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1.
K.?Koyasu M.?Niemietz W.?Westh?user G.?Gantef?r 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2009,53(1):59-62
The decay path of an Ag8(O2)- cluster photoexcited by a 3.1 eV photon is elucidated using time-resolved photoelectron spectroscopy. Photoabsorption results
in the formation of an excited state giving rise to a peak in the photoelectron spectra with well-resolved vibrational finestructure.
With a lifetime of about 100 fs this bound state decays into an anti-bonding state which dissociates into O2 and Ag8- on a timescale of 10 ps. In the photoelectron spectra, this corresponds to a broad maximum shifting gradually towards higher
binding energy while the O2 and Ag8- separate. Finally, the spectrum of bare Ag8- appears. This process is unique to small clusters, because on metal surfaces excited state lifetimes are too short to allow
for direct dissociation. 相似文献
2.
I. L. Garzón M. R. Beltrán G. González I. Guterrez-González K. Michaelian J. A. Reyes-Nava J. I. Rodrguez-Hernández 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2003,24(1-3):105-109
Theoretical and experimental information on the shape and
morphology of bare and passivated gold clusters is fundamental
to predict and understand their electronic, optical, and other
physical and chemical properties. An effective theoretical
approach to determine the lowest-energy configuration (global
minimum) and the structures of low energy isomers (local minima)
of clusters is to combine genetic algorithms and many-body
potentials (to perform global structural optimizations), and
first-principles density functional theory (to confirm the
stability and energy ordering of the local minima). The main
trend emerging from structural optimizations of bare Au clusters
in the size range of 12-212 atoms indicates that many
topologically interesting low-symmetry, disordered structures
exist with energy near or below the lowest-energy ordered
isomer. For example, chiral structures have been obtained as the
lowest-energy isomers of bare Au28 and
Au55 clusters, whereas in the size-range
of 75-212 atoms, defective Marks decahedral structures are
nearly degenerate in energy with the ordered symmetrical
isomers. For methylthiol-passivated gold nanoclusters
[Au28(SCH3)16
and
Au38(SCH3)24],
density functional structural relaxations have shown that the
ligands are not only playing the role of passivating molecules,
but their effect is strong enough to distort the metal cluster
structure. In this work, a theoretical approach to characterize
and quantify chirality in clusters, based on the Hausdorff
chirality measure, is described. After calculating the index of
chirality in bare and passivated gold clusters, it is found that
the thiol monolayer induces or increases the degree of chirality
of the metallic core. We also report simulated high-resolution
transmission electron microscopy (HRTEM) images which show that
defects in decahedral gold nanoclusters, with size between 1-2
nm, can be detected using currently available experimental HRTEM
techniques. 相似文献
3.
H. Kitamura 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2007,43(1-3):33-36
Optimized structures and cohesive energies of small
mercury clusters (HgN; N = 3–7, 13, 19) are calculated with the
spin-orbit diatomics-in-molecules method. The theory takes into account the
effect of s-p mixing which tends to enhance the binding energies in the
ground state. It is shown that excimer clusters have significantly short
optimum bond lengths and their atomic geometries differ considerably from
those in the ground state. Excitation energy gap depends sensitively on both
cluster size and nearest-neighbor separation. Numerical results are compared
with other theories and experiments. 相似文献
4.
G.M. Koretsky M.B. Knickelbein 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》1998,2(3):273-278
The photoionization spectra of Pr2-Pr21 and Ce2-Ce17 have been measured near threshold. The ionization potentials (IPs) of and vary discontinuously with size, but trend downward toward the work function of the bulk metals. In general, the IPs of cerium
clusters display more variation than those of praseodymium clusters. The sudden discontinuities observed in the IPs of both
and is akin to that displayed by clusters of transition metal atoms, suggesting that as in transition metal clusters, the rapid
evolution in geometric structure with size is the source of these discontinuities.
Received: 2 January 1998 / Accepted: 10 March 1998 相似文献
5.
V. Boutou A.R. Allouche F. Spiegelmann J. Chevaleyre M. Aubert Frécon 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》1998,2(1):63-73
The geometrical structure of ground state Ban clusters (n
=2-14) has been predicted from various types of calculations including two ab initio approaches used for the smaller sizes namely HF+MP2(
n
=2-6), DFT (LSDA)(
n
=2-6, 9) and one model approach HF+pairwise dispersion used for all sizes investigated here. The lowest energy configurations
as well as some isomers have been investigated. The sizes n
=4, 7 and 13 are predicted to be the relatively more stable ones and they correspond to the three compact structures: the tetrahedron,
the pentagonal bipyramid and the icosahedron. The growth behavior from Ba7 to Ba13 appears to be characterized by the addition of atoms around a pentagonal bipyramid leading to the icosahedral structure of
Ba13 which is consistent with the observed size-distribution of barium clusters. Values for vertical ionization potentials calculated
for n
=2-5 at the CI level are seen to be in quite good agreement with recent measures.
Received: 14 May 1997 / Received in final form: 2 February 1998 / Accepted: 27 February 1998 相似文献
6.
T.M. Di Palma A. Latini M. Satta A. Giardini-Guidoni 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》1998,4(2):225-229
A photoionization study of the Me(NH3) clusters formed in the reaction of photoablated third group metal vapor with gaseous ammonia is reported. The photoionization
spectra exhibit some features due to vibrational excitation of ionic clusters and to transitions to neutral Rydberg states
leading to autoionization. DFT quantum chemical calculations are performed on the Me(NH3). The cluster geometries are fully optimized imposing the C3v symmetry. The calculated values of the IPs are in agreement with those experimentally determined.
Received: 16 February 1998 / Revised and Accepted: 7 May 1998 相似文献
7.
C.M. Dion O. Dulieu D. Comparat W. de Souza Melo N. Vanhaecke P. Pillet R. Beuc S. Milošević G. Pichler 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2002,18(3):365-370
We present the results of absorption measurements in a cesium vapor around 630 K, together with photoionization spectra through
a resonance-enhanced two-photon absorption of ultracold cesium dimers created after photoassociation of ultracold cesium atoms.
The maximum efficiency of the ultracold molecule ionization is found for wavelengths where absorption at thermal energies
is the strongest, in agreement with our theoretical simulations of both processes, involving the so-called Cs2 diffuse bands. This result will be helpful for further optimization of such a direct way of detection of ultracold molecules.
Received 13 September 2001 相似文献
8.
X. Liang Y.-H. Luo X.-J. Feng T. T. Cao L. X. Zhao 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2008,46(1):93-101
The structures, binding energies, and electronic properties of
Cn and NaCn (n=2–12) clusters have been systematically
investigated using density functional theory (DFT). A number of
previously undiscovered isomers of NaCn clusters are reported,
including fan-like, linear and three-dimensional structures.
Moreover, NaCn clusters with even n are found to be more
stable than those with odd n, in contrast with
the case of Cn clusters. 相似文献
9.
H. Nagao K. Awazu S. Hayakawa K. Iwamoto M. Toyoda T. Ichihara 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2007,45(2):279-287
Various dissociation channels of silver bromide cluster ion
Ag2Br+ and silver cluster ion Ag3
+ were observed in
high-energy collisionally-activated dissociation (CAD) using a Cs target.
The fragment patterns of the high-energy CAD were compared with those of the
metastable dissociation and low-energy CAD. The difference in the fragment
patterns between the high-energy CAD and the other dissociation methods was
explained in terms of the internal energy distributions. The dissociation
mechanisms of neutral silver bromide cluster Ag2Br and silver cluster
Ag3 were also investigated by charge inversion mass spectrometry using
the Cs target. While the fragment ions AgBr- and Ag2
- were
dominantly observed in the charge inversion spectrum of Ag2Br+,
the undissociated ion Ag3
- was observed as a predominant peak in
the case of Ag3
+. The dissociation behavior of Ag2Br*
can be explained on the basis of the calculated thermochemical data.
Contrary to this, the predominant existence of the undissociated
Ag3
- cannot be explained by the reported thermochemical data. The
existence of undissociated Ag3
- suggests that the dissociation
barrier is higher than the internal energy of Ag3
*
(theoretical: 1.03 eV, experimental: 2.31 eV) estimated from the ionization
potentials of Ag3 and Cs. 相似文献
10.
R. von Pietrowski K. von Haeften T. Laarmann T. Möller L. Museur A. V. Kanaev 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2006,38(2):323-336
The electronic and geometric structure of rare gas clusters doped with
rare-gas atoms Rg = Xe, Kr or Ar is investigated with fluorescence excitation
spectroscopy in the VUV spectral range. Several absorption bands are
observed in the region of the first electronic excitations of the impurity
atoms, which are related to the lowest spin-orbit split atomic 3P1
and 1P1 states. Due to influence of surrounding atoms of the
cluster, the atomic lines are shifted to the blue and broadened
(“electronical cage effect”). From the known interaction potentials and
the measured spectral shifts the coordination of the impurity atom in
ArN, KrN, NeN and HeN could be studied in great detail.
In the interior of KrN and ArN the Xe atoms are located in
substitutional sites with 12 nearest neighbours and internuclear distances
comparable to that of the host matrix. In NeN and HeN the cluster
atoms (18 and 22, respectively) arrange themselves around the Xe impurity
with a bondlength comparable to that of the heteronuclear dimer. The results
confirm that He clusters are liquid while Ne clusters are solid for N≥
300. Smaller Ne clusters exhibit a liquid like behaviour. When doping is
strong, small Rgm-clusters (Rg = Xe, Kr, Ar, m≤10 2) are formed
in the interior sites of the host cluster made of Ne or He. Specific
electronically excited states, assigned to interface excitons are observed.
Their absorption bands appear and shift towards lower energy when the
cluster size m increases, according to the Frenkel exciton model. The
characteristic bulk excitons appear in the spectra, only when the cluster
radius exceeds the penetration depth of the interface exciton, which can be
considerably larger than that in free Rgm clusters. This effect is
sensitive to electron affinities of the guest and the host cluster. 相似文献
11.
12.
A. Kanaev L. Museur F. Edery T. Laarmann T. Möller 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2002,20(2):261-268
We have studied the fluorescence of electronically excited OH*, H* and H2O+* dissociation fragments after VUV excitation ( h
ν≥11.6
eV) of rare-gas clusters (Rg = Ne, Ar) doped with H2O molecules. In contrast to a free molecule, where Balmer H-series dominate the UV-visible spectra, only the OH
*
(
A
2
Σ
+
↦
X
2
Π) emission band is observed in neon clusters. No emission of excited water ions has been observed. We find that while higher
excitation energies (Ne vs. Ar) induce higher vibrational excitation of the OH*
(
A
) fragment, the rotational temperature is lower. This effect is attributed to the difference in the geometric position of the
H2O molecule on the surface or inside the Rg-cluster. The rotational relaxation in neon clusters is rapid while the vibrational
relaxation is slow because of the coupling with the low energy matrix phonons.
Received 7 March 2002 / Received in final form 27 May 2002 Published online 19 July 2002 相似文献
13.
G. Chen Z.F. Liu X.G. Gong 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2001,16(1):33-36
We have studied the atomic structure and the electronic properties of Ban clusters by the ab initio molecular dynamics method. We find that a structural transition to the bulk-like structure begins at Ba9 cluster, and the structures of the clusters are transferred to be icosahedral-like around n
= 13. The relatively high stability for Ba4, Ba10 and Ba13 clusters are observed.
Received 1st December 2000 相似文献
14.
F.v. Gynz-Rekowski W. Quester R. Dietsche D. C. Lim N. Bertram T. Fischer G. Ganteför M. Schach P. Nielaba Y. D. Kim 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2007,45(3):409-413
The possibility of using magic Si7 clusters to form a cluster material was studied experimentally and theoretically. In experiments Si7 clusters were deposited on carbon surfaces, and the electronic structure and chemical properties of the deposited clusters
were measured using X-ray photoelectron spectroscopy (XPS). A non bulk-like electronic structure of Si7 was found in the Si 2p core level spectra. Si7 is suggested to form a more stable structure than the non-magic Si8 cluster and Si atoms upon deposition on carbon surfaces. Theoretically it was possible to study the interaction between the
clusters without the effect of a surface. Density functional theory (DFT) calculations of potential curves of two free Si7 clusters approaching each other in various orientations hint at the formation of cluster materials rather than the fusion
of clusters forming bulk-like structures. 相似文献
15.
K. Ohshimo F. Misaizu K. Ohno 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2003,24(1-3):339-342
Cluster anions of a sodium atom with acrylonitrile
molecules,
(n = 0–6), have been studied by
negative-ion photoelectron spectroscopy. In addition,
theoretical calculations by using density functional theory have
been performed to obtain optimized structures and vertical
detachment energies. For Na(AN)–, the
spectrum can be explained by excitation of two different isomers
of the anion. For
, a broad band is found in the
photoelectron spectrum, whose profile is almost identical with
those of previously reported photoelectron spectra of
and a negative ion of chemically
synthesized 1,3,5-cyclohexanetricarbonitrile (CHTCN) molecule.
From this resemblance of band profiles, we conclude that
oligomerization of (AN)3 takes place in
and the CHTCN is formed as the
intracluster reaction product. 相似文献
16.
H. Hess K.R. Asmis T. Leisner L. Wöste 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2001,16(1):145-149
We present results on the ultrafast dynamics of mass-selected neutral Ag4 clusters using NeNePo (negative ion - neutral - positive ion) femtosecond pump-probe spectroscopy. One-color pump-probe spectra
of the Ag4
-/Ag4/Ag4
+ system measured at 385 nm and an internal cluster temperature of 20 K display a complex beat structure over more than 60
ps. The oscillatory structure is attributed to vibrational wave packet dynamics in an excited “dark" state of neutral Ag4. A dominant 740 fs wave packet period as well as wave packet dephasing and rephasing are observed in the spectra. Fourier
analysis of the spectra yields a group of frequencies centered around 45 cm-1 and an anharmonicity χ
e2νχ
eχ
e of 2.65 cm-1 for the active vibrational mode.
Received 30 November 2000 相似文献
17.
N. Hori A. Furuya M. Tsuruta F. Misaizu K. Ohno 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2007,43(1-3):41-44
Photoinduced dissociation in the ultraviolet region has been investigated for Ag nF n-1
+ cluster ions. Photodissociation spectrum of
Ag2F+
in the energy of 3.8–5.6 eV exhibits several sharp bands corresponding to the transition to electronically excited states.
In this dissociation, only the Ag2
+ ion was observed as a fragment ion. Theoretical calculation indicates that the parent Ag2F+ ion has a linear Ag-F-Ag equilibrium geometries in the ground and excited states. Since conformational changes by excitation
of bending vibration are necessary for the fragmentation of an F atom, this indicates that production of Ag2
+ from Ag2F+ is a result of internal conversion and following conformational changes. 相似文献
18.
L. Guo H.-S. Wu 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2007,42(2):259-267
Geometries, electronic states and electron affinities of AlmAsn and AlmAs n (m+n=2–5) clusters have been examined using
four hybrid and pure density functional theory (DFT) methods. Structural
optimization and frequency analyses are performed using a 6-311+G(2df)
one-particle basis set. The geometries are fully optimized with each DFT
method independently. The three types of energy separations reported in this
work are the adiabatic electron affinity (EAad), the vertical electron
affinity (EAvert), and the vertical detachment energy (VDE). The
calculation results show that the singlet structures have higher symmetry
than that of doublet structures. The best functional for predicting
molecular structures was found to be BLYP, while other functionals generally
underestimated bond lengths. The largest adiabatic electron affinity,
vertical electron affinity and vertical detachment energy, obtained at the
6-311+G(2df)/BP86 level of theory, are 2.20, 2.04 and 2.27 eV (AlAs), 2.13,
1.94 and 2.38 eV (AlAs2), 2.44, 2.39 and 2.47 eV (Al2As), 2.09,
1.80 and 2.53 eV (Al2As2), 2.01, 1.57 and 2.36 eV (AlAs3),
2.32, 2.11 and 2.55 eV (Al2As3), 2.40, 1.45 and 3.26 eV
(AlAs4), 1.94, 1.90 and 2.07 eV (Al4As), respectively. However, the
BHLYP method gives the largest values for EAad and EAvert of
Al3As and EAad of Al3As2, respectively. For the
vibrational frequencies of the AlnAsm series, the B3LYP method
produces good predictions with the average error only about 10 cm-1 from available experimental and theoretical values. The other three functionals overestimate or underestimate the vibrational
frequencies, with the worst predictions given by the BHLYP method. 相似文献
19.
F.O. Talbot J.P. Simons 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2002,20(3):389-398
Mass-resolved resonant two photon ionisation (R2PI) and infrared ion dip spectra have been recorded for 4-phenylimidazole
(4PI) and its singly and multiply hydrated clusters 4PI(H2O)n = 0 - 4, under supersonic expansion conditions. In the case of 4PI(H2O)0,1, it has also been possible to record infrared spectra in both the ground (S0) and excited (S1) states. Combining the experimental data with the results of ab initio calculations has led to the structural assignment of each cluster. In each case, the water molecules bind primarily to the
NH site of the imidazole ring. Clusters with n≥ 2 incorporate linear water chains, in which the proton donating terminus bridges either to the π-electron system (n = 2) or to the >N: atom site (n = 3, 4) on the imidazole ring. Despite the creation of a “water wire”, connecting the donor and acceptor sites of imidazole,
there is no evidence of proton transfer in either the ground or excited state.
Received 20 December 2001 Published online 13 September 2002 相似文献
20.
C. Bobbert C.P. Schulz 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2001,16(1):95-97
Nam(H2O)n Clusters ( n = 1...200, m = 1...50) are formed in a recently build pick-up arrangement. Preformed water clusters traverse a sodium oven, where sodium
atoms are picked up. At low sodium vapour pressure ( < 1×10-4 mbar) pure Na(H2O)n clusters are observed in the mass spectra. At high sodium vapour pressure ( > 1×10-3 mbar) the water cluster pick up more than 50 Na atoms and reaction products Na(NaOH)n ( n = 2, 4...50) dominate the mass spectra. The even number of NaOH units in the products indicate that also in a finite cluster
the reaction occurs in pairs as in the macroscopic reaction.
Received 4 December 2000 相似文献