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# Induced-charge Electrokinetic Phenomena: Theory and Microfluidic Applications

## Abstract

We give a general, physical description of “induced-charge electro-osmosis” (ICEO), the nonlinear electrokinetic slip at a polarizable surface, in the context of some new techniques for microfluidic pumping and mixing. ICEO generalizes “AC electro-osmosis” at micro-electrode arrays to various dielectric and conducting structures in weak DC or AC electric fields. The basic effect produces micro-vortices to enhance mixing in microfluidic devices, while various broken symmetries — controlled potential, irregular shape, non-uniform surface properties, and field gradients — can be exploited to produce streaming flows. Although we emphasize the qualitative picture of ICEO, we also briefly describe the mathematical theory (for thin double layers and weak fields) and apply it to a metal cylinder with a dielectric coating in a suddenly applied DC field.

The advent of microfluidic technology raises the fundamental question of how to pump and mix fluids at micron scales, where pressure-driven flows and inertial instabilities are suppressed by viscosity stone01 ; beebe02 . The most popular non-mechanical pumping strategy is based on electro-osmosis — the effective slip, $`\text{u}_{}`$, at a liquid-electrolyte/solid interface due to tangential electric field, $`\text{E}_{}`$. The Helmholtz-Smoluchowski formula,

$$\text{u}_{}=\frac{\epsilon \zeta }{\eta }\text{E}_{},$$
(1)
gives the slip in terms of the permittivity, $`\epsilon `$, and viscosity, $`\eta `$, of the liquid and the zeta potential, $`\zeta `$, across the diffuse part of the (thin) interfacial double layer lyklema . The usual case of constant (possibly non-uniform ajdari95 ) $`\zeta `$, however, has some drawbacks related to linearity, $`\text{u}_{}\text{E}_{}`$: (i) the flow is somewhat weak, e.g. $`u_{}=70\mu `$m/s in aqueous solution with $`E_{}=100`$ V/cm and $`\zeta =10`$ mV and (ii) AC fields, which reduce undesirable Faradaic reactions, produce zero time-averaged flow.

These drawbacks do not apply to AC electro-osmosis, recently discovered by Ramos et al. ramos98  and Ajdari ajdari00 . Nonlinear electro-osmotic slip is produced at micro-electrodes as an AC field acts on induced double-layer charge prior to complete screening. In spite of extensive work, however, this promising effect remains limited to quasi-planar pairs aceo  or arrays acpumping  of electrodes at a single AC frequency, $`\omega _c=\tau _c^1`$, where $`\tau _c=\lambda _DL/D`$ is the “RC time” of an equivalent circuit of bulk resistors of size $`L`$ (the electrode spacing) and double-layer capacitors of thickness, $`\lambda _D`$, the Debye screening length, and $`D`$ is an ionic diffusivity.

How general is this phenomenon? Nonlinear electro-osmotic flows have also been observed at dielectric impurities on electrodes with AC forcing nadal02b  and, more suggestively, at dielectric (non-electrode) micro-channel corners in DC fields thamida02 . Although it is largely unknown (and uncited) in the West, similar flows have also been studied in the Russian literature on polarizable colloids murtsovkin96 , including the effect of such flows on dielectrophoresis simonova01 . The unifying principle in these diverse effects is that an applied field acts on its own induced diffuse charge, so we suggest the term, “induced-charge electro-osmosis” (ICEO), to describe it.

In this Letter, we describe more general ICEO flows which may be produced in microfluidic devices. Before we begin, we stress that ICEO dominates electrokinetics at small total zeta potentials (initial \+ induced), $`\zeta 2(kT/e)\mathrm{log}(L/\lambda _D)`$, where $`kT/e20`$ mV is the thermal voltage. When this condition is violated, as in highly charged colloids, surface conduction leads to other “non-equilibrium electrosurface phenomena” (NESP) dukhin93 , and at very large voltages (above a limiting current) bulk space charge may also drive “second-kind electrokinetic phenomena” dukhin91 . Such exotic effects may be useful in microfluidics ben02 , but we focus on small voltages, which are often preferable in real devices.

ICEO is nicely illustrated by the flow around an uncharged, ideally polarizable cylinder (e.g. an inert metal wire) of radius $`a`$ in a suddenly applied, weak, uniform field, $`\text{E}_b`$. (The analogous problem for a metal colloidal sphere was introduced long ago by Levich levich ; the double-layer polarization was later analyzed in more detail by Simonov and Shilov simonov73b  and the resulting flow by Gamayunov, Murtsovkin and A. S. Dukhin gama86 .) As shown in Fig. 1(a), the initial electric field lines are those of a conducting sphere in vacuum, perpendicular to the surface, but the ionic current, $`\text{J}=\sigma \text{E}`$, affects the field. Without surface conduction or Faradaic reactions to transfer the normal current at the surface, ionic charge accumulates in the double-layer “capacitor”. As shown in Fig. 1(b), a steady state is reached when the bulk field lines are expelled to become those of an insulator, parallel to the surface. The induced diffuse charge (or $`\zeta `$) shown in Fig. 1(b) is non-uniform — negative ($`\zeta >0`$) where the initial current leaves the surface and positive ($`\zeta <0`$) where it enters. Since $`\text{u}_{}\zeta \text{E}_{}`$, we can anticipate the quadrupolar ICEO flow shown in Fig. 1(c), which draws in fluid along the field axis and ejects it radially. Reversing E changes the sign of the induced $`\zeta `$ everywhere, so the same flow also persists in AC fields (up to the charging frequency, $`\omega _c=D/\lambda _Da`$).

The magnitude of the flow follows easily from dimensional analysis. After charging, the double layer acquires the background voltage across the object (non-uniformly), which produces zeta potentials of order $`E_ba`$, and from Eq. (1) typical flow speeds of order,

$$U_0=\frac{\epsilon aE_b^2}{\eta }$$
(2)
(as for a colloidal sphere gama86 ). When the applied voltage, $`E_ba`$, exceeds typical equilibrium zeta potentials (10mV), ICEO flow exceeds that of standard DC electro-osmosis, e.g. $`U_0=0.7`$mm/s in water for $`E_b=100`$ V/cm and $`a=10\mu `$m. In that case, the maximum frequency, $`\omega _c`$, is of order 10 kHz for $`\lambda _D=10`$nm. (For these parameters, we are also justified in neglecting surface conduction lyklema ; dukhin93 .)

The symmetry of ICEO flow in Fig. 1(c) suggests the microfluidic devices sketched in Fig. 2. For example, a metal post in a transverse AC or DC field produces local time-averaged flow as in Fig. 1(c). Placed at a cross junction with two pairs of corner electrodes (Fig. 2a), ICEO draws liquid in along one channel and forces it out the other, and the flow is easily reversed by changing the field direction. An array of posts in a transverse AC field (Fig. 2b) produces micro-vortices to enhance mixing in passing flows. A different design for a T-junction pump (above right) employs a metal surface coating, which could wrap around in the third dimension to reduce viscous drag by replacing more of the channel wall with sources of ICEO. (See also Fig. 4.)

In such devices, streaming flows are easily produced by broken symmetries. As the first example, consider a metal cylinder of non-zero total charge. In a DC field, the ICEO flow shown in Fig. 1(d) (and given below) is simply a superposition of the nonlinear quadrupolar flow described above and the linear streaming flow of electrophoresis, which averages to zero for a freely suspended object. In microfluidic devices, however, there is a new possibility: By controlling an object’s potential, its induced total charge can be made to vary in phase with the applied field to produce time-averaged AC streaming. For example, a thin metal post at position, $`x_0`$, and potential, $`\varphi _0`$, between two electrodes imposing a linear potential, $`\varphi =E_bx=Vx/L`$, generates a streaming flow of order,

$$U_1=\frac{\epsilon (\varphi _0+E_bx_0)E_b}{\eta }.$$
(3)
In the case of the mixer in Fig. 2c, a post grounded to an electrode, $`\varphi _0=V`$, pumps toward the nearest wall with speeds larger than the (superimposed) fixed-total-charge flow by a geometry-dependent factor, $`|U_1/U_0|=(Lx_0)/a`$. Since posts of prescribed potential act as electrodes, this manifestation of ICEO resembles AC electro-osmosis ramos98 ; ajdari00 , but it does not require AC background fields. It is perhaps closer to DC “field-effect flow control” schasfoort99 , although ICEO involves metal surfaces at much smaller voltages coupled directly to the primary electrodes.

As in the case of AC pumping at electrode arrays ajdari00 ; acpumping , other broken symmetries also cause a polarizable object to pump fluid via ICEO, if fixed, or move via “induced-charge electrophoresis” (ICEP), if freely suspended, at the velocity scale, $`U_0`$, in either DC or AC fields. For example, consider a metal cylinder with non-uniform surface properties in a uniform field, as in Fig. 3(b)–(c). If one side has a greater surface capacitance as in (b), then some induced charge ends up immobilized on the surface unable to cause slip, so the other side “wins” in driving ICEP in its direction. If the sphere is partially insulating as in (c), then primarily the conducting portion is polarized, and the steady-state field acts on the shifted diffuse charge to cause ICEP toward the insulating side.

If the object has an irregular shape as in (d) ICEP occurs in the more protruding direction, where the induced charge is better aligned with the tangential field (as in some experiments gama87 ). If the same object in (d) were rotated to break left-right symmetry, it would move in the opposite (more rounded) direction, perpendicular to the field axis, albeit unstable to rotations restoring field alignment. Such “transverse electro-osmosis” has been demonstrated for fixed-charge surfaces in DC fields ajdari95 , but with polarizable surfaces it can also occur in AC fields.

The ICEO flows in Fig. 3 motivate the microfluidic devices in Fig. 4, which pump in one direction while mixing via superimposed circulating flows in either AC or DC fields. For example, asymmetric posts pump and mix in response to an applied field along the channel (a), and the pumping direction may be reversed with a transverse field (not shown). An equivalent design (b) involves asymmetric grooves in a metallic channel wall. Such features may wrap around the channel in the third dimension, further reducing viscous drag.

Finally, we consider non-uniform applied fields. For example, an uncharged metal post in a non-uniform DC or AC field pumps down the field gradient, $`E_b`$, with a typical streaming velocity,

$$U_2=\frac{\epsilon a^2}{\eta }|E_b|^2,$$
(4)
which follows from Eq. (1) since induced variations in $`\zeta `$ are of order, $`a^2|E_b|`$. Such flows profoundly influence dielectrophoresis for polarizable colloidal spheres simonova01  (via ICEP), but non-spherical shapes require further study. More generally, non-uniform fields provide another useful degree of freedom in ICEO devices. As a simple example, one transverse electrode in the mixer of Fig. 2 could be shortened to produce additional pumping toward the opposite wall (and large-scale circulation) driven by the resulting field gradient. All of this flexibility raises interesting open questions of optimal design.

The physical arguments above can be justified by mathematical analysis of the electrokinetic equations lyklema  for weak fields and thin double layers, as described in subsequent papers, beginning with Ref. squires03a . The origin of ICEO and other NESP is an effective boundary condition on the neutral bulk electrolyte which expresses the conservation of the diffuse charge, $`q`$, in a thin double layer:

$$\frac{q}{t}=J_F+\widehat{n}\text{J}+\mathbf{}_s\text{J}_s$$
(5)
where $`J_F`$ the Faradaic current, $`\widehat{n}`$ the outward normal, $`\mathbf{}_s`$ the surface gradient, and $`\text{J}_s`$ the surface current. NESP mostly involve steady surface conduction, $`\widehat{n}\text{J}=\mathbf{}_s\text{J}_s`$, at low AC frequencies, $`\omega D/a^2`$, which produces concentration gradients affecting electro-osmosis at highly charged surfaces murtsovkin96 ; dukhin93 .

In contrast, ICEO derives from the dominant “$`RC`$ coupling” for small $`\zeta `$ (initial + induced) in a homogeneous electrolyte:

$$C_D\frac{\zeta }{t}=\sigma \widehat{n}\text{E}$$
(6)
where $`C_D(\zeta )=\frac{dq}{d\zeta }`$ is the nonlinear differential capacitance per unit area. (Ideal polarizability, $`J_F=0`$, is often a good approximation for small $`\zeta `$ and AC forcing.) The variable $`\zeta `$ in Eq. (1) is then obtained by solving Laplace’s equation, $`^2\varphi =0`$, subject to the boundary condition (6). For linear screening, $`C_D=\epsilon /\lambda _D`$, such analysis has been done for micro-electrode arrays ramos98 ; ajdari00 ; aceo , while nonlinear screening has also been discussed in colloids simonov73b .

Motivated by the devices in Fig. 2, we calculate the ICEO slip for a metal cylinder at potential $`\varphi _0`$ (or $`\zeta _0=(\varphi _0\varphi _b)/(1+\delta )`$) in a suddenly applied, weak background potential $`\varphi \varphi _bE_br\mathrm{cos}\theta `$, where $`\zeta =(\varphi \varphi _0)/(1+\delta )kT/e`$ at $`r=a`$. (Here $`\delta `$ is the capacitance ratio of the compact part to the diffuse part of the double layer ajdari00 .) The bulk potential,

$$\varphi (r,\theta ,t)=\varphi _bE_br\mathrm{cos}\theta \left(1+g(t)\frac{a^2}{r^2}\right)$$
(7)
involves an induced dipole moment, $`g(t)=12e^{t/\tau _q}`$, effectively changing from a conductor ($`g=1`$, $`\tau \tau _q`$) to an insulator ($`g=1`$, $`t\tau _q`$) at the time scale, $`\tau _q=\tau _c/(1+\delta )`$. (For nonlinear screening, the poles charge more slowly, $`dC_D/d|\zeta |0`$, but the steady state is the same.) The slip velocity, $`\text{u}_{}=u_\theta \widehat{\theta }`$, has two terms:

$$u_\theta (\theta ,t)=U_1^{}f(t)\mathrm{sin}\theta +2U_0^{}f(t)^2\mathrm{sin}2\theta .$$
(8)
where $`f(t)=1+g(t)`$, $`U_1^{}=\epsilon (\varphi _b\varphi _0)E_b/\eta (1+\delta )`$, and $`U_0^{}=U_0/(1+\delta )`$. The first term produces pumping past the cylinder while the second, peaked at $`45^{}`$ to the field and growing more slowly, produces a symmetric quadrupolar flow. Both terms have have non-zero time averages in AC fields, $`u_\theta ^{(1)}\zeta _0E_b\mathrm{sin}\theta `$ and $`u_\theta ^{(0)}aE_b^2\mathrm{sin}2\theta `$, respectively, although the former requires controlling $`\varphi _0`$. Finally, we note that a thin dielectric layer (modeled by $`\delta >0`$ as in Ref. ajdari00 ) reduces ICEO flow by $`1/(1+\delta )`$, so care must be taken keep metal surfaces clean in real devices.

In summary, ICEO is a versatile technique for microfluidic pumping using weak AC (or DC) fields, including many new possibilities other than AC electro-osmosis at planar micro-electrode arrays. The remarkable richness of ICEO flows merits further analysis and experiments, especially at moderate voltages where other NESP may become important. Nevertheless, simple drawings, as in Figs. 1-4, suffice for a qualitative understanding in many cases.

This research was supported in part by the U.S. Army through the Institute for Soldier Nanotechnologies, under Contract DAAD-19-02-0002 with the U.S. Army Research Office.


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# Introduction

## Introduction

In , Couch and Torrence found a conformal isometry that interchanges the event horizon and null infinity of an extremal Reissner-Nordström black hole. Related but distinct ideas have also appeared in a string theory context. Here we will show that such a conformal isometry exists also for the case of a positive cosmological constant, provided that the surface gravities of the two horizons are equal. We will leave global issues aside and refer the reader to  for those matters. See also  for a discussion of conserved quantities in asymptotically de Sitter spacetimes from a Hamiltonian point of view.

## The calculation

In the Couch-Torrence case the conformal isometry switches the roles of the event horizon and infinity. With a positive cosmological constant, there is another geometrically distinguished object: the cosmological horizon. As $`\mathrm{\Lambda }0`$, this horizon approaches infinity. Let us therefore provisionally assume that the putative conformal isometry interchanges the black hole horizon and the cosmological horizon since this produces the correct limiting behavior; this assumption will later turn out to be correct.

Assume that the BH horizon is at $`r=a`$ and the cosmological horizon at $`r=b`$. It is convenient to introduce the coordinate $`x`$ defined by

$$x=\frac{ra}{br}\frac{b}{a}$$

The strategy here is to first re-express the above metric in terms of the $`x`$ coordinate. In such a coordinate system, the metric will be manifestly conformally invariant under the inversion $`x1/x`$ as we will now show (note that the surface gravities of the two horizons will remain equal after the inversion since the surface gravity $`\kappa `$, suitably defined, is a conformal invariant).

For a general spherically symmetric black hole, the metric in the standard coordinates is

$$\mathrm{d}s^2=V(r)\mathrm{d}t^2+\frac{\mathrm{d}r^2}{V(r)}+r^2\mathrm{d}\mathrm{\Omega }^2$$
(1)
where $`V(r)`$ is given by

$$V(r)=\frac{12m}{r}+\frac{Z^2}{r^2}\frac{1}{3}\mathrm{\Lambda }r^2$$
(2)
A calculation shows that $`\kappa =|V^{}/2|`$. For the particular case of so-called “lukewarm black holes”, where the surface gravities of the two horizons are equal, Romans has shown that the parameters take the values

$$m=\frac{ab}{a+b}=\pm Z\mathrm{\Lambda }=\frac{3}{(a+b)^2}$$

Note that the mass remains equal to the charge when a cosmological constant is introduced, so in this sense the black hole is still extremal. Inserting those parameter values into $`V(r)`$, one obtains

$$V(r)\frac{1}{r^2}(ra)(rb)(r^2+(a+b)rab)$$

In terms of $`x`$, the right-hand side of (2) becomes

$$W(x)=\frac{x}{(1+x)^2(b+ax)^2}\left(2ab(1+x^2)+x(a+b)^2\right)$$
(3)
We are now in a position to verify that the map $`x1/x`$ is indeed a conformal isometry. The condition for this to hold is that $`\mathrm{d}s^2(x)=f^2\mathrm{d}s^2(1/x)`$ where $`f^2`$ is the conformal factor. The easiest way to verify this is to notice that the $`\mathrm{d}\mathrm{\Omega }^2`$ term in the metric only involves $`x`$ through the $`r^2`$ so we immediately find that the conformal factor $`f^2`$ has to satisfy

$$f^2=\left(\frac{a+bx}{b+ax}\right)^2$$
(4)
One can check that the conformal isometry conditions for the $`\mathrm{d}t^2`$ and the $`\mathrm{d}r^2`$ terms both lead to

$$\frac{W(x)}{W(1/x)}=f^2$$

Since $`f^2`$ is known from (4) and $`W(x)`$ is given by (3), one can simply calculate the left-hand side of the above expression and find that the equality does hold, meaning that the inversion is indeed a conformal isometry.

## Optical geometry

All this can be nicely illustrated in terms of optical geometry222For a more complete exposition of optical geometry for Reissner-Nordström black holes, see . For optical geometry in general, see  or .. The optical geometry is obtained as the spatial part of the conformally rescaled metric

$$\mathrm{d}\stackrel{~}{s}^2=\frac{1}{V(r)}\mathrm{d}s^2=\mathrm{d}t^2+\frac{\mathrm{d}r^2}{V(r)^2}+\frac{r^2}{V(r)}\mathrm{d}\mathrm{\Omega }^2$$

A null geodesic in the full spacetime projects down to a geodesic in the optical geometry, hence its name.

The optical geometry looks roughly like figure 1. As outlined above, we would expect the conformal inversion to interchange the two horizons; in this picture, this would amount to swapping the two spheres at infinity (they appear as circles in the figure). The neck between the spheres is where the optical geometry has its minimal radius; just like in the Schwarzschild case, this occurs at $`r=2m`$, i.e. at $`r=2ab/(a+b)`$. One can verify that this is a fixed point of the conformal inversion $`x1/x`$.

A calculation reveals the curvature scalar of the optical geometry associated with 1 to be

$$R_{opt}=\frac{1}{2r^2}\left(4V4V^23r^2V^2+4rVV^{}+4r^2VV^{\prime \prime }\right)$$

This means that $`R_{opt}3V^2/2=6\kappa ^2`$ as $`ra`$. If we restrict the definition of a Couch-Torrence symmetry to be an isometry of the optical geometry, one obtains in this way a necessary condition for such a symmetry to exist: since $`R_{opt}0`$ when one approaches infinity for an asymptotically flat black hole, $`\kappa `$ must equal zero at the horizon in that case.

## Conclusions and open ends

One may ask the question whether there are other black-hole spacetimes for which a conformal isometry of the Couch-Torrence type exists. This seems to be tricky to answer; since the isometry is discrete, infinitesimal methods using Killing vectors are not likely to be very useful. One could hope for the existence of a sufficient condition something along the lines of the curvature scalar condition referred to above. This remains to be investigated.

## Acknowledgements

I am grateful to Ingemar Bengtsson for suggesting the problem and for providing advice and constructive criticism. I would also like to thank Jörgen Nätterlund for the figure.


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# Four-atom period in the conductance of monatomic Al wires

## Abstract

We present first principles calculations based on density functional theory for the conductance of monatomic Al wires between Al(111) electrodes. In contrast to the even-odd oscillations observed in other metallic wires, the conductance of the Al wires is found to oscillate with a period of 4 atoms as the length of the wire is varied. Although local charge neutrality can account for the observed period it leads to an incorrect phase. We explain the conductance behavior using a resonant transport model based on the electronic structure of the infinite wire.

Metallic chains of single atoms represent the ultimate limit of the miniaturization of electrical conductors. Apart from possible technological applications as interconnects in molecular electronics, the simple structure of these monatomic wires makes them an ideal test ground for developing and validating our understanding of electron transport on the nanometer length scale. The conductance of monatomic wires has been investigated theoretically by several authors using a number of different techniques lang97 ; lang98 ; sim01 ; kobayashi00 ; tsukamoto02 ; havu02 . Lang was the first to study the dependence of the conductance on the number of atoms in the wire. In 1997 he found that the conductance of a chain of Na atoms between jellium electrodes oscillates with a period of 2 atoms as the length of the chain is varied lang97 , and the following year Lang and Avouris observed the same behavior for chains of C atoms lang98 . This even-odd effect was also found in Na wires by Tsukamoto and Hirose tsukamoto02  using a method similar to that of Lang, and by Sim et al. sim01  who combined cluster density functional theory (DFT) calculations with the Friedel sum rule to obtain the conductance. Recently, the even-odd oscillations have been confirmed experimentally for Au, Pt and Ir by means of the mechanically controlled break junction smit03 .

The fact that a large number of metals of rather distinct character exhibit the even-odd effect has lead to the suggestion that this is a universal feature of atomic wires smit03 . In this paper we present calculations based on DFT showing that the conductance of monatomic Al wires varies in an oscillatory manner as the number of atoms in the wire is changed. In contrast to the even-odd effect, however, the oscillation has a period of 4 atoms. Based on a resonant transport picture we show that local charge neutrality can account for the observed 4-atom period. For long wires, however, we find that the occupancy of molecular resonant states and thus the net charge located on the wire is determined by the position of the discrete energy spectrum of the free wire relative to the Fermi level of the electrodes. In general these two effects compete in determining the phase of the conductance oscillation. In the case of Al we find that the latter effect dominates for wires containing more than about 4 atoms, whereas charge neutrality is more important for shorter wires. By relating the electronic structure of the free wire to that of the infinite wire, we arrive at a simple picture for the position of the free-wire valence resonances which accounts for the conductance both qualitatively and quantitatively. In this picture the filling factor of the infinite wire determines the period of the conductance oscillation: a half filled band implies the even-odd effect while a filling factor of 0.25 leads to a 4-atom period.

We represent the combined electrode-wire system in a supercell containing the wire itself together with seven 3x3 sections of the (111) planes in bulk aluminum. An example of such a supercell is shown in Fig. 1. Periodic boundary conditions are imposed on the supercell in the directions perpendicular to the wire axis, and for the DFT calculations also in the parallel direction. The calculational procedure consists of two main steps: (i) first a realistic wire configuration is found by relaxing the ion positions as well as the electrode-electrode distance as determined by the length of the supercell. During the relaxation the wire is constrained to be linear and ions below the surface layer are fixed in the bulk crystal structure. These simulations were performed within DFT using a plane-wave based pseudopotential code dacapo  with an energy cutoff of 15 Ry for the plane-wave expansion. The ion cores are replaced by ultrasoft pseudopotentials vanderbilt90  and to treat exchange and correlation we use the PW91 functional pw91 . The bond lengths in the wires lie in the range 2.36 Å to 2.50 Å with the shorter bond lengths achieved closer to the center of the wire. For the longer wires the bond lengths vary less and approach a value of 2.39 Å which is also found for the infinite wire. No dimerization is found in accordance with previous results for infinite linear chains of Al atoms rubio96 . We mention that Ayuela et al. have found that an infinite linear Al chain has a nonmagnetic groundstate for interatomic distances smaller than 2.7 Å ayuela02 . (ii) The self-consistent effective potential generated by the DFT code is used as input to the Green’s function transport code described in detail in Ref. thygesen03 . The effective potential of the supercell forms the scattering region in the transport problem while the potential in the semi-infinite leads is obtained from a DFT bulk calculation. In this way the scattering region and the leads are treated on an equal footing taking their full atomic and electronic structure into account. The conductance is calculated from the Green’s function of the scattering region which is represented in terms of a system-independent basis set containing wavelets of compact support. All conductance calculations have been converged with respect to the size of the basis set. Due to the limited size of the supercell in the directions perpendicular to the wire, the two-dimensional Brillouin zone is sampled by 8 special $`𝐤`$-points, both in the transport and the DFT calculations.

In Fig. 2 we have plotted the calculated conductance of Al wires containing 1 to 9 atoms and attached to the (111) surface either directly or via a 3-atom basis. We regard an atom as part of the wire if it has a coordination number of 2, see Fig. 1. With this convention the wire couples to the electrodes via a single atom which we refer to as the contact atom. The conductance oscillates with a period of 4 atoms taking values in the range $`0.5G_0`$ to $`1.7G_0`$. The oscillation amplitude increases approximately 10% when the 3-atom basis is used as contact to the electrodes, but otherwise no difference is found between the two geometries.

We can gain some insight into the electronic structure of the current carrying states by studying the eigen-channel resolved conductance brandbyge  as shown in Fig. 3 for $`N=3`$. The valence configuration of atomic Al is $`3s^23p`$, which for the infinite wire leads to a fully occupied $`\sigma `$-band and a degenerate $`\pi `$-band with filling factor $`f=0.25`$. Three channels contribute to the total conductance: two similar $`\pi `$-channels and a single $`\sigma `$-channel. The two $`\pi `$-channels constitute the main part of the conductance, while the $`\sigma `$-channel is a tunneling channel whose contribution decays exponentially with the wire length from $`0.2G_0`$ at $`N=1`$ to $`10^4G_0`$ at $`N=9`$.

To understand the origin of the conductance oscillations we first relate the conductance to the electronic structure of the wire. When a free $`N`$-atom wire is connected to bulk electrodes, the molecular orbitals on the wire hybridize with extended states in the electrode. As a result of this mixing, the $`n`$’th energy level of the free wire is broadened into a resonance described by the projected density of states newns69

$$\rho _n(\epsilon )=\frac{\pi ^1\mathrm{\Delta }_n(\epsilon )}{(\epsilon \epsilon _n\mathrm{\Lambda }_n(\epsilon ))^2+\mathrm{\Delta }_n^2(\epsilon )}.$$
(1)
For each molecular level, the coupling to the electrodes defines a unique orbital, the group orbital, which is located on the contact atoms. In terms of the group orbital we can write $`\mathrm{\Delta }_n(\epsilon )=\pi |V_n|^2\rho _{c,n}(\epsilon )`$, where $`V_n`$ is the matrix element coupling the $`n`$’th molecular level with its corresponding group orbital and $`\rho _{c,n}`$ is the projected density of states for the group orbital in the absence of the wire. For simplicity we shall not distinguish between the group orbitals and thus we set $`\rho _{c,n}=\rho _c`$. If we furthermore neglect interference between the different molecular levels we obtain a simple expression for the conductance

$$G=\frac{2e^2}{h}\underset{n}{}\pi ^2|V_n|^2\rho _c(\epsilon _F)\rho _n(\epsilon _F),$$
(2)
where the sum extends over all molecular levels. From this expression we expect the position of the resonances relative to the Fermi level of the electrodes to be a crucial parameter for the conductance.

So far, local charge neutrality has been considered the main cause of the even-odd oscillations in monovalent wires sim01 ; havu02 ; smit03 . Indeed, for monovalent wires consisting of an odd number of atoms, local charge neutrality pins the Fermi level to the middle of a resonance resulting in a high conductance. On the other hand, for even-numbered wires the Fermi level lies off resonance leading to a lower conductance. In the case of Al the degeneracy of the $`\pi `$-orbitals on the free wire and the fact that each Al atom provides one electron to the $`\pi `$-system, implies that local charge neutrality would cause oscillations in the conductance with a period of 4 atoms. However, the resulting phase of the oscillation would be incorrect. The maxima (minima) occur for half-filled (filled) resonances which should correspond to $`N=2,6,\mathrm{}`$ ($`N=4,8,\mathrm{}`$). These numbers are off by 1 atom as compared to Fig. 2. Consequently, charge neutrality alone cannot account for the conductance of the Al wires. At this point it is interesting to notice that different results have been obtained for the phase of the conductance oscillation in Na wires. As opposed to Tsukamoto and Hirose and Sim et al., Lang lang97  has found a higher conductance for even-numbered than for odd-numbered Na chains. Calculations by Havu et al. havu02  for Na wires between jellium cones show that it is possible to change the phase of the conductance oscillation from even-odd to odd-even by varying the lead opening angle.

To explain the behavior of the conductance, we need to examine more closely the position of the resonances relative to the Fermi level of the electrode-wire-electrode system. As a first step in this direction we consider a linear chain of $`N`$ sites coupled by nearest neighbor hopping. The Hamiltonian is

$$H=\underset{i=1}{\overset{N}{}}\epsilon _0c_i^{}c_i+\underset{i=1}{\overset{N1}{}}t(c_{i+1}^{}c_i+c_i^{}c_{i+1})$$
(3)
where $`c_i`$ annihilates an electron at site $`i`$. The eigenvalues, $`\epsilon _n^N`$, of $`H`$ can be expressed in terms of the band structure of the infinite chain of coupled sites, $`\epsilon (k)`$, as follows:

$$\epsilon _n^N=\epsilon (\frac{n\pi }{N+1}),n=1,\mathrm{},N$$
(4)
where we have set the inter-site distance to 1. Although the above relation is only strictly valid for the model Hamiltonian (3), we can still use it to estimate the spectrum of a free $`N`$-atom wire in terms of the band structure of the infinite wire. As already described, the coupling of the free wire with the electrodes converts the discrete energy spectrum into a set of resonances. Assuming $`\rho _c(\epsilon )`$ to be constant the $`n`$’th resonance of the $`N`$-atom wire becomes a Lorentzian of width $`\mathrm{\Delta }_{N,n}=\pi |V_{N,n}|^2\rho _c`$. Since we are only interested in resonances close to the Fermi energy, it is reasonable to assume an energy independent coupling, $`V_{N,n}=V_N`$. Furthermore, the extended nature of the eigenstates of the free wire causes $`|V_N|^21/N`$. In Fig. 4 we have illustrated in $`k`$-space the evolution of the discrete spectrum of a free wire as a function of the wire length. For each eigenvalue we have indicated the width of the corresponding resonance. The eigenvalues are converted to energy via the valence band of the infinite wire and relation (4). To find the position of the Fermi level in the electrode-wire-electrode system we note that the Fermi energy is fixed by the macroscopic electrodes, and thus independent of the length of the wire. Since we do not expect a wire to charge up as it grows longer the net charge per atom must vanish in the limit of a long wire, and the band filling, $`f`$, must approach that of the infinite wire. In Fig. 4 we have indicated the Fermi level for the Al wire by a vertical line at $`k=\pi /4`$ corresponding to $`f=0.25`$. As $`N`$ increases the resonances move down through the Fermi level in a systematic fashion. The coincidence of the Fermi level with the center of a resonance is a periodic event of period 4 starting at $`N=3`$. Like the local charge neutrality, this picture explains the observed period of the conductance oscillation but in addition it provides information about the actual position of the resonances. The first maximum (minimum) is predicted to occur at $`N=3`$ ($`N=5`$), which indeed gives the correct phase as compared to Fig. 2. The vertical line at $`k=\pi /2`$ indicates the position of the Fermi level for metals with a half-filled valence band such as Na, Au and C. Clearly, our model accounts for the even-odd behavior observed in these wires.

According to the filling of $`\pi `$-resonances as predicted by Fig. 4, the $`N`$-atom Al wire should hold approximately $`N1`$ valence electrons. For short wires the electrostatic potential from the missing electron drags the resonances down in energy thereby increasing the occupancy. The resulting position of the resonances must be determined self-consistently and will in general lead to an occupation somewhere between $`N1`$ and $`N`$. For short wires the simple picture is therefore modified by a charge-neutralization process which tend to shift down the phase of the conductance oscillation by one atom. This effect explains the relatively high conductances found for $`N=1,2`$ as compared to $`N=5,6`$.

To test our simple model quantitatively we have used it to reproduce the first principles results. We use Eq. (2) for the conductance and assume a Lorentzian shape of the projected density of states. The molecular levels given in Eq. (4) are obtained via the $`\pi `$-band of the infinite Al wire calculated within DFT. From the first resonance in Fig. 3 we read off $`\mathrm{\Delta }_{N=3}=0.15`$ eV as the half-width at half-maximum. Due to the $`1/N`$ scaling, all resonance widths then follow from $`\mathrm{\Delta }_{N=3}`$. The result of the model is seen in Fig. 5 together with the first principles calculation, repeated here for convenience. Except for the shortest wires ($`N=1,2`$) where charge transfer as well as conduction through the $`\sigma `$-channel is important, the model gives a good description of the conductance with an average deviation of less than $`15\%`$. The fact that the model gives values above $`2G_0`$ is a consequence of the neglected interference between different molecular levels. Finally, we note that the $`1/N`$-dependence of the resonance width together with the $`N`$-dependence of the resonance spacing implies the existence of conductance oscillations also for longer wires. This is in agreement with previous results in Ref. zeng02 .

In summary, our calculations show that in contrast to the even-odd effect the conductance of monatomic Al wires oscillates with a 4-atom period as the number of atoms in the wire is varied. This behavior is explained by combining a resonant transport picture with the electronic structure of the free Al wire. By relating the electronic structure of a free wire to the valence band of the infinite wire, we find that the period of oscillation is determined by the filling factor of the valence band of the infinite wire. For long wires ($`>4`$ atoms) a simple model based on these ideas was shown to reproduce the first principles conductances while for short wires the simple picture is modified by charge transfer and tunneling effects.

The Center for Atomic-scale Materials Physics is sponsored by the Danish National Research Foundation. We acknowledge support from the Danish Center for Scientific Computing through Grant No. HDW-1101-05.