid membranes, Refs. wagner00 ; murray99  are just two examples of a large literature. As far as the author is aware, there has been no experimental study of adsorption of protein on a highly charged, highly hydrophilic, self-assembled monolayer, but such a system would offer the opportunity to study the effect of electrostatics with minimal interference from other interactions. This is true both for the adsorption of single proteins and of protein crystals.

Our calculations will all be for infinite planar interfaces, despite the fact that our primary interest is in the nuclei of protein crystals against charged surfaces, not bulk crystals against surfaces. Although, nuclei are small, 10s of protein molecules, the part of the free energy which scales with the contact area between the nucleus and the surface will still dominate the edge contribution, as the Debye length is typically a few nms at most. Thus, we consider only the dominant surface term, considering sub-dominant terms within simple theories of simple generic models is not useful. We will also leave consideration of defects in the surface to later work.

In the next section we calculate the electrostatic contributions to the surface free energy. The third section includes example results and a discussion and the last section is a conclusion.

## II Calculation

Here we calculate the electrical double layer contributions to the interfacial free energies of solid–salt-solution, solid–protein-crystal and solution–protein-crystal interfaces. The calculation for the solution–protein-crystal interface is just a repeat of that done in Ref. sear02  and so will not be described in detail. We will use the model of Ref. sear02  for the protein crystal and solution, along with a simple model of a charged solid surface. As we are interested in interfacial free energies it is most convenient to work at constant chemical potential of the salt, and so the appropriate free energy is the grand potential $`\mathrm{\Omega }`$. We will split this grand potential into the part due to the charges on the surface and on the protein molecules, together with the salt and counter ions, $`\mathrm{\Omega }_{el}`$, and another part which includes the rest of the interactions, $`\mathrm{\Omega }_{nel}`$,

$$\mathrm{\Omega }=\mathrm{\Omega }_{nel}+\mathrm{\Omega }_{el}.$$
(1)
$`\mathrm{\Omega }_{nel}`$ includes effects such as the dispersion interactions between the protein molecules and the surface, and any short-range interactions between the surfaces of the proteins and the solid surface. We will not calculate $`\mathrm{\Omega }_{nel}`$, and so will only be able to estimate the absolute values of the interfacial free energies, when $`\mathrm{\Omega }_{nel}`$ is much smaller than $`\mathrm{\Omega }_{el}`$, for example with highly charged, highly hydrophilic, surfaces, and highly charged proteins. However, if we assume that $`\mathrm{\Omega }_{nel}`$ is weakly dependent on the salt concentration, and that the charges on the surface can be varied without varying $`\mathrm{\Omega }_{nel}`$ significantly, our results will describe the variation in the interfacial free energies with surface charge density and the salt concentration.

Rather than considering a specific protein crystal, we take over the jellium concept from the theory of metals to make a general estimate of the effect of salt on the interfacial tension. We replace the detailed charge density due to the protein molecules by a uniform background charge density $`\rho _p`$, cut off abruptly at the interface. In Ref. sear02 , Sear and Warren did so for the protein-crystal–salt-solution interface, and this followed on from the work of Warren warren02  on the bulk phase behaviour. Here when we calculate the interfacial free energy for a protein crystal at the surface, we will assume the protein crystal is flush against the surface and so the charge density is uniform right up to the surface. Our model of the charged surface of the substrate is that of an infinite charged plane at a fixed charge per unit area $`\sigma `$. The solution outside the crystal is taken to be sufficiently dilute that we can neglect any protein molecules in it and treat it as a salt solution at a concentration $`\rho _s`$. For definiteness we take the protein to be positively charged so the counterions are negative and the coions are positive; both are monovalent. The surface is in the $`xy`$ plane at $`z=0`$, with the solid in the $`z<0`$ half-space and either a salt solution or a protein crystal in the $`z>0`$ half-space.

We will use the same notation as in Ref. sear02 , so we work in units where $`e=k_\mathrm{B}T=1`$. In these units, the Coulomb potential energy $`U`$ between a pair of elementary charges separated by $`r`$ is $`U=l_\mathrm{B}/r`$, where $`l_\mathrm{B}`$ is the Bjerrum length, equal to $`0.72\mathrm{nm}`$ in water at room temperature ($`l_\mathrm{B}=e^2/4\pi ϵk_\mathrm{B}T`$). We assume a constant value of $`l_\mathrm{B}`$, and ignore dielectric effects. The counterion and coion densities are $`\rho _{}(z)`$ and $`\rho _+(z)`$, respectively. In the bulk salt solution, both tend to the salt concentration $`\rho _s`$, and inside the protein crystal $`(\rho _{}\rho _+)\rho _p`$.

We will use a grand potential, $`\mathrm{\Omega }_{el}`$, which contains only ideal solution terms for the ions and the associated electric field at the interface. The grand potential $`\mathrm{\Omega }_{el}`$, is sear02 ,

$$\mathrm{\Omega }_{el}=_0^{\mathrm{}}𝑑z\omega (z),\omega =\underset{i=\pm }{}\rho _i(\mathrm{ln}\frac{\rho _i}{\rho _s}1)+\frac{E^2}{8\pi l_\mathrm{B}}.$$
(2)
The first terms in $`\omega `$ are the ideal solution terms (the ions share a common chemical potential $`\mu _\pm =\mathrm{ln}\rho _s`$). The last term is the electrostatic energy, wherein $`E=d\varphi /dz`$ is the electric field strength corresponding to an electrostatic potential $`\varphi `$ which satisfies the Poisson equation,

$$\frac{d^2\varphi }{dz^2}=\{\begin{array}{cc}4\pi l_\mathrm{B}\left(\rho _+\rho _{}\right)\hfill & \text{salt solution}\hfill \\ 4\pi l_\mathrm{B}\left(\rho _+\rho _{}+\rho _p\right)\hfill & \text{protein crystal}\hfill \end{array},$$
(3)
The variational principle $`\delta \mathrm{\Omega }_{el}/\delta [\rho _\pm (z)]=0`$ applied in this problem yields $`\rho _\pm (z)=\rho _s\mathrm{exp}[\varphi ]`$. The electrostatic potential then satisfies the Poisson-Boltzmann equation,

$$\frac{d^2\varphi }{dz^2}\kappa _s^2\mathrm{sinh}\varphi =\{\begin{array}{cc}0\hfill & \text{salt solution}\hfill \\ 4\pi l_\mathrm{B}\rho _p\hfill & \text{protein crystal}\hfill \end{array},$$
(4)
where

$$\kappa _s^2=8\pi l_\mathrm{B}\rho _s.$$
(5)
For our assumption of a planar surface in the $`z=0`$ $`xy`$ plane, with a fixed charge per unit area $`\sigma `$, the boundary condition on $`\varphi `$ at $`z=0`$, is that the electric field at the surface

$$E=\frac{d\varphi }{dz}=\frac{\sigma }{ϵ}=4\pi l_\mathrm{B}\sigma .$$
(6)
The other boundary condition is that $`d\varphi /dz=0`$, $`z\mathrm{}`$.

### II.1 Surface–salt-solution interface

This is just the problem addressed by Gouy and Chapman at the beginning of the last century israelachvili . For simplicity we will only derive the expressions in the regime where the equations may be linearised. Then we will simply state the general result obtained when the equations are not linearised. Linearising the Poisson-Boltzmann equation, Eq. (4), inside the salt solution, and using the boundary conditions, we have

$$\varphi (z)=4\pi l_\mathrm{B}\sigma \kappa _s^1\mathrm{exp}(\kappa _sz)z>0.$$
(7)
A simple exponential decay from a value at the surface, proportional to the surface charge.

The surface free energy is, by definition, the difference between the actual grand potential per unit area of the surface–salt-solution interface and that it would have if the salt solution continued unperturbed right up to solid surface. We therefore have to calculate the grand potential, Eq. (2), then subtract the grand potential for the bulk solution: Eq. (2) with the actual $`\omega (z)`$ replaced by its value in the bulk salt solution, $`\omega (+\mathrm{})`$ note ,

$$\mathrm{\Delta }\gamma _\mathrm{s}=_0^{\mathrm{}}𝑑z\left(\omega (z)\omega (+\mathrm{})\right).$$
(8)
This is a general expression, in the linear regime we can expand out $`\omega `$ of Eq. (2) and keeping only the terms up to quadratic order in $`\varphi `$, we have that $`\omega =2\rho _s+2\rho _s\varphi ^2`$. The bulk value $`\omega (+\mathrm{})=2\rho _s`$, as the potential in the bulk of the salt solution is taken to be zero. The surface free energy is then obtained by substituting these expressions into Eq. (8). Doing this and using Eq. (7), we have

$$\mathrm{\Delta }\gamma _\mathrm{s}=2\pi l_\mathrm{B}\sigma ^2\kappa _s^1\text{linear},$$
(9)
which is positive and proportional to the square of the surface charge and to the screening length, as we might have expected.

If Eq. (4) is not linearised the potential $`\varphi `$ is given by israelachvili ; sear02  $`\varphi =2\mathrm{ln}[(1+Ce^{\kappa _sz})/(1Ce^{\kappa _sz})]`$ where $`C`$ is determined by the boundary condition Eq. (6) and is given by

$$C=\frac{\kappa _s}{2\pi l_\mathrm{B}\sigma }\left[\sqrt{1+\left(\frac{2\pi l_\mathrm{B}\sigma }{\kappa _s}\right)^2}1\right].$$
(10)
Thus, we can evaluate the surface free energy once we have converted Eq. (8) into an expression in terms of $`\varphi `$ only. Equation (4) in the salt solution can be integrated once with respect to $`\varphi `$,

$$\left(\frac{d\varphi }{dz}\right)^2=2\kappa _s^2\left(\mathrm{cosh}\varphi 1\right),$$
(11)
which gives us the electric field term in $`\omega `$. The other, ideal gas, term can be written in terms of $`\rho _s`$ and $`\varphi `$ using $`\rho _\pm (z)=\rho _s\mathrm{exp}[\varphi ]`$. Then $`\mathrm{\Delta }\gamma _\mathrm{s}`$ is given by the integral

$$\mathrm{\Delta }\gamma _\mathrm{s}=2\rho _s_0^{\mathrm{}}𝑑z\varphi \mathrm{sinh}\varphi ,$$
(12)
which is straightforward to evaluate numerically.

### II.2 Surface–protein-crystal interface

As with the surface–salt-solution interface we start with the linear Poisson-Boltzmann equation. Here the potential is that inside the protein crystal so we linearise Eq. (4) and obtain

$$\frac{d^2\varphi }{dz^2}=\kappa _s^2\left(\varphi \frac{\rho _p}{2\rho _s}\right),$$
(13)
where we used Eq. (5) for $`\kappa _s`$. The second term inside the parentheses is minus the Donnan potential $`\varphi _\mathrm{D}`$ inside the protein crystal. The general expression for the Donnan potential is

$$\mathrm{sinh}\varphi _\mathrm{D}=\frac{\rho _p}{2\rho _s},$$
(14)
which when linearised gives $`\varphi _\mathrm{D}=\rho _p/(2\rho _s)`$. Thus, the solution to Eq. (13), with the boundary condition of fixed charge density, Eq. (6), is

$$\varphi (z)=\varphi _\mathrm{D}+4\pi l_\mathrm{B}\sigma \kappa _s^1\mathrm{exp}(\kappa _sz)z>0.$$
(15)
In the bulk protein crystal, $`\varphi =\varphi _\mathrm{D}`$. We expand the $`\omega `$ of Eq. (2) in powers of $`\varphi _\mathrm{D}`$ and keep only the terms up to quadratic order, and find that in the crystal $`\omega (\mathrm{})=2\rho _s+2\rho _s\varphi _\mathrm{D}^2`$ sear02 . Performing the same expansion at the interface, we obtain for the excess grand potential at the interface

$$\omega \omega (\mathrm{})=\rho _s\left[\varphi ^2\varphi _\mathrm{D}^2+2(\varphi \varphi _\mathrm{D})^2\right],$$
(16)
where we used Eq. (15) to obtain the derivative $`d\varphi /dz`$. The interfacial free energy per unit area $`\mathrm{\Delta }\gamma _\mathrm{x}`$ is the integral over all $`z`$ of the excess grand potential of Eq. (16). It is

$$\mathrm{\Delta }\gamma _\mathrm{x}=2\pi l_\mathrm{B}\sigma ^2\kappa _s^1+\sigma \varphi _\mathrm{D}\text{linear},$$
(17)
If we do not linearise the Poisson-Boltzmann equation, Eq. (4), we can still integrate it once to obtain

$$\left(\frac{d\varphi }{dz}\right)^2=2\kappa _s^2\left(\mathrm{cosh}\varphi \mathrm{cosh}\varphi _\mathrm{D}\right)8\pi l_\mathrm{B}\rho _p\left(\varphi \varphi _\mathrm{D}\right).$$
(18)
Combining this with the boundary condition, Eq. (6) we obtain an equation for the potential at the surface $`\varphi (z=0)`$,

$`\left[2\kappa _s^2\left(\mathrm{cosh}\varphi (z=0)\mathrm{cosh}\varphi _\mathrm{D}\right)8\pi l_\mathrm{B}\rho _p\left(\varphi (z=0)\varphi _\mathrm{D}\right)\right]^{1/2}`$
$`=\pm 4\pi l_\mathrm{B}\sigma ,`$ (19)
which can be solved for $`\varphi (z=0)`$, and then once this is known the profile $`\varphi (z)`$ is readily obtained by numerically integrating Eq. (18). On the right hand side the $`+`$ ($``$) sign is taken when $`\sigma >0`$ ($`\sigma <0`$). The interfacial free energy is then obtained from

$$\mathrm{\Delta }\gamma _\mathrm{x}=_0^{\mathrm{}}𝑑z\left(\omega (z)\omega (\mathrm{})\right),$$
(20)
where the grand potential per unit volume in the protein crystal is $`\omega (\mathrm{})=2\rho _s(\mathrm{cosh}\varphi _\mathrm{D}\varphi _\mathrm{D}\mathrm{sinh}\varphi _\mathrm{D})`$. Using $`\rho _\pm (z)=\rho _s\mathrm{exp}[\varphi ]`$, and Eq. (18) for the electric field term in Eq. (2), we have that the electrical double layer contribution to the free energy of the solid-protein interface is given by

$$\mathrm{\Delta }\gamma _\mathrm{x}=2\rho _s_0^{\mathrm{}}𝑑z\varphi [\mathrm{sinh}\varphi \mathrm{sinh}\varphi _\mathrm{D}].$$
(21)
### II.3 Salt-solution–protein-crystal interface

This interface was the subject of Ref. sear02 . In the high salt regime where the Poisson-Boltzmann equation can be linearised the electrical double layer contribution to the free energy of the interface between a protein crystal and a salt solution is

$$\mathrm{\Delta }\gamma _{\mathrm{el}}=\frac{\rho _s\varphi _\mathrm{D}^2}{2\kappa _s}\text{linear}.$$
(22)
See Ref. sear02  for the full nonlinear calculation.

## III Results

We can calculate the free energies of the three interfaces: solid–salt-solution, solid–protein-crystal and salt-solution–protein-crystal. This allows us to see whether a protein crystallite, such as a nucleus or growing crystallite in solution, is attracted or repelled by the surface. It is attracted if the free energy change on bringing a protein crystal from the bulk solution to the surface is negative and repulsive if the change is positive. When a protein crystallite is brought from the bulk of the solution into contact with the surface two interfaces are destroyed, that between the salt solution and the protein crystal and that between the salt solution and the solid, and one is created, that between the solid and the protein crystal. Thus, the free energy change per unit area of protein crystal brought into contact with the solid is

$$\mathrm{\Delta }=\mathrm{\Delta }\gamma _\mathrm{s}\mathrm{\Delta }\gamma _{\mathrm{el}}+\mathrm{\Delta }\gamma _\mathrm{x},$$
(23)
which in the high salt limit is, using Eqs. (9), (17) and (22),

$$\mathrm{\Delta }=\frac{\rho _s\varphi _\mathrm{D}^2}{2\kappa _s}+\sigma \varphi _\mathrm{D}\text{linear}.$$
(24)
The first term comes from the disappearance of the salt-solution–protein-crystal interface and is positive as the electrical double layer contribution to the interfacial tension of this interface is always negative; see Ref. sear02  for a discussion. As $`\varphi _\mathrm{D}`$ has the same sign as that of the charges on the protein molecules (here taken to be positive), the second term is positive if the surface and protein molecules have charges of the same sign and negative if the have opposite signs. As we should expect, surfaces repel crystals of proteins with the same charge. They attract crystals of oppositely charged protein molecules, providing that the surface charge $`\sigma `$ is sufficiently high. If the charge density is small or zero then they repel protein crystals due to the free energy cost of destroying the salt-solution–protein-crystal interface.

Equation (24) is obtained by linearising the Poisson-Boltzmann equation. We have also solved the full equation and present example results in Figs. 2 and 3. The parameters for the protein are those used previously sear02 , and were chosen to model lysozyme. This is a small protein with quite a large net charge for its size, whose behaviour in NaCl solutions has been extensively studied muschol95 ; muschol97 ; guo99 ; poon00 ; warren02 . The model used here has been to shown to give the variation with NaCl concentration of the solubility of lysozyme crystals correctly to within a factor of about 2, it overpredicts the variation poon00 ; warren02 . The agreement between its predictions and the surface force apparatus measurements of Sivasankar et al. sivasankar98  of the repulsion between monolayers of the protein streptavidin, is comparable sear02 . To model lysozyme we took a charge $`Q=10`$ warren02 ; muschol97 ; tanford72 , and a charge density due to the protein $`\rho _p=0.25`$nm<sup>-3</sup>, obtained by taking the volume per lysozyme molecule in the crystal to be 40nm<sup>3</sup>. The surface area of the protein crystal per lysozyme molecule is taken to be $`l^2=12`$nm<sup>2</sup> sear02 . For proteins such as lysozyme which have a significant net charge we would expect our predictions to be approximately as accurate as those of earlier predictions of this theory, i.e., predicting the trends correctly but giving numbers which are a factor of 2 or more out. We expect our predictions to be unreliable if the net charge is small, then the interaction between the dipole moment of the protein and the surface may dominate, or if the charge is distributed on the surface in a way which is highly inhomogeneous. If the charge density within the volume within a few Debye lengths of the surface differs greatly from $`\rho _p`$, then our assumption of uniform charge density due to the protein will be poor. See Ref. sear02  for further discussion of the assumption that the protein crystal can be modeled by a step-function charge density.

In Fig. 2 we see that for lysozyme and solid surfaces with $`\sigma =\pm 1`$nm<sup>-2</sup>, the free energy change of bringing the protein crystal into contact with the solid is substantial unless the salt concentration is around $`1\mathrm{M}`$. Even at a salt concentration of $`1\mathrm{M}`$, the free energy change is close to $`2k_\mathrm{B}T`$ per lysozyme molecule at the surface of the protein in contact with the solid surface. Whereas at salt concentrations of about $`0.1\mathrm{M}`$ and lower the free energy change is of order $`10k_\mathrm{B}T`$ per lysozyme molecule. Note however, that we have assumed that the protein crystal is in a salt solution, i.e., a solution with negligible amounts of protein in it. Decreasing the salt concentration increases the solubility of lysozyme muschol97 , and so this assumption will tend to worsen as the salt concentration drops warren02 ; sear02 . The salt is not only changing the interaction between the protein and the surface but also the interaction in between protein molecules and this needs to be borne in mind.

In Fig. 3 we see that at high salt concentrations, $`1\mathrm{M}`$, the free energy change on bringing a crystal into contact with the surface is never more than a couple of $`k_\mathrm{B}T`$, even for quite highly charged surfaces. However, for more modest salt concentrations of $`0.1\mathrm{M}`$, rather large free energy decreases per protein molecule are easily obtained at modest charges per unit area on the surface. Also, note that $`\mathrm{\Delta }`$ is slightly positive for an uncharged surface. This is due to the fact that the electrical double layer contribution to the protein-crystal–salt-solution interface is negative, Eq. (22), and this contribution is lost when the protein crystal is brought into contact with the surface.

The potential near the surface, both when the salt solution is in contact with the surface and when the protein crystal is, is shown in Fig. 4. When the protein crystal is in contact with the surface the potential tends to its value in the bulk of the crystal: the Donnan potential, which is $`1.48`$ here. The potential at the surface is larger than one, and so the linear approximation is quite poor for the charge $`\sigma =\pm 1`$nm<sup>-2</sup>. In particular, Eq. (24) significantly overestimates the magnitude of $`\mathrm{\Delta }`$ at high surface charges. However, Eq. (24) is reasonably accurate for the smaller charge per unit area, $`\sigma =\pm 0.1`$nm<sup>-2</sup>. As an example, for $`\sigma =1`$nm<sup>-2</sup> and $`\rho _s=0.1\mathrm{M}`$, $`\mathrm{\Delta }l^2=11.1`$ without linearisation, whereas Eq. (24) predicts $`\mathrm{\Delta }l^2=17.0`$.

## IV Conclusion

We have used an existing warren02 ; sear02  generic model of a protein crystal to estimate the electrostatic contribution $`\mathrm{\Delta }`$ to the free energy change when a protein crystal is brought into contact with a surface with a fixed charge density $`\sigma `$. Unsurprisingly, the free energy change is negative for a surface with a charge opposite in sign to that on the protein molecule, and positive if the surface has a charge with the same sign. We quantified this and found that very reasonable charge densities, of 1 elementary charge per nm<sup>2</sup> or less, were sufficient to achieve free energy changes per protein molecule at the surface of several $`k_\mathrm{B}T`$ or more, provided the salt concentration was less than around $`1\mathrm{M}`$. The electrostatic contribution to the free energy is the energy associated with the electrostatic interactions in between the surface, protein molecules, and salt and counterions, and the translational entropy of the salt and counterions. Typically, there will also be non-electrostatic interactions of the proteins with the surface, particularly if the surface is at least moderately hydrophobic. Then the proteins may even unfold resulting in irreversible adsorption. Thus, our results will be relevant only to those surfaces which are sufficiently hydrophilic that the proteins interact only weakly with the surface and do not unfold. However, obtaining such surfaces is relatively straightforward via the use of self-assembled monolayers clark97 ; ostuni99 . Our model of the protein is a very simple one, appropriate for proteins with reasonably large net charges, so that the terms we calculate should be dominant, and where this charge is distributed so that the charge density facing the surface is neither much higher nor much lower than the average charge density on the surface of the protein.

Perhaps the most important reason for considering protein crystals at surfaces is interest in their heterogeneous nucleation. Protein crystals nucleate at surfaces and so without an understanding of crystallites at surfaces we cannot hope to understand how the crystals actually form. Crystallising proteins is essential for the determination of their all-important three-dimensional structure via X-ray crystallography rosenberger96 ; chayen02 . Heterogeneous nucleation is an activated process debenedetti  and so proceeds at a rate which scales as $`\mathrm{exp}(\mathrm{\Delta }F^{}/k_\mathrm{B}T)`$, where $`\mathrm{\Delta }F^{}`$ is the height of the free energy barrier which must be overcome. Typical sizes of the critical nuclei in nucleation are a few 10s of protein molecules, and so one face of a crystalline nucleus has perhaps 10, or a few less, protein molecules. The critical nucleus is that at the top of the barrier, the nucleus which requires a free energy $`\mathrm{\Delta }F^{}`$ to create it debenedetti . Thus, the variation in $`\mathrm{\Delta }F^{}`$ with $`\mathrm{\Delta }`$, will be approximately $`10\mathrm{\Delta }l^2`$. From Figs. 2 and 3, we see that this may easily be 10s of $`k_\mathrm{B}T`$, causing increases or decreases in the rate of heterogeneous nucleation of many orders of magnitude. The barrier to nucleation may be lowered by 10s of $`k_\mathrm{B}T`$, inducing nucleation in solutions which would otherwise be metastable, or it may be raised by 10s of $`k_\mathrm{B}T`$ preventing nucleation from occurring on one part of the surface. The former is required if a surface is to be used as a nucleant: a surface which triggers nucleation mcpherson88 ; chayen01 . The latter is required for spatial control of heterogeneous nucleation sanjoh99 ; sanjoh01 .

Finally, we consider wetting by the crystalline phase of the surface–salt-solution interface. At coexistence, for a bulk solution phase in contact with the surface, a direct surface–salt-solution interface is not the only possibility. It is possible for a slab of the protein crystal to be interposed between the surface and the solution phase. The direct surface–salt-solution interface is then replaced by by a surface–protein-crystal interface plus solution–protein-crystal interface. The protein crystal is said to have wet the surface–salt-solution interface. Wetting occurs at equilibrium whenever it lowers the free energy israelachvili ; bonn01 . Denoting the full interfacial tensions of the surface–salt-solution, surface–protein-crystal and solution–protein-crystal interfaces by $`\gamma _s`$, $`\gamma _x`$ and $`\gamma `$, respectively, we have that the free energy change on interposing a slab of protein crystal between the surface and the solution is $`\gamma _s+\gamma _x+\gamma `$. Note that here the interfacial tension of the solution–protein-crystal interface appears with a positive sign whereas it appears with a negative sign in the definition of $`\mathrm{\Delta }`$, Eq. (23). When a layer of the protein crystal is created so is a solution–protein-crystal interface, whereas when an existing protein crystal surrounded by solution is brought into contact with the surface a solution–protein-crystal interface is destroyed.

Determining the sign of $`\gamma _s+\gamma _x+\gamma `$ is not possible without determining both the electrostatic and non-electrostatic contributions to all three interfacial tensions. However, in Ref. sear02 , the interfacial tension $`\gamma `$ was estimated to be a few $`k_\mathrm{B}T`$ per area of a protein molecule, i.e., $`\gamma l^2=O(1)`$. If we further assume that $`\gamma _s+\gamma _x`$ is dominated by electrostatics, then in the linear regime $`\gamma _s+\gamma _x\sigma \varphi _\mathrm{D}`$, from Eqs. (9) and (17). Thus for the electrostatic attraction between an oppositely charged surface and a protein crystal to drive wetting of the surface–salt-solution interface, we require that $`|\sigma \varphi _\mathrm{D}|l^2>O(1)`$. For highly charged surfaces, $`\sigma `$ of order 1nm<sup>-2</sup>, and low salt concentrations, this inequality is easily satisfied.

If the protein crystal wets the surface–salt-solution interface, then assuming that the layer of protein crystal can itself nucleate on the surface it will do so and the bulk protein crystal can grow from this layer at the surface. Then the barrier to crystallisation will be close to zero and the protein will readily crystallise from solution vlnote . This assumes that the layer itself can nucleate, see Ref. bonn01  for an introduction to wetting layers, both at equilibrium and their nucleation.

###### Acknowledgements.

I would like to thank P. Warren for introducing me to the theory of electrostatic effects in proteins. Work supported by The Wellcome Trust (069242).


text:
# What is coherent in neutrino oscillations

## I  How Neutrinos with different masses can be Coherent

### A Introduction

The standard textbook description shows that a coherent linear combination of neutrino eigenstates with the same momentum and different masses have different energies and oscillate in time. But such time oscillations and coherence between states having different energies are not observed in most realistic experiments. Furthermore coherence or interference between different neutrino mass eigenstates cannot be observed in a “missing mass” experiment where the mass of an unobserved neutrino is unqiuely determined by other measurements and momentum and energy conservation.

The resolution of these contradictions is just simple quantum mechanics. In any experiment which can detect neutrino oscillations, the position of the detector must be known with an error much smaller than the wave length of the oscillation to be observed. The quantum mechanical uncertainty principle therefore forces coherence between neutrino mass eigenstates having the same energy and different momenta. Time behavior, time measurements and stationarity in energy are irrelevant for this conclusion. The location in space already says it all.

This simple physical argument is now spelled out rigorously with simple quantum mechanics and no hand waving. In all realistic experiments the product of the quantum fluctuations in the position of the detector and the momentum range over which coherence is established is a very small parameter. Expanding the exact transition matrix element for the neutrino detection in powers of this small parameter and taking the leading term gives the desired result.

### B No coherence in a missing mass experiment

When a pion decays at rest $`\pi \mu \nu `$ the energies $`E_\mu ,E_\nu `$ and momenta $`\stackrel{}{p}_\mu ,\stackrel{}{p}_\nu `$ of the neutrino and muon can all be known. This is just a “Missing Mass” experiment. The neutrino mass $`M_\nu `$ is uniquely determined by $`M_\nu ^2=(M_\pi E_\mu )^2p_\mu ^2`$. So how can there be coherence and interference between states of different mass? We are guided to the resolution of this paradox by experience in condensed matter physics discussing which amplitudes are coherent in quantum mechanics.

The original Lederman-Schwartz-Steinberger experiment found that the neutrinos emitted in a $`\pi \mu `$ decay produced only muons and no electrons. Experiments now show that at least two neutrino mass eigenstates are emitted in $`\pi \mu `$ decay and that at least one of them can produce an electron in a neutrino detector. The experimentally observed absence of electrons can be explained only if the electron amplitudes received at the detector from different neutrino mass eigenstates are coherent and exactly cancel. This implies that sufficient information was not available to determine the neutrino mass from energy and momentum conservation. A missing mass experiment was not performed.

### C Why quantum-mechanically imposed ignorance is needed

Destruction of information by simple ignorance or stupidity cannot provide coherence. The experimental setup must forbid via the quantum-mechanical uncertainty principle the knowledge of the information necessary to determine the neutrino mass. This paper analyzes the basic physics and presents a rigorous quantitative analysis of the hand-waving uncertainty principle argument. The knowledge of the position of any realistic neutrino detector is shown to be sufficient to provide the uncertainty in momentum needed to create coherence between the amplitudes carried to the detector by components in the neutrino wave function with the same energy, different masses and different momenta.

The initial state of the detector before the interaction with the neutrino is described by a many-body wave function that exists only in a finite region of configuration space. The probability is zero for finding any detector nucleon anywhere in space outside of this volume. This exact property of the exact initial state is rigorously shown below to prevent the detector from recognizing the difference between two incident neutrinos with the same energy and slightly different momenta. It ensures the quantum-mechanical ignorance needed to produce coherence. This physics can be handwaved and called the uncertainty principle. But it can also be proved rigorously.

## II The Basic Physics of Neutrino Detection

### A The neutrino wave packet

The neutrino wave packet traveling between source and detector vanishes outside some finite interval in space at any given time. At any point on its path it also vanishes outside some finite time interval. The packet therefore contains components with different momenta and different energies which are all coherent with well defined phases to cancel out at all points in space and time where the probability of finding the neutrino vanishes.

However, not all the different kinds of coherence present in the wave packet are observable with a conventional detector. The detector is sensitive in very different ways to the different components in the wave packet. .

### B The role of the neutrino detector

Neutrino absorption is a weak interaction described completely by the transition matrix of the weak interaction operator between the exact initial and final states of the lepton and detector, where the exact states include all strong interactions. This matrix element can be expanded in powers of a small parameter, the product of the displacement of the detector nucleon from the center of the detector and a momentum interval which includes all momenta of incident neutrinos having the same energy.

We shall now show that the leading term in this expansion gives the lepton flavor output for each energy component in the initial neutrino wave function as the coherent sum of the contributions from states with the same energy and different momenta. This is exact subject only to corrections of higher order in the small parameter which are negligible as long as the size of the detector is negligibly small in comparison with any neutrino oscillation wave length.

Consider the transition matrix element between an initial state $`|i(E)`$ with energy $`E`$ of the entire neutrino - detector system and a final state $`|f(E)`$ of the system of a charged muon and the detector with the same energy E, where a neutrino $`\nu _k`$ with energy, mass and momentum $`E_\nu `$, $`m_k`$ and $`\stackrel{}{P}_o+\stackrel{}{\delta P_k}`$ is detected via the transition

$$\nu _k+p\mu ^++n$$
(1)
occurring on a proton in the detector. We express the neutrino momentum as the sum of the mean momentum $`\stackrel{}{P}_o`$ of all the neutrinos with energy $`E_\nu `$ and the difference $`\stackrel{}{\delta P_k}`$ between the momentum of each mass eigenstate and the mean momentum,

The transition matrix element depends upon the individual mass eigenstates $`k`$ only in the momentum difference $`\stackrel{}{\delta P_k}`$ and a factor $`c_k`$ for each mass eigenstate which is a function of neutrino mixing angles describing the transition amplitude for this mass eigenstate to produce a muon when it reaches the detector. The transition matrix element can thus be written in a factorized form with one factor $`T_o`$ independent of the mass $`m_k`$ of the neutrino and a factor depending on $`m_k`$.

$$f(E)\left|T\right|i(E)=\underset{k}{}f(E)\left|T_oc_ke^{i\stackrel{}{\delta P_k}\stackrel{}{X}}\right|i(E)$$
(2)
where $`\stackrel{}{X}`$ denotes the co-ordinate of the nucleon that absorbs the neutrino. Then if the product $`\stackrel{}{\delta P_k}\stackrel{}{X}`$ of the momentum spread in the neutrino wave packet and the fluctuations in the position of the detector nucleon is small, the exponential can be expanded and approximated by the leading term

$$f(E)\left|T\right|i(E)=\underset{k}{}f(E)\left|T_oc_ke^{i\stackrel{}{\delta P_k}\stackrel{}{X}}\right|i(E)\underset{k}{}f(E)\left|T_oc_k\right|i(E)$$
(3)
The transition matrix element for the probability that a muon is observed at the detector is thus proportional to the coherent sum of the amplitudes $`c_k`$ for neutrino components with the same energy and different masses and momenta to produce a muon at the detector. A similar result is obtained for the probability of observing each other flavor. The final result is obtained by summing the contributions over all the energies in the incident neutrino wave packet. But as long as the flavor output for each energy is essentially unchanged over the energy region in the wave packet, the flavor ouput is already determined for each energy, and is independent of any coherence or incoherence between components with different energies.

For the case of two neutrinos with energy $`E`$ and mass eigenstates $`m_1`$ and $`m_2`$ the relative phase of the two neutrino waves at a distance $`x`$ is:

$$\varphi _m^E(x)=(p_1p_2)x=\frac{(p_1^2p_2^2)}{(p_1+p_2)}x=\frac{\mathrm{\Delta }m^2}{2p}x$$
(4)
where $`\mathrm{\Delta }m^2m_2^2m_1^2`$, and we have assumed the free space relation between the masses, $`m_i`$ energy $`E`$ and momenta:

The flavor output of the detector is thus seen to be determined by the interference between components in the neutrino wave paclet with the same energy and different masses and momenta. All the relevant physics is in the initial state of the nucleon in the detector that detects the neutrino and emits a charged lepton, together with the relative phases of the components of the incident neutrino wave packet with the same energy.

This result (3-4) is completely independent of the neutrino source and in particular completely independent of whether the source satisfies Stodolsky’s stationarity condition. No subsequent time measurements or additional final state interactions that mix energies can change this flavor output result.

The initial uncertainty in the momentum of the detector nucleon destroys all memory of the initial neutrino momentum and of the initial neutrino mass after the neutrino has been absorbed. The hand-waving justification of the result (3) uses the uncertainty principle and says that if we know where the detector is we don’t know its momentum and can’t use momentum conservation to determine the mass of the incident neutrino. The above rigorous justification shows full interference between the contributions from different neutrino momentum states with the same energy as long as the product of the momentum difference and the quantum fluctuations in the initial position of the detector nucleon is negligibly small in the initial detector state.

This treatment of the neutrino detector is sufficient to determine the output of any experiment in which the incident neutrino wave packet is the same well defined linear combination of mass eigenstates throughout the whole wave packet.

### C At what distance is coherence lost?

The above treatment has not comsidered the effects resulting from the different velocities of neutrino wave packets with different masses. The difference in velocity between components in two wave packets $`(\delta v)_m`$ with the same energy and different mass is just the difference in velocities $`v=p/E`$ for states with different momenta and the same energy,

$$(\delta v)_m=\frac{}{p}\left(\frac{p}{E}\right)_E(\delta p)_m=\frac{(\delta p)_m}{E}$$
(5)
The packets will eventually separate and arrive at a remote detector at different separated time intervals. The detector then sees two separated probability amplitudes, each giving the probability that the detector observes a given mass eigenstate. All coherence between the different mass eigenstates is then lost. The question then arises when and where this occurs; i.e. at what distance from the source the coherence begin to be lost. Two different approaches to this problem give the same answer.

1. The centers of the wave packets move apart with the relative velocity $`(\delta v)_m`$ given by eq. (5). Thus the separation $`(\delta x)_m`$ between the wave packet centers after a time $`t`$ when the centers are at a mean distance $`x`$ from the source is

$$(\delta x)_m=(\delta v)_mt=(\delta v)_m\frac{x}{v}=\frac{\mathrm{\Delta }m^2}{2pE}\frac{xE}{p}=\frac{\mathrm{\Delta }m^2}{2p^2}x$$
(6)
The wave packets will separate when this separation distance is comparable to the length in space of the wave packet. The uncertainty principle suggests that the length of the wave packet $`(\delta x)_W`$ and its spread in momentum space $`(\delta p)_W`$ satisfiy the relation

$$(\delta x)_W(\delta p)_W1/2$$
(7)
The ratio of the separation over the length is of order unity when

$$\left|\frac{(\delta x)_m}{(\delta x)_W}\right|\left|\frac{\mathrm{\Delta }m^2}{p^2}\right|(\delta p)_Wx1$$
(8)
2. Stodolsky has suggested that one need not refer to the time development of the wave packet, but only to the neutrino energy spectrum. The relative phase $`\varphi _m(x)`$ between the two mass eigenstate waves at a distance $`x`$ from the source depends upon the neutrino momentum $`p_\nu `$ as defined by the relation (4).

Coherence will be lost in the neighborhood of the distance $`x`$ where the variation of the phase over the momentum range $`(\delta p)_W`$ within the wave packet is of order unity. For the case of two neutrinos with energy $`E`$ and mass eigenstates $`m_1`$ and $`m_2`$ the condition that the relative phase variation $`|\delta \varphi _m(x)|`$ between the two neutrino waves is of order unity

$$|\delta \varphi _m(x)|=\left|\frac{\varphi _m(x)}{p_\nu }\right|\delta p_\nu x=\left|\frac{\mathrm{\Delta }m^2}{2p_\nu ^2}\right|(\delta p)_Wx1$$
(9)
We find that the two approaches give the same condition for loss of coherence.

## III How incomplete information provides coherence

### A Bragg Scattering

Bragg scattering of photons by a crystal provides an instructive example of coherence arising from incomplete information on momentum conservation. Coherence between the photon scattering amplitudes from different atoms in the crystal produces constructive interference at the Bragg angles and gives peaks in the angular distribution. When a single photon is scattered from a crystal, momentum is transferred to the atom in the crystal that scattered the photon. If the recoil momentum is detected the atom that scattered the photon is identified and coherence is destroyed. Coherence arises when quantum mechanics prevents the measurement of the initial and final momenta of the individual atoms.

The initial and final states of the crystal are many-particle quantum states that are eigenstates of the Hamiltonian of the crystal. The dynamics of the crystal and the interaction with the incident photon allow elastic scattering, in which the photon is scattered by a single atom in the crystal but the quantum state of the crystal is unchanged. This is a purely quantum effect. Transferring momentum classically to an atom in a crystal must change the momentum and the motion of the particular atom and allow the identification of which atom scattered the photon.

The difference produced by quantum mechanics is simply seen in a toy model in which each atom is bound to its equilibrium position in the crystal by a harmonic oscillator potential. The atom that scatters the photon is initially in a definite discrete energy level in the potential. In contrast to the classical case, the atom cannot absorb the momentum transfer according to the energy and momentum kinematics of free particles. The final state of the atom in the potential must be one of the allowed energy levels, and there is a finite probability that the final state is the same as the initial state. In this case of elastic scattering, there is no information available on which atom scattered the photon, and the scattered amplitudes from all scattering atoms are coherent.

This example shows how amplitudes arising from different processes which would be classically distinguishable can be coherent. The quantum mechanics of bound systems can conceal the information which would be classically available from energy-momentum conservation for free particles.

### B Pion Decay

This same effect conceals the mass of the neutrino emitted in pion decay. The initial pion in a beam stop cannot be strictly at rest; it is localized by its electrostatic interaction with the electric charges in the material where it was stopped. It is therefore in some kind of energy level of the bound system and described by a wave function which is a coherent linear combination of different momentum eigenstates. Measuring the energy of the muon determines the energy of the emitted neutrino, since the energy of the initial state is determined. But the momentum of the neutrino is not determined. In a simple toy model where the initial pion is bound by some external potential, it is described by a wave function which is a coherent wave packet in momentum space.

When the neutrino strikes a detector, the amplitudes produced by different mass eigenstates having the same energy and different momenta can be coherent. They are produced from the different momentum components in the initial pion wave function which are coherent with a definite relative phase. This can explain why no electrons are observed at a short distance from the detector.

If the neutrino amplitudes produced in this way propagate as free particles, these considerations determine completely the relative phase between the amplitudes for neutrinos having the same energy but different masses and different momenta. The phase change will produce neutrino oscillations with the same relation between mass differences and phase differences (4) that has been given by the standard treatments.

## IV Time measurements, Momentum and Energy

### A The possibility of time measurements

The preceding analysis does not consider experiments in which the transit time of the neutrino between source and absorber is measured. Experiments have been suggested in which the muon emitted together with the neutrino in a pion decay is observed at the neutrino source and the time that the muon is detected is measured precisely along with the time that the muon or electron is produced by absorbing the neutrino in the detector. The motivation is to use some kind of energy-time uncertainty to detect interference between components having different energies in the neutrino wave function.

However, in any realistic detector the quantum fluctuations in the position of the detector nucleon are small in comparison with the wave length of the neutrino oscillation. Thus the coherence and the relative phase of the components in the neutrino wave function having the same energy and different momenta are preserved. This relative phase completely determines the flavor output of the detector; i.e. the relative probabilities of producing a muon or an electron. In all realistic cases where the separation of wave pakets moving with different velocities is negliible, eqs.(9) and (8) show that these probabilities are essentially independent of energy over the relevant energy range. Thus the relative phases and coherence between components in the neutrino wave function with different energies is irrelevant. All energies give the same muon/electron ratio whether they add coherently or incoherently. Thus time measurements cannot change the muon/electron ratio observed at the detector.

Thus the flavor output from any time of flight experiment that uses a neutrino detector that preserves the coherence between states of the same energy and different momentum is already determined at the single energy level. It is unaffected by any interference between components of the neutrino wave function with different energies.

### B The Difference Between Momentum and Energy

Confusion tends to arise from thinking that momentum and energy should be on the same footing, particularly since relativity implies that they are components of the same four vector. But this is only true for isolated free particles. In any realistic neutrino experiment the neutrino is observed by a weak interaction with a detector. The detector, in its rest frame before the arrival of the neutrino, is in an initial state described by a density matrix in which energy is diagonal and momentum is not. This is the critical difference between energy and momentum There is no coherence and no well-defined relative phase between components in the detector density matrix with different energies. But there must be coherence and well defined relative phases between components with different momenta, as shown rigorously by eq. (2), because we know where the detector is in space and where it isn’t. The form factor (2) is seen to be negligibly different from unity as long as the quantum fluctuations in the position of the detector are small in comparison with the wave length of the oscillation being measured.

## V Conclusions

Coherence between amplitudes produced by neutrinos incident on a detector with different masses and the same energy has been shown to follow from the localization of the detector nucleon within a space interval much smaller than the wave length of the neutrino oscillation. Decoherence between different mass eigenstates results from the separation of wave packets moving with different velocities and is simply described also in terms of the energy dependence of the flavor output of a detector. ,

That coherence must exist in neutrinos emitted from $`\pi \mu `$ decay follows from the original Lederman-Schwartz-Steinberger experiment which saw only muons and no electrons. We now know that at least two different neutrino mass eigenstates are emitted from pi-mu decay and that at least one must couple to electrons. The only explanation for the absence of electrons at the detector is destructive interference from amplitudes produced by different mass eigenstates.

It is a pleasure to thank Eyal Buks, Maury Goodman, Yuval Grossman, Moty Heiblum, Yosef Imry, Boris Kayser, Lev Okun, Gilad Perez, David Sprinzak, Ady Stern, Leo Stodolsky and Lincoln Wolfenstein for helpful discussions and comments.


text:
# Variable electrostatic transformer: controllable coupling of two charge qubits

\[

## Abstract

We propose and investigate a novel method for the controlled coupling of two Josephson charge qubits by means of a variable electrostatic transformer. The value of the coupling capacitance is given by the discretized curvature of the lowest energy band of a Josephson junction, which can be positive, negative, or zero. We calculate the charging diagram of the two-qubit system that reflects the transition from positive to negative through vanishing coupling. We also discuss how to implement a phase gate making use of the controllable coupling.

\]

Following experimental demonstrations of individual qubits implemented with Josephson junctions operated in the charge  or flux  regimes, a lot of interest is now focused on building multi-qubit Josephson circuits. Recently, there has been an encouraging first experimental step  demonstrating quantum-coherent dynamics of two charge qubits coupled directly through a capacitance. The coupling strength could not be varied in this experiment, since there is no simple way of changing the electrostatic capacitance between two metallic islands. A controlled coupling of charge qubits would be highly desirable. Many two-qubit transformations that could be implemented with a controllable coupling become more difficult or impossible at constant coupling, since in the presence of interactions one needs to correct for different dynamic phases of the two-qubit states. Two-qubit gates with untunable couplings have been suggested , however, the gate design becomes significantly more complex.

For flux qubits, the problem of a controlled coupling can be solved with variable flux transformers (see, e.g., ) which can be implemented naturally with the standard tools of superconductor electronics . For other types of “magnetic” qubits, e.g., spin qubits, the possibility to control the qubit coupling both in sign and absolute value has been predicted theoretically  (for recent experimental progress, see ). For charge qubits, however, a comparably natural solution has been lacking although the importance of the interaction control problem has been recognized for some time. Suggested controlled coupling methods include direct spatial separation of qubit states by adiabatic transfer along junction arrays  or coupling through superconducting resonators . The first one is too complicated to be practical at present. The second requires relatively large inductances of small geometric dimension that are fundamentally difficult to produce, in particular without creating additional dissipation at the relevant large frequencies.

The purpose of this work is to analyze a new circuit to implement a controllable coupling of charge qubits. The circuit, shown in Fig. 1, generalizes the simple capacitive coupling used in  and makes use of the following basic feature of an individual small Josephson tunnel junction. If the junction dynamics is confined to the lowest energy band of its band structure, it behaves as a variable capacitance with respect to the injected charge . The magnitude of this capacitance depends on the bias point and can even be made negative. This is important for the application as a controllable coupling element, since it enables one to drive the coupling capacitance to zero. The physics of the capacitance modulation is the transformation of charge, when an injected charge causes a Cooper-pair transfer across the junction that changes the output charge. If, however, the two qubits are coupled directly through a small junction (the coupling scheme considered, e.g., in a somewhat different context in ) this mechanism would not produce a variable-capacitance coupling scheme, since variations of the junction capacitance are compensated by a redistribution of the transferred charge on the capacitances in series with the junction. Nevertheless, if the junction is included “perpendicular” to the coupling direction, as in Fig. 1, the required “variable electrostatic transformer” with a gate-voltage-controlled coupling capacitance is produced.

Indeed, if the voltage $`V`$ is applied to the pair of input terminals (left or right, $`i=1,2`$) of the circuit shown in Fig. 1, the Hamiltonian of the system is that of an individual Josephson junction (or “Cooper-pair box” ) with the charge $`2e(qq^{})`$ injected into it, where $`q=C_{mi}V/2e`$ and $`q^{}=C_{mi}V_g/2e`$. When the junction is in its lowest energy band $`ϵ_0`$, the output voltage $`V_{out}`$ at the opposite terminals varies such that

$$4e^2/C_02eV_{out}/q=^2ϵ_0(qq^{})/q^2.$$
(1)
The input-output interaction strength defined by this relation varies with the charge $`2eq^{}`$ injected by the gate voltage and goes through zero at a bias point dependent on the shape of the energy band $`ϵ_0(q)`$.

If the transformer shown in Fig. 1 is inserted between two charge qubits (Fig. 2), it provides a gate-voltage-controlled qubit coupling. The qubits 1,2 with Josephson coupling energies $`E_{Ji}`$, $`i=1,2`$, are biased by the gate voltages $`V_i`$ through the capacitances $`C_{gi}`$ and are coupled to the central island of the transformer by capacitances $`C_{mi}`$. Inverting the capacitance matrix of this system, we can write the Hamiltonian as

$`H=`$ $``$ $`{\displaystyle \underset{i=1,2}{}}E_{Ji}\mathrm{cos}\phi _i+E_{Ci}(n_iq_i)^2`$ (2)
$``$ $`E_J\mathrm{cos}\phi +E_C(nq(n_1,n_2))^2,`$ (3)
where $`E_C=2e^2/(C_\mathrm{\Sigma }_iC_{mi}^2/C_{\mathrm{\Sigma }i})`$, $`E_{Ci}=2e^2/C_{\mathrm{\Sigma }i}`$, $`n_i`$ is the number of excess Cooper pairs on qubit $`i`$, and $`q_iV_iC_{gi}/2e`$. The qubits are coupled through the charge $`q`$ induced on the transformer junction: $`q=q_g_i(n_iq_i)C_{mi}/C_{\mathrm{\Sigma }i}`$, where $`q_g(V_g/2e)_iC_{mi}(1C_{mi}/C_{\mathrm{\Sigma }i})`$. The Josephson phase differences across the respective junctions are denoted by $`\phi _i`$ and $`\phi `$. Finally, $`C_{\mathrm{\Sigma }i}C_i+C_{gi}+C_{mi}`$, and $`C_\mathrm{\Sigma }C+C_{m1}+C_{m2}`$.

We assume that the degrees of freedom of the transformer junction are fast, and that the junction is confined to the lowest energy band of its band structure. Then we can replace the part of the Hamiltonian related to the transformer by the dispersion relation $`ϵ_0(q)`$ of this lowest band,

$$E_J\mathrm{cos}\phi +E_C(nq(n_1,n_2))^2ϵ_0(q(n_1,n_2)).$$
(4)
This is the analogue of the Born-Oppenheimer approximation which in our case is valid if the characteristic energy gap between the bands of the transformer junction is much larger than the qubit energies. For our qubit coupling, this condition requires that $`E_JE_{Ji}`$ for $`E_JE_C`$, and $`(E_CE_J)^{1/2}E_{Ji}`$ for $`E_JE_C`$ (the qubits are assumed to be in the charging regime).

To determine the qubit coupling provided by the transformer we will use the known properties of the junction bandstructure . Also, we use the fact that in the charge qubit regime ($`E_{Ji}E_{Ci}`$, $`q_i1/2`$), the dynamics of the charges $`n_i`$ in (3) is reduced to two states, so that the charges can be expressed through the Pauli matrices, $`n_i=(\sigma _{zi}+1)/2`$. Assuming that the structure in Fig. 2 is symmetric, i.e., $`C_{m1}/C_{\mathrm{\Sigma }1}=C_{m2}/C_{\mathrm{\Sigma }2}c`$, the transformer term $`ϵ_0(q(n_1,n_2))`$ in the reduced Hamiltonian can be expressed as follows:

$$ϵ_0(q(n_1,n_2))=\nu \sigma _{z1}\sigma _{z2}+\delta (\sigma _{z1}+\sigma _{z2})+\mu .$$
(5)
The coupling coefficient $`\nu `$ is given by

$$\nu =\frac{1}{4}[ϵ_0(q_0+c)+ϵ_0(q_0c)2ϵ_0(q_0)],$$
(6)
where $`q_0=q_g+c_i(q_i1/2)`$. The term linear in $`\sigma _z`$ shifts the qubit bias by $`\delta =[ϵ_0(q_0+c)ϵ_0(q_0c)]/4`$, and the constant term $`\mu =[ϵ_0(q_0c)+ϵ_0(q_0+c)+2ϵ_0(q_0)]`$ affects the energy of all two-qubit states and is not relevant as long as we are discussing one pair of qubits.

Equation 6 is one of the central results of our work. We see that $`\nu `$ has the structure of a discretized second derivative of $`ϵ_0`$ similarly to Eq. (1). Since $`ϵ_0(q)`$ is a periodic function, $`\nu `$ can be positive or negative. For instance, in the tight-binding limit $`E_CE_J`$, when $`ϵ_0(q)=\mathrm{\Delta }\mathrm{cos}(2\pi q)`$, the coupling is:

$$\nu =\frac{\mathrm{\Delta }}{2}\mathrm{cos}(2\pi q_0)(1\mathrm{cos}(2\pi c)),$$
(7)
and $`\delta =(\mathrm{\Delta }/2)\mathrm{cos}(2\pi q_0)\mathrm{cos}(2\pi c)`$. Obviously, the coupling can be controlled by the gate voltage through the average induced charge $`q_0`$, and can change sign. In general, the coupling constant can be calculated numerically from Eq. (6). The results are plotted in Fig. 3 which shows that in accordance with Eq. (7), the $`q_0`$-dependence of $`\nu `$ is harmonic for $`E_CE_J`$, and changes sign at $`q_0\pm 1/4`$. At larger $`E_C`$, $`\nu (q_0)`$ becomes non-harmonic, and for $`E_CE_J`$ and small coupling coefficients $`c`$, approaches $`c^2E_C/2`$ for all $`q_0`$ except for the vicinity of the point $`q_0=\pm 1/2`$, where $`\nu /c^2E_C`$ becomes large in absolute value and negative: $`\nu /c^2E_CE_C/2E_J`$ for $`cE_J/E_C`$, and $`\nu /c^2E_C1/2c`$ for $`E_J/E_Cc1`$. The periodic nature of $`ϵ_0(q)`$ which has a minimum at $`q=0`$ and a maximum at $`q=\pm 1/2`$ implies that the maximum of the absolute value of $`\nu `$ is reached for $`c=1/2`$ and is equal to half the bandwidth, e.g., $`E_C/8`$ for $`E_CE_J`$, and $`\mathrm{\Delta }`$ for $`E_CE_J`$ – see Eq. (7).

The controlled electrostatic coupling of two qubits offers new possibilities to manipulate two-qubit states. The simplest one is the change of the structure of the charging diagram of the transformer-coupled qubits with the gate voltage $`V_g`$. The charging diagram shows the regions of stability of the charge states $`(n_1,n_2)`$ as a function of the induced charges $`q_i`$, for small Josephson coupling $`E_{Ji}E_{Ci}`$. The diagram is periodic with period $`1`$ in both charges $`q_i`$, and has a honeycomb structure in the case of fixed electrostatic coupling. Figure 4 shows examples of the charging diagram. The diagram was obtained by minimizing the electrostatic qubit energy together with the coupling energy (4).

At $`c=0.3`$, the main qualitative features of Fig. 4 can be understood neglecting the difference between $`q_0`$ and $`q_g`$, from the $`q_0`$-dependence of the qubit interaction, see Fig. 3. For $`q_g=0`$, the coupling is positive and the charging diagram has the usual shape characteristic of a fixed electrostatic coupling. The cells of the honeycomb structure are tilted in the $`q_1=q_2`$ direction, since increasing the gate voltage of one qubit makes it easier to add a charge to the other qubit. In the absence of coupling, the degeneracy point of the four charge states $`(0,0)`$, $`(0,1)`$, $`(1,0)`$, $`(1,1)`$ is extended in the $`q_1=q_2`$ direction into the boundary between $`(0,1)`$, $`(1,0)`$, since positive coupling makes the charging energy of these two states lower than that of $`(0,0)`$, $`(1,1)`$. If the coupling is mostly negative, e.g., for $`q_g=0.5`$, the cells of the honeycomb structure are tilted in the $`q_1=q_2`$ direction. The degeneracy point of the four charge states is changed differently, since the states $`(0,0)`$, $`(1,1)`$ now have a lower charging energy than $`(0,1)`$, $`(1,0)`$. The degeneracy point is extended in the $`q_1=q_2`$ direction and creates a direct boundary between $`(0,0)`$ and $`(1,1)`$. Around $`q_g=0.3`$, the qubit coupling is suppressed. Hence, four neighboring stability regions touch in one point, and their shape is approximately rectangular like for non-interacting qubits. In contrast to the case of fixed coupling, all the cells in Fig. 4 are curved, since changing $`q_1`$, $`q_2`$ also changes the effective charge $`q_0`$ of the transformer island, so that the effective qubit coupling constant $`\nu `$ and the renormalization $`\delta `$ of the qubit bias change with $`q_i`$. This effect is largest for values of $`q_g`$ around which $`\nu (q_0)`$ varies strongly, like e.g., $`q_g=0.4`$, see Figs. 3 and 4.

The possibility to switch the coupling between two qubits on and off is important for the realization of practically all types of two-qubit gates. An advantage of our scheme is that the effective qubit coupling can be suppressed even in presence of a small direct positive geometric capacitance between the qubit islands. This “parasitic” capacitance only shifts the values of the gate voltages at which the total coupling vanishes. As an example, we show how our proposal can be used to directly realize a phase gate, a transformation that changes the sign of the $`|11`$ state and does not change the amplitudes of the other three two-qubit states. If the qubit tunneling amplitudes are tuned to zero, the Hamiltonian of the two-qubit system (Fig. 2) with coupling (5) is

$$H=\nu \sigma _{z1}\sigma _{z2}+\eta (\sigma _{z1}+\sigma _{z2}),$$
(8)
where $`\eta =\delta (q_i1/2)E_{Ci}`$. (For simplicity, we again discuss only the symmetric structure, which for the purpose of realizing the phase gate also implies identical qubit charges $`q_i`$. All results of our work can be directly extended to the asymmetric case.) By adjusting the three gate voltages $`V_1`$, $`V_2`$, and $`V_g`$ such that $`\nu (q_0=q^{})=0`$ and $`q_i=1/2+\delta (q^{})/E_{Ci}`$ one can make the Hamiltonian (8) vanish. For $`E_JE_C`$ such a stationary qubit state is realized when $`q_i=1/2`$ and $`q_0=q_g=1/4`$. By applying gate-voltage pulses one can temporarily switch on both the interaction and the qubit bias in such a way that the qubit states accumulate dynamic phases . To obtain a phase gate, i.e., to have the state $`|11`$ accumulate the phase $`\pi `$ up to an irrelevant common phase of all four qubit states, the phase $`\varphi _\nu =𝑑t\nu (t)`$ due to the interaction energy and the phase $`\varphi _\eta =𝑑t\eta (t)`$ due to the qubit bias should be chosen as $`\varphi _\nu =\varphi _\eta =\pi /4`$.

These conditions fix only the time integral of the gate-voltage pulses. Their shape can be chosen to reduce the excitation amplitude of the upper energy band of the transformer junction that would invalidate our Born-Oppenheimer approximation (4) and effectively entangle the qubit states with the states of the transformer creating an additional decoherence mechanism. Transitions to the upper energy bands are suppressed if the pulses are sufficiently slow on the scale of the transformer energies. In this case, the amplitude $`\alpha _k(t)`$ of an excitation process to the $`k`$th band can be calculated by standard adiabatic perturbation theory as

$$\alpha _k=^t𝑑\tau \frac{k|H/\tau |0}{ϵ_k(\tau )}e^{i_\tau ^tϵ_k(\tau ^{})𝑑\tau ^{}},$$
(9)
where $`ϵ_k`$ is the energy of the $`k`$th band relative to $`ϵ_0`$. Since the total phases accumulated by the qubit states during the gate-voltage pulses are of the order of $`\pi `$, the adiabatic condition also means that the pulse amplitude should be small, i.e., $`q_0=q^{}+x(t)`$, $`x1`$. Therefore, the energies and matrix elements in Eq. (9) can be evaluated at $`q_0=q^{}`$, and Eq. (9) reduces to

$$|\alpha _k|=2E_C|k|(nq)|0||x(ϵ_k)|.$$
(10)
Here, $`x(ϵ_k)=𝑑\tau x(\tau )e^{iϵ_k\tau }`$ is the Fourier component of $`x(t)`$ which decreases exponentially in $`ϵ_k\tau _0`$ for smooth pulses, where $`\tau _0`$ is the characteristic pulse time. For $`E_JE_C`$, the energy-band gap of the transformer is of the order of $`E_J`$, and this sets a lower limit for the pulse time through Eq. (10). For $`E_JE_C`$, the gap between the energy bands grows and the adiabaticity condition is easier to satisfy (see the discussion after Eq. (4).

In conclusion, we have proposed a method to couple two Josephson charge qubits by an electrostatic transformer that produces an effective coupling that can be varied in magnitude and sign. We have given an explicit expression of this coupling as a discretized second derivative of the energy band of a small Josephson junction. Our proposal works even for asymmetric structures and in the presence of parasitic capacitances. It allows the implementation of a variety of two-qubit gates, and we have explicitly demonstrated how to build a phase gate.

C. B. would like to thank the University of Stony Brook for its hospitality during a one-month stay. The authors acknowledge discussions with K.K. Likharev which stimulated this work, and useful discussions of the results with J.E. Lukens and Yu.A. Pashkin. This work was supported in part by the NSF under grant # 0121428, by ARDA and DOD under the DURINT grant # F49620-01-1-0439 (D.V.A.), and by the Swiss NSF and the NCCR Nanoscience (C. B.).