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# Continuous-variable quantum teleportation of entanglement

## I Introduction

Quantum teleportation Ben93 , whereby a quantum state of a system can be transferred by a sender Alice to a remote receiver Bob through the use of classical communication and a shared entanglement resource, is a remarkable demonstration of how non-local correlations in quantum mechanics can be used to advantage. More than simply a novelty, quantum teleportation is useful for quantum information processing; for example, it can be used as a universal primitive for quantum computation Got99 , as a fundamental component to quantum computation with linear optics KLM01 , and as a means to implement non-local quantum transformations Eis00 . One realization is the quantum teleportation of continuous variables (CV) Bra98 , which teleports states of dynamical variables with continuous spectra; such a realization allows for the teleportation of quantum states of light.

Any realistic (imperfect) quantum teleportation device can be characterized by a figure of merit to quantify its ability to perform successful teleportation. The *fidelity* $`F`$ is useful as a measure of the distinguishability of the output state from the input state, although the threshold for demonstrating genuine quantum teleportation is debatable. One such threshold demonstrates that an entanglement resource was used during the experiment Bra98 . Another threshold Ben93 ; Gro01  is that Alice teleports the state to Bob without learning about the state in question. For teleportation of a distribution of states in a set $`𝒞`$, one can define the average fidelity $`\overline{F}`$ of the device as the average of the fidelity $`F`$ over $`𝒞`$. The average fidelity provides a figure of merit for the device to teleport states in this set.

However, any quality measure for a useful quantum teleportation apparatus must be based on its intended application. One important application is that the device allows for the teleportation of entanglement, i.e., that entanglement is preserved between the teleported system and another (unteleported) one Tan99 . Consider a user, Victor, who acts to verify that the device functions as advertised. Alice and Bob claim that their device teleports coherent states with a particular average fidelity, as in experimental quantum teleportation Fur98 . Victor wishes to test the ability of this device to teleport entanglement, but is restricted to supplying Alice with coherent states according to the advertised capability (that is, Alice must receive states in the specified set $`𝒞`$).

One option is for Victor to employ a two-mode entangled coherent state (ECS) San92 . By supplying Alice with only one mode, Victor can conceal from her and Bob that they are teleporting only one portion of a two-mode entangled state. Bob returns the state to Victor so that he can test whether the ECS is reconstructed with high fidelity or not, and thus whether the teleportation has preserved the entanglement. Alice and Bob specified that the advertised $`\overline{F}`$ applies only to coherent states. However, if they decide to check, they will indeed see that they are receiving a mixture of coherent states from Victor, so the supply of states from Victor does not violate the specification that these states are drawn from a distribution of coherent states. Thus, Victor uses these ECSs to quantify the capability of this quantum teleportation to preserve entanglement. Provided that these states are entanglements of coherent states that are nearly orthogonal, Alice and Bob cannot detect that Victor is using ECSs to verify the efficacy of the scheme.

We show in this paper that ECSs are useful for testing the ability of a device to teleport entanglement. Moreover, we show that this entanglement fidelity does not depend on using these ECSs, but applies generally to the teleportation of entanglement for a device that teleports coherent states. We note that quantum teleportation of ECSs has been studied, but in entirely different contexts. One such investigation is the teleportation of ECSs in their entirety Wan01 , and another consideration has been to use an ECS as a substitute for the standard entanglement resource provided by the two-mode squeezed vacuum state Enk01c . Our study is quite different from these two cases; in our investigation, Victor employs ECSs to replicate the conditions that Alice and Bob experience in the experiment of Furusawa *et al* Fur98 , and Victor uses a second entangled mode to verify that quantum teleportation of entanglement is taking place.

The paper is constructed as follows. In Sec. II, we develop the theory of quantum teleportation of coherent states according to a formalism that is useful for subsequent sections. In Sec. III, we discuss the quantum teleportation using ECSs as a means of verifying the capability of teleporting entanglement; we include a discussion of the entanglement fidelity as a measure of this capability. We define a noisy quantum teleportation scheme in Sec. IV, and present the result that the entanglement fidelity for the noisy quantum teleportation of ECSs is extremely sensitive to very small errors in Alice’s measurement. We conclude with Sec. V.

## II Quantum teleportation of coherent states

Quantum teleportation was proposed Ben93  as a means by which a quantum state can be transferred from a system A (Alice) to a remote system B (Bob) by employing only classical communication and a shared entanglement resource. Let Alice hold an arbitrary quantum state $`|\psi _1_1`$ that she wishes to send to Bob. In CV quantum teleportation, $`_1`$ is an infinite dimensional Hilbert space; typically, the Hilbert space for a harmonic oscillator is used. In addition to this quantum system, Alice holds a second quantum system with Hilbert space $`_2`$, and Bob holds a third with Hilbert space $`_3`$. These two systems are in the two-mode squeezed state Enk99

$$|\eta _{23}=\sqrt{1\eta ^2}\underset{n=0}{\overset{\mathrm{}}{}}\eta ^n|n_2|n_3,$$
(1)
with $`|n`$ the $`n`$-boson Fock state. In the limit that $`\eta 1`$, Alice and Bob share a maximally entangled Einstein-Podolsky-Rosen (EPR) state.

To perform quantum teleportation of the unknown state $`|\psi _1`$, Alice begins by performing a joint projective measurement on $`_1_2`$ of the form

$$\mathrm{\Pi }_\alpha =D_1(\alpha )|\eta _{12}\eta |D_1^{}(\alpha ),$$
(2)
where $`D_1(\alpha )`$ is the displacement operator on system $`1`$ defined by

$$D_1(\alpha )=\mathrm{exp}(\alpha \widehat{a}_1^{}\alpha ^{}\widehat{a}_1),\alpha .$$
(3)
A measurement result is a complex number $`\alpha _0=x_0+ip_0`$. Such a measurement can be implemented by mixing the two states on a beamsplitter and performing balanced homodyne detection on each of the two output modes Bra98 . Alice sends this measurement result via a classical channel to Bob, who performs a displacement operation $`D_3(\alpha _0)`$ (realizable by mixing with a strong coherent field with adjustable amplitude and phase) on his system $`_3`$. Bob’s system is now in the state $`|\psi _3`$, which is identical to the initial state $`|\psi _1`$ received by Alice in the limit $`\eta 1`$.

In an experiment Fur98 , various constraints (including finite squeezing and imperfect projective measurements) limit the performance of the quantum teleportation. One must then define a figure of merit to describe how well a physical quantum teleportation device approximates the ideal case. One such measure is the *average fidelity* of the process. Consider a pure input state $`|\psi _1`$, which is imperfectly teleported such that Bob receives the generally mixed state $`\rho _3`$. The fidelity of the output state compared to the input state is given by

$$F(|\psi _1,\rho _3)=_1\psi |\rho _3|\psi _1.$$
(4)
(Note that some authors define the fidelity to be the square root of this quantity.)

For a given distribution $`𝒞`$ of input states to be teleported, the average fidelity $`\overline{F}`$ is defined to be the weighted average of the fidelity over $`𝒞`$. In the experiment by Furusawa *et al* Fur98 , a distribution of coherent states with fixed amplitude varied over all phases was chosen to test the teleportation. It is also possible to employ a distribution over both amplitude and phase Bow02 .

## III Quantum teleportation of entangled coherent states

The average fidelity serves well as a figure of merit for certain applications. However, any measure quantifying the performance of a quantum teleportation device must be placed in the context of its intended use. In particular, one may ask how well a device performs at the important task of teleporting entanglement.

Victor, who wishes to test Alice and Bob’s quantum teleportation device, supplies Alice with a (possibly mixed) quantum state $`\rho `$, and after the teleportation, Bob returns a state $`\rho ^{}`$ to Victor. Victor can then perform measurements on $`\rho ^{}`$ to determine the success or failure of the quantum teleportation.

In offering their services, Alice and Bob can be expected to quote Victor a measure of performance of their quantum teleportation device (such as the average fidelity), as well as a restriction on the type of states that they can quantum teleport. For example, they may advertise an average fidelity $`\overline{F}`$ for quantum teleportation of coherent states sampled from some distribution. Depending on his intended use of the quantum teleportation device, these particular measures of performance may not be adequate.

### III.1 Entangled coherent states

For example, Victor may wish to teleport one component of an entangled state, and ensure that the final state returned by Bob is still entangled with the system he kept. If Alice and Bob advertise that they can only teleport distributions of coherent states, it is important that the state $`\rho `$ that Victor supplies to Alice is indeed in the allowed set. Consider the two-mode ECS San92

$$|\mathrm{\Psi }(\alpha ,\beta )_{ab}=N\left(|\alpha _a|\beta _b|\beta _a|\alpha _b\right),\alpha \beta ,$$
(5)
with $`N=(22\mathrm{exp}(|\alpha \beta |^2))^{1/2}`$ the normalization. This state is not separable, and thus possesses entanglement between modes $`a`$ and $`b`$ Man95 . The reduced density matrix for mode $`b`$ is

$`\rho _b`$ $`=\mathrm{Tr}_1\left(|\mathrm{\Psi }(\alpha ,\beta )_{ab}\mathrm{\Psi }(\alpha ,\beta )|\right)`$
$`=N^2\left(|\alpha _b\alpha |+|\beta _b\beta |\alpha |\beta |\alpha _b\beta |\beta |\alpha |\beta _b\alpha |\right).`$ (6)
For the case where the overlap $`\alpha |\beta `$ is negligibly small, this reduced density matrix is indistinguishable from

$$\rho _b=\frac{1}{2}\left(|\alpha \alpha |+|\beta \beta |\right);$$
(7)
i.e., a mixture of two coherent states. Thus, a quantum teleportation device that functions for coherent state inputs should function equally well for such a state. Note that the issues of overlaps can be avoided if Victor instead uses a two-level system for $`a`$ (such as a two-level atom), and entangles coherent states of mode $`b`$ to orthogonal states in $`a`$. States of this form have been experimentally realized Bru96 .

### III.2 Entanglement fidelity

The average fidelity may not be a good indicator of the quality of quantum teleportation. In particular, it overstates the capability to teleport entanglement. *Entanglement fidelity* Sch96 ; Bra98  is a superior measure to quantify the ability of a process to preserve entanglement, and reduces to the standard fidelity for the case of pure states (e.g., coherent states).

Consider a process (quantum channel) described by a superoperator $``$ and a generally mixed state $`\rho `$ as input. Let $`\rho ^{}=(\rho )`$ be the corresponding output state. We introduce $`|\mathrm{\Gamma }`$ as a purification of $`\rho `$, i.e., a pure state obtained by introducing an ancilla system $`A`$ such that $`\mathrm{Tr}_A(|\mathrm{\Gamma }\mathrm{\Gamma }|)=\rho `$. The entanglement fidelity

$$_e(\rho ,)\mathrm{\Gamma }|(_A)\left(|\mathrm{\Gamma }\mathrm{\Gamma }|\right)|\mathrm{\Gamma },$$
(8)
has many exceptional properties; see Nie00 . It is independent of the choice of purification, meaning that it depends only on the reduced density matrix $`\rho _b`$ supplied to Alice. This property will be useful in testing quantum teleportation, as Victor can choose any purification (any choice of entanglement between the state he supplies Alice and the state he retains) and achieve the same measure. Also, if $`\rho =|\psi \psi |`$ is a pure state, the entanglement fidelity $`_e(|\psi \psi |,)`$ reduces to the standard fidelity $`F(|\psi \psi |,(|\psi \psi |))`$. Thus, the results of tests employing the entanglement fidelity can be directly compared to the fidelity of teleporting pure coherent states.

## IV Noisy quantum teleportation

In this section, we consider a noisy quantum teleportation device that includes finite squeezing of the entanglement resource, propagation errors, imperfect detectors, and other errors that introduce a stochastic error given by a Gaussian distribution. We show that, whereas the average fidelity for quantum teleportation of coherent states is quite robust against such errors, the entanglement fidelity for the quantum teleportation of distributions of coherent states of the form (7) drops off very rapidly even with highly squeezed states and small errors.

In quantum teleportation, Alice must measure a complex amplitude $`\alpha _0`$ via a joint measurement of the form (2) and report this measurement result to Bob. Bob then performs a displacement $`D(\alpha _0)`$ on his state conditioned on this result. If there is a measurement error, however, Alice may send to Bob the values $`\alpha _0+z_i`$, where $`z_i`$ is a complex error (an error in both position and momentum) sampled from some ensemble $`Z=\{z_i\}`$ with corresponding probabilities $`P=\{p(z_i)\}`$. Bob then performs the displacement $`D(\alpha _0+z_i)`$ rather than $`D(\alpha _0)`$. (Equivalently, Bob’s displacement operation could be subject to a similar error.) The result is that the quantum teleportation process will no longer be ideal; it becomes a noisy process described by some superoperator $``$.

The probability distribution we employ is a Gaussian distribution with variance $`\sigma `$, defined such that vacuum noise has a variance $`1/2`$. (Note that $`\sigma `$ has the units of the square of the coherent state complex amplitude $`\alpha `$.) Using a perfect teleportation scheme (involving ideal EPR states of the form of Eq. (1) and ideal projective measurements given by Eq. (2)), but with a Gaussian-distributed error, the teleported state $`\rho ^{}`$ will be related to the input state $`\rho `$ by

$$\rho ^{}=\frac{\mathrm{d}^2z}{\pi \sigma }\mathrm{exp}\left(\frac{|z|^2}{\sigma }\right)D(z)\rho D^{}(z)_\sigma (\rho ).$$
(9)
One can view $`_\sigma `$ as the transfer superoperator for this (noisy) process.

In Bra98 , Braunstein and Kimble considered the effects of finite squeezing ($`\eta <1`$) and imperfect detectors. Both of these effects lead to Gaussian noise, described by the same superoperator as given by Eq. (9). Also, propagation losses can be compensated for by linear amplification, which introduces an associated Gaussian noise described similarly. Thus, the variance for the total error is given by the sum of the variances for the individual errors as

$$\sigma =\sigma _G+\sigma _\eta +\sigma _\nu +\sigma _{\mathrm{other}},$$
(10)
where $`\sigma _G`$ is the variance for the noise introduced by linear amplification with gain $`G`$, $`\sigma _\eta =\mathrm{exp}(2\mathrm{tanh}^1\eta )`$ describes the effect of finite squeezing, $`\sigma _\nu =(1\nu ^2)/\nu ^2`$ describes the noise due to finite homodyne detection efficiency $`\nu `$, and $`\sigma _{\mathrm{other}}`$ describes other sources of Gaussian noise Bra98 . Again, all of these variances are defined such that $`\sigma =1/2`$ is the level of vacuum noise. Thus, an effective $`\sigma `$ describes the cummulative effects of a wide variety of noise and errors in the quantum teleportation process.

In a classical picture, without employing a squeezed resource ($`\eta 0`$), we find that $`\sigma _\eta =1`$, i.e., that the output state acquires two units of vacuum noise. This noise is what Braunstein and Kimble refer to as “quantum duty”, or quduty Bra98 : one unit of vacuum noise is acquired by each pass across the quantum/classical border (one by Alice’s measurement and one by Bob’s reconstruction).

For an input state given by a pure coherent state $`|\alpha `$, it is straightforward to calculate the entanglement fidelity of the operation. (As the state is pure, the entanglement fidelity $`_e`$ will equal the standard fidelity $`F`$.) The entanglement fidelity for the coherent state $`|\alpha `$,

$$_e(|\alpha \alpha |,_\sigma )=\frac{1}{1+\sigma },$$
(11)
is independent of $`\alpha `$. The lower bounds on fidelity for quantum teleportation discussed in the introduction are clear from this equation. The bound of $`F>1/2`$ by Braunstein and Kimble Bra98  can only be satisfied if $`\sigma <1`$; i.e., the variance must be less than twice the vacuum noise, verifying the use of an entangled resource. The more stringent bound $`F>2/3`$, set by Grosshans and Grangier Gro01  using an argument of no-cloning, requires $`\sigma <1/2`$ or up to one unit of vacuum noise.

If the state to be teleported is one mode of an ECS, the calculation of the entanglement fidelity is more involved. Fortunately, a purification of the state (III.1) is already provided: it is the ECS itself. As noted earlier, the entanglement fidelity is independent of the choice of purification. The entanglement fidelity for the noisy quantum teleportation of the $`b`$ mode is given by

$`_e(\rho _b,_\sigma )`$ $`=\mathrm{\Psi }(\alpha ,\beta )\left|(_a_{\sigma b})\left(|\mathrm{\Psi }(\alpha ,\beta )\mathrm{\Psi }(\alpha ,\beta )|\right)\right|\mathrm{\Psi }(\alpha ,\beta )`$
$`={\displaystyle \frac{\mathrm{d}^2z}{\pi \sigma }\mathrm{exp}\left(\frac{|z|^2}{\sigma }\right)\left|\mathrm{\Psi }(\alpha ,\beta )|D_b(z)|\mathrm{\Psi }(\alpha ,\beta )\right|^2}.`$ (12)
The expression is complicated by the nonorthogonality of coherent states, but the overlap drops rapidly as the coherent states are increasingly separated in phase space. To simplify this expression, we assume that $`|\alpha \beta |`$ is sufficiently large that we can ignore terms bounded above by $`|\alpha |\beta |^2=\mathrm{exp}(|\alpha \beta |^2)`$. Again, we note that these overlaps can be avoided if Victor chooses to couple coherent states in $`b`$ to orthogonal modes in $`a`$, and that this choice of purification gives identical results for the entanglement fidelity. Using this assumption,

$`_e(\rho _b,_\sigma )`$ $`N^4{\displaystyle \frac{\mathrm{d}^2z}{\pi \sigma }\mathrm{exp}\left(\frac{|z|^2}{\sigma }\right)\left\{|\alpha |\alpha +z|^2+|\beta |\beta +z|^2+2\mathrm{R}\mathrm{e}\left(\mathrm{exp}\left(i\mathrm{Im}((\alpha \beta )z^{})\right)\alpha +z|\alpha \beta |\beta +z\right)\right\}}`$
$`{\displaystyle }{\displaystyle \frac{\mathrm{d}^2z}{2\pi \sigma }}\mathrm{exp}({\displaystyle \frac{|z|^2}{\sigma }})\mathrm{exp}(|z|^2)(1+\mathrm{cos}\left(2\mathrm{I}\mathrm{m}((\alpha \beta )z^{})\right)){\displaystyle \frac{1}{2}}\left({\displaystyle \frac{1}{1+\sigma }}\right)(1+\mathrm{exp}(|\alpha \beta |^2\sigma _{\mathrm{eff}})),`$ (13)
where $`\sigma _{\mathrm{eff}}=\sigma /(1+\sigma )`$.

The entanglement fidelity for the noisy quantum teleportation of one mode of an ECS differs from that of a pure coherent state (Eq. (11)) due to a term that drops exponentially in $`|\alpha \beta |^2`$. As this term becomes negligibly small (for even small errors described by $`\sigma 1`$), the entanglement fidelity for the teleportation of ECSs approaches half the value for that of a pure coherent state.

In Fig. 1, we compare the standard fidelity for teleportation of a pure coherent state $`|\alpha `$ to the entanglement fidelity for teleporting the ECS with $`\beta =\alpha `$ for two values, $`\alpha =2`$ and $`\alpha =10`$.

One key feature to notice is that the entanglement fidelity for all cases is reduced significantly for a variance on the order of the vacuum noise $`\sigma 1/2`$. Thus, the precision of quadrature phase measurements must be very good on the scale of the standard quantum limit Cav81 . For the ECSs, the rapid decrease of the entanglement fidelity to approximately half that of the pure coherent states is clearly evident. Consider ECSs of the form $`|\mathrm{\Psi }(\alpha ,\alpha )`$ with mean photon number $`\overline{n}=|\alpha |^2`$. In order to maintain a constant entanglement fidelity $`_e(\rho _b,_\sigma )>1/2`$, the variance of the errors must scale as $`\sigma 1/\overline{n}`$. Thus, quantum teleportation of a single mode of an ECS with high entanglement fidelity becomes increasingly difficult as the mean photon number of the state is increased.

Note that, for any distribution $`𝒞`$ of coherent states that leads to an average fidelity for quantum teleportation, one can also calculate an average entanglement fidelity both for pure coherent states and ECSs sampled from the same distribution. In the experiment of Furusawa *et al*, an average fidelity of $`\overline{F}=0.58`$ has been obtained for the set $`𝒞=\{|\alpha _0e^{i\phi };0\phi <2\pi \}`$, where $`|\alpha _0e^{i\phi }`$ is the coherent state with $`|\alpha _0|^2100`$ the mean photon flux and $`\phi `$ is the phase of the coherent state Fur98 ; Ralph . This phase is uniformly distributed over the domain $`[0,2\pi )`$. The experimental result Fur98  can be compared against our calculation for teleportation of ECSs of the form $`|\mathrm{\Psi }(\alpha _0,\alpha _0)`$ with $`\alpha _0=10`$, presented in Fig. 1. Whereas the entanglement fidelity for the pure coherent state is very high for small $`\sigma `$, the entanglement fidelity for the ECS is less than $`0.5`$ even for $`\sigma =0.01`$ (corresponding to a total error around 2% of the vacuum noise). Note that with otherwise perfect conditions (no propagation loss, detector noise, etc.), at least 8.5 dB of squeezing is required to achieve an entanglement fidelity of greater than $`0.5`$ for this state; this amount of squeezing represents a target for high entanglement fidelity quantum teleportation of distributions of coherent states.

## V Conclusions

We have shown that the average fidelity is not necessarily a good measure of successful quantum teleportation, and in particular is shown to be a poor indicator for the capability of quantum teleportation to preserve entanglement. On the other hand, the entanglement fidelity provides a useful figure of merit for the quantum teleportation of entanglement. We demonstrate that entanglement with other systems can be used to test claims of quantum teleportation, even for a restricted set of allowed input states. In particular, ECSs can be used to test quantum teleportation devices that advertise only teleportation of mixtures of coherent states. We show that the entanglement fidelity of distributions of coherent states is extremely fragile, and can be drastically reduced from the fidelity of the pure coherent states by the effects of finite squeezing, imperfect detection, propagation errors, or small stochastic errors in Alice’s measurements (or Bob’s transformations).

An important application of teleporting coherent states is in a distributed quantum network that employs only Gaussian states and Gaussian-preserving operations, i.e., linear optics Bar02b . In such a network, the appropriate figure of merit for the teleportation of entanglement between nodes is clearly the entanglement fidelity.

###### Acknowledgements.

This project has been supported by an Australian Research Council Grant. TJJ has been financially supported by the California Institute of Technology, and appreciates the hospitality of Macquarie University where this project was undertaken. SDB acknowledges the support of Macquarie University. We acknowledge useful discussions with T. C. Ralph and T. Tyc.


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# Proton Wires in an Electric Field: the Impact of Grotthuss Mechanism on Charge Translocation

## I INTRODUCTION

Translocation of protons over long distances has a key importance for biological and chemical systems. It is believed that proton migration along the chains of water molecules formed between the interior of proteins and the solvent, establishes electrochemical potential gradients playing an important functional role gennis ; lanyi . Experimental evidence indicates that the dominant mechanism responsible for proton transport in transmembrane proteins (for instance, in bacteriorhodopsin of Halobacterium halobium stoeckenius ; nagle  and in gramicidin A channels levitt ; nagle ) is the diffusion of H+ ions which is faster than the hydrodynamic flow of hydronium species (H3O)+. Especially at low hydrogen concentrations in channels, proton conduction is determined by a two-stage Grotthuss-type mechanism cukierman ; onsager  shown schematically in Fig. 1(a). The first stage involves the intrabond proton tunnelling along the hydrogen bridge which is connected with the formation and transfer of ionic positive (H3O+) and negative (OH-) charged defects. To sustain a flux of H+ in such proton wire, the inter-molecular proton transfer due to the reorientations of molecular group with proton is assumed. Reorientation motion leads to the breaking of the hydrogen bond (so-called orientational Bjerrum L-defect) and location of proton between another pair of molecular groups bjerrum . Consequently, the reorientation step in the presence of the second proton may induce high-energy configuration with both of the protons shared by two adjacent oxygen ions (Bjerrum D-defect).

Unlike the translocation of monovalent ions like Cs+, Na+ or K+ via gramicidin requiring the net diffusion of the whole water column in the channel, the existence of the Grotthuss-type selective migration of H+ through the H-bonded chain is supported by the absence of streaming potentials during H+ permeation akeson ; levitt . In contrast to the bulk water, the reorientation motion in one-dimensional water wire involving a migration of Bjerrum defects with the period of reorientations about $`10^{10}`$ s, is much slower than the proton intra-bond hopping ($`10^{12}`$ s)nagle1 ; chernyshev . This is also closely related to the fact that the mobility of Bjerrum defects ($`10^4`$ cm3V-1s-1) is much lower than that of the ionic defects ($`10^2`$ cm3V-1s-1) eisenberg . Moreover, as appears from the results of molecular dynamics simulations pomes3 , the translocation of the ionic defects in proton wires is almost activationless process, whereas the orientation defects involving an activation energy of about 5 kcal/mol in the chain containing eight water molecules, constitute a limiting step for the proton migration. Besides the orientation defects, the recent experiments indicate that another possible rate-limiting step for the proton migration in gramicidin channels can be at the membrane-channel/solution interfacechernyshev ; godoy .

As was pointed in cukierman , the experimental analysis of the proton flow in bioenergetic proteins and the mechanism of proton translocation is very difficult because of its intrinsically transient nature. To shed more light on the microscopic nature of the proton transport and to analyze the influence of quantum effects and interaction with proton surrounding, theoretical modeling remains to be essentially important. Recently, much attention has been focused on the theoretical studies of the dynamics of ionic defects using soliton models zol1 ; zol2  and molecular dynamics simulations tuck1 ; tuck2 ; schumaker ; schumaker2 . Proton transfer in water was shown to be strongly coupled with the dynamics of local environment, and the density of ionic defects was found to increase exponentially with the increasing temperaturezol1 . However, since the concentration of slow Bjerrum defects in water solutions is much higher ($`c_B=210^7`$ at $`10^{}`$ C) than that of fast ionic ($`c_I=310^{12}`$)eisenberg , the investigations of the reorientation step of proton migration are necessary for the better understanding of the proton transport process.

The goal of the present work is to study proton wire containing a finite number of water molecules by the use of quantum statistical mechanics methods which are extremely effective in the description of the collective nature of the proton transfer and in the quantum treatment of the light H nuclei davydov2 . To describe correctly the proton transport process, we employ here two-stage proton transport model jps  incorporating quantum effects such as proton tunneling and zero-point vibration energy. In earlier papers pavlenko1 ; pavlenko2 ; pavlenko3  we applied the two-stage model to analyze the effect of coupling between protons and molecular group vibrations on proton conductivity in infinite H-bonded chains and proton-conducting planes. In particular, it was shown that the proton-lattice vibration interactions induce structural instabilities and charge ordering in system pavlenko1 , whereas the Grotthuss-type transport mechanism manifests itself in nontrivial temperature- and frequency dependences of the proton conductivity pavlenko2 ; pavlenko3 ; pavlenko4 .

In this work we analyze the influence of proton-proton correlations, comparing two different protonated chains containing one and two excess protons respectively. We find that the reaction of protonation of water chain is extremely sensitive to the reorientation energy barrier of proton motion and the barrier for the chain protonation. We show that the increase of the reorientation energy results in the drastic decrease of the proton charge density at the boundary between the chain and surrounding with consequent localization of protons near the inner water molecules. As appears from our modeling, the application of external electric field induces the step-like threshold-type effects with the ordering of proton charge and stabilization of Bjerrum D-defects in the wire. We analyze the temperature dependence of proton polarization and D-defect concentration, and examine the role of the interplay between different factors (such as orientation energy, external field and temperature) in the dynamics of Bjerrum defects.

## II  MODEL SPECIFICATION AND METHOD OF CALCULATION

To model a proton wire, we consider a linear chain containing $`N`$ hydrogen bonds and $`l=1,2,\mathrm{},N,N+1`$ molecular groups. The outer left ($`l=1`$) and right ($`l=N+1`$) molecular complexes mimic the surrounding of the proton wire and differ from the inner ($`l=2,\mathrm{},N`$) water molecules. The transport of an excess proton through the wire proceeds via the following two steps:
(i) proton can be transferred within a H-bond (process shown by short arrows in Fig. 1(a)) which is modelled by a simple double-well potential, with the corresponding energy barrier $`\mathrm{\Omega }_T`$ for the proton transfer between the two minima:

$$H_T=\mathrm{\Omega }_T\underset{l=1}{\overset{N}{}}(c_{la}^+c_{lb}+c_{lb}^+c_{la}),$$
(1)
where $`c_{l\nu }^+`$($`c_{l\nu }`$) are the operators of the proton creation(annihilation) in the position ($`l`$, $`\nu `$) (the index $`\nu =\{a,b\}`$ denotes the left/right position for the proton within the H-bond);
(ii) a water molecule together with covalently bonded hydrogen ion can be rotated, and this process causes the breaking of the H-bond and location of H+ between two another nearest water molecules of the wire (process depicted by long arrows in Fig. 1(a)):

$$H_R=\mathrm{\Omega }_R\underset{l=1}{\overset{N}{}}(c_{l+1,a}^+c_{lb}+c_{lb}^+c_{l+1,a}),$$
(2)
where $`\mathrm{\Omega }_R`$ is the effective energy barrier for the proton hopping between the states $`|l+1,a`$ and $`|l,b`$ (reorientation of the $`l`$-th molecular group together with proton). As is shown in pomes2  by the computation of the proton mean-force potential, this transition between donor-acceptor and acceptor-donor states reverses the chain dipole moment and requires a substantial energy barrier about $`5.5`$ kcal/mol for the whole chain containing up to eight water molecules.

Besides the transport process, we incorporate the following two types of interactions between protons in the chain:
(iii) different short-range configurations of the protons near an inner water molecule as well as an outer molecular group can appear due to the different nature of bonding (shorter covalent or longer H-bond). The energies of possible configurations (shown in Fig. 1(b)) are described by the following terms:

$`H_1=\stackrel{~}{\epsilon }_1(1n_{1a})+\stackrel{~}{w}_1n_{1a},H_{N+1}=\stackrel{~}{\epsilon }_{N+1}(1n_{Nb})+\stackrel{~}{w}_{N+1}n_{Nb},`$ (3)
$`H_l=w^{}(1n_{l+1,a})(1n_{lb})+wn_{l+1,a}n_{lb}+\epsilon (1n_{lb})n_{l+1,a}+\epsilon n_{lb}(1n_{l+1,a}).`$
The parts $`H_1`$ and $`H_{N+1}`$ describe the energies of the boundary proton configurations near the left and the right surrounding molecular groups (we assume for simplicity $`\stackrel{~}{\epsilon }_1=\stackrel{~}{\epsilon }_{N+1}=\stackrel{~}{\epsilon }`$ and $`\stackrel{~}{w}_1=\stackrel{~}{w}_{N+1}=\stackrel{~}{w}`$ in the boundary configurations shown in the upper scheme of Fig. 1(b)). The terms $`H_l`$ ($`l=2,\mathrm{},N`$) contain the configuration energies for the water molecules in the interior of the wire (the lower part in Fig. 1(b)). Here the proton occupancy operators $`n_{l\nu }=c_{l\nu }^+c_{l\nu }=\{0,1\}`$;
(iv) a strong repulsion between two nearest protons shared by two neighboring oxygens (so called Bjerrum D-defect) with a repulsion energy $`U`$ is represented by the term:

$$H_C=U\underset{l=1}{\overset{N}{}}n_{la}n_{lb}.$$
(4)
In our following analysis we use the value of $`U10`$ kcal/mol corresponding to the energy of relaxed $`D`$-defect estimated in campbell  on the basis of quantum chemical calculations.

To model a field exerted by the surrounding, we apply an external electric field of a strength $`E`$ to the proton wire, which is described by the following term

$$e_pE\underset{\genfrac{}{}{0pt}{}{l=1}{\nu =\{a,b\}}}{\overset{N}{}}R_{l\nu }n_{l\nu },$$
(5)
where $`R_{l\nu }`$ is the coordinate of the proton position ($`l`$, $`\nu `$) with respect to the center of the chain, and $`e_p`$ denotes the proton charge.

In order to analyze the dynamics of the proton wire embedded in the surrounding under the influence of the field, as well as the effect of rotational motions of covalent groups with proton, we will focus our attention on the polarization of the proton wire defined here as

$$P=e_p\underset{\genfrac{}{}{0pt}{}{l=1}{\nu =\{a,b\}}}{\overset{N}{}}R_{l\nu }n_{l\nu },$$
(6)
where $`\mathrm{}`$ denotes the statistical average with respect to the system energy (1-5). The average probabilities $`n_{l\nu }`$ of occupation of the position ($`l`$, $`\nu `$) by proton describe the distribution of the proton charge in the wire, and thus is another very important characteristics to track the proton migration.

To calculate exactly the above-mentioned statistical averages, we need to know the quantum energy levels determined by the energy (1-5). This can be done by a mapping of the proton states ($`l`$,$`\nu `$) on the multi-site basis $`|i=|n_{1a},n_{1b},\mathrm{},n_{Nb}`$. Then, using the projection operators $`X^{ii^{}}=|ii^{}|`$ acting on the new basis $`|i`$ we rewrite the system energy (1-5) in a convenient form (see Appendix):

$$H=H^0H^1\mathrm{}H^{2N}.$$
(7)
Each term $`H^{n_p}`$ in (7) corresponds exactly to $`n_p`$ protons in the chain ($`n_p=_{l,\nu }n_{l\nu }=0,1,\mathrm{},2N`$). This means in fact that the mapping on the states $`|i`$ allows to decompose the terms (1-5) and analyze the cases of different number of protons in the wire separately.

The energy barrier for the protonation of the chain is described by the parameter $`\mathrm{\Delta }`$ which appears in (7) after the decomposition procedure (see Appendix). As follows from the definition (26), $`\mathrm{\Delta }`$ is the difference between the energies of the proton attraction to the boundary and to the inner water molecules. As the PMF-studies of the H-bonded chain dynamics pomes2  show that the inner H-bonds are stronger (shorter O-O separation distances) than the outer H-bonds, it is reasonable to consider below the case $`\mathrm{\Delta }<0`$ (we take $`|\mathrm{\Delta }|=0.85`$ kcal/mol in our numerical calculations), when the proton is attracted to the surrounding and needs to overcome the boundary energy barrier $`|\mathrm{\Delta }|`$ to protonate the water chain.

The parameter $`J=w+w^{}2\epsilon `$ (see Fig. 1(b)) is related to the effective short-range interactions between the protons near the water molecule. It describes, in fact, the energy of the formation of the pair of ionic defects: I+=H3O+ ($`w\epsilon `$) and I-=OH- ($`\epsilon w^{}`$) from two water molecules at the dissociation reaction (2H2O $``$ H3O++OH-). Since the value of $`J`$ is about $`22`$ kcal/mol eisenberg ; rao  and is more than twice as much as $`U`$, we exclude in our following analysis an appearance of the pair of ionic defects in the system.

Due to the two types of motions we have two different contributions to the proton dipole moment: the orientational part $`\mu _r=e_pR_r`$ and the transfer part $`\mu _{ab}=e_pR_{ab}`$ where $`R_{ab}=R_{lb}R_{la}`$ denotes the distance H-H between the two nearest proton positions of the double-well H-bond. In our calculations, we use the values $`\mu _{ab}=3.5`$ D and $`\mu _{ab}=4.5`$ D corresponding to the moderately strong H-bond with an O-O distance $`R_{ab}+2R_r=2.6\AA `$ and the covalent O-H bond of a length $`R_r=0.94\AA `$.

## III CASE STUDY: ONE EXCESS PROTON IN CHAIN

As the starting point, in this section we mimic the situation when one proton is moved towards the water chain embedded into the solvent. To examine the behavior of the protonated chain with $`N`$ H-bonds and $`n=1`$ excess proton, we consider $`H^1`$ part of the energy given by (22). Since the zero-point vibration energy for protonated chains is larger than the potential energy barrier for the proton transfer between two shared oxygens pomes , the quantum tunneling is not required for the intra-bond H+ transfer. Thus, in our modelling we set $`\mathrm{\Omega }_T0`$. With this assumption, the energy levels of $`H^1`$ can be found exactly:

$`\lambda _{1,2}`$ $`=`$ $`\mathrm{\Delta }\pm \left((N1)\mu _r+{\displaystyle \frac{N}{2}}\mu _{ab}\right)E,`$
$`\lambda _{3,\mathrm{},2N}`$ $`=`$ $`\{\begin{array}{cc}\pm i(\frac{\mu _{ab}}{2}+\mu _r)E\pm p(i=1,3,\mathrm{},N2),\text{for odd}N\hfill & \\ \pm i(\frac{\mu _{ab}}{2}+\mu _r)E\pm p(i=0,2,\mathrm{},N2),\text{for even}N\hfill & \end{array}`$ (10)
where $`p=\sqrt{\mu _r^2E^2+\mathrm{\Omega }_R^2}`$.

To analyze the role of $`\mathrm{\Omega }_R`$ we consider first the case without external field ($`E=0`$). Depending on the value of $`\mathrm{\Omega }_R`$, two different regimes may be stabilized in the system. In the first small-$`\mathrm{\Omega }_R`$ regime, the two lowest energy levels $`\lambda _{1,2}`$ correspond to the superposition of the two boundary states

$`|10\mathrm{}00\mathrm{and}`$ $`|00\mathrm{}01`$ (11)
with the proton located in the surrounding near the left or the right outer molecular groups. In the second large-$`\mathrm{\Omega }_R`$ regime the proton is shared between the inner water molecules of the chain and the ground state of the system corresponds to the superposition of the states

$`|010\mathrm{}00,|0010\mathrm{}00,\mathrm{},`$ $`|00\mathrm{}010`$ (12)
with the energies $`\lambda _4,\lambda _6,\mathrm{},\lambda _{2N}`$. The ”critical” value $`\mathrm{\Omega }_R^{}=\mathrm{\Delta }`$ separating these two regimes, reflects the transition of the proton from the surrounding to the states where the proton is shared by the chain water molecules, which corresponds to the protonation chemical reaction. Fig. 2 shows the variation of the average occupancies of proton sites with $`\mathrm{\Omega }_R`$ for the chains containing $`N=2`$ and $`N=3`$ H-bonds. For low temperatures (see the case $`T=30K`$) the boundary proton occupancies $`n_{1a}=n_{Nb}`$ drop drastically to zero at $`\mathrm{\Omega }_R=\mathrm{\Omega }_R^{}`$, whereas the occupation numbers of the central positions $`n_{1b}=\mathrm{}=n_{Na}`$ increase up to the value $`\frac{1}{2(N1)}`$, reflecting the redistribution of collectivized proton between the inner sites in the wire. It should be noted here that $`\mathrm{\Omega }_R^{}`$ reflects the change of the ground state of the system and is determined as the solution of the equation $`\lambda _{1,2}=\lambda _{4,6,\mathrm{},2N}`$ at $`E=0`$ which does not depend on temperature. However, as all statistical averages, the average proton occupancies (for example, of the states $`|1,b=\frac{1}{\sqrt{2}}(\stackrel{~}{|1,b}+\stackrel{~}{|2,a})`$ and $`|2,a=\frac{1}{\sqrt{2}}(\stackrel{~}{|1,b}+\stackrel{~}{|2,a})`$ where $`\stackrel{~}{|1,b}`$ and $`\stackrel{~}{|2,a}`$ are the diagonalized states corresponding to $`\lambda _4`$ and $`\lambda _3`$ respectively), are temperature dependent. Thus the value of $`\mathrm{\Omega }_R^{}(T)\mathrm{\Delta }+kT\mathrm{ln}2`$ where $`n_{1a}=n_{2b}`$, for $`T0`$ is not equal to $`\mathrm{\Omega }_R^{}`$ (see Fig. 2, case $`T=300K`$). This difference shows that the inner proton states (12) are stabilized already at lower $`\mathrm{\Omega }_R=\mathrm{\Omega }_R^{}<\mathrm{\Omega }_R^{}(T)`$, although the occupancies of the inner positions at $`\mathrm{\Omega }_R=\mathrm{\Omega }_R^{}`$ are still slightly lower then of the outer due to the temperature-induced fluctuations. As $`T0`$, the fluctuations decrease and $`\mathrm{\Omega }_R^{}(T)\mathrm{\Omega }_R^{}`$.

The effect of the proton localization inside the chain is supported by the results reported in pomes ; pomes2  showing that in H-bonded finite chains, the excess charge is best solvated by the central H-bonds. However, as results from the presented above analysis, the effect of proton localization is drastically influenced by the competition between two different tendencies: (i) for small $`\mathrm{\Omega }_R`$, the proton is located near the surrounding/wire interface due to the nonzero protonation barrier $`\mathrm{\Delta }`$; (ii) to overcome the barrier between the surrounding and the wire, the reorientation energy should be sufficiently large ($`\mathrm{\Omega }_R>\mathrm{\Delta }`$) in order to stabilize the inner proton configurations. These conclusions show that in general, these two different factors (interface barrier and orientations) can be rate-limiting for the charge translocation and proton conductivity of the wire. As was shown in phillips , the effective reorientation barrier can be influenced by temperature factor or applied voltage (for example, the reorientation rate of the wire decreases exponentially with $`T`$ decrease). Thus, one can also expect that the increase of the temperature can result in the lower orientation barrier $`\mathrm{\Omega }_R`$, delocalization of proton and consequently in higher values for the proton conductivity through the channel. However, more detailed theoretical analysis is needed to understand better the role of the interface in the behavior of the conductivity.

We turn now to an analysis of the proton translocation directed by the external field (the case $`E0`$). Fig. 3 shows the field-dependences of $`P`$ and $`n_{l\nu }`$ for the chain containing $`N=2`$ H-bonds. We note that the behavior in the first small- and in the second large-$`\mathrm{\Omega }_R`$ regime differs drastically. In the small-$`\mathrm{\Omega }_R`$ regime the polarization increases smoothly with $`E`$ approaching finally its maximal saturation value $`P_{max}=\mu _r+\mu _{ab}`$ (Fig. 3(a), inset). In contrast to this, in the large-$`\mathrm{\Omega }_R`$ regime the field dependence is rather nontrivial: first, for $`E<E_{thresh}`$, $`P`$ changes very slowly, and than, at $`EE_{thresh}`$ a strong increase of $`P`$ to $`P=P_{max}`$ is observed in Fig. 3(a). This rapid step-like change of the proton polarization reflects the threshold-type effect where the threshold electric field value at low $`T`$ is given by

$`E_{thresh}={\displaystyle \frac{\mathrm{\Delta }\mu _H+\sqrt{\mathrm{\Delta }^2\mu _r^2+\mathrm{\Omega }_r^2(\mu _H^2\mu _r^2)}}{\mu _H^2\mu _r^2}},(\mu _H=\mu _r+\mu _{ab})`$ (13)
and does not depend on the chain size $`N`$ ($`E_{thresh}0.1510^7`$ V/cm for the chains with $`N=2`$ as can be observed in Fig. 3(a)). As we see in Fig. 3(b), the proton charge translocation under the influence of the field in this case proceeds not smoothly, but has a step-like character. As results from (13), the threshold value $`E_{thresh}`$ (which is needed to overcome a barrier for pumping between the inner localized states (12) and the boundary state $`|00\mathrm{}01`$ in the direction of field) increases for larger $`\mathrm{\Omega }_R`$ (Fig. 3(a), the cases with $`\mathrm{\Omega }_R=1.5`$ kcal/mol and $`\mathrm{\Omega }_R=2.15`$ kcal/mol). This implies that the conductivity of protonated chains can drop with an increasing $`\mathrm{\Omega }_R`$ which can occur in system for example due to the temperature-induced fluctuations of $`\mathrm{\Omega }_R`$. However, as was shown in phillips , the reorientation rate increases at increased voltage, which corresponds in our case to the smaller values of $`\mathrm{\Omega }_R`$ for $`E0`$. Thus, we can expect that the external field-induced lowering of the orientation barrier for the proton translocation results in the increase of the proton conductivity in the wire.

The drastic change of $`P`$ at $`E=E_{thresh}`$ leads to a strong qualitative difference in the temperature shapes of the polarization profiles shown in Fig. 4(a) for the large-$`\mathrm{\Omega }_R`$ regime. For $`E<E_{thresh}`$ and $`\mathrm{\Omega }_R>\mathrm{\Omega }_R^{}`$, the excess proton is located in the central sites, and the increase of $`T`$ results in a disorder-induced transfer of the proton from the inner positions to the chain boundary giving the increase of $`P`$ at $`300`$ K as compared to $`50`$ K (Fig. 4(a), cases $`E=0.0210^7`$ V/cm and $`E=0.110^7`$ V/cm). As the proton is located in the outer state $`|00\mathrm{}01`$ for $`E>E_{thresh}`$ (corresponding to $`P=1`$ for $`T0`$), the dominant effect of $`T`$ in this case is the the disorder-induced proton redistribution between all sites in the chain leading to the lowering of total polarization (Fig. 4(a), cases $`E=0.210^7`$ V/cm and $`E=0.310^7`$ V/cm). The profiles of the polarization for $`\mathrm{\Omega }_R`$ below $`\mathrm{\Omega }_R^{}`$ shown in Fig. 4(b) appear to be very similar to the high-field profiles in Fig. 4(a). Since for $`\mathrm{\Omega }_R<\mathrm{\Omega }_R^{}`$ the proton is located in the outer states (11) near the chain boundary already at low $`E`$, the increase of $`T`$ suppresses the polarization due to the increasing proton disorder.

## IV ROLE OF PROTON-PROTON CORRELATIONS

In order to examine the influence of proton correlations, we consider next the translocation of two excess protons in the wire which is described by the part $`H^2`$ of the total energy (22). Since the presence of two protons in wire may lead to the formation of Bjerrum D-defect, the energy $`H^2`$ for the chain with $`N=2`$ H-bonds given by the expression (24), contains the terms with the energy $`U`$ of the repulsion between two nearest-neighboring protons.

Analogously to the 1-proton wire, we analyze first the behavior of the chain without the electric field. For $`N=2`$ and $`\mathrm{\Omega }_T0`$ the energy levels found from (24) have the following form:

$`\lambda _{1,2}={\displaystyle \frac{1}{2}}(U\pm q_{})+\mu _HE,`$
$`\lambda _3=\mathrm{\Delta },\lambda _4=\mathrm{\Delta }+J,`$ (14)
$`\lambda _{5,6}={\displaystyle \frac{1}{2}}(U\pm q_+)\mu _HE,(q_\pm =\sqrt{(U2\mu _rE)^2+4\mathrm{\Omega }_R^2})`$
and correspond to the following states of the wire:

$`|\stackrel{~}{1}={\displaystyle \frac{p_{}}{\sqrt{\mathrm{\Omega }_R^2+p_{}^2}}}|6+{\displaystyle \frac{\mathrm{\Omega }_R}{\sqrt{\mathrm{\Omega }_R^2+p_{}^2}}}|7,`$
$`|\stackrel{~}{2}={\displaystyle \frac{\mathrm{\Omega }_R}{\sqrt{\mathrm{\Omega }_R^2+p_{}^2}}}|6{\displaystyle \frac{p_{}}{\sqrt{\mathrm{\Omega }_R^2+p_{}^2}}}|7,`$
$`|\stackrel{~}{3}=|8,|\stackrel{~}{4}=|9,`$ (15)
$`|\stackrel{~}{5}={\displaystyle \frac{\mathrm{\Omega }_R}{\sqrt{\mathrm{\Omega }_R^2+p_+^2}}}|10+{\displaystyle \frac{p_+}{\sqrt{\mathrm{\Omega }_R^2+p_+^2}}}|11,`$
$`|\stackrel{~}{6}={\displaystyle \frac{p_+}{\sqrt{\mathrm{\Omega }_R^2+p_+^2}}}|10+{\displaystyle \frac{\mathrm{\Omega }_R}{\sqrt{\mathrm{\Omega }_R^2+p_+^2}}}|11`$
with $`p_\pm =\frac{1}{2}(U\pm q_\pm )\mu _rE`$.

To study the influence of $`\mathrm{\Omega }_R`$, we analyze (IV) and (IV) for $`E=0`$ assuming $`JU`$ and neglecting in this way by the formation of ionic defects described by the configuration $`|9=|0110`$. Similarly to the 1-proton wire, the two different regimes can exist in the system depending on the value of the reorientation energy. In the first small-$`\mathrm{\Omega }_R`$ regime (for $`\mathrm{\Omega }_R<\mathrm{\Omega }_R^{(2)}=\sqrt{\mathrm{\Delta }^2U\mathrm{\Delta }}`$), each proton is located near the outer molecular group and the state $`|8=|1001`$ has the lowest energy $`\lambda _3=\mathrm{\Delta }`$. As $`\mathrm{\Omega }_R`$ increases and approaches the ”critical” value $`\mathrm{\Omega }_R^{(2)}`$, the transition to the large-$`\mathrm{\Omega }_R`$ regime occurs. In this regime (for $`\mathrm{\Omega }_R>\mathrm{\Omega }_R^{(2)}`$) the lowest energy levels $`\lambda _2=\lambda _6=\frac{1}{2}(Uq)`$ ($`q=q_+(E=0)=q_{}(E=0)`$) correspond to the states $`|\stackrel{~}{2}`$ and $`|\stackrel{~}{6}`$ in (IV), with one proton located in the interior of the wire. However, in contrast to section III, the transition between these two regimes is $`U`$-dependent, because $`\mathrm{\Omega }_R^{(2)}`$ contains the energy of the D-defect $`U`$. Fig. 5(a) shows the variation of the proton occupation numbers $`n_{l\nu }`$ with $`\mathrm{\Omega }_R`$ for $`U=9.4`$ kcal/mol and $`U=1.9`$ kcal/mol (plotted in the inset). The ”critical” value $`\mathrm{\Omega }_R^{(2)}3`$ kcal/mol for the repulsion energy $`U=9.4`$ kcal/mol is larger as compared with $`\mathrm{\Omega }_R^{(2)}1.5`$ kcal/mol for $`U=1.9`$ kcal/mol. So far as the repulsion energy $`U`$ is significant, $`\mathrm{\Omega }_R^{(2)}>\mathrm{\Omega }_R^{}`$. However, as $`U0`$, $`\mathrm{\Omega }_R^{(2)}`$ approaches the ”critical” value $`\mathrm{\Omega }_R^{}`$ for the one-proton case . As we can see from (IV) and (19), the ground states $`|\stackrel{~}{2}`$ and $`|\stackrel{~}{6}`$ in the large-$`\mathrm{\Omega }_R`$ regime are represented by the superpositions of the normal configurations $`|7`$ and $`|10`$ and the states $`|6`$ and $`|11`$ containing the D-defect. Thus the transition to the large-$`\mathrm{\Omega }_R`$ regime stabilize D-defects inside the chain. The formation of the D-defect states is clearly observed in Fig. 5(a) where the occupation numbers of the D-defect states $`|6`$ and $`|11`$ significantly increase for $`\mathrm{\Omega }_R>\mathrm{\Omega }_R^{(2)}`$.

Analogously to the one-proton case, the temperature fluctuations lead to the slight temperature-induced increase of the value $`\mathrm{\Omega }_R^{(2)}(T)`$ (corresponding to $`n_{\stackrel{~}{3}}=n_{\stackrel{~}{2}}=n_{\stackrel{~}{6}}`$), as compared to $`\mathrm{\Omega }_R^{(2)}`$ where the states $`|\stackrel{~}{2}`$ and $`|\stackrel{~}{6}`$ are already stabilized. In fact, for $`\mathrm{\Omega }_R>\mathrm{\Omega }_R^{(2)}(T)`$ the states corresponding to protonated chains with significant concentration of D-defects prevail ($`n_{\stackrel{~}{2}}=n_{\stackrel{~}{6}}>n_{\stackrel{~}{3}}`$), whereas the states with the protons located at the boundaries in the surrounding dominate for $`\mathrm{\Omega }_R<\mathrm{\Omega }_R^{(2)}(T)`$ ($`n_{\stackrel{~}{3}}>n_{\stackrel{~}{2}}=n_{\stackrel{~}{6}}`$). For small $`\mathrm{\Omega }_RU`$, $`\mathrm{\Omega }_R^{(2)}`$ can be given by

$$(\mathrm{\Omega }_R^{(2)}(T))^2=\frac{\mathrm{\Omega }_R^{(2)}}{2}\left[1+\sqrt{1+\frac{8kTU^2(U/2\mathrm{\Delta })}{\mathrm{\Delta }^2U\mathrm{\Delta }}}\right]$$
(16)
Since the line $`\mathrm{\Omega }_R^{(2)}(T)`$ found from (16), is tilted with respect to $`T`$ in the state diagrams ($`T`$, $`\mathrm{\Omega }_R^{(2)}(T)`$) (Fig. 5(b)), the effect of temperature for the chain in the large-$`\mathrm{\Omega }_R`$ regime is crucial: with the increasing $`T`$, the temperature fluctuations can destroy the D-defects and redistribute the proton charge between the other chain sites. See for example the case of $`\mathrm{\Omega }_R^{(2)}(T)=3`$ kcal/mol and $`U=9.4`$ kcal/mol plotted in Fig. 5(b) where the D-defects annihilate at $`T100`$ K.

As $`U\mathrm{}`$, the weight constants for the D-defect states in (IV) become smaller: $`\frac{\mathrm{\Omega }_R}{\sqrt{\mathrm{\Omega }_R^2+p_\pm ^2}}=\frac{\mathrm{\Omega }_R}{\sqrt{\mathrm{\Omega }_R^2+\frac{1}{4}(U\pm q)^2}}0`$. Thus, the contribution of the D-defect-states to the stable wire configuration goes down as $`\frac{1}{U}`$ for the stronger proton repulsion $`U`$ (see for the comparison $`n_6=n_{11}`$ for different $`U`$ plotted in Fig. 5(a)).

The fact that the variation of temperature can lead to formation or annihilation of the D-defects is also observed in the $`T`$-dependence of the proton polarization. Note that especially for weak external field $`E`$, the behavior of $`P(T)`$ in the small-$`\mathrm{\Omega }_R`$ (Fig. 6(a), $`E=0.410^7V/cm`$) and in the large-$`\mathrm{\Omega }_R`$ regime (Fig. 6(b), $`E=0.110^7V/cm`$) is drastically different. In the first case, at low $`T`$, the predominantly occupied symmetric ground state $`|10\mathrm{}01`$ has the total polarization $`P=0`$. However, with $`T`$ increasing, protons tend to occupy the excited states with non-symmetric charge distribution that results in an increase of $`P`$. Fig. 7(a) demonstrates that the population of all excited states, in particular those containing D-defects (Fig. 7(a), inset), grows with $`T`$. Although the concentration of the D-defect states $`|0011`$ and $`|1100`$ is of 3-4 orders lower than that of the normal states (see Fig. 7(a), inset), it significantly increases up to 1-2 orders with the temperature increase from $`50`$ to $`300`$ K.

In contrast to this, in the large-$`\mathrm{\Omega }_R`$ regime the protons and stable D-defects migrate in the direction of applied field $`E`$ for $`T0`$ giving a non-zero $`P`$ (Fig. 6(b)). As $`T`$ increases, the population of the excited non-defect state with the protons redistributed at the boundaries grows (see Fig. 7(b)) which gives the lower chain polarization. The D-defects, located near the end of the chain for finite $`E`$ ($`|0011`$), are redistributed between another chain positions with $`T`$, which is observed in Fig. 7(b) showing a decrease of $`|0011`$\- together with a slight increase of the $`|1100`$-state population at $`T=300`$ K as compared to lower temperatures.

We study now the electric field effect in correlated chains. Fig. 8 shows the variation of polarization and redistribution of protons with increasing $`E`$. Consider first the small-$`\mathrm{\Omega }_R`$ regime. In distinct to the 1-proton wire, where the polarization increases smoothly to its maximal value $`P_{max}`$ (Fig. 3(a), inset), we observe here two different threshold effects. The first transition from the state $`|8`$ of (19)(the ground state of the wire in the small-$`\mathrm{\Omega }_R`$ regime at $`E=0`$) to the state $`|10`$ (where both of the protons are ordered in the right position of each H-bond in the direction of the field) occurs at the threshold field value

$`E_1={\displaystyle \frac{\mathrm{\Delta }}{(N1)(2\mu _r+\mu _{ab})2\mu _r}}.`$ (17)
The distribution of the occupation probabilities $`n_8`$ and $`n_{10}`$ for the states $`|8`$ and $`|10`$ is plotted in Fig. 8(b). We observe at $`E=E_1`$ the abrupt increase of $`n_{10}`$, while at the same field value $`n_8`$ drops to zero. Furthermore, we conclude from (17) that the value $`E_1`$ lowers with the number $`N`$ of the water molecules in the chain. This effect can be observed in Fig. 9 where the jumps of the polarization are plotted for different $`N`$. Finally, for very long water chain ($`N\mathrm{}`$) $`E_10`$. In contrast to the strong $`N`$-dependence of $`E_1`$, the second threshold effect appears at

$`E_2={\displaystyle \frac{U}{2\mu _r}}`$ (18)
essentially due to the proton correlations and does not depend on the chain length. The strong increase of $`P`$ at $`E=E_2`$ shown in Fig. 8(a) and Fig. 9 is related to the second drastic redistribution of the proton charge in the wire. As can be observed in Fig. 8(b), at $`E=E_2`$ the occupation probability $`n_{11}`$ of the D-defect-state $`|11`$ drastically increases to 1, whereas $`n_{10}`$ drops to zero. Thus, as resulted from our model, the formation of D-defect in external electric field has a step-like character proceeding via the threshold mechanism. In the large-$`\mathrm{\Omega }_R`$ regime, where the protons are stabilized at the inner water molecules already at $`E=0`$, the first threshold phenomenon at $`E=E_1`$, observed for the small-$`\mathrm{\Omega }_R`$ case, does not occur. However, the transition at $`E=E_2`$ with the increase of the D-defect concentration appears in this regime similarly to the regime of small $`\mathrm{\Omega }_R`$, that can be observed in the $`P`$-profile for $`\mathrm{\Omega }_R=3`$ kcal/mol shown in Fig. 8(a). Note that the effect of the increasing double occupancy due to membrane potentials has been observed in the current/concentration plots in gramicidin channels phillips , thus supporting our main conclusions about the role of the external electric field.

The discussed above formation of the D-defects for $`\mathrm{\Omega }_R>\mathrm{\Omega }_R^{}`$ in the high electric field results in the increase of $`P`$ for lower temperatures as shown in Fig. 6(b). Basically, the essential effect of $`T`$ observed in the $`P(T)`$-profiles in Fig. 6, is the suppression of the total polarization due to proton disorder. However, the shapes of the polarization in Fig. 6(a) are drastically different for $`E<E_1`$ and $`E>E_2`$. For low fields ($`E<E_1`$) the polarization first increases (reflecting the fluctuation-induced expansion of proton charge from the outer symmetric positions $`|10\mathrm{}01`$ with $`P=0`$ to the inner positions of the chain accompanied by the formation/annihilation of D-defects), and then smoothly decreases due to the disorder effect. In contrast to this, as the increasing electric field induces the step-like formation of D-defects in the small-$`\mathrm{\Omega }_R`$ regime, the temperature behavior of $`P`$ in this case is similar to the the large-$`\mathrm{\Omega }_R`$ case (compare Fig. 6(a) and Fig. 6(b) with $`E=110^7`$ V/cm) showing the smooth disorder-induced decrease of $`P`$ with $`T`$.

We also note that the stable configurations with double proton occupancy require the additional reorientation steps for the proton translocation and can result in the smaller values for the proton conductivity. This fact has been observed in the measurements of the proton conductance in two different stereoisomers of the gramicidin cukierman , thus supporting a possibility of stabilization of the D-defect states in proton wires.

## V SUMMARY

In this work we studied the process of proton translocation in 1D-chains mimicking protonated water channels embedded in surrounding. We have analyzed the role of the reorientation motion of protons, as well as the effect of electric field and proton correlations on the chain dynamics. We have shown that the increase of the reorientation energy results in the transition to the large-$`\mathrm{\Omega }_R`$ regime characterized by the transfer of the proton charge from the surrounding to the inner water molecules in the chain. The process of proton migration along the chain in the external electric field has the step-like character leading to the appearance of the electric field threshold-type phenomena with drastic redistribution of proton charge. The correlations between protons in the chain increase the ”critical” reorientation energy $`\mathrm{\Omega }_R^{}`$ necessary for the transition into the large-$`\mathrm{\Omega }_R`$ regime, where the protonated chain contains a finite concentration of Bjerrum defects. The temperature fluctuations induce a slight increase of $`\mathrm{\Omega }_R^{}(T)`$ separating the state with the protons located in surrounding near the outer groups, and the protonated state with D-defects. For the correlated chains, this temperature dependence of the ”critical” reorientation energy can lead to the redistribution of proton charge and annihilation of D-defects with increasing $`T`$. The electric field applied to the correlated chains induces first the formation of ordered dipole structures for the lower $`E`$ values, and than, with the further $`E`$ increase, the stabilization of the states with the Bjerrum D-defects.

Generally, the increase of temperature suppresses the total polarization in the chain due to the increasing disorder. However, especially in the low electric fields, the shapes of the temperature profiles of the polarization appear to be drastically different in the small- and large-$`\mathrm{\Omega }_R`$ regimes demonstrating the complex interplay between the reorientation energy and temperature.

Finally, as follows from our analysis, the following factors strongly influence the formation of Bjerrum defects: (i) the high electric fields can form the defects and pump them in the chain in the direction of field; (ii) the increase of the orientational energy barrier leads to the stabilization of D-defects; (iii) the increase of temperature in the large-$`\mathrm{\Omega }_R`$ regime results in the formation/annihilation of D-defects, whereas for small $`\mathrm{\Omega }_R`$ the concentration of D-defects significantly increases up to 1-2 orders at the room temperatures as compared to the low $`T50`$ K.

## Appendix A DECOMPOSITION OF THE PROTON STATES IN THE SYSTEM WITH $`N=2`$ H-BONDS

We demonstrate below the procedure of the mapping in the system with $`N=2`$ H-bonds on the multi-site states. For $`N=2`$ the basis $`|i`$ includes $`2^{2N}=16`$ states $`|n_{1a},n_{1b},n_{2a},n_{2b}`$:

$`|1=|0000,`$ $`|2=|1000,`$ $`|3=|0100,`$
$`|4=|0010,`$ $`|5=|0001,`$ $`|6=|1100,`$ (19)
$`|7=|1010,`$ $`|8=|1001,`$ $`|9=|0110,`$
$`|10=|0101,`$ $`|11=|0011,`$ $`\mathrm{}|16=|1111.`$
We can derive the relations between $`c_{l,\nu }`$ and $`X^{ii^{}}=|ii^{}|`$:

$`c_{l,\nu }={\displaystyle \underset{i,j}{}}i|c_{l,\nu }|jX^{ij},`$ (20)
where the expectation numbers $`i|c_{l,\nu }|j`$ can be found using the usual antisymmetric rules for Fermi-operators davydov . Specifically, for the case $`N=2`$ the expressions (20) yield:

$`c_{0,a}=X^{1,2}+X^{3,6}+X^{4,7}+X^{5,8}+X^{9,12}+X^{10,13}+X^{11,14}+X^{15,16}`$
$`c_{1,a}=X^{1,4}X^{2,7}X^{3,9}+X^{5,11}+X^{6,12}X^{8,14}X^{10,15}+X^{13,16}`$ (21)
$`c_{0,b}=X^{1,3}X^{2,6}+X^{4,9}+X^{5,10}X^{7,12}X^{8,13}+X^{11,15}X^{14,16}`$
$`c_{1,b}=X^{1,5}X^{2,8}X^{3,10}X^{4,11}+X^{6,13}+X^{7,14}+X^{9,15}X^{12,16}`$
Using the relations (21) and the fact that $`X^{ii^{}}X^{ll^{}}=\delta _{i^{}l}X^{il^{}}`$ (due to the orthogonality of the states $`|i`$), we decompose (1-5) in terms of $`X^{ii^{}}`$ operators into the following 5 terms:

$`H=H_2^0H_2^1H_2^2H_2^3H_2^4,`$ (22)
where

$`H_2^0`$ $`=`$ $`a_2^0,`$
$`H_2^1`$ $`=`$ $`(\mathrm{\Delta }+(\mu _r+\mu _{ab})E)X^{2,2}+\mu _rE(X^{3,3}X^{4,4})+`$
$`(\mathrm{\Delta }(\mu _r+\mu _{ab})E)X^{5,5}+\mathrm{\Omega }_T(X^{2,3}+X^{3,2})+`$
$`\mathrm{\Omega }_T(X^{4,5}+X^{5,4})+\mathrm{\Omega }_R(X^{3,4}+X^{4,3})+a_2^1,`$
$`H_2^2`$ $`=`$ $`(U+(2\mu _r+\mu _{ab})E)X^{6,6}+\mu _{ab}(X^{7,7}X^{10,10})+`$ (24)
$`\mathrm{\Delta }X^{8,8}+(J\mathrm{\Delta })X^{9,9}+(U(2\mu _r+\mu _{ab})E)X^{11,11}+`$
$`\mathrm{\Omega }_T(X^{7,8}+X^{8,7})+\mathrm{\Omega }_T(X^{8,10}+X^{10,8})+\mathrm{\Omega }_T(X^{9,10}+X^{10,9})+`$
$`\mathrm{\Omega }_R(X^{6,7}+X^{7,6})+\mathrm{\Omega }_R(X^{10,11}+X^{11,10})+a_2^2,`$
$`H_2^3`$ $`=`$ $`(U+J\mathrm{\Delta }+(\mu _r+\mu _{ab})E)X^{12,12}+(U+\mu _rE)X^{13,13}+`$
$`(U\mu _rE)X^{14,14}+(U+J\mathrm{\Delta }(\mu _r+\mu _{ab})E)X^{15,15}+`$
$`\mathrm{\Omega }_T(X^{12,13}+X^{13,12})+\mathrm{\Omega }_T(X^{14,15}+X^{15,14})+`$
$`\mathrm{\Omega }_R(X^{13,14}+X^{14,13})+a_2^3,`$
$`H_2^4`$ $`=`$ $`(2U+J)X^{16,16}+a_2^4.`$
Since the parameter

$$\mathrm{\Delta }=(\stackrel{~}{w}\stackrel{~}{\epsilon })(\epsilon w^{})$$
(26)
in (A)-(A) is the difference between proton configuration energies at the boundary ($`l=1`$ or $`l=N+1`$ surrounding molecular groups), and at the inner ($`2<l<N`$) water molecule, it describes, in fact, the energy barrier for the protonation of the water chain. For our analysis $`\mathrm{\Delta }`$ has the key importance, because the other energy constants in (A)-(A)

$`a_2^0=a_2^2(\stackrel{~}{w}\stackrel{~}{\epsilon })(\epsilon w^{}),`$ $`a_2^1=a_2^2(\stackrel{~}{w}\stackrel{~}{\epsilon }),`$
$`a_2^3=a_2^2+(\stackrel{~}{w}\stackrel{~}{\epsilon }),`$ $`a_2^4=a_2^2+(\stackrel{~}{w}\stackrel{~}{\epsilon })+(\epsilon w^{}),`$
$`a_2^2=\stackrel{~}{w}+\stackrel{~}{\epsilon }+\epsilon `$
which appear due to the boundary effects, are independent of the proton location in the wire and thus do not influence the statistical characteristics like (6).

By the similar way the energy (1-5) can be rewritten for the systems with any finite value of $`N`$.