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# 1 Introduction

## 1 Introduction

It’s not often when sophisticated techniques developed for astronomy can answer an earthly mystery that has persisted for thousands of years. Yet there is a direct link joining the Cosmic Background Explorer (COBE) spacecraft and lunar laser-ranging to the precise dating of a celebrated historical event - the fall of Babylon to the Hittites in the second millennium B.C.

One of the most famous cities in the ancient world, Babylon was strategically located on the Euphrates River. There it wielded political power and controlled trade throughout a large region of Mesopotamia (modern-day Iraq). Yet we remember it today as a fount for our scientific heritage. Babylonian astronomy is directly echoed in the Almagest of Claudius Ptolemy (about A.D. 140), which epitomized this science until the time of Copernicus 14 centuries later. Even nowadays our culture is bound to such inventions as the sexagesimal system and the zodiac.

My involvement with Babylonian astronomy started in 1995, when I met Hermann Gasche, a leading European archaeologist, coordinator of excavations in various areas of Mesopotamia, and author and editor of many books on the archaeology of the region. Our association seemed preordained. Several years earlier, while visiting Armenia, Gasche became aware of unpublished works prepared in the 1920s and ’30s by the archaeologist Ashkharbek Kalantar, my grandfather, and he arranged for their publication.

As we sat in his Paris studio full of pictures of pottery, Gasche excitedly told me about a problem he had been working on with two American researchers, archaeologist James Armstrong and Assyriologist Steven Cole. The vessel shapes he had studied at various archaeological sites couldn’t be accommodated within the time frame of the so-called Middle Chronology (see box) of Mesopotamia, which was the most commonly accepted scheme but also the most criticized. (Archaeologists frequently use pottery evidence to help date ancient cultures.) To reconcile what Gasche and his colleagues had found required shortening the Middle Chronology by about a century.

Part of the reason behind Gasche’s excitement was a group of tablets recently unearthed at a site in a Baghdad suburb called Tell Muhammad. Among these tablets were two bearing references to a lunar eclipse that occurred 38 years after Babylon was resettled. He wanted to see whether I could use that eclipse and other astronomical sources to establish an absolute chronology for around the time Babylon fell and perhaps simultaneously resolve the pottery enigma. Such a chronology can only be established through astronomical records like those on the eclipse tablet. Indeed, the standard Near Eastern chronology from about 1400 B.C. to 700 B.C. - based on the so-called Assyrian Kinglist - is anchored by records of the solar eclipse of June 15, 763, B.C.

My first step was to carefully examine the existing literature and the methodology of ancient Babylonian astronomers and mathematicians. It soon became evident that chronologies for eras earlier than 1400 B.C. - based on the so-called Venus Tablet from the reign of King Ammisaduqa of Babylon \- were flawed. The reason is trivial: although the tablet contains sightings of the planet that could conceivably be dated, its 20 identified fragments are actually corrupted copies made about a thousand years after the events took place.

The Venus Tablet is one (Number 63) of a series of some 70 tablets collectively known as Enuma Anu Enlil. Two others (Numbers 20 and 21) record a pair of lunar eclipses connected with the Third Dynasty of Ur, which dominated Babylonia around 4,000 years ago.

## 2 Unscrambling the Evidence

I started with a reexamination of the Venus Tablet. This remarkable text, identified in the 1910s by the Jesuit Franz Kugler, contains data on first and last visibilities of Venus during a 21-year period that is believed to involve the reign of King Ammisaduqa, who governed a little over a century after the famous Babylonian king Hammurabi.

Following an orbit inside Earth’s, Venus becomes temporarily invisible when it aligns itself either between the Earth and Sun (inferior conjunction) or beyond the Sun (superior conjunction). These passages mark when Venus switches from being a Morning Star to an Evening Star or vice versa. Very important to the Babylonian astronomers, as documented in the Venus Tablet, is that these morning/evening visibility cycles repeat almost precisely in the sky every 8 years. (Five of Venus’s conjunction-to-conjunction periods of 584 days equal 8 years within a couple of days.)

Almost from the time of its discovery it became evident that the Venus Tablet contains errors made by the original scribe as well as later copyists. Also, parts of it are obscured and unreadable. So it’s not surprising that scholars have disagreed on its usefulness for dating events in the ancient Babylonian world. Erica Reiner and David Pingree, for example, claimed it was impossible to extract reliable chronological information from the tablet. Nevertheless, researchers have continued to rely on the Venus Tablet to generate chronologies for the centuries preceding the fall of Babylon.

In modern jargon, we can say the tablet has ”noisy” data, and that’s where my experience with COBE proved useful. In 1996 I worked with COBE team member Sergio Torres on ways to pluck real signals from COBE’s complete data set. This was no easy task because of pervasive contamination by noise from the cosmos, the Earth’s atmosphere, and the detectors themselves. We were analyzing the distortion of ”hot” and ”cold” spots in sky maps of the cosmic microwave background, and we finally detected a tiny signal that matched a theoretical prediction to suggest the universe might have negative curvature and expand forever. (We published the result in Astronomy and Astrophysics, Vol. 321, page 19, 1997.)

When I applied the same kind of sifting to the Venus Tablet, I came up empty-handed. The Monte Carlo technique of random sampling, as well as other statistical schemes, revealed noise but no significant signal except for that of the 8-year Venus cycle.

Another lesson from COBE is that the nature of the noise itself can be studied - in other words, some corruptions might be identified because they have a systematic character. The opportunity to apply such modern analytical techniques to archaeology is new and might lead to important insights about ancient texts.

Then I turned to dating the two lunar eclipses recorded during the Third Dynasty of Ur, which occurred more than 400 years before Babylon’s fall. The problem was to accurately match up modern predictions of what should have been seen with what was actually observed. At first glance this seems to be a simple task. Indeed, there is plenty of software for home computers that can do the calculations, and there are lists that tell where eclipses occurred thousands of years ago and give such circumstances as their beginning and ending times to an accuracy of minutes.

However, before utilizing such resources one has to clearly understand the approximations inherent in both the input data and in the algorithms for the calculation. A program can work well over short time spans but not over long ones, because planetary motions are essentially nonlinear and initial errors propagate exponentially. Therefore, for an orbit to be precisely defined over a given span of time, the input data have to be sufficiently accurate and all planetary perturbations have to be properly taken into account. The perturbations, particularly, are responsible for many unforeseen effects, including chaos and other unpredictables.

Archaeologists are basically interested in two consequences of such calculations. One is the determination of the moment the Moon arrives at a point in its orbit opposite the Sun, when it can pass through the Earth’s shadow and be eclipsed. The second is to find the local time an observer’s clock would show for the event. The physical interrelated effects that contribute to uncertainty include tidally and nontidally induced variations in the Earth’s rotation rate and the gradually increasing distance of the Moon from Earth. With events that happened 4,000 years ago, like the Ur eclipses, these effects can result in prediction errors of up to two hours, not merely minutes, despite using the most accurate data available.111My work owes a debt to visionaries at the dawn of space flight. Historically, lunar occultations of stars provided information about the Moon’s position. But a dramatic improvement in the accuracy of the data occurred after Apollo astronauts placed laser reflectors on the Moon. Kenneth Nordtvedt, the initiator of the project, told me how he once deliberately took the same plane as physicist Robert Dicke, then chairman of NASA’s Physical Science Committee, so he could convince him to include the laser-ranging reflectors on forthcoming Apollo missions. As a result, we now have much better knowledge of the parameters that define the Moon’s orbit, its principal perturbations by the Sun, Venus, and Jupiter, and other factors.

My search was constrained by the textual evidence in Tablets 20 and 21 of the Enuma Anu Enlil. The two eclipses described there had been linked by ancient astrologers with decisive events in Babylonian history: the death of the greatest of the kings of Ur, Sulgi, and the destruction of Ur at the hands of the Elamites. The ancient scribes preserved important descriptive information about these eclipses that is crucial for dating them correctly: the time of day that each began and where the Moon was in the sky. We also know that the eclipses had to occur 41 to 44 years apart because we know the relative dates of the two historical events to which they were connected.

My colleagues and I agreed that I should attempt to identify the two eclipses by scanning a 300-year interval centered on date of the fall of Ur (2005 or 2004 B.C., according to the Middle Chronology). As it turned out, across these three centuries only the eclipses of June 27, 1954, B.C. and March 16, 1912, B.C. fit the ancient descriptions of the eclipses within possible inaccuracies of interpretation.

## 3 Assembling the Case

Now we could fix a date for the fall of Babylon. We had the date of the fall of Ur, and the ancient records were detailed enough for us to establish, within only a few years, the length of time that separated Ur’s collapse from events that took place in Babylon several centuries later. Next, the Venus Tablet allowed us to link the reign of Ammisaduqa and the 8-year cycle of Venus. Only simple arithmetic was needed to identify the possible Venus-derived dates for the fall of Babylon. When those were compared with the information from the lunar eclipses, the date of Babylon’s fall could be fixed as 1499 B.C. This date, some 96 years more recent than the Middle Chronology date of 1595 B.C., fits well with the pottery evidence that led Gasche to ask me to look at the ancient astronomical records in the first place.

Having established this date, I could now look at the information about the eclipse as recorded on the tablets from Tell Muhammad and determine when Babylon was resettled. However, in contrast with the Enuma Anu Enlil record, I was not dealing with eclipse descriptions. The Tell Muhammad tablets simply mention the eclipse in a so-called year-name that can be translated as ”The year that the Moon was eclipsed.” The two tablets also bear a second date formula as well: ”Year 38 that Babylon was resettled.”

It is unusual for texts to be dated according to two different systems. What is probably going on with these and other Tell Muhammad tablets is that an old, local year-name dating system was being gradually replaced by a new, Babylon-oriented one, and during the changeover the scribes used both kinds of dates. In any case, this redundancy allows us to date the resettlement of Babylon after its fall to the Hittites. Based on the available evidence, the Tell Muhammad eclipse most likely occurred on May 16, 1459, B.C., so Babylon was resettled in 1496 B.C., only three years after its collapse.222In Babylon, each year was named for something noteworthy that occurred, such as a military victory or building project. However, this name was applied to the year following the memorable event. Thus, the so-called name-year, ”the year of the eclipse,” referring to the May 16, 1459, B.C. eclipse, is 1458 B.C.

## 4 Epilogue

Our absolute chronology follows work by generations of scholars. This quest has been important because any change in the Babylonian chronology affects dates of events in other ancient kingdoms of the Near East. Elamite dynasties, the Old Hittite Kingdom, the Levant in the Middle Bronze Age, and the Second Intermediate Period in Egypt must now be fitted into this new scheme.

Subsequent to our study, my colleagues and I learned of independent investigations that strongly support our new chronology. In particular, Guido Gualandi, who has studied the seals from the ancient city of Terqa in eastern Syria, reports that only by using a ”low” chronology like ours can he make sense of the similarities among seals of the city’s different kings. These similarities are simply too great to be easily explained if the rulers involved are separated from one another by spans of time as long as those necessitated by the traditional Middle or High Chronologies. Furthermore, studies of records in Egyptian papyruses from around 1800 and 1500 B.C. by Rolf Krauss also support our results rather than the Middle Chronology, which Krauss says nobody ever really believed! This prominent scholar confessed to me that he had been almost certain that the absolute chronology of the Near East would not be determined during his lifetime.

Best of all, the morning after we had established the date of the fall of Babylon, I visited the British Museum with my daughter, Diana. The Babylonian kings there were smiling at us!

## 5 Babylonian Chronologies

Comments by James A. Armstrong

Using ancient records, historians can reconstruct the Babylonian chronology very precisely back to 500+ years before Babylon’s defeat at the hands of the Hittite king Mursili I. However, providing absolute dates over this half-millennium span has proved to be very difficult, particularly because it is separated from the earliest reliable Mesopotamian dates, which cluster around 1400 B.C., by an intervening period of unknown length.

Since simply ”counting back” from 1400 B.C. is not possible, researchers have turned to the Venus Tablet for help (see text above). They identified observational cycles of 56 and 64 years that seemed to underlie the data recorded on the tablet and, as a result, were able to propose a series of alternative chronologies. The three most frequently cited, commonly referred to as ”High,” ”Middle,” and ”Low,” place the fall of Babylon in 1651, 1595, and 1531 B.C., respectively. Even though the reliability of the Venus data has been seriously questioned, Mesopotamian scholars have generally utilized one or another of these chronologies.

Vahe Gurzadyan has now shown that the 56- and 64-year cycles, which had the practical effect of limiting the number of viable chronologies, cannot be extrapolated from the Venus Tablet data. Instead, there is only an 8-year cycle, which, theoretically at least, permits many alternative chronologies for the 5 centuries leading up to Babylon’s fall. However, because Gurzadyan has also been able to identify and date a pair of lunar eclipses from the early part of this half-millennium span, the fall of Babylon can be confidently pegged at 1499 B.C.


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# Pore dynamics of osmotically stressed vesicles

## Abstract

We present a theory for pore dynamics of osmotically stressed vesicles. When a liposome with an internal concentration of solute is placed inside a solute-depleted medium, an osmotic flow of solvent through the lipid bilayer leads to swelling of vesicle and to increase in membrane surface tension. This can result in membrane rupture and opening of thermal pores. Depending on the internal concentration of solute and the size of the vesicle, pores can close rapidly or be long-lived. We find that the life span of the long-lived pores scales non-trivially with the size of the liposome. Closure of the long-lived pore is followed by a rapid flicker-like opening and closing of short-lived pores. Our model is consistent with the observation of long-lived pores in red blood cell ghosts.

Opening of stable pores in cellular phospholipid membranes is an important step for drug delivery and gene therapy. A number of methods have been explored to this end. Electroporation BeBeZi79  is the method of choice when gene delivery is performed in vitro. It is, however, associated with a significant cell mortality limiting its practical use. Holes in cellular membranes have also been opened by intense illumination BaFrMo95 ; MoNeBa97 . The mechanism leading to pore formation under these circumstances is still not fully understood. It, however, appears to be similar to the action of laser tweezers Gr00 , a part of the low dielectric constant lipid membrane is sucked into the laser trap, stretching the membrane until rupture.

For drug delivery the goal is to introduce a controlled amount of substance to the specific disease site. The delivery system should minimize the potential side-effects by selectively targeting the affected region of the organism MaFeCu01 . Liposomes can be made to contain drugs or genes and can be introduced into blood stream without provoking an immune system response. Liposomal affinity for specific tissue can be increased by varying the membrane lipidic composition or by including ligands that recognize and bind to specific receptors Pa02 . One example of this is the drug called Doxirubicin used in cancer chemotherapy. The liposomal encapsulation of Doxirubicin has been shown to efficiently deliver it to tumors, while minimizing the side effects, such as damage to heart muscle tissue.

When liposome ruptures, its content leaks out. It is precisely the dynamics of this rupture that is the subject of the present Letter. In particular, our goal is to understand the mechanism of pore opening and closure in the osmotically stressed vesicles. The situation which we attempt to model is the following. Liposomes are prepared inside a solution containing small molecules impermeable to lipid membrane at concentration $`c_0`$. They are then placed into a purified aqueous solution. The imbalance in solute concentration inside and outside the vesicles leads to osmotic flow of solvent through the semi-permeable lipid membrane, resulting in swelling of vesicles and stretching of their membranes. As the tension increases, the energy barrier to pore nucleation decreases DeGu62 . If there is enough solute inside the liposome, the barrier height eventually becomes comparable to the energy of thermal fluctuations. When this happens, membrane raptures and a pore opens TaDvSa75 . One interesting question is what is the life span of this pore? Specifically, as a pore opens it relaxes the membrane tension. However, opening of a pore exposes the hydrophobic interior of membrane to water, leading to pore line (edge) tension. This hydrophobic effect induces a force which tries to re-seal the pore. Furthermore, a hole in membrane results in efflux of both solute and solvent, reducing the vesicle volume and surface tension. All these effects lead to an intricate interplay of time and length scales which control the pore closure.

We shall designate the radius of a vesicle as $`R`$ and the radius of a pore as $`r`$. The conservation of mass then leads to

$$4\pi \rho R^2\frac{dR}{dt}=j_w\pi r^2\rho v,$$
(1)
where $`\rho `$ is the density of water, $`j_w`$ is the osmotic flux and $`v`$ is the leak-out velocity. The leak-out velocity HaBr86 ; ZhNe93 ; SaMoBr99 ; BrGeSa00  is determined by the balance between the shear stress, proportional to $`\eta v/r`$, and the osmotic pressure inside the vesicle $`\mathrm{\Delta }p`$,

$$v=\frac{\mathrm{\Delta }pr}{3\pi \eta },$$
(2)
where $`\eta `$ is the solvent viscosity. Inside a swollen vesicle the osmotic pressure is compensated by the Laplace pressure, so that

$$\mathrm{\Delta }p=\frac{2\sigma }{R},$$
(3)
where $`\sigma `$ is the tension of a stretched membrane. In this work we shall concentrate on vesicles with fairly large internal concentrations of solute, close to $`1`$ M. This corresponds to osmotic pressures as high as $`20`$ atmospheres. Of course, before these extreme pressures can be built, the lipid membrane will rapture, leaking out some of the internal content and releasing the surface stress. At these high pressures, the thermal undulations of membrane can be ignored, and the membrane tension is controlled by the stretching modulus HeSe84 ; EvRa90 ; SeIs02  $`K_s`$. The membrane elastic energy takes a Hook-like form

$$E_s=\frac{1}{2}K_s(AA_0)^2,$$
(4)
where $`A_0=4\pi R_0^2`$ is the equilibrium surface area of the unstretched membrane. As the membrane is stretched beyond the elastic limit, pores are nucleated reducing the membrane tension. The elastic energy of a membrane with a pore is

$$E(R,r)=\frac{1}{2}K_s[4\pi (R^2R_0^2)\pi r^2]^2+2\pi \gamma r,$$
(5)
where $`r`$ is the pore radius and $`\gamma `$ is the pore line tension. The membrane surface tension is,

$$\sigma (R,r)=\frac{E_s}{A}=K_s(4\pi (R^2R_0^2)\pi r^2).$$
(6)
The osmotic current $`j_w`$ is determined by the membrane permeability $`P`$, the concentration difference of solute inside and outside the vesicle, and the Laplace pressure. A simple phenomenological expression for the osmotic current of water into the vesicle can be written as,

$$j_w=P(4\pi R^2\pi r^2)\left[c\frac{2\sigma }{10^3k_BTN_AR}\right],$$
(7)
where $`k_B`$ is the Boltzmann constant and $`N_A`$ is the Avogadro number. If the difference of molar $`(M)`$ solute concentration $`c`$, inside and outside the vesicle is not very large, the integrity of membrane will not be compromised, and a stationary state with $`j_w=0`$ will be achieved. Under these conditions the osmotic pressure is completely compensated by the Laplace pressure, resulting in zero net flux of solvent. For sufficiently large internal concentration $`c_0`$, a stationary state will not be achieved before membrane ruptures. It is precisely in this regime that we expect to see some interesting physics.

The growth of a pore is controlled by the rate at which the elastic energy is dissipated by the membrane viscosity $`\eta _m`$ DeMaBr95 ,

$$\eta _ml\frac{dr}{dt}=\sigma (R,r)r\gamma ,$$
(8)
where $`l`$ is the membrane width. Since the membrane is impermeable to solute particles the internal solute concentration is modified only through the osmotic influx of solvent and the efflux of solute through the open pore, after membrane has ruptured. The continuity equation expressing this is

$$\frac{4\pi }{3}R^3\frac{dc}{dt}=4\pi R^2c\frac{dR}{dt}\pi r^2cv,$$
(9)
where we have assumed that solute is uniformly distributed inside the vesicle.

We are now in position to study the evolutionary dynamics of an osmotically stressed vesicle. The characteristic values of the parameters appearing in the above equations are: $`4\pi R_0^2K_s=0.2J/m^2`$, $`l=3.5nm`$, $`\gamma =10^{12}J/m`$, $`\eta _m=100Pas`$ , $`\eta _w=10^3Pas`$ and $`P=1.8\times 10^4kg/m^2sM`$.

The energy necessary to open a pore or radius $`r`$ is $`\mathrm{\Delta }E(R,r)=E(R,r)E(R,0)`$. The form of $`\mathrm{\Delta }E(R,r)`$ as a function of pore size is plotted in Fig. 1 for various values of $`R`$.

As the osmotic flow of solvent stretches the membrane, a minimum in $`\mathrm{\Delta }E(R,r)`$ for $`r0`$ indicates energetic favorability of pore formation. However, to reach this minimum a sufficiently large thermal fluctuation is necessary to overcome the energy barrier. The probability of such a fluctuation occurring is proportional to the Boltzmann factor

$$P(r)e^{\beta \mathrm{\Delta }E(R,r^{})},$$
(10)
where $`\beta =1/k_BT`$ and $`r^{}`$ is the critical pore size. Pores with $`r<r^{}`$ will shrink and close while pores with $`rr^{}`$ will grow. The waiting time for appearance of a thermal fluctuation with enough energy to open a pore of radius $`r^{}`$ is very long, unless $`\mathrm{\Delta }E(R,r^{})k_BT`$.

In the limit of large surface tensions the critical pore size is $`r^{}\gamma /\sigma `$ and the barrier height is

$$\beta \mathrm{\Delta }E_b\frac{\pi \gamma ^2}{\sigma k_BT}.$$
(11)
We note that when membrane tension reaches $`\sigma _c=10^3J/m^2`$, the barrier height is approximately $`k_BT`$. This value of $`\sigma _c`$ is in agreement with the tensions found to be necessary to rupture a mechanically stretched membrane Ti74 ; WeCh96 . The minimum solute concentration necessary for a pore to open is

$$c_0^{min}\frac{2\sigma _c}{10^3k_BTN_AR_0},$$
(12)
which for a vesicle of $`100`$ nm is approximately $`10mM`$.

The dynamics then proceeds as follows: Eqs. (1),(8), and (9) are solved numerically, using Euler’s method with a stepsize of $`\delta t=0.1\mu s`$, to find the evolution of $`R(t)`$, $`r(t)`$, and $`c(t)`$. When the surface tension becomes such that, $`\mathrm{\Delta }E_bk_BT`$, a pore of size $`r^{}`$ opens, see Fig. 2, and the internal content of the liposome begins to leak-out. This process reduces the volume of the vesicle and decreases the membrane tension, until the pore closes. Once this happens, the osmotic swelling of the liposome re-starts. As the energy barrier to pore nucleation drops down to $`k_BT`$ a new pore is opened, etc. The process stops when the internal solute concentration reaches $`c_0^{min}`$ and a stationary state with $`j_w=0`$ is established.

For small vesicles, pores open and close very quickly with the characteristic time $`\tau _f10^2`$, resulting in a periodic flickering. For liposomes with $`R_0>R_0^c(c_0)`$ a long-lived pore appears, see Fig. 3. The critical size of a liposome $`R_0^c(c_0)`$, necessary for nucleating a long-lived pore depends on the internal solute concentration. Larger the initial solute concentration $`c_0`$, smaller will be the size of the vesicle which supports a long-lived pore. The long life span of these pores is the result of a “wash-out” effect in which the osmotic flux is almost completely compensated by the leak-out rate of solute through the pore. When solute concentration inside the vesicle drops below the critical value, $`c_c(R_0)`$, the long-lived pore closes. This value is insensitive to the initial solute concentration $`c_0`$, but depends strongly on the vesicle size $`R_0`$. The life span of a long-lived pore $`\tau `$ scales with the vesicle size $`R_0`$,

$$\tau R_0^\nu ,$$
(13)
with $`\nu 2.32.4`$, see Fig. 3. After the long-lived pore has closed, it is followed by a sequence of short-lived pores with the characteristic life span $`\tau _f`$.

We have checked that the pore dynamics is not sensitive to the specific mechanism of pore opening. In particular, even if the pores are opened stochastically, with the probability given by the Boltzmann distribution, the rate of leakage and the life span of the long-lived pores is affected very little.

Up to now we have not taken into account the diffusive efflux of solute through the open pores. The diffusive current through a pore of size $`r`$ is approximately

$$j_D\pi r^2c\frac{D}{R_0}.$$
(14)
This leads to the decline of internal solute concentration governed by the conservation equation,

$$\frac{4\pi }{3}R_0^3\frac{dc}{dt}=j_D,$$
(15)
the solution of which is

$$c(t)=c_0e^{\frac{t}{\tau _e}},$$
(16)
where the effusion time $`\tau _e`$ is

$$\tau _e=\frac{4R_0^4}{3r^2D}.$$
(17)
Using $`D10^9m^2/s`$, appropriate for small organic molecules such as sucrose, and $`r=r^{}\gamma /\sigma _c1nm`$, we see that for liposomes with $`R_0=50nm`$, the time for effusion is $`\tau _e10^2`$ s. This is comparable to the flicker time $`\tau _f`$. Therefore, for small vesicles effusion is an important mechanism for the loss of solute. On the other hand, for liposomes with $`R_0=100nm`$ and above, effusion is only marginally relevant.

Long lived pores have been observed in red blood cell ghosts St70 ; StKa74 , their size dependent on the ionic strength of the surrounding medium LiSt82 . No theory, up to date, was able to account for these long-lived pores. Holes were predicted to either grow indefinitely, which would result in ghost vesiculation, or to close completely BeBr99 . Our model provides a dynamical mechanism for pore stabilization, consistent with the experimental observations. In the specific case of red blood cell ghosts the ratio $`\gamma /K_s`$ has to be ajusted to account for the large radius $`r/R_0`$ observed in these experiments St70 ; StKa74 .

In aqueous solutions the phospholipid membranes acquire a net negative charge. At physiological concentrations, $`154mM`$ of $`NaCl`$, the Debye length, however, is quite short, less then $`1nm`$ and the electrostatic interactions are strongly screened Le02 . We, therefore, do not expect that electrostatics will significantly modify the basic conclusions of our theory, beyond the renormalization of membrane line BeBr99  and surface tension. However, further, investigations in this direction are necessary and will be the subject of future work.

Finally, it is curious to note a strong similarity between the rupture of osmotically stressed liposomes and bursting of Hydra cells aggregates MoAlTh01 . Hydra and marine sponges can generate functional organisms from random cell aggregates purely through the intercellular interaction. This morphogenesis is characterized by the cavity formation followed by swelling and violent bursting, which expels the internal fluid and dead cells, see Fig. 5.

Unlike the liposomes, cellular aggregates are too massive for temperature to be of any relevance. Instead the cellular Brownian motion is driven by the metabolic fluctuations of the cytoskeleton MoGl96 . We can, therefore, expect that a theory similar to the one presented above for the liposomes, might also apply to osmotically driven bursting of cellular aggregates.

The authors are grateful to Ms. V. A. Grieneisen for kindly providing the photos of bursts in hydra aggregates, Fig. 4. This work was supported in part by the Brazilian agencies CNPq and FAPERGS.


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# First-principles study of electron transport through C20 cages

## Abstract

Electron transport properties of C20 molecules suspended between gold electrodes are investigated using first-principles calculations. Our study reveals that the conductances are quite sensitive to the number of C20 molecules between electrodes: the conductances of C20 monomers are near 1 G0, while those of dimers are markedly smaller, since incident electrons easily pass the C20 molecules and are predominantly scattered at the C20-C20 junctions. Moreover, we find both channel currents locally circulating the outermost carbon atoms.

preprint: Otani2003

As new techniques for the atomic-scale manipulation and modification of materials progress, electron transport properties of nanostructures have attracted considerable interest Datta . To date, special attention has been focused on atomic and molecular systems, such as organic molecules and fullerenes, because they are expected to be the ultimate size limit of functional devices and show unique behaviors different from those of macroscopic systems Molecular . Joachim et al. Joachim  indicated experimentally that a deformed C60 molecule has the possibility of being a nanoscale electrical amplifier. Recently, a C20 cage solely with pentagons has been produced from C20H20 Prinzbach , which is the smallest fullerene that is one of the candidates of much minuter electronic devices. While these prospects of fullerene-based devices are exciting, there remains much to be learned about their electronic characteristics.

On the theoretical side, first-principles calculations have been employed to provide insight into geometric and electronic properties of nanostructures. Concerning C20 cage systems, Miyamoto et al. miyamoto  studied C20 one-dimensional infinite chains to indicate that some stable chain structures can be formed and one of them possesses semiconductivity. Later, Roland et al. Roland  presented electron-conduction properties of one-dimensional short chains made of several C20 molecules suspended between Al or Au leads, and they summarized that the conductances do not depend on the number of molecules contained in the chains. Although these studies give us certain knowledge about fullerene-based devices, a transparent view on the quantized electron transport, which can contribute to designing future devices, has not been provided yet, and further examinations of the conduction properties and the current flowing through the devices are indispensable.

In this Rapid Communication, we present elaborate first-principles calculations for electron transport properties, in particular, the conduction channels and their current distributions of C20 molecules suspended between two semi-infinite Au electrodes. To the best of our knowledge, this is the first report focusing on how incident electrons can flow and reflect within the system of C20 molecules intervening between the electrodes. Our main findings are as follows: (1) contrary to the conclusion reported by Roland et al. Roland , the number of C20 molecules between the electrodes largely affects the electron transport behavior. The conductances of C20 monomers are around 1 G0(=2$`e^2/h`$), and on the other hand, those of dimers are markedly smaller. (2) Electron currents are found to pass along the C-C bonds, and not to directly cross through to inside the C20 cages. Backscattering of incident electrons occurs at both the C20-electrode interfaces and the C20-C20 junctions of the dimers, while reflection seldom takes place within the C20 molecules. (3) Channel current distributions exhibit local loops around the outermost carbon atoms.

Our first-principles molecular-dynamics simulation is based on the real-space finite-difference method rsfd , which enables us to determine the self-consistent electronic ground state and the optimized atomic geometry with a high degree of accuracy, by making use of the timesaving double-grid technique tsdg  and the direct minimization of the energy functional dmef . The norm-conserving pseudopotentials ncps  of Troullier and Martins tmpp  are adopted and exchange-correlation effects are treated by the local density approximation lda  of the density functional theory. The electron transmission at the Fermi level is calculated by the Landauer formula in cooperation with the overbridging boundary-matching method fujimoto . Figure 1 shows the calculation models employed here. For C20 monomers sandwiched between electrodes, we examine the two models, a double-bonded one shown in Fig.1(a) and a single-bonded one shown in Fig.1(b). In the cases of dimers, we adopt the double-bonded and single-bonded dimers indicated in Figs.1(c) and (d), respectively, the orientations of which are in accordance with those proposed by Miyamoto et al. miyamoto . The C20 monomers and dimers, which are individually optimized in advance comment-geometry , are put between the electrodes. Since many first-principles investigations using structureless jellium electrodes are in almost quantitative agreement with experiments Lang ; Kobayashi ; Okamoto ; Tsukamoto , we substitute jellium electrodes for crystal ones. The distance between the edge atoms of inserted molecules and the jellium electrode is set at 0.91 a.u.

We first determine the stable structures of C20 monomers and dimers suspended between the Au electrodes. For structural optimization, a conventional supercell is employed under the periodic boundary condition in all directions. The size of the supercell is $`L_x=L_y=21.6`$ a.u. and $`L_z=L_{mol}+25`$ a.u., where $`L_x`$ and $`L_y`$ are the lateral lengths of the supercell in the $`x`$ and $`y`$ directions parallel to the electrode surfaces, $`L_z`$ is the length in the $`z`$ direction, and $`L_{mol}`$ is the length of the inserted molecules. We take a cutoff energy of 110 Ry, which corresponds to a grid spacing of 0.30 a.u., and a higher cutoff energy of 987 Ry in the vicinity of nuclei with the augmentation of double-grid points tsdg . Structural optimizations of the molecules between the electrodes are further implemented until the remaining forces acting on atoms are smaller than 1.65 nN. Consequently, all models become shorter along the $`z`$ axis shorter .

Next, we explore the electronic conductance and channel transmissions of the C20 molecules at the zero-bias limit with the Landauer formula G=tr(TT)G0, where T is a transmission matrix. The eigenchannels are investigated by diagonalizing the Hermitian matrix (TT) Kobayashi . Here, we impose the nonperiodic boundary condition in the $`z`$ direction and employed semi-infinite Au jellium electrodes. A cutoff energy (a higher cutoff energy around nuclei) is set at 62 (555) Ry. The results of the conductances and channel transmissions at the Fermi level are collected in Table 1. Although an isolated C20 molecule has a small gap between highest occupied molecular orbital and lowest unoccupied molecular orbital Kashenock , considerable electron conductions are observed in the C20 molecules suspended between the electrodes. The high conduction property is attributed to a significant amount of charge transfer from the electrodes to molecules comment-ChargeTransfer , which is localized at the interface between the electrodes and molecules. As be seen in Table 1, there are four channels that actually contribute to electronic conduction in both the monomer models: the monomer models exhibit the high conductance of 1.57 G0 for the double-bonded one and 0.83 G0 for the single-bonded one. The difference in the conductance between the two monomer models is caused by the number of atoms facing the jellium electrodes. In the case of the dimer models, the conductances of the double-bonded one and the single-bonded one are 0.18 G0 and 0.17 G0, respectively. In spite of more atoms facing the electrodes, the double-bonded dimer has an approximately equal conductance to that of the single-bonded one, which cannot be expected from the above results of the monomer models. The higher conductance of the single-bonded dimer is consistent with the previous calculation that the band gap of an infinite single-bond chain is significantly smaller than that of a double-bonded one miyamoto . As for the conductance dependency on the number of molecules between electrodes, Roland et al. Roland  demonstrated that the conductance at the Fermi level does not decrease even when the number of molecules increases. This discrepancy between our results and theirs is mainly brought about by the difference of the molecular orientations; we adopted the models of the most stable geometry.

Figure 2 shows channel electron distributions at the Fermi level, where the cross sections at the center of the models along the $`z`$ direction are depicted. Scatterings of incident electrons are found at the entrances and exits of the molecules rather than within the C20 cages. Moreover, in the case of dimers, electrons are clearly reflected at the C20-C20 junctions. Channel current distributions at the Fermi level are illustrated in Fig.3, in which electrons are observed to conduct along the C-C bonds of the C20 cages rather than inside the cages. We found a more striking feature that local loop currents are induced around the outermost carbon atoms.

In summary, we have investigated electron conduction properties of C20 molecules connected to semi-infinite Au jellium electrodes using the overbridging boundary-matching method, which allows us to carry out first-principles transport calculations. Our results indicate that conductances greatly depend on the number of C20 molecules between the electrodes: the conductances are around 1 G0 for the monomer models, and extremely small for the dimer models. We find that the electron currents follow the C-C bonds, and do not cross the C20 cages. Incident electrons are predominantly scattered at both the C20-electrode interfaces and the C20-C20 junctions while they are hardly reflected within the C20 molecules. In addition, the channel currents are observed to form local loops circulating around the outermost carbon atoms. The present analysis is applicable to various kinds of nanostructures, and will enable the elucidation of their conduction properties.

This research was partially supported by the Ministry of Education, Culture, Sports, Science and Technology, Grant-in-Aid for Young Scientists (B), 14750022, 2002. The numerical calculation was carried out by the computer facilities at the Institute for Solid State Physics at the University of Tokyo, and Okazaki National Institute.