4 research outputs found
Pathways of Growth of CdSe Nanocrystals from Nucleant (CdSe)<sub>34</sub> Clusters
The initial steps in the growth of
quantum platelets from the wurtzite-type
(CdSe)<sub>34</sub> clusters are simulated using density functional
theory with the generalized gradient approximation. The nucleant (CdSe)<sub>34</sub> cluster has been chosen for simulations because it has experimentally
been found to be a magic-size nucleant for the low-temperature growth
of CdSe quantum platelets. According to the results of our calculations,
the growth is anisotropic and favors the (0001) direction, which is
consistent with the experimental findings. We found that growth in
other directions lowers the symmetry of the resulting clusters and
that the asymmetrical positioning of rhombic defects causes the growing
platelet to bend due to the surface strain, which appears to be the
limiting factor of growth. An alternative pathway to quantum platelet
growth could proceed via the decomposition of (CdSe)<sub>34</sub> to
(CdSe)<sub>13</sub> in electron-donating media, which was found to
be thermodynamically favorable. Side product (CdSe)<sub>21</sub> generated
in this process is capable of growing via hexagonal stacking as well
as propagating as a nanotube
Joint Studies of Spin Frustration Induced by Doping Small ZnSe Nanoparticles with Fe Atoms
Abstract As a 1.8 nm ZnSe nanocrystal is progressively doped with 1%, 5%, and 10% Fe, it shows a progressive change in its magnetic properties from a superparamagnetic FMâdominated exchange type to an onset of AFM exchange with evidence of spin frustration. Magnetization measurements allow to obtain exchange coupling constants that are compared to the results of a BrokenâSymmetry Density Functional Theory (BSâDFT) model of a doped (ZnSe)34 cluster. DFT shows a capability to reproduce the experimental pattern of the increasing influence of AFM exchange as doping concentration increases. The material phase segregates at the edges where strained rhombic surface sites are the preferred doping sites of iron. Large concentrations of iron leads to the formation of Fe clusters and complex exchange patterns that result in spin frustration in some iron trimers but none in the others. The spin frustration of these complex systems by assuming mirror symmetry of the sites when fitting by using BSâDFT formalism is classified and analyzed. While some individual J constants obtained have significant errors, the averaged exchange constants are generally in good agreement with our experimental data
Structure and magnetic properties of Fe
The electronic, geometrical, and magnetic structures of iron clusters Fen substituted
with a single Gd atom are studied using density functional theory with generalized
gradient approximation for n =
12 â 19. An all electron basis set of a triple-ζ quality is chosen for the
iron atoms whereas an effective core potential and the basis set of a
triple-ζ
quality are used for the Gd atom in optimizations of FenGd clusters.
The lowest total energy state of a FenGd cluster was found to possess a
geometrical structure where the Gd atom substitutes for a surface Fe atom of the
Fen+1 cluster at given n. The total spin of a
substituted cluster is larger than the total spin of the lowest total energy state of a
unary iron cluster with the same number of atoms. The binding energy per atom in a
substituted Fenâ1Gd cluster is somewhat smaller than the
binding energy per atom in a non-substituted Fen cluster. That is, the Gd
substitution increases the total spin magnetic moment but destabilizes substituted iron
clusters
Dissociation of Singly and Multiply Charged Nitromethane Cations: Femtosecond Laser Mass Spectrometry and Theoretical Modeling
Dissociation pathways of singly- and multiply charged gas-phase nitromethane cations were investigated with strong-field laser photoionization mass spectrometry and density functional theory computations. There are multiple isomers of the singly charged nitromethane radical cation, several of which can be accessed by rearrangement of the parent CH3âNO2 structure with low energy barriers. While direct cleavage of the CâN bond from the parent nitromethane cation produces NO2+ and CH3+, rearrangement prior to dissociation accounts for fragmentation products including NO+, CH2OH+, and CH2NO+. Extensive Coulomb explosion in fragment ions observed at high laser intensity indicates that rapid dissociation of multiply charged nitromethane cations produces additional species such as CH2+, H+, and NO22+. âŻOn the basis of analysis of Coulomb explosion in the mass spectral signals and pathway calculations, sufficiently intense laser fields can remove four or more electrons from nitromethane