text:
# A Study of Quasi-Exactly Solvable Models within the Quantum Hamilton-Jacobi Formalism

## I Introduction

This paper reports an investigation of quasi-exactly solvable (QES) models within the quantum Hamilton-Jacobi (QHJ) formalism. One of the earliest investigations on QES models was done by V. Singh et.al  . The QES models have been studied extensively and for a general review and references we refer the reader to the book by Ushveridze . In the recent years, a lot of interesting work has been done on QES periodic potentials. We refer the reader to references \[3-13\]. A complete list of canonical forms for the QES models has been obtained in . The QES models have a characteristic property that, when the potential parameters satisfy a specified condition, analytic expressions for a few energy levels and their corresponding eigenfunctions can be obtained exactly. This condition between the parameters of the potential will be referred to as quasi-exactly solvability condition.

A well known example of QES model is the sextic oscillator in one dimension, corresponding to the potential $`V(x)=\alpha x^2+\beta x^4+\gamma x^6`$. The condition of quasi-exactly solvability is found to be $`\frac{1}{\sqrt{\gamma }}[\frac{\beta ^2}{4\gamma }\alpha ]=3+2n`$, where $`n`$ is a non-negative integer which is related to the number of levels for which exact energy eigenfunctions and eigenvalues can be computed. A number of other QES models have been constructed and studied within algebraic and group theoretical approach. Interesting connections have been established between the sextic oscillator and second order linear differential equations within a new approach to second order linear differential equations .

In this paper we study the sextic oscillator and a few other QES models in one dimension. In each of these cases the condition of quasi-exactly solvability is derived within the QHJ approach. The next section contains an overview of QHJ formalism and how it is used in the present paper to study the QES models. In the following four sections we investigate the sextic oscillator, sextic oscillator with a centrifugal barrier, a hyperbolic potential and a circular potential. The last section contains our conclusions about exact solvability and quasi-exactly solvability.

## II Quantum Hamilton-Jacobi Formalism

The QHJ formalism was initiated by Leacock and Padgett  and was successfully applied to several exactly solvable models (ESM) in one dimension in quantum mechanics by Bhalla et.al \[16-18\]. Our discussions in this paper will be limited to the QES problems in one dimension only. The Schr$`\ddot{o}`$dinger equation is

$$\frac{\mathrm{}^2}{2m}\frac{d^2}{dx^2}\psi +V(x)\psi =E\psi .$$
(1)
On substituting $`\psi =\mathrm{exp}(iS/\mathrm{})`$, in (1) we obtain the following equation for $`S`$

$$\left(\frac{dS}{dx}\right)^2i\mathrm{}\left(\frac{d^2S}{dx^2}\right)=2m[EV(x)].$$
(2)
We define $`p(x)=\frac{dS}{dx}`$ which satisfies the Riccati equation

$$p^2(x)i\mathrm{}\frac{d}{dx}p(x)=2m[EV(x)].$$
(3)
In the limit $`\mathrm{}0`$, (2) becomes the classical Hamilton-Jacobi equation and $`p(x)p_{cl}`$, the classical momentum which is

$$p_{cl}=\sqrt{2m[EV(x)]}.$$
(4)
Therefore (2) and (3) will be referred to as QHJ equations, $`p(x)`$ will be called the quantum momentum function (QMF) and $`S`$ will be the quantum action. In terms of the eigenfunction $`\psi `$ of the energy, the QMF is given by

$$p(x)=i\mathrm{}\frac{1}{\psi }\frac{d\psi }{dx}.$$
(5)
An important step in the QHJ formalism is to regard $`x`$ as a complex variable and to extend the definition of $`p(x)`$ to the complex plane. From (5) it is obvious that the zeros of the wavefunction correspond to the poles of the QMF. It is known that the bound state solutions of (1) corresponding to the $`n^{th}`$ level has $`n`$ real zeros correspondingly the QMF has $`n`$ poles on the real line. From (3) it can be seen that if $`x`$ is a point at which $`V(x)`$ is analytic and $`p`$ has a pole, the pole must be of first order and the residue at that pole will be $`i\mathrm{}`$. Therefore the integral of the QMF taken along the contour $`C`$, which encloses these poles, will have the value $`n\mathrm{}`$. Thus we get

$$\frac{1}{2\pi }_Cp(x)𝑑x=n\mathrm{}.$$
(6)
and this is an exact quantization condition in one dimension . This exact quantization condition (6) has been used to obtain bound state energy levels without solving for the eigenfunctions for several ESM \[16-18\]. For this purpose one needs to know the location of singularities and their corresponding residues of the QMF in the complex plane. The QMF has the two kinds of singularities, fixed and the moving singularities. The fixed singularities correspond to the singularities of the potential and will be present in every solution of the Riccati equation, their location being independent of the initial conditions. The position of the moving singularities depends on the initial conditions. It is known that for the solutions of a Riccati equation only poles can appear as moving singularities. Therefore if the potential is meromorphic, the solutions will also be meromorphic. Coming back to the QMF corresponding to the solutions of the Schr$`\ddot{o}`$dinger equation, in addition to the poles, corresponding to the $`n`$ real zeros of the $`n^{th}`$ excited state, in general there may be other moving poles. The knowledge about these poles is needed to apply QHJ method. The residue at any fixed pole can be computed from (3). This, being a quadratic equation, will lead to two solutions and therefore a boundary condition on the QMF is needed to pick up the physical solutions. Leacock and Padgett proposed that one should make use of the condition,

$$\underset{\mathrm{}0}{lim}p(x)p_{cl}.$$
(7)
From (4) it should be noted that the classical turning points become the branch points of $`p_{cl}`$. It has to be emphasized here that, when $`x`$ is a complex variable, $`p_{cl}`$ is a double valued function. A full definition of $`p_{cl}`$ in the complex plane as a function of a complex variable $`x`$, requires us to select a particular branch of $`p_{cl}`$ which is assumed to have a branch cut in the classical region and a positive value just below the branch cut. Locating the singular points of the QMF and imposing the boundary conditions discussed above are two crucial but usually difficult steps in arriving at the correct solutions. In the earlier studies of ESM, it was easy to guess the singularity structure of the QMF and it was found that, there were no moving poles away from the real axis. For the QES models studied in this paper, it is very difficult to find the location of the singularities of the QMF. In order to be able to make some progress we make a simplifying assumption about the moving poles and the nature of the singularity at infinity. The details of moving and possible fixed poles will be given in each case separately as and when we discuss the model. We now state our main assumption, common to all models studied, i.e, the point at infinity is an isolated point and that it is a pole of finite order and not an essential singularity. Under these assumptions we show that, imposing the exact quantization condition leads to the condition of QES in each case.

## III Sextic Oscillator

The potential for the sextic oscillator is

$$V(x)=\alpha x^2+\beta x^4+\gamma x^6,\gamma >0.$$
(8)
From now onwards we set $`\mathrm{}=2m=1`$. For the $`n^{th}`$ exited state, QMF has $`n`$ moving poles on the real axis and we assume that there are no other moving poles. In order to use the quantization condition (6) we need to evaluate the integral $`J(E)`$

$$J(E)=\frac{1}{2\pi }_Cp(x)𝑑x$$
(9)
along the contour $`C`$. As a first step, it is convenient to deform the contour $`C`$ to a large circular contour $`\mathrm{\Gamma }`$, with the center at the origin and big enough to enclose all the singularities of the QMF in the finite complex plane. This is possible because the point at infinity is assumed to be an isolated singularity and the value of the integral remains unchanged. Hence

$$J(E)=\frac{1}{2\pi }_\mathrm{\Gamma }p(x)𝑑x.$$
(10)
In order to evaluate the integral along the large circle $`\mathrm{\Gamma }`$, we apply an inversion mapping $`xy=\frac{1}{x}`$. Under this mapping the circular contour $`\mathrm{\Gamma }`$ gets mapped to another circular contour $`\gamma `$ in the $`y`$ plane. The only singular point inside this contour is the point $`y=0`$, which is the image of the point at infinity in the $`x`$-plane. Thus we obtain from (10)

$$J(E)=\frac{1}{2\pi }_\gamma \stackrel{~}{p}(y)\frac{1}{y^2}𝑑y.$$
(11)
To evaluate the integral in (11) a Laurent expansion of $`\stackrel{~}{p}(y)`$ is made.

$$\stackrel{~}{p}(y)=\underset{n=1}{\overset{3}{}}\frac{b_n}{y^n}+\underset{n=1}{\overset{\mathrm{}}{}}a_ny^n.$$
(12)
Substituting this expansion in (11) and integrating term by term, we get

$$J(E)=ia_1.$$
(13)
It only remains to compute the coefficient $`a_1`$ of the Laurent expansion given in (12). To do this we start from the QHJ equation

$$\stackrel{~}{p}^2(y)+iy^2\frac{d}{dy}\stackrel{~}{p}(y)=E\frac{\alpha }{y^2}\frac{\beta }{y^4}\frac{\gamma }{y^6}.$$
(14)
Substituting the Laurent expansion and equating the coefficients of different powers of $`y`$ in both sides of the equation (14), we successively get the following equations.

$$b_3^2=\gamma .$$
(15)
$$b_2=0.$$
(16)
$$2b_1b_3=\beta .$$
(17)
$$b_1^2+b_3(2a_13i)=\alpha .$$
(18)
It is important to know that, we would get two solutions for $`b_1`$ corresponding to the two solutions of $`b_3=\pm i\sqrt{\gamma }`$. This happens due to the fact that the QHJ is quadratic in the QMF. Thus one needs a boundary condition to pick the correct solution. We propose to use the square integrability of the wavefunction instead of the original boundary condition, explained in the introduction, which was proposed by Leacock and Padgett. This is because the original boundary condition is difficult to implement in the present case due to the presence of six branch points in the $`p_{cl}`$. In order to find the restrictions coming from the square integrability, we compute the wavefunction

$$\psi (x)=\mathrm{exp}\left(ip(x)𝑑x\right)$$
(19)
for large $`x`$ as follows. The most important term in the Laurent expansion (12) for small $`y0`$, corresponding to large $`x`$, is

$$\stackrel{~}{p}(y)\frac{b_3}{y^3}$$
(20)
and the wavefunction for large $`x`$ becomes

$$\psi (x)\mathrm{exp}\left(i\frac{b_3x^4}{4}\right)dx.$$
(21)
Out of the two solutions, $`b_3=\pm i\sqrt{\gamma }`$, $`\psi `$ is square integrable only for $`b_3=i\sqrt{\gamma }`$. Using this value of $`b_3`$ and calculating $`J(E)`$ from (13), the quantization condition gives

$$\frac{1}{\sqrt{\gamma }}\left(\frac{\beta ^2}{4\gamma }\alpha \right)=3+2n.$$
(22)
In order to compare the result in (22) with the known condition , we write

$`\gamma =a^2,\beta =2ab.`$ (23)
Thus we get $`\alpha =b^2a(3+2n)`$ which agrees with known result.

## IV Sextic Oscillator with the centrifugal barrier

This kind of model was first studied by A.P.Houtot . The potential we discuss here is

$$V(x)=4(S\frac{1}{4})(S\frac{3}{4})\frac{1}{x^2}+[b^24a(S+\frac{1}{2}+M)]x^2+2abx^4+a^2x^6$$
(24)
and the range of $`S`$ is taken to be $`4S>3`$. We note that the potential goes to $`\mathrm{}`$ as $`x0`$ and $`x\mathrm{}`$. Hence the classical turning points will be on the positive real axis. The physical motion in both classical and quantum situations will be confined to positive real axis only. As, has been discussed earlier there will be n moving poles in the classical region which are enclosed by the contour $`C`$ in the quantization condition stated in (6). When we extend the definition of $`x`$, to take all the complex values, we expect $`n`$ additional moving poles on the negative real axis. These come from the symmetry of the potential under the transformation $`xx`$. Just as in the quantization condition (6), we have

$$\frac{1}{2\pi }_{C_1}p(x)𝑑x=n$$
(25)
where $`C_1`$ is the contour which encloses the $`n`$ additional moving poles on the negative real axis. The QHJ equation for this potential is

$$p^2(x)i\frac{d}{dx}p(x)=E4(S\frac{1}{4})(S\frac{3}{4})\frac{1}{x^2}[b^24a(S+\frac{1}{2}+M)]x^22abx^4a^2x^6.$$
(26)
We observe that in addition to the 2$`n`$ moving poles, $`x=0`$ is a fixed pole. In this case we assume that there are no other singularities in the finite complex plane. As in the case of the sextic oscillator, in order to evaluate $`J(E)`$ in (9), we deform the contour $`C`$ to a large circular contour $`\mathrm{\Gamma }`$, which will enclose the 2$`n`$ moving poles and the fixed pole at $`x=0`$. Therefore we have,

$$_\mathrm{\Gamma }p(x)𝑑x=_{\gamma _0}p(x)𝑑x+_Cp(x)𝑑x+_{C_1}p(x)𝑑x$$
(27)
where $`\gamma _0`$ is the contour enclosing only the fixed pole at $`x=0`$. Expanding $`p(x)`$ in the Laurent series, in the powers of $`x`$

$$p(x)=\frac{b_1}{x}+\underset{n=0}{\overset{\mathrm{}}{}}a_nx^n$$
(28)
we get

$$\frac{1}{2\pi }_{\gamma _0}p(x)𝑑x=ib_1.$$
(29)
We fix $`b_1`$ by substituting the Laurent series in (26). Thus we obtain,

$`b_1={\displaystyle \frac{i}{2}}[4S3],b_1={\displaystyle \frac{i}{2}}[4S1].`$ (30)
The choice for the value of $`b_1`$ consistent with square integrability in the specified range is

$$b_1=\frac{i}{2}[4S1].$$
(31)
Thus (27) becomes

$$\frac{1}{2\pi }_\mathrm{\Gamma }p(x)𝑑x=ib_1+2n.$$
(32)
The integral along $`\mathrm{\Gamma }`$ is computed by changing the variable from $`xy=\frac{1}{x}`$ and proceeding in the same way as was done for the sextic oscillator. From (31) we then obtain

$$M=n.$$
(33)
which is the quasi-exact solvability condition for the sextic oscillator with the centrifugal barrier.

## V  Circular Potential

The potential for this model is

$$V(x)=\frac{A}{\mathrm{sin}^2x}+\frac{B}{\mathrm{cos}^2x}C\mathrm{sin}^2x+D\mathrm{sin}^4x$$
(34)
where,

$$A=4(S_1\frac{1}{4})(S_1\frac{3}{4}),B=4(S_2\frac{1}{4})(S_2\frac{3}{4})$$
(35)
$$C=q_1^2+4q_1(S_1+S_2+M),D=q_1^2$$
(36)
and the ranges of $`S_1`$ and $`S_2`$ are $`2S_1>1`$ and $`2S_2>1`$. The QHJ equation is

$$p^2(x)i\frac{d}{dx}p(x)=E\frac{A}{\mathrm{sin}^2x}\frac{B}{\mathrm{cos}^2x}+C\mathrm{sin}^2xD\mathrm{sin}^4x$$
(37)
and the quantization condition is

$$\frac{1}{2\pi }_Cp(x)𝑑x=n$$
(38)
Define $`\mathrm{sin}^2x=t`$, the QHJ equation becomes

$$\stackrel{~}{p}^2(t)2i\sqrt{t(1t)}\frac{d}{dt}\stackrel{~}{p}(t)=E\frac{A}{t}\frac{B}{1t}+CtDt^2$$
(39)
where $`\stackrel{~}{p}(t)p(x)`$. Defining $`q`$ by $`\stackrel{~}{p}=\sqrt{t(1t)}q`$ we obtain the QHJ equation in $`t`$ variable as follows,

$$q^22i\frac{d}{dt}q+\frac{i(12t)q}{t(1t)}=\frac{E}{t(1t)}\frac{A}{t^2(1t)}\frac{B}{t(1t)^2}+\frac{C}{1t}\frac{Dt}{1t}.$$
(40)
The quantization condition (38) becomes

$$\frac{1}{2\pi }_C\frac{q(t)}{2}𝑑t=n.$$
(41)
We observe that QMF has fixed poles at $`t=1,0`$ and proceeding in a way similar to §4, we obtain the quasi-exact solvability condition as

$$M=n.$$
(42)
## VI Hyperbolic Potential

The QHJ equation for this potential is

$$p^2(x)i\frac{d}{dx}p(x)=E+\frac{A}{\mathrm{cosh}^2x}\frac{B}{\mathrm{sinh}^2x}+C\mathrm{cosh}^2xD\mathrm{cosh}^4x$$
(43)
where

$$A=4(S_1\frac{1}{4})(S_1\frac{3}{4}),B=4(S_2\frac{1}{4})(S_2\frac{3}{4})$$
(44)
$$C=q_1^2+4q_1(S_1+S_2+M),D=q_1^2$$
(45)
and the ranges of $`S_1`$ and $`S_2`$ are $`2S_1>1`$ and $`2S_2>1`$. A change of variable from $`xt=\mathrm{cosh}x`$ changes $`p(x)\stackrel{~}{p}(t)=p(\mathrm{cosh}^1x)`$, then defining

$$\stackrel{~}{p}(t)=\sqrt{t^21}q(t).$$
(46)
The QHJ equation becomes

$$q^2i\frac{d}{dt}q\frac{itq}{t^21}=\frac{E}{t^21}+\frac{A}{t^2(t^21)}\frac{B}{(t^21)^2}+\frac{Ct^2}{t^21}\frac{q_1^2t^4}{t^21}$$
(47)
The quantization condition is

$$\frac{1}{2\pi }q(t)𝑑t=n$$
(48)
We expect 2$`n`$ moving poles on the entire real line as in Sec. IV, and fixed poles at $`t=0,\pm 1`$. These poles together with a pole of finite order at infinity lead to the condition

$$M=n.$$
(49)
which agrees with known condition of QES of this model.

## VII Conclusions

In the limit $`\mathrm{}0`$ QMF of the sextic oscillator goes to $`p_{cl}`$ which has six branch points. Therefore, in general we expect a complicated singularity structure for the sextic and also for other models studied in this paper. In the analysis presented in the previous sections it was assumed that there are no moving poles off the real axis. A closer look at the derivation of the condition of quasi-exact solvability shows that the assumption“ no moving poles of the QMF off the real axis ” can be replaced by a weaker assumption, “ QMF has a finite number of moving poles in the complex plane ” without altering any of the results. In fact it can be seen from explicit solutions in  that the algebraic eigen functions do have complex zeros. For all the models that have been studied here, the algebraic part of the spectrum and eigenfunctions are well known and in all the cases QMF has a pole at infinity. Thus we conclude that, for the class of potentials studied here, QES models are the only models for which QMF has a pole at infinity and a finite number of moving poles in the complex plane. For each model the known algebraic eigenfunctions correspond to QMF having singularity structure as postulated. For completeness it must be mentioned that the assumption of finite number of poles is not independent of the assumption that the point at infinity is a pole. For a large class of potentials which are analytic everywhere, except for isolated singularities, the moving singularities of solutions of QHJ can only be poles. An infinite number of such poles will, therefore, have an accumulation point at infinity and making it $`z=\mathrm{}`$ a non-isolated essential singular point.
The parameter $`n`$ that appears in the exact quantization condition is related to the number of moving poles in QMF and has different roles to play for ESM and QES models. In ESM each value of n corresponds to an energy level and an eigenfunction with $`n`$ real zeros. In case of the QES models, $`n`$ appears as a parameter in the expression for the potential and picks out a particular QES model within a family of potentials ; varying $`n`$ gives rise to a different potential within the family. Recalling that $`n`$ also determines the number of moving poles of the QMF it appears reasonable to expect that all the algebraic eigenfunctions for a given QES models (fixed $`n`$) will have the same number of the complex zeros determined by $`n`$. An explicit check reveals that this expectation is true for the sextic oscillator. A preliminary study reveals that, the poles of the QMF for QES periodic potentials have a richer structure. A detailed study of the location of the poles of the QMF in different QES models will be reported elsewhere.

Acknowledgments The authors acknowledge useful discussions with P.K. Panigrahi. KGG would like to thank UGC for the financial support. AKK acknowledges useful discussions with S. Chaturvedi and V. Srinivasan.

References

1. Singh V, Biswas S N, Datta K, 1978 Phys. Rev D18 1901
2. Ushveridze A 1994 Quasi-exactly Solvable Models in Quantum Mechanics (Bristol: Institute of Physics Publishing)
3. Gon$`\stackrel{´}{z}`$alez-L$`\stackrel{´}{o}`$pez A, Kamran N and Olver P J 1993 Commun. Math. Phys 153 117
4. Gon$`\stackrel{´}{z}`$alez-L$`\stackrel{´}{o}`$pez A, Kamran N and Olver P J 1994 Contemp. math 160 113
5. Bagchi B, Mallik S, Qussne C and Roychoudhary R (2001) Phys Lett A  289
6. khare A and Mandal B P (2000) Phys Lett A 272
7. Dunne G V and Shiffman M (2002)Annals Phys 299 143
8. Khare A (2001) Phys Lett A 288 69
9. Thatuk V M and Voznyak O (2002) Phys Lett A 301 177
10. Bender C M and Boettcher S (1998) Jour Phys A  Math and Gen 31 L273
11. Turbiner A V and Ushveridze A G (1987) Phys Lett A  126 No 3 181
12. Dunne G and Mannix J (1998) Phys Lett B 428 115
13. Panigrahi P K and Atre R, (under preparation) Quasi-Exactly Solvable Problems : A New Approach and an approximation Scheme
14. Leacock R A and Padgett M J, 1983 Phys. Rev. Lett. 50 3
15. Leacock R A and Padgett M J, 1983 Phys. Rev. D28 2491
16. Bhalla R S, Kapoor A K and Panigrahi P K 1997 Am. J. Phys. 65 1187 (1997).
17. Bhalla R S, Kapoor A K and Panigrahi P K 1997 Mod. Phys. Lett. A12 295
18. Jayanthi S 1998 Study Of One Dimensional Potential Problems using Quantum Hamilton Jacobi Formalism, M.Phil thesis submitted to the University of Hyderabad
19. Hautot A P 1972 Phys. Lett. 38A 305


format: text

text:
# Disproportionation Phenomena on Free and Strained Sn/Ge(111) and Sn/Si(111) Surfaces

\[

## Abstract

Distortions of the $`\sqrt{3}\times \sqrt{3}`$ Sn/Ge(111) and Sn/Si(111) surfaces are shown to reflect a disproportionation of an integer pseudocharge, $`Q`$, related to the surface band occupancy. A novel understanding of the $`(3\times 3)`$-1U (“1 up, 2 down”) and 2U (“2 up, 1 down”) distortions of Sn/Ge(111) is obtained by a theoretical study of the phase diagram under strain. Positive strain keeps the unstrained value $`Q=3`$ but removes distorsions. Negative strain attracts pseudocharge from the valence band causing first a $`(3\times 3)`$-2U distortion ($`Q=4`$) on both Sn/Ge and Sn/Si, and eventually a $`(\sqrt{3}\times \sqrt{3})`$-3U (“all up”) state with $`Q=6`$. The possibility of a fluctuating phase in unstrained Sn/Si(111) is discussed.

\]

Disproportionation, namely the spontaneous differentiation of initially equivalent sites into states of unlike valence or charge, is well known in solid state chemistry, for example in organic charge-transfer salts and also in transition metal and mixed valence rare earth compounds. Common features are an enlarged unit cell, due to ordering of the disproportionated sites, and the presence of a well defined quantum number (e.g., the valence) that is integer, even when the actual charge inbalance is generally not integer. Here we propose that a disproportionation, driven in this case by a different physics, but equally characterized by integer valencies, is at the origin of the well known but only incompletely understood two-dimensional phase transition observed in 1/3 monolayer Sn-covered Ge(111) and Si(111) surfaces. Moreover we present theoretical suggestions that the disproportionated state could be changed, or even removed altogether, by external strain.

The 1/3 monolayer Sn-covered Ge(111) and Si(111) surfaces have received considerable attention since the discovery of a transition from a room-temperature phase with $`\sqrt{3}\times \sqrt{3}R30^{}`$ periodicity to a low-temperature $`3\times 3`$ phase, first seen in Pb/Ge(111), then in Sn/Ge(111), and unsuccessfully searched for in Sn/Si(111). The main reason of interest lies in the electronic driving force behind the transition, namely the presence of a half filled surface state, suggestive of a two-dimensional surface charge-density wave (SCDW) mechanism. Recent X-ray data show that the transition is accompanied by static freezing and long-range ordering of a $`3\times 3`$ periodic structural distortion, consisting mainly of a “buckling” of Sn adatoms by $`0.35`$ Å along the surface normal. In the distortion, adatoms are generally believed to follow a “1 up, 2 down” (1U) pattern, but there is evidence that under some as yet unclear circumstances a non-negligible portion of the surface distorts with the opposite phase, namely a “2 up, 1 down” (2U) pattern. The precise mechanism underlying the phase transition has led to debate. While the driving role of the partly filled surface states is unquestioned, the 2D Fermi surface area and nesting properties of Sn/Ge(111) do not fit a $`3\times 3`$ periodicity as expected for SCDWs. Due to the large electron-electron repulsion, a Mott insulator or a spin-density wave state with negligible distortion could prevail, as in the isoelectronic case of SiC(0001). The large observed distortion and the order-disorder nature of the phase transition however rule out both the weak-coupling SCDW and the Mott insulator. First-principles electronic structure calculations, initially negative, later correctly favored the 1U distortion, with surface electronic bands in agreement with experiment. The calculated energy gain was about 10 meV/adatom, mostly of Jahn-Teller nature. Multi-band and bond-density wave aspects were also pointed out as crucial factors that stabilize the 1U distortion relative to the Mott insulator. Surprisingly, these calculations showed no energy gain for a 2U distortion, contrary to the known readiness of 2U to show up experimentally in Sn/Ge. The order-disorder character of the phase transition, well confirmed by simulations, is in agreement with the persistence of a 1U-like Sn $`4d`$ core level splitting in nominally undistorted Sn/Ge at high temperature. However a puzzling 2U-like persistent core splitting in apparently undistorted Sn/Si remains unexplained. Finally, substitutional defects play an important role. A Ge (Si) adatom replacing Sn acts as an electron donor in the Sn/Ge (Sn/Si) surface, triggering a local distortion of roughly 2U type. However the defect is also likely to exert a negative local strain, effectively squeezing the neighboring Sn adatoms outwards relative to the substrate, so that strain and charge donation apparently conspire. One is eventually led to wonder about the general role of strain, and about whether some of these open questions could be addressed by studying primarily the effect of strain on these surfaces. We report here the surprising results of a theoretical study of the Sn/Ge(111) and Sn/Si(111) systems under uniform strain. Besides predicting new strain-driven phase transitions, we find that these surface distortions are in the nature of disproportionation phenomena.

We carried out electronic structure calculations within the gradient corrected local density approximation (GC-LDA) where, in the absence of strain, a stable ($`3\times 3`$)-1U distortion was established for the Sn/Ge(111) surface, whereas Sn/Si(111) is still marginally undistorted. We used slab geometries consisting of three Ge (Si) bilayers, a planar $`3\times 3`$ cell with 18 atoms/bilayer, 3 Sn adatoms per cell in the $`T_4`$ position, and 9 hydrogen atoms saturating the bottom surface of the slab. We employed the PWSCF parallel code with a well checked plane-wave cutoff of 12 Ry, and k-summation schemes based on 6 Monkhorst-Pack k-points in the irreducible zone, extended when necessary to 16 and 36 k-points. We strained the slab cell isotropically in the surface plane, by increasing or decreasing its $`(x,y)`$ sides by up to $`\pm 5\%`$, full relaxation allowed along $`z`$, the surface normal, so that inside the slab the three dimensional strain tensor was effectively uniaxial. For each strain value, the stable surface geometry was sought for through a series of relaxation runs performed by constraining the value of the adatom buckling $`\mathrm{\Delta }z`$, (the $`z`$-difference between “up” and “down”adatoms) and relaxing all other atomic coordinates, except for the lowest Ge (Si) monolayer, held fixed and bulk-like (or strained), along with the saturating H layer.

Figure 1 summarizes the zero-temperature phase diagram versus strain, the order parameter and energy gain being given for the $`3\times 3`$ distorted state relative to the corresponding fully relaxed $`\sqrt{3}\times \sqrt{3}`$ state at the same strain, for both Sn/Ge and Sn/Si. At zero strain, in agreement with experiment and with previous calculations, Sn/Ge is 1U distorted, with $`\mathrm{\Delta }z0.34`$ Å, whereas Sn/Si is 0U (undistorted). Positive strain (in-plane expansion) causes Sn/Ge to lose its distortion, through a 1U-0U transition. By mechanically attracting the Sn adatoms closer to the Ge substrate, strain pushes the half filled dangling bond band upwards in energy towards the middle of the gap. In line with our earlier finding that the $`3\times 3`$ distortion is a multi-band effect, in this restored single-band situation the surface reverts to the undistorted $`\sqrt{3}\times \sqrt{3}`$ state. The resulting narrow half-filled surface band metallic state should actually be prone to other instabilities. We did check with spin-polarized calculations for a possible antiferromagnetic (Mott-Hubbard) state similar to that of isoelectronic SiC(0001); but up to 5% strain we did not find one, at least in Sn/Ge. Negative strain (in-plane compression) on the contrary pushes the adatoms upwards and that, beyond a critical strain of $`3\%`$, stabilizes a 2U distortion, with a 1U-2U transition in Sn/Ge, and a 0U-2U transition in Sn/Si. Within our approximation, the 2U order parameter $`\mathrm{\Delta }z`$ at $`\epsilon =4\%`$ is 0.49 Å with an energy gain with respect to the 0U configuration of 39.5 meV/adatom in Sn/Ge, and 0.4 Å with an energy gain of 30 meV/adatom in Sn/Si. In both cases the energy gain is suggestive of a 2U-disordered transition at relatively large critical temperature. At still larger negative strains $`5\%`$, all adatoms are finally forced up, with a 2U-3U transition, and an optimal 3U state for both Sn/Ge, and Sn/Si. This state should be seen as uniformly distorted – same symmetry as the “0U” undistorted $`\sqrt{3}\times \sqrt{3}`$ state, but with quite different physics as we shall see.

Closer examination of the distorted geometries reveals a striking feature: the Sn adatoms’ height above the substrate is bimodal, approximately quantized for all strains and states. A given Sn adatom can be either U or D, but not in between. This is reminiscent of static mixed valence, or disproportionated states, where an individual ion site is endowed with a choice between two integer valence states, the overall proportion between them controlled by a chemical potential. The valence state can either fluctuate dynamically with time, or be frozen in a static regular or irregular spatial pattern. In that case, all local properties, including the surrounding ion geometry, display a bimodal distribution. We found, by analysing the electronic structure, that in our case the role of effective valence is played by a surface state occupancy $`q`$, which is 2 in all U adatoms, 1 in all adatoms of the undistorted (“0U”) phase, 0.5 in D adatoms of the 1U phase of Sn/Ge, and zero in the D adatoms of 2U phases. This conclusion was established with the help of a separate Sn/Ge calculation, where a single Sn adatom was confined in the $`3\times 3`$ slab cell. The six remaining first-layer Ge atoms were saturated by six hydrogens, effectively decoupling the Sn adatom from its replicas. When a variable electron number was introduced with a net electron excess between $`1`$ and $`+1`$ (charge neutrality obtained through a matching uniform positive background), it was found that the population change was restricted to the Sn dangling bond surface state, its occupancy $`q`$ correspondingly varying from zero to 2. For each $`q`$ value, the total energy was minimized as a function of adatom height $`z`$ over the substrate, and the optimal $`z_0(q)`$ was determined. The calculations were repeated for various strains and the results reported in Fig. 2 (dashed lines). The comparison of the calculated $`z_0(q)`$’s with the individual adatom heigths previuosly calculated in the 0U, 1U, 2U and 3U stable phases of Sn/Ge is striking and provides a strong evidence of quantization of the individual $`q_i`$’s at four and only four heigth values, corresponding within a few percent error to the occupancies 2, 1, 1/2, and 0 indicated above. These quantized charges $`q_i`$ are actually pseudocharges, not to be confused with real, physical electron charges on the adatoms. An approximate Mulliken analysis of valence charges showed in fact that the actual charge redistribution among adatoms is always less than 0.1 $`e`$. A negligible redistribution of true, total charge is also in good accord with the observed $`4d`$ Sn core level splitting, consisting of one deep and one shallow levels in a 1:2 intensity proportion, attributable to U and D adatoms respectively. Had the true charge inbalance even only resembled that of the pseudocharges, $`2`$ and $`0.5`$ for U and D adatoms, respectively, the sign of the splitting should have been the opposite, and its magnitude much larger. We calculated the magnitude of the core level splitting between U and D adatoms in Sn/Ge-1U in the final-state approximation, and obtained 0.20 eV, in reasonable agreement with 0.32 eV, observed both in ($`3\times 3`$)-1U and for the high temperature $`\sqrt{3}\times \sqrt{3}`$ phase of Sn/Ge(111). The split core level intensity ratio should be instead 2:1 for a 2U distorted surface, the U and D adatoms being now in that proportion, opposite to the 1:2 of the 1U case. Repeating our core level calculation for the $`3\%`$ strained Sn/Si(111) ($`3\times 3`$)-2U surface we obtained a Sn $`4d`$ splitting of $`0.20`$ eV, in qualitative agreement with $`0.4`$ eV observed on the nominally undistorted Sn/Si(111) $`\sqrt{3}\times \sqrt{3}`$ surface. We shall return to this point below.

We are now in a position to address directly the physics behind the pseudocharge and its disproportionation, with and without strain, in connection with the electronic structure. In the 0U $`\sqrt{3}\times \sqrt{3}`$ phases, the surface state band is isolated inside the gap, each adatom contributing one electron to it, whence $`q_i=1`$ and $`Q=\mathrm{\Sigma }q_i=3`$. This is an undistorted metal state, at least within GC-LDA. In the ($`3\times 3`$)-1U phase, the surface band hybridizes much more with the valence bands, especially with the Ge-Ge bonding state directly underneath the adatom. There is still on average one electron/adatom; however the total pseudocharge $`Q=3`$ per cell disproportionates, $`q=2`$ electrons now filling the U adatom’s dangling bond (Figure 3a), the remaining one shared between the other two D adatoms, each with $`q=0.5`$. The onset of the ($`3\times 3`$)-1U ground state in Sn/Ge is thus favored by the small Ge bandgap, and by the consequent energy proximity of the surface band to bulk valence bands. That is consistent with the absence of distortion in Sn/Si(111), and in SiC(0001), where the surface band is more isolated in the wider bandgap. In the strain-induced 2U phase, both U adatoms have $`q=2`$, while D has $`q=0`$. The total pseudocharge $`Q`$ is now 4: one extra electron has been drawn from bulk valence bands into the surface band. For strain values in the 2U range, the surface bands (Figure 3b) drop in fact enough in energy to overlap the bulk valence bands, now slightly above $`E_F`$. Furthermore, because the difference $`q_Uq_D`$ is greater than in the 1U phase (2 compared to 1.5), the optimal distortion is larger (0.49 Å compared to 0.34 Å in Sn/Ge). The 2U distortion amplitudes and energy gains are correspondingly smaller in the stiffer, wide-gapped Sn/Si. Finally, in the ($`\sqrt{3}\times \sqrt{3}`$)-3U phase, all adatoms are equivalent with $`q=2`$. The surface band lies entirely below $`E_F`$, and 3 electrons are transferred from bulk to surface, so that $`Q=6`$. In this sense, the 3U state is fundamentally different from the 0U state, despite its sharing the same symmetry. In all these distorted states, the surface state band breaks up into narrow adatom-localized levels. Their filling and emptying leads to a Jahn-Teller-like energy gain, and that explains the quantization of the pseudocharge $`q`$. Negative strain acts as a chemical potential, and disproportionation arises out of the necessity to distribute an increasing electron number through integer surface state occupancies. In chemical terms, U adatoms could perhaps be compared with “tetravalent” Sn, D to “divalent” Sn.

These results and predictions should be amenable to experimental test, particularly if the strains required to provoke the transitions could realistically be introduced, e.g., by heteroepitaxy. Even if our calculated critical strain values are probably affected by systematic errors of order 1–2%, connected with lattice parameter errors and with imperfect handling of incipient strong correlations by the density functional calculation, the strain-induced sequence of transitions seems inescapable. Among the phenomena that are already observed, the 2U patches reported on Sn/Ge seem now very likely to be induced by some local strain. The puzzling 2U core level signature of nominally unstrained Sn/Si is likely to be due to a dynamical, fluctuating 2U state. Assuming in fact a 0U-2U zero-temperature, classical transition to occur in reality at some small positive strain (instead of a small negative strain as in the GC-LDA calculation), the long range order could simply be destroyed by thermal fluctuations, still leaving a local 2U distorted structure. Of additional interest is the possibility of quantum mechanical fluctuating states, analogous to dynamical mixed valence. Close to the critical strain values separating two classical distortion states, such as 0U-1U, 0U-2U, 1U-2U, 2U-3U, tunneling across low barriers could lead to quantum melting of the classical long-range order. This kind of polaronic state could entail the exotic but real possibility of surface state superconductivity when, as the case for 0U-2U, the pseudocharge fluctuation takes place in units of two, thus realizing a bipolaron state. The large distortions involved suggest however that this novel strong-coupling surface polaronic metals and bipolaronic superconductors might be attainable only at very low temperatures.

This work was supported by MIUR through COFIN, and by INFM through INFM/F and ”Iniziativa Trasversale Calcolo Parallelo”. We are grateful to S. Modesti for his invaluable help.


text:
# Torsional response and stiffening of individual multi-walled carbon nanotubes

## Abstract

We report on the characterization of torsional oscillators which use multi-walled carbon nanotubes as the spring elements. Through atomic-force-microscope force-distance measurements we are able to apply torsional strains to the nanotubes and measure their torsional spring constants and effective shear moduli. We find that the effective shear moduli cover a broad range, with the largest values near the theoretically predicted value. The data also suggest that the nanotubes are stiffened by repeated flexing.

The motivating vision of the future for nano-electro-mechanical systems (NEMS) Craighead00 ; Erbe01 ; Cleland98 ; Yang01  is the emergence of high frequency, high sensitivity devices which are commercially useful and also will serve as nanolabs for fundamental investigations into physics of the mesoscale. The goal of high mechanical resonance frequency along with high sensitivity (high quality factor $`Q`$) requires that devices are small (low mass), stiff (high elastic modulus) and structurally defect free (low phonon scattering). Carbon nanotubes (CNTs) may provide several advantages over etched bulk semiconductors in this regard. They are naturally nanometer-scale objects, so little processing of the CNT itself is required. Furthermore, their surfaces are atomically ordered, and they have relatively low chemical reactivity, so they may not suffer from some of the surface-to-volume ratio issues that limit the $`Q`$ of semiconductor-based devices Lifshitz00 ; Carr99 .

Because of these factors as well as their unique mechanical and electrical properties Postma01 ; Bachtold01 , CNTs may be ideal candidates for use in NEMS. Nevertheless, there have been only a handful of reports of CNTs used in an electromechanical setting Poncharal99 ; Kim99 . We report here on the incorporation of CNTs into nano-electro-mechanical devices which allows the direct measurement of the CNTs’ torsional properties.

Torsional or ”paddle” oscillators are commonly studied MEMS structures Cleland98 ; Evoy99 ; Carr00 . We fabricate paddle oscillators with multi-walled carbon nanotubes (MWNTs) as the spring elements (Fig. 1). Fabrication is described in detail elsewhere Williams02b . Briefly, MWNTs are dispersed onto silicon wafers which have 400-500 nm of oxide. Electron-beam lithography is used to pattern large metal pads over the two ends of each MWNT to pin them down, and a strip of metal over the center of each MWNT to form the paddle. The metal is thermally evaporated, 15 nm of Cr followed by 100 nm of Au. The oxide is etched such that the paddles are completely undercut but the larger pads pinning the MWNT ends are not Nygard01 . The samples are then critical-point-dried.

Force measurements are performed in a hybrid atomic force microscope (AFM)/scanning electron microscope (SEM) system; a Thermomicroscopes Observer AFM mounted inside a Hitachi S-4700 cold-cathode SEM. Using coarse-translation motors, we position the AFM tip above a paddle such that the entire paddle is within the range of the AFM scan tube. Vertical force vs. distance curves are taken at positions along the length of the paddle. Figure 2 shows an example of a force vs. distance curve in progress, and typical curves resulting from such measurements. In all of our analyses, we use the data taken while the tip is being extended towards the sample. The data taken during tip retraction are similar. The AFM cantilevers are Si Nanosensor cantilevers with nominal resonance frequencies of 70-80 kHz and force constants $`K_c=13`$ N/m.

With the AFM we can apply forces to the paddles and measure their displacements. We use these data to deduce the torsional properties of the MWNT spring-elements. Before performing a quantitative analysis, we check the assumption that the MWNTs twist uniformly along their lengths, rather than being strained in a localized region. We fabricated a device with two paddles suspended from one MWNT (Fig. 1b). When one of the paddles was tilted with the AFM tip such that its end was pinned to the substrate, the other deflected by about half as much (Fig. 1c). The suspended portions of the MWNT are all of similar length, so this suggests that the MWNT is uniformly strained.

To measure force quantitatively with an AFM, we must characterize the AFM cantilever. We measure its dimensions with the SEM and its resonance frequency with the AFM. These values are used to calculate the spring constant ($`K_c`$) of the cantilever. Also, vertical force-distance traces, which result in linear plots of photodiode signal vs. piezo-distance-traveled ($`Z_p`$), are taken on the substrate. Under the assumption that the substrate is effectively an infinitely hard surface, the slopes of these traces ($`S_{sub}`$) give us the relationship between the detector signal and the cantilever deflection (Fig. 2d) Luthi95 .

To characterize an oscillator, vertical force-distance curves are taken on the paddle itself, which yield traces with slopes $`S_{pad}`$ (Fig. 2d). The force applied to the paddle is $`F=K_cZ_p\frac{S_{pad}}{S_{sub}}`$ and the vertical displacement of the point of contact with the AFM tip is $`\mathrm{\Delta }Z=Z_p(1\frac{S_{pad}}{S_{sub}})`$. The torsional compliance of the MWNT can be described by a torsional spring constant ($`\kappa `$), which relates the applied torque ($`T=F(xx_0)`$, where $`xx_0`$ is the lever arm from the axis of the MWNT) to the angular deflection ($`\theta `$) of the paddle. The vertical compliance can be characterized by a vertical spring constant ($`K_z`$), which relates $`F`$ to the vertical displacement ($`\mathrm{\Delta }h`$) of the MWNT pivot-point paddlestiff :

$$T=\kappa \theta ,F=K_z\mathrm{\Delta }h.$$
(1)
$`\mathrm{\Delta }h`$ and $`\theta `$ combine to yield the displacement of the point of contact with the AFM tip, $`\mathrm{\Delta }Z=\mathrm{\Delta }h+(xx_0)\theta `$. Combining these equations, we obtain:

$$S_{pad}=\frac{S_{sub}}{1+\frac{K_c}{K_z}+\frac{K_c}{\kappa }(xx_0)^2}.$$
(2)
On each paddle, we measure the slopes from a series of force-distance curves at various positions $`x`$. Equation 2 is fit to the resulting points to yield $`K_z`$ and $`\kappa `$.

The panels in Fig. 3, from left to right, depict three sets of data consecutively measured on device C. It is surprising, therefore, that $`\kappa `$ changes from one panel to the next. A rise in $`\kappa `$ is seen in all of the devices we measure, and the percent change in $`\kappa `$ from one pass to the next is roughly correlated with the number of deflections performed in the previous pass. $`\kappa `$ values for some of our measurements are summarized in Table 1.

We also positioned the AFM tip near the end of paddle D and repeatedly performed vertical force-distance measurements (Fig. 4). After 330 force curves, the tip was moved away from the device and then returned to within 50 nm of the original position. In spite of the break in the data, the trend is clear; the effective torsional stiffness of the paddle increases until about 400 deflections are performed, and then it saturates, showing a net change in stiffness of about an order of magnitude.

In principle, the MWNT could be accruing amorphous carbon deposited during SEM imaging of the device, but this is unlikely to explain its change in stiffness. In Fig. 3, we imaged the device during pass 1, but we turned off the electron beam for the next two passes, and the stiffness still increased. For the data in Fig. 4, the electron beam was off for most of the measurement, but the stiffness increases smoothly. After the measurements on the paddles were completed, we used the AFM to image the edges of the regions the SEM had been scanning, and saw no topographical step. The AFM has a vertical resolution on the order of 1 nm, so if a significant thickness of carbon had been deposited during the measurement, it would have appeared as a topographical feature in the AFM image. To show that the stiffening is not an instrumental artifact, both $`S_{sub}`$ and the cantilever resonance frequency were measured before and after each experimental run, and they showed no significant change. Also, we repeatedly deflected one AFM cantilever with another $`600`$ times and saw no change in stiffness. This implies that the repeated twisting of the nanotube is making it stiffer! The shear strain applied to the MWNT was typically $`0.5\%`$. The applied tensile strain was very small.

Most existing studies focus on the tensile properties of CNTs; we look to these results to gain some insight. Experiments have shown that MWNTs can withstand tensile strains of between 10% and 20% before breaking Falvo97 ; Yu00 , although details of the structural behavior before the actual break are not known. Simulations of single-walled nanotubes under tension predict that Stone-Wales defects can form at tensile strains of $`5\%`$ and defect motion may occur at tensile strains as low as $`3\%`$ Nardelli98 . We are repeatedly applying shear strains of about $`0.5\%`$ to the MWNTs, and few times in each pass approaching $`1\%`$. There are two structural changes that could stiffen the MWNTs. The individual shells of the MWNTs could be stiffened or the mechanical coupling between different shells could be increased. It is unlikely that changes in the connection between the nanotube and either the pinning metal or the paddle would result in an increase in device stiffness. Mechanical flexing of those joints would be expected to weaken them, which would result in a decrease in measured stiffness.

From the $`\kappa `$, and the paddle dimensions, we can calculate the devices’ expected torsional resonant frequencies, which are in the 1-10 MHz range. In principle, we should also be able to extract $`K_z`$ from our fits to Eqn. 2. For most of the devices, however, including device C shown in Fig. 3, $`S_{pad}`$ at $`(xx_0)=0`$ is within experimental error of $`S_{sub}`$. This means that there is negligible vertical deflection of the paddle, and that $`K_c/K_z0`$. We cannot accurately measure $`K_z`$ using a cantilever with $`K_c<<K_z`$. Nevertheless, given our experimental uncertainty in $`K_c`$, we can estimate a lower bound for $`K_z`$. We return to this point below in our discussion of moduli.

In order to make comparisons between MWNTs of different dimensions, we use the continuum mechanics model for the shear ($`G`$) and Young’s ($`E`$) moduli. We use beam bending equations Young89  combined with Eqs. 1:

$$\kappa =\frac{\pi (r_{out}^4r_{in}^4)G}{2l},K_z=\frac{48\pi E(r_{out}^4r_{in}^4)}{l^3},$$
(3)
where $`r_{out}`$ and $`r_{in}`$ are the outer and inner radii and $`l`$ are the lengths of the suspended MWNT sections. Since the moduli depend on $`r_{out}^4r_{in}^4`$, taking $`r_{in}`$ to be 0 yields moduli only $`6\%`$ smaller than taking $`r_{in}/r_{out}`$ to be $`0.5`$. Based on TEM observations, $`r_{in}`$ of our arc-grown MWNTs are typically much less than half of $`r_{out}`$. We therefore approximate the MWNTs as solid cylinders and calculate effective shear moduli $`G_e`$, which are summarized in Table 1.

Uncertainty in $`r_{out}`$ contributes the bulk of the uncertainty in $`G_e`$. AFM $`r_{out}`$ measurements of the metal surface under which the MWNTs were buried, and of MWNTs pushed down to the substrate with the AFM tip, varied by more than a factor of two for a given MWNT. The $`r_{out}`$ reported in Table 1 were arrived at by averaging the full-width at half-maximum of the SEM image brightness along lines perpendicular to the suspended MWNTs. Applying this technique to multiple SEM images of the same MWNT, taken under different imaging conditions (i.e. different image brightness, secondary electron detector, etc.), yielded a variation in the measured $`r_{out}`$ of about $`20\%`$, corresponding to an uncertainty in $`G_e`$ of about a factor of 2. It is also possible that there is a systematic error in the estimation of $`r_{out}`$ from SEM images, which can exaggerate nanotube diameters.

As mentioned, the MWNTs increased in stiffness as the experiment progressed. Since the cause of this increase is still unknown, we initially discuss data from the first pass on each paddle, where the MWNT has been least affected by the experiment. The $`G_e`$ calculated from the first pass on each paddle range over about an order of magnitude. We hypothesize that these differences are due to differences in the mechanical coupling between the shells of the MWNTs in the various devices. Cumings and Zettl have shown, by pulling inner shells of a MWNT out from the outer ones, that it is possible to have a very low intershell mechanical resistance Cumings00 . Yu’s et al. study of the tensile failure modes of MWNTs shows that the individual shells are not equally strained in all MWNTs, since some break at widely separated places along the tube’s length Yu00 . Our wide range of $`G_e`$ suggests that in some MWNTs, the stress is evenly distributed among many shells, while in others the stress is concentrated only in the outer shell or few shells while the inner ones slide easily. Since our MWNTs are clamped by evaporating metal onto their outer shells, it is conceivable that the inner shells may be sliding both where the MWNTs pass through the paddle and where they pass through the metal pinning the MWNT ends. Observations have shown that some MWNTs have circular cross-sections, while others have polygonal cross-sections Liu94 . Such polygonal MWNTs could have greater inter-shell coupling than circular MWNTs under rotational strain. This would explain the large range of effective $`G_e`$ calculated from the solid rod model where the entire diameter of the MWNT is assumed to share the stress. Other contributors to the large range of measured $`G_e`$ could include defects in the MWNTs or imperfect pinning of the nanotubes within the metal.

In Ref. Lu97, , using a model which assumes that all shells are strained, Lu predicted $`G=541`$ GPa for a ten-wall 7.8 nm-diameter CNT. For comparison, in diamond $`G=576`$ GPa and in graphite the basal plane $`G=440`$ GPa. Our largest measured $`G_e`$ are consistent with the theoretical value. The experimental values which fall below this prediction can be explained by sliding of the inner shells when only the outer shell or few shells are clamped by the evaporated metal. Indeed, assuming that only the outer shell carries the load, and using the inter-shell spacing as the effective thickness of that shell, we can calculate a shell shear modulus $`G_s`$. Some of these results are also in Table 1. For devices B, C, and D, which initially have small $`G_e`$, $`G_s`$ is near the theoretical value. The stiffening of the MWNTs with repeated twisting suggests that the inter-shell coupling can be modified. Both devices B and D are stiffened by more than on order of magnitude, resulting in $`G_e`$ consistent with the theoretical values. It is noteworthy that device D shows a saturation at this value. These results are consistent with the idea that, initially, only the outer shell is strained, and that repeated deflections increase the inter-shell coupling until all shells are strained. A more accurate $`r_{out}`$ measurement is required to confirm this conclusively. For Young’s modulus, if we calculate lower bounds using the lower bound values of the $`K_z`$, we find $`E`$ is typically greater than a few hundred GPa, which is consistent with previous experimental and theoretical results Yu00 ; Lu97 .

In conclusion, we have fabricated and characterized CNT paddle oscillators. We repeatedly apply torsional strains to the MWNT spring-elements and measure their torsional spring constants. We find that the MWNTs become stiffer with repeated deflection. The effective shear moduli of the nanotubes calculated by approximating the MWNTs as solid cylinders vary by nearly two orders of magnitude, from near the theoretically predicted value to significantly less than it. The results suggest that the inter-shell mechanical coupling varies widely from one MWNT to the next and can be modified by applying strain.

###### Acknowledgements.

We thank the ONR and the NSF for funding for this project.


text:
# Cyclical Quantum Memory for Photonic Qubits

## Abstract

We have performed a proof-of-principle experiment in which qubits encoded in the polarization states of single-photons from a parametric down-conversion source were coherently stored and read-out from a quantum memory device. The memory device utilized a simple free-space storage loop, providing a cyclical read-out that could be synchronized with the cycle time of a quantum computer. The coherence of the photonic qubits was maintained during switching operations by using a high-speed polarizing Sagnac interferometer switch.

One of the most attractive features of an all-optical approach to quantum computing is that photons can serve as ideal carriers of quantum information in a modular system connecting various quantum logic gates and memory devices. However, the implementation of the memory devices and logic gates is difficult in an optical approach because photons are relatively difficult to store, and nonlinear interactions between single photons are typically very weak. Although recent developments in linear optics quantum computing  have shown that logic gates can be operated  without direct nonlinear interactions, the implementation of a practical quantum memory for photons remains a challenging problem. In this paper we report on a proof-of-principle experimental demonstration of a such a quantum memory device.

Earlier suggestions for a quantum memory for photons have involved storing the quantum states in high-Q cavities  or reversibly transferring them to collective atomic excitations (see, for example ). In contrast, the quantum memory demonstrated here is based on the storage of single-photons in a simple free-space optical loop . The photons stored in this loop can be switched out after any number of round trips, providing a cyclical quantum memory (CQM) that could be synchronized with the cycle time of an optical quantum computer.

The CQM presented here is an extension of our earlier work on a source of single-photons on pseudo-demand, which was realized by using straightforward polarization-based electro-optic switching techniques to release single-photons from a storage loop at a desired time . The key requirement in converting that system into the present cyclical quantum memory device was the development of interferometric-based switching techniques that work equally well for any polarization state, and are capable of maintaining the coherence of the polarization-encoded single-photon qubits. As will be described below, this was accomplished by using a high-speed electro-optic device to apply controlled $`\pi `$-phase shifts in a balanced polarizing Sagnac interferometer. During each passage through the interferometric switch, the output port taken by the photon could be controlled by the $`\pi `$-phase shifts, thereby sending the photon back into the storage loop for another cycle, or releasing it from the memory device.

A schematic illustrating the basic features of the CQM is shown in Figure 1. The polarizing Sagnac interferometer switch is formed by mirrors $`m_a`$ and $`m_b`$, and a polarizing beamsplitter (PBS) which reflects vertical polarizations and transmits horizontal polarizations The electro-optic device (EO) inside the interferometer is a Pockels cell that is configured in such a way that when it is turned “on” it will rotate horizontal polarizations into vertical, and vice-versa ($`|H|V`$), and when it is turned “off” it will do nothing. The storage line is formed by the upper port of the PBS and mirror $`m_c`$.

The logical values 0 and 1 are represented by the horizontal and vertical polarization states of a single-photon, so that an input qubit has the form $`|\psi _{in}=\alpha |H+\beta |V`$, where $`\alpha `$ and $`\beta `$ are arbitrary coefficients. A qubit enters the CQM device from the right, and much of the operation of the device can be understood by first considering the case when the Pockels cell is never turned “on”. In this case, the vertical component of the incident qubit travels clockwise through polarizing Sagnac and is reflected up into the storage line, while the horizontal component travels counter-clockwise and is transmitted up into the storage line. Upon reflection from mirror $`m_c`$, the process essentially runs in reverse, providing an output state $`|\psi _{out}`$ after one cycle of the quantum memory.

If there were no losses and no polarization-dependent phase shifts, the output state would emerge in the same coherent superposition state as the input, $`|\psi _{out}=|\psi _{in}`$. Although there were, of course, losses and small birefringent phase-shifts in our experiment, the practical benefit of the polarizing Sagnac interferometer is that the counter-propagating horizontal and vertical components experience the same physical path, essentially eliminating the much larger thermally or vibrationally induced phase shifts that would otherwise ruin the coherence of the qubit in, for example, a comparable Mach-Zehnder interferometer.

In order for the CQM to store the qubit for more than one cycle, the Pockels cell must be quickly turned “on” while the photon is propagating in the storage line for the first time. Upon subsequent passes through the Sagnac interferometer, the counter-propagating horizontal and vertical components of the qubit are therefore repeatedly flipped ($`|H|V`$), and the photon remains trapped in the device as long as the Pockels cell is left “on”. When the Pockels is finally turned “off”, it can be seen that the final values of the counter-propagating components are those required to release the photon from the device.

Consequently, one of the interesting features of the CQM is that qubits stored for an even number of cycles emerge as the bit-flipped value of input qubit, $`|\psi _{even}=\widehat{\sigma }_x|\psi _{in}=\alpha |V+\beta |H`$, while qubits released after an odd number of cycles are not bit-flipped, $`|\psi _{odd}=|\psi _{in}`$. For quantum computing applications, the feed-forward control techniques that we have previously demonstrated  could be used to re-flip qubits read-out after even numbers of cycles in the CQM; alternatively, the CQM round-trip time could be designed to be half the cycle time of the computer.

For all of the data that will be presented in this paper, the qubits were prepared in the arbitrarily chosen superposition state:

$$|\psi _{in}=\frac{\sqrt{3}}{2}|H+\frac{1}{2}|V$$
(1)
which corresponds to a linear polarization state at $`30^o`$. A graphical representation of the expected output qubits after both even and odd numbers of cycles is shown in Figure 2.

A more important consequence of the repeated flipping of the polarization components is that certain types of errors automatically correct themselves. For example, unwanted polarization-dependent phase shifts imparted in the storage line affect each of the two components of the original qubit an equal number of times for those qubits switched out after an even number of round trips. As a result, the accumulated relative phase-shift becomes an overall phase-shift that simply factors out of the final state. Similarly, the net relative phase shift error of this kind for qubits switched out after an odd number $`n`$ of cycles is only that due to the final round-trip, and not the accumulation of the phase errors due to the previous $`n1`$ round-trips.

A schematic representation of the actual experiment, which utilized true heralded single-photons from a parametric down-conversion source , is shown in Figure 3. As shown in the upper part of Figure 3, our down-conversion source consisted of a 1 mm thick BBO crystal pumped by roughly 30 mW of the 351.1 nm line of a continuous-wave Argon-Ion laser. The crystal was cut for Type-II degenerate phase matching and produced pairs of collinearly propagating, but orthogonally polarized photons at 702.2 nm . The photons of a given pair were separated by a polarizing beamsplitter (PBS-1). The detection of the “trigger photon” by detector $`D_t`$ signalled the presence of the “qubit photon”, and provided a relative start time for the cyclical device.

The polarizing Sagnac interferometer switch, which can be seen in roughly the center of Figure 3, was formed by polarizing beamsplitter PBS-2, and mirrors $`m_1`$ through $`m_3`$. The Pockels Cell (PC) was placed inside the Sagnac, with its fast axis rotated by $`45^o`$ from the vertical direction. An additional half-wave plate (labelled $`\frac{\lambda }{2}^{}`$) was inserted next to the PC; this half-wave plate was usually oriented so that it had no effect, but it could be rotated as needed for various diagnostic tests during initial alignment.

The storage line was formed by the upper port of PBS-2 and mirrors $`m_4`$ and $`m_5`$ (the storage line was folded due to space constraints). The length of the storage line was roughly 3.5 m which, when combined with the .5 m length of the Sagnac, gave a total round-trip time of roughly 13.3 ns, which was longer than the 10 ns rise-time of the Pockels cell, as required . In order to minimize beam divergence and maximize the possible storage time (number of cycles) of the CQM, a 1 m focal length lens was placed in the storage line, and longitudinally adjusted to form a standard 2f Gaussian transmission line.

The qubit state preparation was implemented by using a half-wave plate (labelled $`\frac{\lambda }{2}`$) to rotate the vertical polarization of the qubit photon to any desired linear polarization state. The state of the output qubit was measured using a polarization analyzer ($`\theta _q`$) and another single-photon detector $`D_q`$. Background noise was reduced to a negligible level by using 10 nm bandwidth filters (f) centered at 700 nm in front of the trigger and qubit photon detectors.

In order to allow for the time required to produce and process the classical detection signal of the trigger photon, the qubit photon was delayed by a 120 m fiber optic delay line before being sent into the CQM . A standard fiber polarization controller (fpc) was used to negate the effects of birefringence in the fiber, as well as to pre-compensate for small birefringent phase-shifts of three additional steering mirrors (not labelled) and a 50/50 non-polarizing beamplitter (NPBS) that was used to couple the qubits into the CQM input channel.

The electronics used for the real-time active switching, which are seen in the lower part of Figure 3, are described in detail in reference . Briefly, the “on” to “off” transitions of the Pockels Cell were driven by the front and back edges of two different pulses ($`p_1`$ and $`p_2`$ from delay generators GD1 and GD2), which allowed the use of TTL pulses whose width (100ns) was greater than the cycle time.

The accumulation of data involved the use of conventional coincidence counting techniques to record the time of arrival of the qubit photon at detector $`D_q`$ relative to the arrival time of the trigger photon at detector $`D_t`$. Accumulated histograms of data would therefore show various peaks separated by 13.3 ns time intervals, corresponding to different numbers of round trips through the CQM.

The data shown in Figure 4 demonstrates the ability to actively switch out the qubit after a chosen number of cycles through the CQM. For the data shown in Figure 4, the qubit polarization analyzer $`\theta _q`$ was removed in order to clearly demonstrate the switching performance and assess any losses in the CQM. The area under the peak of interest in each successive plot is seen to decrease in approximate agreement with the 19% loss per cycle that was measured in auxiliary experiments . Of this 19%, we estimate that roughly 15% was due to reflection and transmission losses of the various optical components, with the remaining 4% being due to imperfect focussing in the 2f Gaussian transmission line. Small switching errors  which resulted in undesired noise peaks can also be seen in Figure 4.

A test of the key feature of the CQM, the ability to maintain the coherence of the stored qubits, is summarized in Figure 5. For the data shown in Figure 5, the qubit polarization analyzer $`\theta _q`$ was used to measure the polarization states of the stored qubits and compare them with the predicted output states shown in Figure 2. For qubits stored for an odd number of cycles the output states in Figure 5 are seen to be in good agreement with the linear input polarization state of $`30^o`$, while for even number cycles the expected (bit-flipped) linear polarization output state at $`60^o`$ is evident.

For each of the successive plots in Figure 5 the maximum counting rate and the quality of the output state is seen to decrease for qubits stored for longer times, as might have been expected. We believe the degradation of the qubit quality was primarily due to small misalignments of the mirrors, which produce spatial offsets that accumulate with each round-trip and can reduce the spatial overlap of the horizontal and vertical components in the output, thereby reducing the interference conditions required to maintain the coherence of the qubit. We expect to be able to greatly reduce these errors by using fiber optic components in future implementations of the CQM.

In conclusion, we have performed a proof-of-principle demonstration of a new type of all-optical cyclical quantum memory device (CQM) based on the storage of photonic qubits in a simple free-space optical loop. The ability to maintain the coherence of the qubits was accomplished here by the application of electro-optic-based controlled $`\pi `$-phase shifts in a balanced polarizing Sagnac interferometer switch . An optical approach to quantum computing will most likely involve the use of trains of intense laser pulses, such as those from mode-locked Ti-Sapphire lasers. Because these pulse trains provide a natural clock cycle, a cyclical quantum memory device of the kind presented here should be ideally suited for an optical approach to quantum computing, and these initial experiments may provide a first step in that direction.

This work was supported in part by ONR, ARO, NSA, ARDA, and IRAD. We would like to acknowledge useful discussions with B.C. Jacobs, M.J. Fitch, and M.M. Donegan.