108 research outputs found
Optical absorption in boron clusters B and B : A first principles configuration interaction approach
The linear optical absorption spectra in neutral boron cluster B and
cationic B are calculated using a first principles correlated
electron approach. The geometries of several low-lying isomers of these
clusters were optimized at the coupled-cluster singles doubles (CCSD) level of
theory. With these optimized ground-state geometries, excited states of
different isomers were computed using the singles configuration-interaction
(SCI) approach. The many body wavefunctions of various excited states have been
analysed and the nature of optical excitation involved are found to be of
collective, plasmonic type.Comment: 22 pages, 38 figures. An invited article submitted to European
Physical Journal D. This work was presented in the International Symposium on
Small Particles and Inorganic Clusters - XVI, held in Leuven, Belgiu
Infrared electron modes in light deformed clusters
Infrared quadrupole modes (IRQM) of the valence electrons in light deformed
sodium clusters are studied by means of the time-dependent local-density
approximation (TDLDA). IRQM are classified by angular momentum components
20, 21 and 22 whose branches are separated by cluster
deformation. In light clusters with a low spectral density, IRQM are
unambiguously related to specific electron-hole excitations, thus giving access
to the single-electron spectrum near the Fermi surface (HOMO-LUMO region). Most
of IRQM are determined by cluster deformation and so can serve as a sensitive
probe of the deformation effects in the mean field. The IRQM branch 21 is coupled with the magnetic scissors mode, which gives a chance to detect
the latter. We discuss two-photon processes, Raman scattering (RS), stimulated
emission pumping (SEP), and stimulated adiabatic Raman passage (STIRAP), as the
relevant tools to observe IRQM. A new method to detect the IRQM population in
clusters is proposed.Comment: 22 pages, 6 figure
Optical response of small silver clusters
The time-dependent local density approximation is applied to the optical
response of the silver clusters, Ag_2, Ag_3, Ag_8 and Ag_9^+. The calculation
includes all the electrons beyond the closed-shell Ag^{+11} ionic core, thus
including for the first time explicitly the filled d-shell in the response. The
excitation energy of the strong surface plasmon near 4 eV agrees well with
experiment. The theoretical transition strength is quenched by a factor of 4
with respect to the pure s-electron sum rule in Ag_8 due to the d-electrons. A
comparable amount of strength lies in complex states below 6 eV excitation. The
total below 6 eV, about 50% of the s sum rule, is consistent with published
experiments.Comment: 13 pages RevTex and 9 Postscript figure
Structure and properties of small sodium clusters
We have investigated structure and properties of small metal clusters using
all-electron ab initio theoretical methods based on the Hartree-Fock
approximation and density functional theory, perturbation theory and compared
results of our calculations with the available experimental data and the
results of other theoretical works. We have systematically calculated the
optimized geometries of neutral and singly charged sodium clusters having up to
20 atoms, their multipole moments (dipole and quadrupole), static
polarizabilities, binding energies per atom, ionization potentials and
frequencies of normal vibration modes. Our calculations demonstrate the great
role of many-electron correlations in the formation of electronic and ionic
structure of small metal clusters and form a good basis for further detailed
study of their dynamic properties, as well as structure and properties of other
atomic cluster systems.Comment: 47 pages, 16 figure
Evolution of electronic and ionic structure of Mg-clusters with the growth cluster size
The optimized structure and electronic properties of neutral and singly
charged magnesium clusters have been investigated using ab initio theoretical
methods based on density-functional theory and systematic post-Hartree-Fock
many-body perturbation theory accounting for all electrons in the system. We
have systematically calculated the optimized geometries of neutral and singly
charged magnesium clusters consisting of up to 21 atoms, electronic shell
closures, binding energies per atom, ionization potentials and the gap between
the highest occupied and the lowest unoccupied molecular orbitals. We have
investigated the transition to the hcp structure and metallic evolution of the
magnesium clusters, as well as the stability of linear chains and rings of
magnesium atoms. The results obtained are compared with the available
experimental data and the results of other theoretical works.Comment: 30 pages, 10 figures, 3 table
Optical absorption spectra of finite systems from a conserving Bethe-Salpeter equation approach
We present a method for computing optical absorption spectra by means of a
Bethe-Salpeter equation approach, which is based on a conserving linear
response calculation for electron-hole coherences in the presence of an
external electromagnetic field. This procedure allows, in principle, for the
determination of the electron-hole correlation function self-consistently with
the corresponding single-particle Green function. We analyze the general
approach for a "one-shot" calculation of the photoabsorption cross section of
finite systems, and discuss the importance of scattering and dephasing
contributions in this approach. We apply the method to the closed-shell
clusters Na_4, Na^+_9 and Na^+_(21), treating one active electron per Na atom.Comment: 9 pages, 3 figure
Theoretical exploration of ultrafast spectroscopy of small clusters
We present the ultrafast multistate nuclear dynamics involving adiabatic and
nonadiabatic excited states of non-stoichiometric halide deficient clusters
(NanF) characterized by strong ionic bonding and one-excess electron
for which the "frozen ionic bonds" approximation has been justified allowing to
consider the optical response of the single excess electron in the effective field of
the other electrons. We combined the Wigner-Moyal representation of the
vibronic density matrix with the ab initio multi state molecular dynamics in
the ground and excited electronic states including the nonadiabatic couplings
calculated "on the fly" at low computational demand.
This method allows the simulation of femtosecond pump-probe and pump-dump signals
based on an analytical formulation, which utilizes temperature dependent ground
state initial conditions, an ensemble of trajectories carried out on the electronic
excited state as well as on the ground state after the passage through the conical
intersection in the case of nonadiabatic dynamics and for probing either in the
cationic state or in the ground state. The choice of the systems we presented
has been made in order to determine the timescales of the fast
geometric relaxation leaving the bonding frame intact as during the dynamics
in the first excited state of Na4F3, and of the bond breaking processes leading to
conical intersection between the first excited state and the ground state as
in Na3F2. The former is the smallest finite system prototype
for an surface F-center of bulk color centers. The latter allows to study the photo
isomerization in full complexity taking into account all degrees of freedom.
In the case of Na4F3 after the fast geometric
relaxation in the excited state leading to deformed cuboidal structure
without breaking of bonds, different types of internal vibrational redistribution
(IVR) processes have been identified in pump-dump signals by tuning the dump laser.
In contrast,
from the analysis of the pump-probe signals of Na3F2
cluster, the timescales for the metallic and the
ionic bond breaking, as well as for the passage through conical
intersection have been determined. Finally the
conditions under which these processes can be experimentally observed have been
identified
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