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TV drama reopens debate about Germans' war guilt
by frank jordans, associated press
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berlin | With the wartime generation rapidly disappearing, a television drama about five young Germans in World War II has revived debate in Germany about the role ordinary men and women played in the Nazis' murderous campaign to conquer Europe.
Millions tuned in last week to watch the three-part series "Our Mothers, Our Fathers," which follows five young Germans — two brothers, a nurse, an aspiring female singer and a Jewish tailor — as they struggle through one of the bloodiest conflicts in history.
Three of the characters, including the Jew, survive — disillusioned and physically broken — to confront each other and their own demons in the final episode in the ruins of Berlin.
The mixed reactions to the series underscore how, nearly 70 years after World War II, the conflict remains a source of bitterness in Europe, even for people born after the fighting ended.
Many critics have praised the series as a milestone in Germany's troubled reckoning with its past and an overdue examination of individual guilt in the war. But some accuse the film of sidelining the Holocaust and depicting Germans as victims rather than a nation responsible for starting a war and committing genocide.
"A film about World War II that omits the bothersome question of 6 million dead Jews," remarked columnist Jennifer Nathalie Pyka in Jüdische Allgemeine, Germany's leading Jewish weekly.
Jan Sueselbeck, a researcher at the University of Marburg, said the series reflects wishful thinking rather than historical facts. The drama glosses over Hitler's rise to power and the outbreak of war by beginning the story in 1941, two years into the European conflict.
"This film depicts Germans once more the way they would like to have been, but in fact the broad masses were never like that," Sueselbeck said.
Many Germans born after the war remain largely ignorant of what their parents did because, like many combat veterans or survivors, the elders don't want to talk about it.
Hofmann said one of his goals was to encourage a national debate among the generations "to speak for the first time about the experience" of the war. He said the third and final episode drew a 20.5 percent market share among viewers 14-59 years old, which he described as "extremely high."
A full, dispassionate accounting of German actions during the war never occurred because the Cold War division of Europe forced former enemies on both sides of the Iron Curtain to set aside their differences to confront a new set of rivals.
Until German reunification in October 1990, communist East Germany promoted the notion that Hitler and his fellow Nazis alone were responsible for the war and that Germans who were not Nazi party members were victims, too. Despite mountains of evidence to the contrary, many Germans still believe that ordinary soldiers didn't participate in and were ignorant of the atrocities committed by Hitler's feared SS and SA units.
"Were German soldiers really so brutal?" the mass-circulation daily Bild newspaper asked after one episode showed German soldiers killing civilians in revenge for a partisan attack.
In fact, soldiers killed thousands of civilians throughout the war and assisted death squads in the large-scale extermination of Eastern Europe's Jews. Some 3 million Russian soldiers died in German captivity, while the final stages of the war saw fanatical Hitler loyalists hand out thousands of death sentences to deserting German soldiers and so-called defeatists.
Since the series aired, newspapers and online forums have been filled with comments by descendants of the war generation, with many saying their parents rarely, if ever, spoke of their experiences.
The debate comes at a sensitive time for Germany's army, which broke with the postwar taboo of sending soldiers abroad only 20 years ago. Today, some 5,000 German soldiers are serving alongside American and British troops in Afghanistan. Others are involved in international missions in Kosovo, Lebanon and Mali.
"I can imagine that in many families where there are survivors there will be conversations," said Jens Wehner, a historian at the German military museum in Dresden.
Many families will have missed the opportunity to do so, because the number of Germans old enough to have participated in the war and still alive today is dwindling fast.
"Soon nobody will be left who experienced [the war]," warned Frank Schirrmacher, publisher of the conservative daily Frankfurter Allgemeine Zeitung. He praised the series "for the earnestness, the love of detail and the unwillingness to compromise," which allowed it to have "what it takes to touch the soul of the country."
Hofmann said he produced the series partly for his own father, who volunteered to join Hitler's army at 18, nearly died from wounds and to this day won't say if he took part in atrocities.
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Posts with tag "Fox"
Why Did Cheryl Cole Get Booted From U.S. 'X Factor'?
Posted May 26th 2011 at 02:56 PM by Elizabeth Yun- Filed under:
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It's official: British beauty Cheryl Cole has been ousted from her judging seat on the U.S. edition of the 'The X Factor' in favor of Pussycat Dolls lead singer Nicole Scherzinger. Scherzinger previously served as a guest judge on the original U.K. version of the singing competition where she thoroughly impressed both producers and her fellow judges. Cole rose to fame when she won a competition...
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Posted Mar 26th 2010 at 12:30 PM by Zach Dionne- Filed under:
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Sorry, Team Coco, but whispers that Conan O'Brien is inching ever closer to a late-night gig at FOX remain mere rumors. Big Red's manager told FOX News' Pop Tarts yesterday that the former 'Tonight Show' host's future is "far from a done deal." "He is not even close [to signing a new contract]," manager Gavin Polone said. "I don't know where that's all coming from. We've met with a few places ...
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Posted Mar 25th 2010 at 03:00 PM by Ben Widdicombe- Filed under:
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Conan O'Brien salvaged a public relations victory from his messy divorce with 'The Tonight Show' earlier this year by using his charm and wit to connect with audiences. But while the public still loves him, NBC's decision not to let O'Brien take part in Fox's 'Idol Gives Back' charity show has exposed an attitude in the television industry that thinks the former host made out like a bandit in the ...
Conan O'Brien 'Talking' to FOX, Others About TV Return
Posted Mar 19th 2010 at 06:55 AM by PopEater Staff- Filed under:
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Those waiting anxiously for Conan O'Brien to regularly appear on their televisions again are getting closer to having their wishes come true. O'Brien, who was ousted from 'The Tonight Show' by NBC and can't return on any network until September, is examining his options -- including FOX. "They are definitely talking," O'Brien's rep Leslee Dart said, The Associated Press reports. But she m...
'Glee Live! In Concert!' to Hit Stages Soon
Posted Mar 1st 2010 at 03:00 PM by PopEater Staff- Filed under:
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It's a great day for 'Glee' fans! As reported on Ryan Seacrest's radio show, the 'Glee' cast will be hitting the road for a four-city, seven-date tour this spring. The traveling cast will include all the members of New Directions, who took sectionals by storm before the show went on winter hiatus (it returns to Fox on April 13). However, fans will be sad to learn that Mr. Schuester, the group's...
Eliza Dushku Doesn't Expect To Ever Play In 'Dollhouse' Again
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Scores of Joss Whedon fans were disappointed to hear that his latest show, 'Dollhouse' has been canceled by Fox. We'll get to see the remaining episodes, and they had the news in time to wrap up the story, but that's cold comfort for most of us. We caught up with star Eliza Dushku on the red carpet for the US Weekly Hot Hollywood event, where she was being honored as "Cult Fave of the Year". While...
Oh, Ernie! Anchor Drops F-Bomb on Air
Posted Sep 17th 2009 at 09:33 AM by PopEater Staff- Filed under:
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In New York City, local Fox anchor Ernie Anastos is nothing short of a cuddly teddy bear, bringing the news with a smile every night. Sadly, his G-rated persona took a hit on Wednesday night when he dropped the dreaded F-bomb on air. Watch it (NSFW!) after the jump, and check out the amazing reaction by co-anchor Dari Alexander!...
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Moving from country to country in South America, reporting from across the drugs frontline and interviewing top-level international politicians this film exposes the human cost of one of ... See full summary »
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Likelihood-free estimation of model evidence
Didelot, Xavier, Everitt, Richard G., Johansen, Adam M. and Lawson, Daniel J. (2010) Likelihood-free estimation of model evidence. Working Paper. Coventry: University of Warwick. Centre for Research in Statistical Methodology. Working papers, Vol.2010 (No.12).
WRAP_Didelot_10-12w.pdf - Published Version - Requires a PDF viewer such as GSview, Xpdf or Adobe Acrobat Reader Download (809Kb) |
Official URL: http://www2.warwick.ac.uk/fac/sci/statistics/crism...
Statistical methods of inference typically require the likelihood function to be computable
in a reasonable amount of time. The class of "likelihood-free" methods termed Approximate
Bayesian Computation (ABC) is able to eliminate this requirement, replacing the evaluation
of the likelihood with simulation from it. Likelihood-free methods have gained in efficiency
and popularity in the past few years, following their integration with Markov Chain Monte
Carlo (MCMC) and Sequential Monte Carlo (SMC) in order to better explore the parameter
space. They have been applied primarily to the estimation of the parameters of a given
model, but can also be used to compare models.
Here we present novel likelihood-free approaches to model comparison, based upon the
independent estimation of the evidence of each model under study. Key advantages of these
approaches over previous techniques are that they allow the exploitation of MCMC or SMC
algorithms for exploring the parameter space, and that they do not require a sampler able to
mix between models. We validate the proposed methods using a simple exponential family
problem before providing a realistic problem from population genetics: the comparison of
different growth models based upon observations of human Y chromosome data from the
terminal generation.
Item Type: | Working or Discussion Paper (Working Paper) |
Subjects: | Q Science > QA Mathematics |
Divisions: | Faculty of Science > Statistics |
Library of Congress Subject Headings (LCSH): | Mathematical statistics, Bayesian statistical decision theory, Mathematical models |
Series Name: | Working papers |
Publisher: | University of Warwick. Centre for Research in Statistical Methodology |
Place of Publication: | Coventry |
Official Date: | June 2010 |
Volume: | Vol.2010 |
Number: | No.12 |
Number of Pages: | 35 |
Status: | Not Peer Reviewed |
Access rights to Published version: | Open Access |
Version or Related Resource: | Didelot, X., et al. (2011). Likelihood-free estimation of model evidence. Bayesian Analysis, 6(1), pp. 49-76. http://wrap.warwick.ac.uk/id/eprint/41188 |
Related URLs: | |
References: | Beaumont, M. A., Zhang, W., and Balding, D. J. (2002). Approximate Bayesian |
URI: | http://wrap.warwick.ac.uk/id/eprint/35076 |
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Page 1
Coordination-dependent surface atomic
contraction in nanocrystals revealed by
coherent diffraction
1Department of Materials Science and Engineering, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA
2Frederick Seitz Materials Research Laboratory, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA
3Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA
*Present address: Condensed Matter Physics and Materials Science Department, Brookhaven National Laboratory, Upton, NewYork 11973, USA
Published online: 9 March 2008; doi:10.1038/nmat2132
surfaces. Far less is known about the surface structures of nanocrystals. Here, we show that coherent diffraction patterns recorded
from individual nanocrystals are very sensitive to the atomic structure of nanocrystal surfaces. Nanocrystals of Au of 3–5nm in
diameter were studied by examining diffraction intensity oscillations around the Bragg peaks. Both results obtained from modelling
differentiates the structural dynamics of nanocrystals from bulk crystalline surfaces.
Bond length contraction of surface layers has been observed in a
number of simple, two-dimensional (2D), metallic systems using
experimental techniques such as medium-energy ion scattering,
low-energy electron diffraction and X-ray reflectivity1. The results
of these studies show that displacements of the first, or two, atomic
layer(s) normal to the surface are generally sufficient to describe
the surface contraction1. The driving force for this contraction has
been attributed to the smoothing of surface electron density and
a resulting electrostatic force that pulls the surface ions towards
the bulk2,3, or to a change in chemical bonding4where the lowered
coordination numbers strengthen the remaining bonds. In both
models, the bond length contraction is expected to be stronger
on a curved surface, where facet, edge, step and corner atoms
of different coordination coexist with each other. In addition,
in nanocrystals, surface atom relaxation must be accommodated
in accordance with constraints imposed by neighbouring atoms.
Understanding these effects is important because of the large
impact they have on surface energy and many related nanoscale
phenomena, including interfacial stability5, the heterogeneous
catalysis of chemical reactions6and the mesoscopic influences seen
in the mechanical and electronic properties of nanocrystals7,8.
The available techniques for studying nanoparticle structure
include X-ray diffraction and electron microscopy9. Experimental
X-ray diffraction data for Au decahedral nanoclusters, for
example, showed an overall 2% contraction in the clusters,
which was obtained by fitting the powder diffraction data
with a population of structural models10. Extended X-ray
absorption fine structure, which probes the average bond distances
in nanocrystals, reveals a similar contraction11–13. In each of
these cases, however, the measurements do not distinguish
bond length contractions affecting either surface or interior
atoms. Resolving surface atoms requires both surface sensitivity
and atomic resolution. Recently, Jadzinsky et al. succeeded in
crystallizing p-mercaptobenzoic-acid-protected Au nanoclusters
(102atoms) (ref. 14). This enabled structure determination with
1.1˚A resolution by X-ray crystallography, which then revealed
a capped, chiral, Marks' decahedron structure influenced by
Au–S bonds14. The success of this technique depended on the
synthesis and crystallization of monodispersed nanoclusters. For
many heterogeneous nanostructures used in applications, surface
structure analysis requires a local probe that can sample an
individual nanocrystal.
Here, we used nano-area coherent electron diffraction to probe
range of 3–5nm. Such clusters are of considerable current interest
because of their size-dependent catalytic activity15,16. Electron
diffraction patterns were recorded from individual nanocrystals
using a 40-nm-diameter parallel electron beam17. An example of
the electron diffraction pattern recorded from a Au nanocrystal
of 4nm in diameter and the electron probe used for diffraction
is shown in Fig. 1. The lateral coherent length of the electron
beam is about 35nm, as estimated from the speckle pattern
appearing around the graphite reflections. The electron coherent
each atom in the particle interfere coherently. The interference is
recorded in our experimental set-up by using (1) a small electron
probe to illuminate only a single particle and (2) a graphene
support to reduce the background intensity in the diffraction
pattern. We call this technique coherent electron diffraction to
differentiate it from the conventional diffraction techniques where
nature materials VOL 7 APRIL 2008 www.nature.com/naturematerials
© 2008 Nature Publishing Group
Page 2
the interference is lost either by averaging over many particles
or buried by strong diffraction intensities from the support.
The interference of atomic scattering is clearly seen in Fig. 1;
the diffraction intensity oscillations are asymmetric about the
strong diffraction peak. Similar intensity modulation and the local
asymmetry around Bragg peaks were also observed in coherent
X-ray scattering experiments but from much larger nanocrystals
(hundreds of nanometres in diameter); Robinson and co-workers
showed that such asymmetry is an indication of strain within
the nanocrystal17,18. The asymmetry observed here arises as a
consequence of the bonding involving the surface atoms alone, as
we will show below.
To extract surface structural information from the diffraction
patterns, we choose modelling. The advantage of modelling is
that it enables systematic examination of dominant features in
The model we developed is a radial surface contraction model.
(The simple picture where all surface atoms are contracted by a
single amount regardless of their coordination numbers is found
to be inefficient to reproduce the diffraction features observed in
the experiment.) In this model, the surface atoms are selected by
their coordination numbers and are displaced towards the centre of
the nanocrystal by a distance ?r proportional to the natural log of
the coordination number following the formulation of Pauling4:
?r =α·κ(h,k,l)·r·ln(12/n)/r0
where r is the distance to the centre, r0is the average radius of
the nanocrystal, n is the coordination number (defined by the
number of nearest neighbouring atoms), α is the scaling parameter
and κ(h,k,l) is a ratio used to describe the facet-dependent
contraction. Only a few parameters are involved in this, which is
an advantage in terms of fitting. The model is limited to radial
contraction (positive α) or expansion (negative α). As we show
below, this captures most, but not all, of the surface relaxation
pattern on a nanocrystal. The shape of the nanocrystal is modelled
using three distances, N, M and R, as shown in Fig. 2b. The radius,
R, is used to create rounded edges and vicinal facets between {111}
and {100} facets. The three distances are first adjusted to match
the recorded high-resolution electron microscopy (HREM) images
and then fine-tuned by matching with the experimental diffraction
pattern as described below. For matching the experimental HREM
image, we first determined the particle orientation by matching the
intensity ratios of the Bragg peaks of the experimental diffraction
pattern. The HREM images of the model nanocrystal were then
simulated using the multislice method along the determined
crystal orientation.
Figure 2 shows the results of modelling a diffraction pattern
recorded from a Au nanocrystal of 3.5nm in diameter (an
image of the nanocrystal is shown in Fig. 2c; the full diffraction
pattern is shown in the Supplementary Information). Simulated
diffraction patterns are shown for models with and without surface
contraction. Two surface contraction models are shown: one
using equation (1) and the other obtained directly from molecular
dynamics simulation. The experimental diffraction pattern was
rotated about the (00¯2) direction 1.5◦away from the [110] zone
axis. The model nanocrystal was constructed using the following
parameters: N = 32.64˚A, M = 20.4˚A and R = 19.17˚A, which
gives 1,050 atoms in the nanocrystal. The radius R is adjusted
pattern. The off-zone axis orientation is used for analysis where the
Ewald sphere intersects, or is very close to, the centres of several
Bragg peaks. For a nanocrystal, the angular width of the Bragg
peak is about 2π/D (D is the diameter of the nanocrystal). For
a nanocrystal of 3.5nm in diameter, for example, the range of
Figure 1 Coherent electron diffraction pattern recorded froma single, faceted,
Au nanocrystal (∼4nmin size). The diffraction pattern is selected fromthe vicinity
of the (111) Bragg peak. The probe used for diffraction is about 40nm in diameter
and the nanocrystal is visible in the probe image (inset). The intensity oscillation
seen around the Bragg peak is due to the interference of atomic scattering from a
finite-sized crystal. The direction to the direct beam is indicated by the long white
arrow. The diffraction spot inside the circle is a reflection from the graphite support.
The scale bar in the inset is 10nm.
acceptable tilting angles for intersecting with the first-order Bragg
peaks is about ±2.5◦with 200kV electrons. From simulations,
we found that the essential features in the diffraction pattern
(such as the direction of asymmetry around the Bragg peaks) for
characterizing the nanocrystal surface are observed if the Ewald
sphere intersects with the Bragg peak within ±1.5◦for the first-
order reflections. Deviation from the Bragg diffraction condition
results in a decrease of the angular width of the central maximum.
The difference between the diffraction patterns simulated
with and without surface contraction in Fig. 2 is the asymmetry
observed in the first-order intensity oscillation around the Bragg
peak. Such asymmetry is characterized by a redistribution of
diffraction intensities: from low to high scattering angles across
the Bragg peak for surface contraction or the opposite for
surface expansion. Model calculations also show that the degree
of asymmetry, A, increases monotonically with the amount of
surface contraction α for small α. We measure A by integrating
the intensity difference for the first-order oscillation around the
diffraction peak using
where u1 and u2 are the approximate radius of the intensity
minimum before and after the first-order oscillation and b
is the background intensity. The direction of the asymmetry,
characterized by a vector pointing from the high- to the low-
intensity region (see the dashed arrows in Fig. 2a), is also sensitive
to the relative magnitudes of surface contractions on different
facets. On the basis of kinematical calculations, the direction of the
asymmetry tends to follow the direction of the facet with the largest
surface contraction.
Using the above-described characteristics of diffraction
intensity asymmetry, we looked for the best fit between the
nature materials VOL 7 APRIL 2008 www.nature.com/naturematerials
© 2008 Nature Publishing Group
Page 3
Molecular dynamicsModel
dkx (Å–1)
2 nm
00.02 0.06
dky (Å–1)
dky (Å–1)
dky (Å–1)
– –
Figure 2 Experimental diffraction intensities of a Au nanocrystal and their modelling. a, A comparison between experimental and simulated diffraction patterns
generated from a nanocrystal with surface atoms remaining in their original bulk position (unrelaxed), surface atoms relaxed according to equation (1) and surface atoms
relaxed by molecular dynamics. Experimental diffraction patterns are shown in the left column for the (¯11¯1), (00¯2) and (1¯1¯3) Bragg peaks (upper, middle and lower panel).
The three experimental patterns were selected from a diffraction pattern recorded near the [110] zone axis orientation. The solid white arrows in the pattern point towards
the central beam in the experiment. The dashed white arrows indicate the directions of ?200? in the reciprocal space. b, Schematic diagram showing the three distances
used to model the nanocrystal: from the centre to the octahedral vertex (N), centre to the {100} facets (M) and the radial cutoff distance (R). c, The experimental (left) and
simulated (lower right) high-resolution TEM images and the Au nanocrystal model (upper right), which is 3.5nm in diameter. The scale bar is 2nm.
experiment and the surface configurations generated with
equation (1). The asymmetry observed in Fig. 2 rules out the
possibility of surface expansion for the Au nanocrystal, which
would result in an intensity shift around Bragg peaks towards
the central beam. Table 1 lists the calculated diffraction intensity
asymmetry around the (002) diffraction peak for several radial
contraction models with different κ(100)/κ(111) ratios and α.
The asymmetry is very sensitive to α; the best fit is obtained with
α = 0.37. The experiment pattern gives A(002) = 0.46 ± 0.03.
From this and Table 1, we estimated an uncertainty of 0.03 in
α. The ratio of κ(100)/κ(111) is determined from the angular
distribution of the first-order intensity oscillation. We found a
minimum ratio of 1/0.45 is required to reproduce the features in
the experimental diffraction pattern; a comparison between the
experiment and models for the (002) reflection indicates the best
fit with κ(100)/κ(111) = 1/0.35 or 1/0.25 (see Supplementary
Informationforfurtherinformation).Figure 2showsthecalculated
diffraction patterns for three Bragg peaks, (¯11¯1), (00¯2) and (1¯1¯3)
using κ(1,0,0) = 1, κ(1,1,1) ≈ 0.35 and α = 0.37 together with
the experiment. The solid arrows give the directions towards the
central beam in the diffraction pattern. A key feature shown in
the data is that the direction of the asymmetry (dashed arrows) is
nature materials VOL 7 APRIL 2008 www.nature.com/naturematerials
© 2008 Nature Publishing Group
Page 4
Distance to centre (Å)
Coordination number
Average bond length (Å)
Out-of-plane bond length (Å)
Molecular dynamics
Molecular dynamics
Figure 3 Bond length distributions in the Au nanocrystal obtained by modelling the experimental diffraction pattern. a, Average bond length versus the radial distance
to the centre for the best-fit radial contraction model and molecular dynamics simulation. b, The out-of-plane bond length (bond length between atoms in different atomic
layers) as a function of the atomic coordination number.
pointing along the ?200? direction, which is reproduced only when
κ(100)/κ(111) is much larger than 1.
The bond length distribution obtained with the best-fit radial
contraction model is shown in Fig. 3a. In the fit, the average atomic
bond lengths at the surface are found to reduce by 1–8% with
respect to the interior of the particle. The amount of contraction
in the model increases with decreasing coordination number
(Fig. 3b). The edge and the vertex atoms (with coordination
number ≤ 7) contract by the largest amount (0.22˚A on average).
The model also predicts an average out-of-plane bond length
of 2.76˚A (a 0.13˚A contraction compared with the bulk Au–Au
bond length of 2.885˚A) for {100} and 2.83˚A (0.05˚A with a
distribution from 0.03 to 0.07˚A) for {111} surface atoms. The
uncertainty is about 0.02˚A and 0.01˚A for edge and {100} surface
atoms respectively on the basis of the estimated error of α. The
lowest value of κ(100)/κ(111) to yield an asymmetric intensity
distribution around the [200] Bragg peak matching with the
experimental diffraction pattern is 1/0.45, which corresponds to
a minimal difference of 0.07˚A between the amounts of contraction
on the {100} and {111} facets. In comparison, calculations of
2D surfaces for Au using the embedded atoms method potential
predicted a first-layer contraction of 6.3% and 4.2% for the
{100} and {111} surfaces respectively19. The corresponding out-
of-plane bond length is 2.795˚A for {100} and 2.805˚A for {111}.
Other theories predicted either a much smaller contraction or
expansion20. The small, 0.01˚A difference in bond contraction
predicted for 2D {100} and {111} surfaces is unlike what the model
revealed here for the Au nanocrystal. It should be noted that the
periodic reconstructions that are seen on 2D Au surfaces21,22have
here and thus are not observed.
The average bond distance in the nanocrystal can be measured
on the basis of the Bragg peak positions. We measured the peak
positions by fitting the diffraction peaks using a gaussian function
for the intensity profiles of the (1¯11) and (200) Bragg peaks in the
experimental pattern. The average length of the Au–Au bond of
the nanocrystal was determined to be 2.885±0.005˚A using the
supporting graphene lattice as calibration. This value is close to the
bond distance of bulk Au crystals. This indicates that overall the
particle is not strained by the graphene substrate, which is expected
from the weak interaction between Au and graphite23. The Bragg
peak position is mainly determined by the average lattice of the
interior atoms for the nanocrystal examined here. As the size of
Table 1 Diffraction intensity asymmetry around the (002) diffraction peak
calculated using equation (2) for different radial contraction models. For
comparison, the asymmetry is 0.46±0.03 in the experimental diffraction pattern
and 0.456 fromthe molecular dynamics simulations.
α =0.24
the nanocrystals decreases, we expect the surface contribution to
increase and also broader, less-well-defined, Bragg peaks.
To verify the surface radial contraction model for Au
nanocrystals, we also carried out molecular dynamics simulations
by relaxing the nanocrystal model described above at 500K
using the embedded atoms method potential. Diffraction patterns
were simulated using the atomic coordinates obtained from the
molecular dynamics simulation. The results are shown in Fig. 2 for
the three Bragg peaks of (¯11¯1), (00¯2) and (1¯1¯3). Good agreements
are obtained between the experimental patterns and the simulated
patterns from molecular dynamics; both the shapes of the central
maxima and the main features of the intensity distributions of
the first-order oscillations are reproduced by molecular dynamics.
(The agreement can be further improved by energy-filtering
the experimental diffraction pattern, which includes a small
amount of blurring due to inelastic scattering. Thermal diffuse
scattering was approximated here as a constant background. For
large nanocrystals, non-uniform thermal diffuse scattering must
be considered by including phonon scattering in modelling.)
In particular, the intensity around (00¯2) in the experimental
diffraction pattern shifts away from the central beam, whereas
around (¯11¯1) and (1¯1¯3), the asymmetry directions are along
?200?. These trends are also observed in our radial contraction
model. Overall, the molecular dynamics simulation improves
the agreement with the experiment, which is not surprising
because the molecular dynamics simulation takes account of forces
between atoms.
To examine the difference between surface atom contractions
in molecular dynamics and the radial contraction model, we
calculated the atomic displacements in the molecular dynamics
simulation from the initial unrelaxed crystal. A comparison
nature materials VOL 7 APRIL 2008 www.nature.com/naturematerials
© 2008 Nature Publishing Group
Page 5
Figure 4 Surface atomcontraction obtained fromthe molecular dynamics simulation. a,b, Surface atom displacements shown as vectors for atoms possessing a
coordination number less than 9 (a, mostly are {100} atoms and neighbouring vicinal facet atoms) and equal to 9 (b, mostly are {111} surface atoms). The upper right inset
in b shows a magnified {111} facet viewed parallel to the facet, whereas the lower right inset shows the same facet viewed normal to the facet (which is tilted slightly to
avoid atoms on the other facets). The magnitudes of the displacements are rendered using colours. The corresponding atoms in the nanocrystal model are shown in the inset
at the top left corner; the atoms whose displacements are shown are coloured in grey. Both maps have the same display scale in the magnitude of displacement.
and the molecular dynamics is shown in Fig. 3. Overall, the general
dependence on the radial distanceand the coordination number is
well reproduced by the radial contraction model. The difference
between the two models is in the details of bond deformation.
Figure 4 shows the atomic displacements as 3D vector maps,
with both the magnitudes and directions of the surface atom
displacements represented. For clarity, we also distinguish atoms
of different coordination numbers. The displacements for atoms
on the {100} surfaces (including step atoms on {100} facets) and
edges are on average larger than those on the {111}, except for
those close to the edge of the {111} facets. The magnitude of
displacement of the {100} atoms varies from ∼0.09 to 0.21˚A,
whereas the displacement of {111} atoms varies from 0.14˚A for
atoms close to the edges, to 0.02˚A for atoms near the centre
of the facets. The radial contraction model predicted an average
displacement of 0.05˚A for the {111} atoms. The biggest difference
between the model and molecular dynamics is in the pattern of
surface displacements. In molecular dynamics, the atoms on the
vicinal facets (between{111} and{100}) have the largest magnitude
of contraction (the largest is ∼0.21˚A). Whereas the displacement
vectors of the {100} atoms predominantly point perpendicular
to the surfaces, vectors of the {111} atoms have larger in-plane
components. The farther the atoms are located away from the
components. This suggests that surface atoms on different facets
must accommodate each other, which is not included in the radial
contraction model. From the molecular dynamics simulations,
atomic displacements on the {111} surfaces seem to be partially
relaxation dynamics involving collective atomic rearrangements
with different coordination numbers is unique to nanocrystal
surfaces, which is not expected for bulk, 2D, surfaces.
The agreement between experiment and molecular dynamics
simulations is not limited to this specific 3.5-nm-diameter
nanocrystal. Similar agreement is also found for other nanocrystals
3.8, 4.3 and 5.1nm in diameter (see the Supplementary
Information). To check whether the diffraction features we
observed come from the internal strain of the nanocrystal,
we intentionally removed the surface layer from both the
molecular-dynamics-relaxed and the unrelaxed nanocrystals, and
compared the diffraction patterns simulated from the remaining
cores of the two cases. The diffraction pattern from the molecular
dynamics simulation without the surface layer closely resembles
that of the unrelaxed model. This result suggests that the
contribution from the internal strain is small; the asymmetry
observed in the diffraction patterns is dominated by the relaxation
of the surface atoms. According to the continuum elasticity
die off exponentially (to 1/e) into the bulk with a decay length of
L/2π, where L is the period of the wave along the surface. With
L ≈ 4nm, which is twice the width of the {111} facets, we expect
the strain to decay within a depth of two atomic layers, roughly in
agreement with our molecular dynamics results.
In summary, surface atoms contract in nanometre-sized Au
nanocrystals. The contraction is coordination dependent and
in contractions on the {100} and {111} facets is much larger than
that predicted on the basis of the properties of bulk crystals.
Modelling was used to extract structural information from the
experimental diffraction patterns; this approach was shown to
be effective in the absence of a general method to determine
the position of every atom in a single nanocrystal by recording
3D diffraction intensities and solving the phase problem19,20. The
sensitivity of coherent diffraction to the atomic bonding present
on nanocrystal surfaces suggests a general approach to study the
surface of nanocrystals.
The procedures used to prepare the Au nanocrystals are as follows. First,
thiolate-capped Au nanocrystals were synthesized using a modified literature
procedure16, purified and then dispersed onto ultrathin graphene films. The
flake material obtained from Alfa Aesar. The nanoparticles were then annealed
at 600◦C in a high-vacuum chamber (base pressure 5.0×10−7torr). Annealing
nature materials VOL 7 APRIL 2008 www.nature.com/naturematerials
© 2008 Nature Publishing Group
Page 6
the nanocrystals removes the ligands and promotes surface facet formation
(physicabsorbed thiol desorbs at 320–420K and chemiabsorbed thiolate
desorbs at around 500–620K according to the literature26,27). Experimental
observations were carried out at a 200kV electron accelerating voltage using
a JEOL 2010F transmission electron microscope with a field-emission gun
(Peabody). A highly parallel electron beam of 40nm in diameter was formed
with a 10µm condenser aperture to isolate individual nanocrystals (Fig. 1,
inset) for diffraction. Nanocrystals of 3 to 5nm in diameter were selected
for study. HREM was used for the initial examination of nanoparticles. The
results showed that the nanocrystals are single crystalline and faceted. There
are also indications in the HREM images for rounded edges, or vicinal facets,
between the low-index crystal facets. Rounded edges and vicinal facets are
expected from thermal excitations of the under-coordinated atoms at edges and
corners28. No evidence was found for epitaxy between the nanocrystals and the
graphite support, consistent with a weak interfacial interaction between Au and
graphite23. Diffraction patterns were recorded using image plates (FUJI FDL
5000) of 25µm pixel size. The electron dose for a single recording was estimated
to be ∼103electrons˚A−2, which is much less than the electron dose typically
used in high-resolution imaging of metallic nanocrystals29. Comparison
between the high-resolution images of the nanocrystals before and after the
diffraction pattern recording shows no visible change in the image contrast,
indicating no significant effect of electron radiation on the structures of the
nanocrystals during diffraction.
Received 9 July 2007; accepted 25 January 2008; published 9 March 2008.
1. Bohnen, K. P. & Ho, K. M. Structure and dynamics at metal surfaces. Surf. Sci. Rep. 19,
99–120 (1993).
2. Smoluchowski, R. Anisotropy of the electronic work function of metals. Phys. Rev. 60, 661 (1941).
3. Finnis, M. W. & Heine, V. Theory of lattice contraction at aluminium surfaces. J. Phys. F 4,
4. Pauling, L. Atomic radii and interatomic distances in metals. J. Am. Chem. Soc. 69, 542–553 (1947).
5. Ibach, H. The role of surface stress in reconstruction, epitaxial growth and stabilization of mesoscopic
structures. Surf. Sci. Rep. 29, 195–263 (1997).
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appearance of nonmetallic properties. Science 281, 1647 (1998).
7. Gilbert, B., Huang, F., Zhang, H., Waychunas, G. A. & Banfield, J. F. Nanoparticles: Strained Stiff. Sci.
305, 651–654 (2004).
8. Alivisatos, A. P. Semiconductor clusters, nanocrystals, and quantum dots. Science 271,
933–937 (1996).
9. Marks, L. D. Experimental studies of small particles structures. Rep. Prog. Phys. 57, 603 (1994).
10. Cleveland, C. L. et al. Structural evolution of smaller gold nanocrystals: The truncated decahedral
motif. Phys. Rev. Lett. 79, 1873 (1997).
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monolayer-protected clusters as revealed by X-ray absorption spectroscopy and transmission electron
microscopy. J. Phys. Chem. B 110, 14564–14573 (2006).
13. Zhang, P. & Sham, T. K. X-ray studies of the structure and electronic behavior of
alkanethiolate-capped gold nanoparticles: The interplay of size and surface effects. Phys. Rev. Lett. 90,
245502 (2003).
14. Jadzinsky, P. D., Calero, G., Ackerson, C. J., Bushnell, D. A. & Kornberg, R. D. Structure of a thiol
monolayer-protected gold nanoparticle at 1.1 angstrom resolution. Science 318, 430–433 (2007).
15. Haruta, M. Catalysis of gold nanoparticles deposited on metal oxides. Catal. Technol. 6, 102 (2002).
16. Freund, H.-J., Libuda, J., Baumer, M., Risse, T. & Carlsson, A. Clusters, facets and edges:
Site-dependent selective chemistry on model catalysts. The Chem. Record 3, 181 (2003).
17. Williams, G. J., Pfeifer, M. A., Vartanyants, I. A. & Robinson, I. K. Three-dimensional imaging of
microstructure in Au nanocrystals. Phys. Rev. Lett. 90, 175501 (2003).
18. Pfeifer, M. A., Williams, G. J., Vartanyants, I. A., Harder, R. & Robinson, I. K. Three-dimensional
mapping of a deformation field inside a nanocrystal. Nature 442, 63–66 (2006).
19. Foiles, S. M., Baskes, M. I. & Daw, M. S. Embedded-atom-method functions for the fcc metals Cu,
Ag, Au, Ni, Pd, Pt, and their alloys. Phys. Rev. B 33, 7983–7991 (1986).
20. Haftel, M. I., Bernstein, N., Mehl, M. J. & Papaconstantopoulos, D. A. Interlayer surface relaxations
and energies of fcc metal surfaces by a tight-binding method. Phys. Rev. B 70 (2004).
21. van Hove, M. A. et al. The surface reconstructions of the (100) crystal faces of iridium, platinum and
gold .1. Experimental-observations and possible structural models. Surf. Sci. 103, 189–217 (1981).
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reconstructed Au(100) surface. Surf. Sci. 127, 223–242 (1983).
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surface strain. Phys. Rev. B 76, 115425 (2007).
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spectrometry of mixed self-assembled monolayers on gold. Langmuir 18, 1528–1534 (2002).
27. Kondoh, H., Kodama, C., Sumida, H. & Nozoye, H. Molecular processes of adsorption and
desorption of alkanethiol monolayers on Au(111). J. Chem. Phys. 111, 1175–1184 (1999).
28. Bonzel, H. P. 3D equilibrium crystal shapes in the new light of STM and AFM. Phys. Rep. 385,
1–67 (2003).
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616–619 (1986).
The work was supported by NSF Career Award, DMR 0449790 (W.J.H., J.M.Z.), DOE DEFG02-
01ER45923 (R.S., J.T., J.M.Z.) and DEFG02-03ER15476 (R.G.N., L.D.M.). The electron microscopy
work was carried out in the Center for Microanalysis of Materials, University of Illinois, which is
partially supported by the US Department of Energy under grant DEFG02-91-ER45439.
Correspondence and requests for materials should be addressed to J.M.Z.
Supplementary Information accompanies this paper on www.nature.com/naturematerials.
Author contributions
W.J.H., R.S., J.T. and J.M.Z. carried out the diffraction experiment, modelling and analysis. L.D.M. and
R.G.N. carried out particle synthesis.
Reprints and permission information is available online at http://npg.nature.com/reprintsandpermissions/
nature materials VOL 7 APRIL 2008 www.nature.com/naturematerials
© 2008 Nature Publishing Group


text:
Mixed fortunes on high streets
The polarisation of the high street was illustrated further yesterday when a number of Britain's leading retailers delivered sharply contrasting verdicts on Christmas trading.
Boots, Carpetright and Signet, the jewellery group, reported healthy sales increases. But Storehouse (BhS and Mothercare) and Sears (Selfridges and Freemans) reported disappointing sales.
The figures follow the pattern established yesterday when Next and Dixons unveiled bumper sales increases while House of Fraser, the department store group issued a profits warning blaming the mark-down of excess stock.
John Richards, retail analyst at NatWest Securities said: "It is very clear that consumers have a very good idea of the retailers which can be relied on to deliver quality and value and those that cannot."
Sears delivered a downbeat trading statement saying group sales were down 2 per cent on a like-for-like basis in the six months to Janaury.
Comparative sales in the shoe shops, which include Dolcis, Shoe Express, and the under-performing Saxone and Curtess, were down 11 per cent. Selfridges reported sales up 12.5 per cent while Adams, the childrenswear chain, also did well. Ladieswear performed poorly.
Shares in Storehouse fell 20.5p to 300.5p when it surprised the market with flat like-for-like sales in the six weeks up to and including Christmas Eve.
At BhS, sales of womenswear and homeware did well but childrenswear performed poorly. Mothercare suffered in what the company claimed was a difficult market.
The best performance of the day came from Carpetright, Sir Phil Harris' fast expanding carpet chain. Like-for-like sales in the six months to October were 10 per cent ahead of last year's. level's. Sales have also exceeded forecasts over Christmas and New Year.
Boots was also positive with sales in the third quarter to December up 5.4 per cent on last year.
Boots the Chemists, which is traditionally the group's best performer, led the way with a like-for-like sales increase of 5.1 per cent. Other divisions struggled. Like-for-like sales were flat at Halfords, down 6.4 per cent at Do it All and down 5.8 per cent at AG Stanley, the Fads and Homestyle division.
Consumers seem to have warmed to jewellery this Christmas, according to a bullish report from Signet.
Like-for-like sales for the eight weeks before Christmas were 6 per cent up on last year, a much better performance than expected.
Ernest Jones, the more upmarket chain did well but H Samuel struggled and saw sales fall by 3 per cent. Sterling, the American business has also done well reporting a 10 per cent increase in pre-Christmas trading.
Analysts have now upgraded their profits forecast for the full year from around pounds 15m to pounds 20m.
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News in Brief
U.S. Says Schools Got Tainted Peanut Foods
The U.S. Department of Agriculture said last week that potentially contaminated peanut butter and roasted peanuts processed by the Peanut Corp. of America were sent to schools in California, Idaho, and Minnesota for the free school lunch program in 2007.
A salmonella outbreak blamed on the company has sickened at least 575 people in 43 states. At least eight have died. More than 1,300 foods that used ingredients from the company's processing plant in Blakely, Ga., have been recalled.
While the outbreak appears to be slowing down, new illnesses are still being reported.
Agriculture Department spokeswoman Susan Acker said schools in the states received the suspected peanut products between January and November of 2007. Federal officials notified the schools and told them to destroy any of the uneaten food, most of which had been consumed.
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Nov 5 |
comment |
How to improve Windows perfomance when running inside KVM
I was never able to add VirtIO drivers on an migrated-existent Windows image. Redefining the Disk bus to VirtIO and Windows would not start; and try to install the VirtIO drivers without the right Diskbus I would have like to have been allowed. |


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Tech Helproom
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spywareblaster 4.5
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Thanks for the news. All downloaded and installed without any problems.
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Thanks. THe new version includes auto update. Hope it will not interfere with my free Avira anti virus.
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kdt, Thanks, the update is a little more complicated than usual, asking for the old version to be uninstalled first. I wrongly assumed the update offer was free.
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April 15, 2015


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Spend a day with photographer Michael Forsberg as he shares his vision of the Great Plains with a group of students from Grand Island. Visit the Mennonite Park, a labor of love that preserves the Mennonite heritage of Henderson. But will it outlive its founders? Go behind the scenes as Omaha artist Jun Kaneko proposes startling costumes and groundbreaking animation for the premieres of the Magic Flute by Opera Omaha and the San Francisco Opera. And finally, meet Phillip Smith, an up-and-coming composer whose contemporary work is earning raves from musicians.
live streaming schedule & on demand videos
09:00 am | NDE Board Meeting: October 2015 NDE Board Meeting |
02:00 pm | Nebraska Department of Education: November 2015 NDE Work Session |
09:00 am | NDE Board Meeting: November 2015 NDE Board Meeting |
02:00 pm | Nebraska Department of Education: December 2015 NDE Work Session |
09:00 am | NDE Board Meeting: December 2015 NDE Board Meeting |
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