524 research outputs found
Structures and Stabilities of Doubly-charged (MgO)nMg2+ (n=1-29) Cluster Ions
Ab initio perturbed ion plus polarization calculations are reported for
doubly-charged nonstoichiometric (MgO)nMg2+ (n=1-29) cluster ions. We consider
a large number of isomers with full relaxations of the geometries, and add the
correlation correction to the Hartree-Fock energies for all cluster sizes. The
polarization contribution is included at a semiempirical level also for all
cluster sizes. Comparison is made with theoretical results for neutral (MgO)n
clusters and singly-charged alkali-halide cluster ions. Our method is also
compared to phenomenological pair potential models in order to asses their
reliability for calculations on small ionic systems. The large
coordination-dependent polarizabilities of oxide anions favor the formation of
surface sites, and thus bulklike structures begin to dominate only after n=24.
The relative stabilities of the cluster ions against evaporation of a MgO
molecule show variations that are in excellent agreement with the experimental
abundance spectra.Comment: Final version accepted in Journal of Chemical Physics; 8 pages plus 8
figures (6 GIFs and 2 PSs). The main difference with respect to the original
submission is the inclusion of coordination-dependent polarizabilities for
oxide anions. That results in substantial changes in the result
Determination of the lowest energy structure of Ag from first-principles calculations
The ground-state electronic and structural properties, and the electronic
excitations of the lowest energy isomers of the Ag cluster are calculated
using density functional theory (DFT) and time-dependent DFT (TDDFT) in real
time and real space scheme, respectively. The optical spectra provided by TDDFT
predict that the D dodecahedron isomer is the structural minimum of
Ag cluster. Indeed, it is borne out by the experimental findings.Comment: 4 pages, 2 figures. Accepted in Physical Review A as a brief repor
Breaking Bonds with the Left Eigenstate Completely Renormalized Coupled-Cluster Method
The recently developed [P. Piecuch and M. Wloch, J. Chem. Phys.123, 224105 (2005)] size-extensive left eigenstate completely renormalized (CR) coupled-cluster (CC) singles (S), doubles (D), and noniterative triples (T) approach, termed CR-CC(2,3) and abbreviated in this paper as CCL, is compared with the full configuration interaction (FCI) method for all possible types of single bond-breaking reactions between C, H, Si, and Cl (except H2) and the H2SiSiH2 double bond-breaking reaction. The CCL method is in excellent agreement with FCI in the entire region R=1–3Re for all of the studied single bond-breaking reactions, whereR and Re are the bond distance and the equilibrium bond length, respectively. The CCL method recovers the FCI results to within approximately 1mhartree in the region R=1–3Reof the H–SiH3, H–Cl, H3Si–SiH3, Cl–CH3, H–CH3, and H3C–SiH3bonds. The maximum errors are −2.1, 1.6, and 1.6mhartree in the R=1–3Re region of the H3C–CH3, Cl–Cl, and H3Si–Clbonds, respectively, while the discrepancy for the H2SiSiH2 double bond-breaking reaction is 6.6 (8.5)mhartree at R=2(3)Re. CCL also predicts more accurate relative energies than the conventional CCSD and CCSD(T) approaches, and the predecessor of CR-CC(2,3) termed CR-CCSD(T)
Accurate <i>ab initio</i> ro-vibronic spectroscopy of the X<sup>2</sup>∏ CCN radical using explicitly correlated methods
Explicitly correlated CCSD(T)-F12b calculations have been carried out with systematic sequences of correlation consistent basis sets to determine accurate near-equilibrium potential energy surfaces for the X<sup>2</sup>∏ and a<sup>4</sup>Σ<sup>−</sup> electronic states of the CCN radical. After including contributions due to core correlation, scalar relativity, and higher order electron correlation effects, the latter utilizing large-scale multireference configuration interaction calculations, the resulting surfaces were employed in variational calculations of the ro-vibronic spectra. These calculations also included the use of accurate spin-orbit and dipole moment matrix elements. The resulting ro-vibronic transition energies, including the Renner-Teller sub-bands involving the bending mode, agree with the available experimental data to within 3 cm<sup>−1</sup> in all cases. Full sets of spectroscopic constants are reported using the usual second-order perturbation theory expressions. Integrated absorption intensities are given for a number of selected vibronic band origins. A computational procedure similar to that used in the determination of the potential energy functions was also utilized to predict the formation enthalpy of CCN, ΔH<sub>f</sub>(0K) = 161.7 ± 0.5 kcal/mol
Unexpected Magnetism of Small Silver Clusters
The ground-state electronic, structural, and magnetic properties of small
silver clusters, Ag (2n22), have been studied using a linear
combination of atomic Gaussian-type orbitals within the density functional
theory. The results show that the silver atoms, which are diamagnetic in bulk
environment, can be magnetic when they are grouped together in clusters. The
Ag cluster with icosahedral symmetry has the highest magnetic moment per
atom among the studied silver clusters. The cluster symmetry and the reduced
coordination number specific of small clusters reveal as a fundamental factor
for the onset of the magnetism.Comment: 4 pages, 4 figure
Emergence of Bulk CsCl Structure in (CsCl)nCs+ Cluster Ions
The emergence of CsCl bulk structure in (CsCl)nCs+ cluster ions is
investigated using a mixed quantum-mechanical/semiempirical theoretical
approach. We find that rhombic dodecahedral fragments (with bulk CsCl symmetry)
are more stable than rock-salt fragments after the completion of the fifth
rhombic dodecahedral atomic shell. From this size (n=184) on, a new set of
magic numbers should appear in the experimental mass spectra. We also propose
another experimental test for this transition, which explicitely involves the
electronic structure of the cluster. Finally, we perform more detailed
calculations in the size range n=31--33, where recent experimental
investigations have found indications of the presence of rhombic dodecahedral
(CsCl)32Cs+ isomers in the cluster beams.Comment: LaTeX file. 6 pages and 4 pictures. Accepted for publication in Phys.
Rev.
Lattice Distortions Around a Tl+ Impurity in NaI:Tl+ and CsI:Tl+ Scintillators. An Ab Initio Study Involving Large Active Clusters
Ab initio Perturbed Ion cluster-in-the-lattice calculations of the impurity
centers NaI:Tl+ and CsI:Tl+ are pressented. We study several active clusters of
increasing complexity and show that the lattice relaxation around the Tl+
impurity implies the concerted movement of several shells of neighbors. The
results also reveal the importance of considering a set of ions that can
respond to the geometrical displacements of the inner shells by adapting
selfconsistently their wave functions. Comparison with other calculations
involving comparatively small active clusters serves to assert the significance
of our conclusions. Contact with experiment is made by calculating absorption
energies. These are in excellent agreement with the experimental data for the
most realistic active clusters considered.Comment: 7 pages plus 6 postscript figures, LaTeX. Submmited to Phys, Rev.
Ga+, In+ and Tl+ Impurities in Alkali Halide Crystals: Distortion Trends
A computational study of the doping of alkali halide crystals (AX: A = Na, K;
X = Cl, Br) by ns2 cations (Ga+, In+ and Tl+) is presented. Active clusters of
increasing size (from 33 to 177 ions) are considered in order to deal with the
large scale distortions induced by the substitutional impurities. Those
clusters are embedded in accurate quantum environments representing the
surrounding crystalline lattice. The convergence of the distortion results with
the size of the active cluster is analyced for some selected impurity systems.
The most important conclusion from this study is that distortions along the
(100) and (110) crystallographic directions are not independent. Once a
reliable cluster model is found, distortion trends as a function of impurity,
alkali cation and halide anion are identified and discussed. These trends may
be useful when analycing other cation impurities in similar host lattices.Comment: LaTeX file. 7 pages and 2 pictures. Accepted for publication in J.
Chem. Phy
Structural and Electronic Properties of Small Neutral (MgO)n Clusters
Ab initio Perturbed Ion (PI) calculations are reported for neutral
stoichiometric (MgO)n clusters (n<14). An extensive number of isomer structures
was identified and studied. For the isomers of (MgO)n (n<8) clusters, a full
geometrical relaxation was considered. Correlation corrections were included
for all cluster sizes using the Coulomb-Hartree-Fock (CHF) model proposed by
Clementi. The results obtained compare favorably to the experimental data and
other previous theoretical studies. Inclusion of correlaiotn is crucial in
order to achieve a good description of these systems. We find an important
number of new isomers which allows us to interpret the experimental magic
numbers without the assumption of structures based on (MgO)3 subunits. Finally,
as an electronic property, the variations in the cluster ionization potential
with the cluster size were studied and related to the structural isomer
properties.Comment: 24 pages, LaTeX, 7 figures in GIF format. Accepted for publication in
Phys. Rev.
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