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1.
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
2.
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
3.
E. Kasabova D. Alamanova M. Springborg V. G. Grigoryan 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2007,45(3):425-431
The soft deposition of Ni13 and Cu13 clusters on Ni(111) and Cu(111) surfaces is studied by
means of constant-energy molecular-dynamics simulations.
The atomic interactions are described by the Embedded Atom Method.
It is shown that the shape of the nickel clusters deposited on Cu(111) surfaces remains rather intact,
while the copper clusters impacting on Ni(111) surfaces collapse forming double and triple layered
products. Furthermore, it is found that for an impact energy of 0.5 eV/atom the structures of all
investigated clusters show the lowest similarity to the original structures, except for the case of
nickel clusters deposited on a Cu(111) surface. Finally, it is demonstrated that when cluster and
substrate are of different materials, it is possible to control whether the deposition results in
largely intact clusters on the substrate or in a spreading of the clusters. This separation into
hard and soft clusters can be related to the relative cohesive energy of the crystalline materials. 相似文献
4.
Q. Sun Q. Wang X.G. Gong V. Kumar Y. Kawazoe 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2002,18(1):77-81
We report results of the atomic and electronic structures of Al7C cluster using ab initio molecular dynamics with ultrasoft pseudopotentials and generalized gradient approximation. The lowest energy structure is
found to be the one in which carbon atom occupies an interstitial position in Al7 cluster. The electronic structure shows that the recent observation [Chem. Phys. Lett. 316, 31 (2000)] of magic behavior of Al7C- cluster is due to a large highest occupied and lowest unoccupied molecular orbital (HOMO-LUMO) gap which makes Al7C- chemically inert. These results have further led us to the finding of a new neutral magic cluster Al7N which has the same number of valence electrons as in Al7C- and a large HOMO-LUMO gap of 1.99 eV. Further, calculations have been carried out on (Al7N)2 to study interaction between magic clusters.
Received 28 July 2001 相似文献
5.
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
6.
M. Bertolus V. Brenner P. Millié 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2000,11(3):387-394
An ab initio study of the Nan(OH)n, Nan(OH)n-1
+, Agn(OH)n, and Agn(OH)n-1
+ clusters with n up to four is presented. The results of this study show that, in accordance with experimental observations, the sodium hydroxide
clusters are almost purely ionic, while the Ag-O bond exhibits a significant covalent character. The perturbation caused by
the non-spherical OH- group relatively to an atomic anion, as well as the influence on structures and energies of the covalent character of the
metal-oxygen bond are determined. The appearance of metal-metal bonds in the silver hydroxide clusters is also discussed.
Finally, the theoretical results obtained on the Na-OH clusters are compared to experimental results available on the dissociation
of the Nan(OH)n-1
+ clusters.
Received 9 August 1999 and Received in final form 1st December 1999 相似文献
7.
Metastable fragmentation of silver bromide clusters 总被引:2,自引:0,他引:2
J.-M. L'Hermite F. Rabilloud L. Marcou P. Labastie 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2001,14(3):323-330
The abundance spectra and the fragmentation channels of silver bromide clusters have been measured and analyzed. The most
abundant species are AgnBrn - 1
+ and AgnBrn + 1
- and Ag14Br13
+ is a magic number, revealing their ionic nature. However, some features depart from what is generally observed for alkali-halide
ionic clusters. From a certain size, AgnBrn - 1
+ is no more the main series, and AgnBr n - 2, 3
+ series become almost as important. The fast fragmentation induced by a UV laser makes the cations lose more bromine than
silver ions and lead to more silver-rich clusters. Negative ions mass spectra contain also species with more silver atoms
than required by stoichiometry. We have investigated the metastable fragmentation of the cations using a new experimental
method. The large majority of the cations release mainly a neutral Ag3Br3 cluster. These decay channels are in full agreement with our recent ab initio DFT calculations, which show that Ag+-Ag+ repulsion is reduced due to a globally attractive interaction of their d orbitals. This effect leads to a particularly stable trimer (AgBr)3 and to quasi-planar cyclic structures of (AgBr)n clusters up to n = 6. We have shown that these two features may be extended to other silver halides, to silver hydroxides (AgOH)n, and to cuprous halide compounds.
Received 9 November 2000 and Received in final form 25 January 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.
M. B. Torres L. C. Balbás 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2007,43(1-3):217-220
We present a first-principles pseudopotential optimization of
the lower energy equilibrium structure of SinSc- anions for
n=14-18. We find that Si16Sc- is more stable than its
neighbors clusters, in agreement with recent experimental mass spectra. We
also optimize the geometry of pure Sin neutral clusters in the range
n=14-18, and compare our results with those from previous
first-principles calculations. 相似文献
10.
K. Nagaya H. Murakami H. Iwayama Y. Ohmasa M. Yao 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2007,43(1-3):69-72
The spectra of deep inner-core excited mixed rare-gas clusters were recorded by using electron ion coincidence (EICO) and
multi-hit momentum imaging (MHMI) techniques.
The EICO spectra for Ar99Kr1 clusters reveal that singly charged ions are emitted from the inner-core excited clusters in addition to the multiple charged
ions.
The dependence of the EICO spectra on photon energy and cluster size suggests that the holes created through vacancy cascade
on the krypton atoms are transferred to the surrounding atoms, and that the singly charged ions are the primary product of
the krypton photoabsorption.
Charge localization is suggested for the inner-core excited mixed rare-gas clusters from the analysis of the EICO peak width.
The MHMI measurements give us direct evidence for the strong charge migration from X-ray absorbing atoms to surrounding atoms.
The photon energy dependence of the PSD image for fragment ions suggests that the momentum of the fragment ions depends on
the number of charges generated by the vacancy cascade. 相似文献
11.
C. Coudray G. Blaise M.J. Malliavin 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2000,11(1):127-136
With the help of ab initio methods the clusters [(MgO)13Mg]
Q+
are simulated for Q = 0, 1, 2. Then, vacancy clusters [(MgO)12Mg2]
Q+
obtained by removing one oxygen atom are computed for Q running from 0 to 4. These clusters exhibit a slight sphericity and generally shorter interatomic distances than in the crystal.
The electronic densities variations are studied in function of Q. In particular, it is observed that the electronic density in the oxygen vacancy goes to a maximum when Q = 2. The ionisation potentials vary from approximately 4 to 14 eV when Q varies from 0 to 3, with a more rapid increase from Q = 1 to Q = 2. The stability study of vacancy clusters show that they experience a phase transition when their charge becomes equal
to 2, in accordance with the features mentioned above.
Received 14 September 1999 and Received in final form 2 December 1999 相似文献
12.
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
13.
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
14.
M.L. Gardel R. Vandenbosch B.P. Henry C. Cooper D.I. Will 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》1999,7(1):79-81
The destruction cross-section for 22.5 and 50 keV C1- , for 10 and 50 keV C8
1- and for 50 and 75 keV C60
1- clusters in collisions with H2 has been measured by an attenuation method. The destruction of the cluster anions is dominated by electron detachment rather
than fragmentation and is of the order of the geometric cross-section. The cross-sections vary little with bombarding energy.
Received: 16 September 1998 / Received in final form: 23 February 1999 相似文献
15.
C. Bréchignac Ph. Cahuzac B. Concina J. Leygnier I. Tignères 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2000,12(1):185-192
The cross-sections for collisional charge transfer between singly charged free clusters M
n
+ (M = Li, Na; n=1...50) and atomic targets A (cesium, potassium) have been measured as a function of collisional relative velocity in laboratory
energy range 1–10 keV. For each cluster size, the experimental values of the charge transfer cross-section are fitted with an universal parametric curve with two independent parameters and vm, the maximum cross-section and the corresponding velocity. For small size clusters (), the characteristic parameters show strong variations with the number of atoms in the cluster. Abrupt dips observed for n=10 and n=22 are attributed to electronic properties. Charge transfer patterns observed for various collisional systems present similarities,
which appear more sensitive to cluster quantum size effects than to collision energy defects. In their whole, the and vm parameters show differences in both their size evolution and their absolute values discussed in term of projectile and target
electronic structures.
Received 13 April 2000 and Received in final form 29 June 2000 相似文献
16.
P. Mélinon F. Tournus B. Masenelli A. Perez M. Pellarin J. Lermé M. Broyer B. Champagnon 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2001,16(1):337-340
This paper deals with a new type of SiC bonding where silicon atom seems to bridge C60 molecules. We have studied films obtained by deposition of (C60)nSim clusters prepared in a laser vaporization source. Prior deposition, free ionized clusters were studied in a time-of-flight
mass spectrometer. Mixed clusters (C60)nSim were clearly observed. Abundance and photofragmentation mass spectroscopies revealed the relatively high stability of the
(C60)nSi
n
+
, (C60)nSi
n - 1
+
and (C60)nSi
n - 2
+
species. This observation is in favor of the arrangement of these complexes as polymers where the C60 cages may be bridged by a silicon atom. Free neutral clusters are then deposited onto substrate making up a nanogranular
thin film (≃ 100 nm). The film is probed by Auger and X-ray photoemission spectroscopies, but above all by surface enhanced Raman scattering.
The results suggest an unusual chemical bonding between silicon and carbon and the environment of the silicon atom is expected
to be totally different from the sp3 lattice: ten or twelve carbon neighbors might surround silicon atom. The bonding is discussed to the light of the so-called
fullerene polymerization as observed for pure fullerite upon laser irradiation. This opens a new route for bridging C60 molecules together with an appreciable energy bonding, since the usual van der Waals bonding in fullerite could be replaced
by an ionocovalent bond. Such an assumption must be checked in the future by XAS and EXAFS experiments.
Received 15 November 2000 相似文献
17.
S. Tomita J.S. Forster P. Hvelplund A.S. Jensen S.B. Nielsen 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2001,16(1):119-122
We have measured attenuation cross sections and fragmentation cross sections for protonated water clusters H(H2O)n
+ (n = 1 to 100) colliding with noble gas atoms (He and Xe) at a laboratory energy of 50 keV. In collisions with He, a transparency
effect in the attenuation cross section was observed. For the case of fragmentation in collisions with Xe, a strong enhancement
of small clusters was observed which we attribute to multifragmentation.
Received 30 November 2000 相似文献
18.
M. Vogel K. Hansen A. Herlert L. Schweikhard 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2001,16(1):73-76
The decay pathway competition between monomer and dimer evaporation of photoexcited cluster ions Au
+
n, n = 2-27, has been investigated by photodissociation of size-selected gold clusters stored in a Penning trap. For n > 6 the two decay pathways are distinguished by their experimental signature in time-resolved measurements of the dissociation.
For the smaller clusters, simple fragment spectra were used. As in the case of the other copper-group elements, even-numbered
gold cluster ions decay exclusively by monomer evaporation, irrespective of their size. For small odd-size gold clusters,
dimer evaporation is a competitive alternative, and the smaller the odd-sized clusters, the more likely they decay by dimer
evaporation. In this respect, Au
+
9 shows an anomalous behavior, as it is less likely to evaporate dimers than its two odd-numbered neighbors, Au
+
7 and Au
+
11. This nonamer anomaly is typical for copper-group cluster ions M
+
9 (M = Cu, Ag, Au) and a similar behavior is found in the anionic heptamers M
-
7. It is discussed in terms of the well-known electronic shell closing at n
e = 8 atomic valence electrons.
Received 2 November 2000 相似文献
19.
T. Gleitsmann M. E. Vaida T. M. Bernhardt V. Bonačić-Koutecký C. Bürgel A. E. Kuznetsov R. Mitrić 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2007,45(3):477-483
The electronic structure of supported mass-selected Ag3 clusters is analyzed by joint femtosecond photoemission spectroscopy and ab initio theoretical investigations. A wide band
gap insulating magnesia ultra-thin film on Mo(100) has been chosen as substrate in order to minimize the electronic interaction
between metal clusters and support. After magnesia ultra-thin film preparation no photoemission from the molybdenum substrate
is observed anymore, instead very weak two photon photoemission is detected possibly originating from surface or subsurface
oxide defect states. Soft-landing deposition of 2
of atomic monolayer equivalents of Ag3 clusters results in the disappearance also of the MgO two photon photoemission signal, while a strong single photon photoemission
signal is detected from states located directly below the Fermi level. The theoretical study of structural, electronic and
optical properties of Ag3 at two model sites of MgO (100), the stoichiometric MgO(100) and an FS-center defect, based on the DFT method and the embedded cluster model provides insight into the interactions between the
cluster and the support which are responsible for the characteristic spectroscopic features. 相似文献
20.
S. Neukermans N. Veldeman E. Janssens P. Lievens Z. Chen P.v.R. Schleyer 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2007,45(2):301-308
We report a combined experimental and computational
investigation of small AlnOm species (n ≤20, m ≤
12), produced in a laser vaporization cluster source. The oxygen
content in the clusters was tuned by varying the oxygen
concentration in the carrier gas. Ionization energies are
bracketed using different ionizing photon energies in the energy
range between 5.37 and 7.89 eV. Among the singly doped AlnO
species, Al3O and Al15O are found to have relatively low
ionization energies, which can be related to the magic character
of the corresponding cations. Peculiarly low ionization energies
also are observed for specific oxygen rich species (m > 1),
suggesting the formation of ionically bound subunits. The
structures and ionization energies of singly doped AlnO0,+
(n = 1 - 7) clusters were determined using density functional
theory (B3LYP/6-311+G(d)).
Electronic supplementary material Supplementary Online Material 相似文献