共查询到20条相似文献,搜索用时 31 毫秒
1.
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
2.
T.W Schmidt 《Journal of Molecular Spectroscopy》2003,222(1):86-92
Electronic spectra of a series of weakly bound clusters consisting of argon (Arn, n=1-4) bound to the butadiyne cation, C4H2+, have been recorded in the visible range from 440 to 520 nm by photodissociation. The C4H2+ fragment signal was recorded as a function of the laser wavelength during excitation of the A←X electronic transition. The observed transitions were assigned to the band origin of the cationic complexes and to vibronic bands involving excitation of the ν3 and ν7 vibrational modes of the C4H2+ moiety, as well as combination bands of these modes. Comparison of the photodissociation spectra of the various clusters reveals a small blue shift, 25 cm−1 of the band maxima relative to the corresponding transitions reported from gas phase spectra of the bare C4H2+ cation. The magnitude of the blue shift of each band increases with successive Ar solvation up to n=3. Furthermore, each band becomes increasingly broadened towards the red with the addition of Ar atoms due to an increasing number of unresolved transitions involving excited intermolecular modes. 相似文献
3.
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
4.
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
5.
F.A. Fernández-Lima C.R. Ponciano E. Pedrero E.F. da Silveira 《Applied Surface Science》2006,252(23):8171-8177
Experimental results of laser sputtering of cesium and rubidium iodide secondary ions are presented. A TOF mass spectrometer, operating in linear mode, continuous extraction for positive or negative ions, was used for the analysis of (CsI)nCs+, (CsI)nI−, (RbI)nRb+ and (RbI)nI− ion emission as a function of the laser irradiance. Experimental data show that the cluster ion emission yields decrease exponentially with n, for all the laser irradiances applied. Theoretical analysis of the clusters structure was performed using density functional theory at the B3LYP/LACV3P level, for the positive and negative cluster series. A quasi-equilibrium evolution of the clusters is proposed to extract a parameter characteristic of the cluster recombination process: the effective temperature. The hypothesis of the atomic species’ recombination (during the expansion of a high density highly ionized cloud) leading to cluster formation is confirmed to some extent in a second set of experiments: the UV laser ablation of a mixed and non-mixed cesium iodide and potassium bromide targets. These experiments show that the emission yields contain contributions from both the recombination process and from the sample stoichiometry, even for high laser irradiances. 相似文献
6.
The question of whether the linear absorption spectra of metal clusters can be interpreted as density oscillations (collective
“plasmons”) or can only be understood as transitions between distinct molecular states is still a matter of debate for clusters
with only a few electrons. We calculate the photo-absorption spectra of Na2 and Na5
+ comparing two different methods: quantum fluid dynamics and time-dependent density functional theory. The changes in the
electronic structure associated with particular excitations are visualized in “snapshots” via transition densities. Our analysis
shows that even for the smallest clusters, the observed excitations can be interpreted as intuitively understandable density
oscillations. For Na5
+, the importance of self-interaction corrections to the adiabatic local density approximation is demonstrated.
Received: 1 July 2001 / Published online: 10 October 2001 相似文献
7.
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
8.
F. Stienkemeier J. Higgins W. E. Ernst G. Scoles 《Zeitschrift für Physik B Condensed Matter》1995,98(3):413-416
Large helium clusters, ranging in size from a few hundred to several thousand atoms, are produced in a nozzle expansion. Combining this source with a pick-up scattering cell in which the clusters can be seeded with chromophores allows us to probe the influence of the helium environment on the atoms and molecules attached to the clusters. Using an alkali as chromophore we recorded laser induced fluorescence spectra of Na atoms and molecules attached to helium clusters. Apart from the spectrum of the Na monomer, we have found spectroscopic bands which can unambiguous be assigned to two bound Na atoms. The first of this bands is due to 11
+
(A) 11
g
+
(X) excitations of the covalently bound singlet Na2 molecule while the second is due to 13
g
+
13
+
excitations for the van der Waals bound triplet Na2 dimer. Both bands have been vibrationally resolved. Furthermore we found very large fluorescence intensities in the region 605–635 nm which are likely due to the excitation of a species containing three Na atoms attached to a helium cluster. 相似文献
9.
M.-H. Schaffner F. Patthey U. Heiz W.-D. Schneider O. Kuffer H.-V. Roy P. Fayet J.K. Gimzewski R. Berndt 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》1998,2(1):79-82
The emission of photons in the visible wavelength range from mass-selected Ag+
n, Cu+
n, Pt+
n and Pd+
n () clusters is observed. Photons are detected 10-4 s after the cluster generation in a sputter source. The emission intensities display distinct variations with cluster size
and material. The observations are interpreted in terms of the decay of metastable states which are excited during the high-energy
sputtering process used for the generation of these clusters.
Received: 28 October 1997 / Revised: 5 January 1998 / Accepted: 30 January 1998 相似文献
10.
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
11.
M. Vogel K. Hansen A. Herlert L. Schweikhard 《Applied physics. B, Lasers and optics》2001,73(4):411-416
The pathway competition between neutral monomer and neutral dimer evaporation from optically excited odd-size gold cluster
ions Au+
n, n=7–15, has been investigated as a function of cluster size and excitation energy. Gold cluster ions of these sizes are
the only ones to show observable pathway competition while all other sizes exclusively evaporate either neutral monomers or
neutral dimers. The investigation has been performed by photoexcitation of stored size-selected gold cluster ions with a single
10-ns laser pulse. Subsequent time-resolved observation of the delayed dissociation allows us to quantitatively determine
the relative fragment yields of the respective decay channels as a function of excitation energy. Contrary to theoretical
expectations, the dimer-to-monomer branching ratio of evaporated particles is found to decrease monotonously with increasing
excitation energy for all cluster sizes under investigation. Possible explanations for this behaviour are discussed.
Received: 9 July 2001 / Revised version: 24 September 2001 / Published online: 15 October 2001 相似文献
12.
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
13.
C. Bréchignac Ph. Cahuzac B. Concina J. Leygnier 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2001,16(1):91-94
We have studied experimentally the collisional charge transfer between a neutral atom and a multicharged metal-atom cluster.
The charge transfer cross section measured for Na 31
+ + + Cs is in the range of 400 ?2. The time-of-flight mass analysis of the singly charged collision products demonstrates that an energy of about 0.5 eV is
deposited in the cluster fragment during the charge transfer collision. This effect can be interpreted as a charge transfer
to an excited state of the metal cluster. The measured cross section for Na 31
+ + + Cs is larger than the one for Na 31
+ + Cs collisions. This difference between these two systems is due to the existence, for the first one, of a Coulombic repulsion
term in the collision output channel.
Received 24 October 2000 相似文献
14.
V. O. Nesterenko W. Kleinig P. -G. Reinhard 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2002,19(1):57-64
Recent experimental data on the dipole plasmon in axial sodium clusters Na N + with 11 ≤ N ≤ 57 are analyzed within a self-consistent separable random-phase approximation (SRPA) based on the deformed Konh-Sham functional. Good agreement with the data is achieved. The calculations show that, while in light clusters plasmon properties (gross structure and width) are determined mainly by deformation splitting, in medium clusters with N τ 50 the Landau fragmentation becomes decisive. Moreover, in medium clusters shape isomers come to play with contributions to the plasmon comparable with the ground state one. As a result, commonly used methods of the experimental analysis of cluster deformation become useless and correct treatment of cluster shape requires microscopic calculations. 相似文献
15.
T. Ritschel Ch. Zuhrt L. Zülicke P. J. Kuntz 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2007,41(1):127-141
ArnHCl+ van-der-Waals clusters for n = 1–13 are investigated
with the “minimal diatomics-in-molecules (DIM) model”
using ab-initio input data obtained from multi-reference
configuration-interaction calculations plus subsequent projection onto
valence-bond wavefunctions.
The results for the complexes with n = 1–3 are checked against
ab-initio calculations at the
coupled-cluster (CCSD) level with the same one-electron atomic basis set as
for the input data generation (aug-cc-pVTZ from Dunning).
In addition to the electronic ground state,
the first excited
state for the triatomic
complex (n = 1) is also studied.
The results
from the DIM model are shown to be in fair agreement with those from
advanced conventional ab-initio calculations, although there are
differences in detail. The comparison
justifies the extension of the DIM approach to n > 3.
Systematic analysis of the local minima of the multi-dimensional
potential-energy surfaces (PESs), carried out with the combined
method
described in part I (Monte-Carlo sampling plus subsequent steepest-descent
optimization), reveals simple building-up regularities for the most
stable structures (i.e. those corresponding to the global PES minimum)
at each n: apart from always having a nearly linear
(Ar–H–Cl)+ fragment as core, the aggregates show little
or no symmetry. Secondary local minima are also determined and their
structures interpreted.
The PESs for the low-lying excited states reveal a much more complicated
topography compared to the ArnH+ clusters allowing a variety
of photo-processes.
The energy level sequence of the first five excited electronic states
and the stability of the clusters in these states is studied
as a function of the cluster size n. 相似文献
16.
U. Heiz 《Applied Physics A: Materials Science & Processing》1998,67(6):621-626
We report on the size-dependent chemical reactivity of nickel clusters with up to 30 atoms. Monodispersed Ni30 clusters show a higher reactivity for CO dissociation than Ni11 and Ni20. Under our experimental conditions the smallest nickel clusters (Nix, x<4) produce nickelcarbonyl complexes. These results demonstrate that such small clusters are unique for catalytic reactions
not only due to their high surface-to-volume ratio but also essentially because of the distinctive properties of different
cluster sizes. In addition thermal desorption spectroscopy of CO shows that on average four molecules are weakly adsorbed
per Ni11 at saturation coverage. Using an isotopic mixture of 12CO and 13CO, infrared spectroscopy reveals the existence of a vibrational coupling interaction between the four COs. A semi-classical
model of interacting dipoles is applied to correlate the observed vibrational frequency shifts with the arrangement of the
COs on the cluster. This simple analysis favors a three-dimensional structure for the deposited clusters.
Received: 23 March 1998/Accepted: 25 August 1998 相似文献
17.
F. Fehrer P. M. Dinh M. Bär P.-G. Reinhard E. Suraud 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2007,45(3):447-458
We investigate the dynamical evolution of a Na8 cluster embedded in Ar matrices of various sizes from N=30 to 1048.
The system is excited by an intense short laser pulse leading to high
ionization stages.We analyze the subsequent highly non-linear motion of cluster and Ar environment in terms of trajectories,
shapes, and energy flow.
The most prominent effects are: temporary stabilization of high charge states for several ps, sudden stopping of the Coulomb
explosion of the embedded Na8
clusters associated with an extremely fast energy transfer to the Ar
matrix, fast distribution of energy throughout the Ar layers by a sound wave.
Other ionic-atomic transfer and relaxation processes proceed at slower
scale of few ps. The electron cloud is almost thermally decoupled
from ions and thermalizes far beyond the ps scale. 相似文献
18.
19.
M.A. Gaveau M. Briant P.R. Fournier J.M. Mestdagh J.P. Visticot F. Calvo S. Baudrand F. Spiegelman 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2002,21(2):153-161
Spectroscopic experiments have been performed, providing emission and excitation spectra of calcium atoms trapped on argon
clusters of average size 2 000. The two experimental spectra fall in the vicinity of the calcium resonance line 1P 1 → 1S0 at 422.9 nm. The excitation spectrum consists in two bands located on each side of the resonance line of the free calcium.
In addition, Monte Carlo calculations, coupled to Diatomics-In-Molecule potentials are employed to simulate the absorption
spectrum of a single calcium atom in the environment of a large argon cluster of average size 300. The theoretical absorption
spectrum confirms the existence of two bands, and shows that these bands are characteristic of a calcium atom located at the
surface of the argon cluster and correspond to the excited 4p orbital of calcium either perpendicular or parallel to the cluster surface. The precise comparison between the shape of the
absorption spectrum and that of the fluorescence excitation spectrum shows different intensity ratios. This could suggest
the existence of a non adiabatic energy transfer that quenches partly the fluorescence of trapped calcium. Another explanation,
although less likely, could be a substantial dependence of the calcium oscillator strength according to the alignment of the
calcium excited orbital with respect to the cluster surface. The emission spectrum always shows a band in the red of the resonance
line which is assigned to the emission of calcium remaining trapped on the cluster. When exciting the blue band of the excitation
spectrum, the emission spectrum shows a second, weak, component that is assigned to calcium atoms ejected from the argon clusters,
indicating a competition between ejection and solvation.
Received 7 May 2002 Published online 1st October 2002
RID="a"
ID="a"e-mail: jmm@drecam.saclay.cea.fr
RID="b"
ID="b"URA 2453 du CNRS
RID="c"
ID="c"UMR 5626 du CNRS 相似文献
20.
T. Döppner S. Teuber M. Schumacher J. Tiggesbäumker K.H. Meiwes-Broer 《Applied physics. B, Lasers and optics》2000,71(3):357-360
Clusters of heavy metal atoms in strong femtosecond laser-light fields undergo multi-ionization with the loss of hundreds
of electrons. The cross section largely exceeds that of corresponding isolated atoms, which leads in the case of PbN to a complete ionization of the 4f shell with a light intensity of 1.2×1015 W/cm2. Experimental investigations on Pb and Pt clusters with variable pulse widths and, for the first time, with the pump&probe
technique give insight into the dynamics of the coupling of electromagnetic radiation into the clusters. Both approaches support
the picture according to which, after an initial charging, the clusters expand due to Coulomb forces. This expansion is accompanied
by a reduction of the electron density and at the same time by an increase of the optical sensitivity. Once the plasmon energy
of the diluted nanoplasma approaches the photon energy, the charging efficiency increases significantly. The experimental
observations are confirmed by random-phase approximation (RPA) calculations of the optical response, including molecular-dynamics
simulations of the expanding systems.
Received: 11 November 1999 / Published online: 13 July 2000 相似文献