surface science

ELSEVIER Surface Science 386 (1997) 115 123 ,

Fundamental considerations in the manipulation of a single C60 molecule on a surface with an S T M

H. Tang a M.T. Cuberes b, C. Joachim a.., J.K. Gimzewski b
a CEMES-CNRS, 29, Rue J. Marvig, 31055 Toulouse, Cedex, France b IBM Research Division, Science and Technology, Zurich Research Laboratory, CH-8803 Raschlikon, Switzerland

Received 5 November 1996; accepted for publication 4 February 1997

Abstract
We discuss the conditions needed to perform mechanics on the nanoscale. Various modes for adsorbates manipulation using a scanning tunneling microscope (STM) are presented. Amongst those, which include sliding, pulling and pushing, we find that molecules such as fullerene C6o are repositionable by pushing. This mechanism is modeled using molecular mechanics calculations, which provide the threshold STM tunnel junction resistance necessary to translate C6o parallel and perpendicular to a step edge on a Cu(100) surface. Perpendicular translation provides the opportunity for more complex mechanics on the nanoscale such as the control of the kinetic energy of a single adsorbate. 1997 Elsevier Science B.V.
Keywords." Diffusion and migration; Fullerenes; Scanning tunneling microscopy; Semi-empirical models and model calculations; Surface diffusion; Tunneling

1. Introduction
In the macroscopic world, the law of inertia, the equations of motion and the law of action and reaction constitute the basis of Newtonian mechanics [1 ]. The ability offered by the scanning tunneling microscope (STM) to manipulate molecules on a individual basis [2,3] opens the way to perform mechanics on the nanoscale and to compare their differences with macroscopic scale mechanics. On the nanoscale, mechanics differ arising from the ultra low masses of the objects (10 -21 g), from the very small momentum transfer and from the large number of internal degrees of freedom in a molecule. However, the internal
* Corresponding author. Tel: (+ 33) 5 62257800; fax: (+ 33) 5 62257999; e-mail: joachim@cemes.fr 0039-6028/97/$17.00 1997 Elsevier Science B.V. All rights reserved. P l l S0039-6028 ( 97 ) 00308-7

behavior of recently synthesized molecular shuttles [4] or turnstile molecules [5] are usually described in terms of the macroscopic mechanics. Furthermore, chemistry at the nanoscale may be viewed as a particular branch of mechanics: two reactants adsorbed on a surface can actually be forced to react if controlled scattering occurs between them [6]. In this paper, the mechanical operations, which can be achieved experimentally using an STM, with a single C6o adsorbed on a metal surface are discussed in terms of the laws of inertia and actionand-reaction. In Section2, the important role played by the surface diffusion barrier as opposed to the adsorbate mass on the nanometer scale is analyzed. In Section 3, different STM manipulation modes of an adsorbate are discussed in relation to the experimental repositioning of a C6o

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molecule with an STM tip. This repositioning is calculated along a step edge with and without the presence of a kink site. In Section 4, the pushing of a C6o molecule perpendicular to the step edge is considered and the analysis compared with experimental data. Finally, based on these results, we discuss future directions and open questions relating to intramolecular mechanics on the nanoscale.

2. What is the role of inertia on the nanoscale?

Fig. 1. UHV-STM constant current image of a single C6o molecule stabilized at room temperature by a mono-atomic step edge 2.54 ,~, in height of a Cu( 111 ) surface.

The corrugation of the potential energy surface creates conditions to stabilize an adsorbate position on a given surface site. Below a given threshold surface temperature and with no net force applied to the adsorbate, it will not experience acceleration. However, the inertia law does not exactly hold here. This is because it is the diffusion barrier height rather than the adsorbate mass which controls the relation between the net force applied to the adsorbate and its resulting acceleration. The associated threshold temperature depends both on the chemisorbed or physisorbed character of adsorption process and on surface electronic corrugation [7]. For example, the threshold value is below a temperature of 10 K for a rare gas atom such as Xe physisorbed on a metallic (110) surface [8]. In contrast, conditions can be found for large molecules to be readily immobilized on metallic surfaces even at room temperature [3]. To perform mechanics with an STM tip on a molecule such as the fullerene C6o, it is essential to firstly stabilize its lateral position at T= 300 K. Experimentally, the adsorption of C6o molecules on Cu( 111 ) was imaged with a ultra-high vacuum (UHV) STM (Fig. 1). At room temperature, the molecules were found to both be immobilized and nucleated along atomic step edges or on defect sites as illustrated in Fig. 1. A step edge creates an energy potential guide or "groove" for repositioning to be feasible at room temperature. To gain an understanding on this "groove", we have calculated the energy barrier for surface diffusion of a C6o molecule on a Cu(100) surface modeled with a single mono-atomic step (Fig. 2). In the model, C6o was considered physisorbed on

this surface which is a justified approximation since the metal Fermi level lies within the C6o Highest Occupied Molecular Orbital-Lowest Unoccupied Molecular Orbital (HOMO-LUMO) gap on Cu(100) [9]. What is critical in our calculations, however, is the Cu-C interaction potential. Here, we have chosen a Buckingham potential within the molecular mechanic (MM2) routine [10] to describe each of the Cu-C interactions while preserving the standard MM2 description of the C6o internal mechanics. The advantage of the MM2 routine was to enable the calculation of C6o repositioning within realistically achievable computation time limitations compared to the use of first principle calculations [ 11] or even an Atom Superposition and Electron Delocalization (ASED) approach [12]. Furthermore, the parametrization used here can be optimized first by ab initio calculations before inclusion in MM2. There are 572 atoms on the Cu(100) surface (Fig. 2) with no cyclic boundary conditions included to avoid spurious effects like tip-tip direct interactions between the unit cells. The tip is made of 236 atoms arranged in a squared base pyramid (1-4-9-16...) with (111) facets. The potential energy characteristics for a C6o molecule diffusing both along and perpendicular to a mono-atomic step edge on Cu(100) (illustrated in Fig. 2) are presented in Fig. 3. These curves were calculated by minimizing the potential energy of the Cro-surface system at each position along one trajectory of the C6o molecule. This leads to a very small diffusion barrier on a defect free surface and also along the step edge. In contrast, perpendicular to the step edge, C6o experi-

1t. Tang et al. / Surface Science 386 (1997) 115-123

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Fig. 2. Representation of the Cu(100) surface used for C6o manipulation calculations. The kink introduced along the mono-atomic step stabilizes the C6o position.

ences a deep minimum down the step and a large change on the top edge of this step. Consequently, at room temperature, C6o molecules diffuse on a free of defect Cu(100) surface until they reach defects such as a step edge where they are stabilized for example by a kink or a defect along the edge as shown in Fig. 1. These stable sites are the starting point of mechanics experiments on a single C6o molecule.

3. Mechanics of C6o motion induced by an STM tip When an adsorbate is stabilized on a surface, there are at least three ways to remove it from its adsorption site: an increase of the surface temperature, a photon absorption by the adsorbate and more recently by the mechanical action of an STM tip apex. Increasing the temperature is a very efficient method to induce motion of an adsorbate. It can either oscillate about its equilibrium position or diffuse. For example, an ad-atom will remain only 10 -7 s in its equilibrium site at 77 K for a 0.1 eV diffusion barrier [13]. Nevertheless, this is a very inefficient way to conduct directionaUy controlled mechanics since impulse transfer from a hot surface to an adsorbate is a random process with no directionality unless the surface is highly aniso-

tropic such as the A u ( l l 0 ) - ( 2 x 1) reconstructed surface. Furthermore, the average speed of the center of mass of a molecule does not vary in time after thermalization. Absorption of photons by the adsorbate to transfer momentum to the adsorbate via momentum conservation rules is another possibility. To the first order, this involves no selective directionality. Repositioning with an STM tip apex is a recent approach. With average tip scanning speeds of ca 10-~m s -~, and with adsorbates mass typically < 10 -2~ g, momentum transfer from the tip apex to the adsorbate may be considered negligible. Therefore, "kicking" an adsorbate out of its equilibrium site by a lateral impulse using an STM tip is not realizable. The tip apex-adsorbate mechanical interactions will only permit dragging or pushing the adsorbate. Depending on the position of the adsorbate under the tip during its interaction with the tip apex, three mechanical manipulation modes have been identified: a sliding process [8]; a pulling process [14]; and a pushing process [3]. Identification of the repositioning mode can be obtained by recording the STM "tunnel current intensity-tip apex displacement" I(x) characteristic for a constant height manipulation or the STM "z-piezo feedback Az signal-tip apex displacement" Az(x) for a constant current mode of operation

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enough, a van der Waals trap is created under the tip [16] and the adsorbate will remain under the apex without escaping sideways from the trajectory defined. When the potential energy gain by the adsorbate under the apex is larger than the adsorbate diffusion barrier, the trapped adsorbate follows arbitrary slow displacements of the apex [8,16 ]. When this tip displacement is conducted in a constant current mode, the Az(x) signal is regular, modulated only by the difference in altitude of the adsorbate passing from top to hollow sites during its lateral displacement (Fig. 4a). During a pulling process [14], the adsorbate is situated behind the tip apex with respect to the desired lateral repositioning direction. The tip apex is first approached laterally towards the adsorbate during a constant current scan. Here, the current intensity is selected to a value such that z is larger than the adsorbate height to optimize tip-adsorbate interactions. Arriving at the adsorbate, z changes and the adsorbate is attracted by the tip apex. The apex passes over the adsorbate during the scan. However, due to fine initial tuning of z,

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Fig. 3. Potential energy curve for a C6o molecule diffusing: (a) along the step edge on the lower terrace; and (b) perpendicular to the step edge on the Cu(100) surface presented in Fig. 2. The small slope in (a) is due to the limited size of the slab taken to model the surface.

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[15]. Notably, none of these manipulation modes result in an increase in kinetic energy of the adsorbate for a temperature lower than the threshold value The adsorbate is almost equilibrated with the surface during these processes and will remain at a position reached from the manipulation when the tip is retracted into the image mode. During a sliding process [8], the adsorbate remains under the tip apex [6]. The tip apex is first.positioned on the top of the adsorbate. The adsorbate is then gently "squeezed" between the tip apex and the surface by reducing the apex to surface distance, z. If this squeezing is weak

(b)

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Fig. 4. Schematic representation of the different possible manipulation modes with an STM tip. (a) Sliding mode, (b) pulling mode and (c) pushing mode. In each case the Az(x) STM feedback loop signal characteristic of the manipulation in a constant current mode is shown.

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the adsorbate will remain attracted by the rear facet of tip apex. If the adsorbate diffusion barrier is lower than this attractive force, the adsorbate will be pulled by the tip apex. The corresponding Az(x) signal has sawtooth form (Fig. 4b) and the pronounced steps are associated with the discontinuous attraction of the adsorbate by the tip apex. During a pushing process [3], the adsorbate is in front of the tip. The apex is first approached laterally towards the adsorbate in the constant current mode. Contrary to the pulling mode, z is now selected such that it is less than the overall height of the adsorbate. In that case, the adsorbate is pushed by the advancement of the tip apex [3] due to core-core repulsion. This process works for a molecule better than for an atom because a small displacement of the tip apex parallel to the surface will result in the lateral escape of the atom. The associated Az(x) STM signal has also a sawtooth form, but with the reverse asymmetry of its form compared to the pulling mode (Fig. 4c). The Az(x) signal can be measured experimentally in all the sliding, pulling and pushing modes [15] which makes this signal very important to record in any adsorbate manipulation. Usually, the result of a manipulation is known after, by imaging the surface to prove that the adsorbate had been displaced. With Az(x), the adsorbate position and conformation under the tip apex can be followed during a manipulation. Experimentally, it has been demonstrated that C6o molecules can be individually repositioned along a Cu( 111 ) mono-atomic step edge in a well defined manner [17] using an STM manipulation junction resistances ca 1.4 Mf~ (Fig. 5). There, the tip apex is positioned in the constant current STM imaging mode to the close proximity of a single C6o. The STM tip bias voltage is then reduced to lower the tip apex towards the surface. As the tip apex is subsequently scanned along the step edge, repositioning of the C6o to the desired location occurs along the step [17]. We have calculated which of the possible three processes leads to this repositioning. To reproduce a sliding mode, the tip apex was approached on the top of a C6o molecule stabilized along a step edge. For different values of z, the conformation of the C6o cage was optimized under the tip apex

Fig. 5. ExperimentalSTM image of the pushing process of a single C6o moleculealong a Cu(lll ) surface step edge. (a) An STM imagebefore the pushing, (b) an STM imageat an intermediate C6o position and (c) an STM image at the end of the pushing process.

constraint using the MM2 (Molecular Mechanics) routine [10]. Keeping z constant, the tip apex was scanned under conditions where we expect a sliding motion of C6o. Surprisingly, no evidence of molecular repositioning was found. Analysis of the data indicates that deformations of C6o by the apex does not change the C6o stabilization energy on the surface. Here, the C60 cage acts as a tip constrain damper. For a pushing, the tip was scanned once again at constant altitude towards a C6o molecule stabilized along the step edge on the Cu(100) surface. This calculation was done for a range of z values using our molecular mechanic approach [3]. Following the Ehrenfest theorem, a molecular dynamic approach is not required. The C6o mass is so small that the acceleration term in the semiclassical Ehrenfest equation of motion describing the dynamics of the C6o center of mass is zero. Furthermore, the time interval between two elementary tip scan increments is orders of magnitude longer than the C6o vibration relaxation time, even for the coherent low frequency vibration or rotation modes. Table 1 summarizes our different results and the corresponding threshold STM junction resistance where molecular motion occurs.

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Table 1 Conditions for pushing a single C~o molecule along a step on a Cu( 100)surface Altitude (A) 13 12 11 10 9 Tunneling junction resistance (Mf~) 536.7 14.4 1.05 Translation by pushing No No Yes Yes Yes Experimental resistance (M~) 500 1.4

The altitude is the tip apex to surface distance, the STM tunnel junction resistance is before the pushing. The corresponding experimental threshold resistance for translating C6o by pushing is also given.

Translation of the C6o molecule along the step edge sets in with a STM junction resistance < 10 M~. Knowing the conditions for C6o manipulation, the I(x) STM signal was calculated for constant height scans using both the STM-ESQC (Elastic Scattering Quantum Chemistry) technique to calculate the tunneling current [18] and the MM2 routine for the determination of the pushing mechanics. This calculation was performed at a surface temperature of 0 K. As evident from Fig. 6, I(x) has the sawtooth signal characteristic of pushing, but it is not as regular as the idealized signal presented in Fig. 4. We ascribe the complex struc80.0

ture in Fig. 6 to the conformation of the C6o cage under pressure which is sequentially passing over top and hollow sites in a more or less random manner. These small conformation changes modify the tunneling channels through C6o and their mixing, inducing the irregularities in the I(x) signal presented in Fig. 6. Having previously found no evidence of pulling for this large adsorbate, this results implies that the lateral tip apex attraction of C6o is damped by C6o cage deformations. At room temperature, rotation of the C6o molecule in its equilibrium position can occur and this "sawtooth" form is then time averaged. The internal C6o mechanics during pushing (Fig. 7) follows the surface corrugation along the step edge with only small deformations of the cage. Here, it is not possible to induce a coherent rotation of the C6o cage along a regular step edge. This is a direct consequence of the negligible inertial momentum of a C6o molecule. To understand the role of mechanics in a more complex and realistic situation, we have included a kink along the step edge (Fig. 2). When the C6o molecule is pushed by the tip as it approaches the kink edge, C6o rotates to avoid the kink edge as illustrated in Fig. 8. However, this rotation stops after it passes the kink edge and the normal pushing sequence resumes.

4. Action and reaction on the molecular scale

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Fig. 6. The calculated I(x) signal for pushing with a constant tip apex-to-surface distance height; - - - for z = 12 ,~, and - for z = 7 A,. There is no repositioning of the molecule for z = 12Pt (see Table 1).

Kinetic energy is not supplied to an adsorbate during an apex manipulation process with an STM tip. When the scanning is stopped and the tip retracted, the adsorbate resumes an immobilized state. Consequently, mechanics without kinetic energy is rather limited. One approach we suggest to provide kinetic energy to an adsorbate is to increase first its internal potential energy. Part of this energy may be converted in kinetic energy, the other part being randomized within the adsorbate vibration manifold. A significant increase of the adsorbate potential energy might be achieved by pushing the adsorbate against a "hard wall" such as a step edge. With a sliding or a pulling process, no lateral constrains are exerted on the adsorbate. The compression will

H. Tang et al. / Surface Science 386 (1997) 115-123

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Fig. 8. Representation of the trajectory in the x - y plane of two carbon atoms (O, O) of the C6o cage for a repositioning along the Cu(100) step edge equipped with a mono-atomic kink for z = 7 ,~.; - - - is for the open circle atom, and is for the plain circle atom. The kink position is at y= 14.05 ,~ (Fig. 2).

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Fig. 7. Representation of the trajectory in the (a) x-y plane and (b) in height of the C6o cage pushed along the Cu(100) step edge for z = 7 ,~ (see Table 1). Two typical carbon atoms have been selected on the cage (O, ) . The solid line is the trajectory of the filled circle atom and the dotted line is that of the open circle atom.

Fig. 9. Experimental STM images of a pushing of a C6o molecule perpendicular to a Cu( 111 ) surface step edge. (a) A STM image before pushing, (b) during pushing and (c) after pushing. Note that the step edge has been deformed during pushing. The C6o molecule passes to the upper terrace and localizes by a defect close to the step edge. d u r i n g such a process, r e p r o d u c i n g by c a l c u l a t i o n a p u s h i n g a c t i o n t o w a r d s a step edge b u t w i t h o u t searching for the step edge d e f o r m a t i o n m e c h a nism, o u r interest being here on the C6o internal energy only. First, the tip a p e x altitude r e q u i r e d for C6o to reach the u p p e r terrace was d e t e r m i n e d using the same p r o c e d u r e as r e p o r t e d in Section 3. This is shown in Table 2. T h e t r a j e c t o r y o f the C6o cage d u r i n g this p r o c e d u r e is p r e s e n t e d in Fig. 10. A cage r o t a t i o n can result if the tip apex

increase the internal p o t e n t i a l energy o f the a d s o r b a t e until it " p o p s " o u t to the u p p e r terrace o r escapes a l o n g the edge on the lower terrace. E x p e r i m e n t a l l y , a d s o r b a t e s have been easily slide over step edges [19]. A s shown o n the experim e n t a l sequence p r e s e n t e d in Fig. 9, C6o can be p u s h e d t o w a r d s a step edge. D u r i n g the c o m p r e s sion, C6o can reach the u p p e r terrace. But the step edge is often f o u n d d e f o r m e d a f t e r w a r d s as presented in Fig. 9. We have e v a l u a t e d the gain in p o t e n t i a l energy

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Table 2 Conditions for pushing a single C6o molecule towards a step edge on a Cu(100) surface (see Table 1 for details) Altitude Tunnelingjunction Translation C6o Internal (A) resistance (Mf~) by pushing energy(kcal mol-1)
12 11 10 9 7 5 14.4 1.05 0.10 No No Yes Yes Yes Yes 3.88 23.52 22.65 12.16 11.64 7.51

motion of the C60 center of mass and the part which would be converted into C60 cage rotation.

5. Conclusion In analogy to the macroscopic world, mechanics on the nanoscale with a single adsorbate requires first the definition of a fixed point to start the mechanics. We have shown that it is the surface diffusion barrier and not the mass of the adsorbate which determines the stabilization of the adsorbate at a specific location on the surface. Through mechanical action with an STM tip apex, atoms can be repositioned one by one using a variety of manipulation modes: sliding; pulling; or pushing. For large adsorbates like C6o only the pushing mode operates. But none of these modes provide kinetic energy to the adsorbate because of the very slow scanning speed of an STM tip. To be able to create a sustained motion away from the tip on the nanoscale, one has to be able to efficiently store and release potential energy to the adsorbate and to convert it to transactional motion. One approach suggested is to utilize the equivalence between potential and kinetic energy to produce a single adsorbate with a definite center of mass speed on a surface by compressing the adsorbate over a surface step edge. At a high enough compression, this adsorbate will escape the tip and translate before accommodation of its kinetic energy with surface phonons. The discussion on the prospect to control the position, motion and speed of the center of mass of an adsorbate is a generalized consideration of the internal mechanics of an adsorbate. H o w one can control in a coherent manner the motion of part of a molecule or induce only its rotation in a definitive direction is a challenge that could be achieved through the computer aided design and synthesis of molecular systems.

For the maximum C60 internal potential energy obtained at the step edge, the self C60 energy has been taken as the zero point.
10.0

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6.0

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-7.0 -3.0 Tip position (A)

1.0

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Fig. 10. Representation of the C6o center of mass altitude as a function of the tip apex position when C60 is pushed towards a mono-atomic step edge on the Cu(100) surface; - - - is for the open circle atom, and for the plain circle atom as in Fig. 7. is not too close to the lower terrace at the starting of the pushing operation. In this case, the front facet of the apex interacts weakly with C6o and rotation is induced by the C6o interaction with the top of the step edge. When the cage is compressed further, rotation is actually blocked. An appreciable quantity of potential energy can be stored in such a pushing. If we suppose that this energy is totally converted into kinetic energy, the lateral velocity achievable, for example, for 1 0 k c a l m o 1 - 1 is 3 0 0 m s -1. On the nanoscale, most of this energy will randomize in the C60 vibration manifold and decay into the surface phonons. We are currently trying to evaluate what part of this potential energy can be converted into

Acknowledgements
We thank G. Meyer and K.H. Rieder for their interesting discussions. This work is partially funded by the G D R 1145 " N a n o m i p s " (CNRS)

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and the EU ESPRIT project PRONANO via the Swiss Federal Office for Education and Science.

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