17,577 research outputs found
Theoretical investigation of the scope of sequential ligand tuning using a bifunctional scorpionate tris(1,2,4-triazolyl)borate-based architecture
The donor properties of a series of tripodal mixed N-donor/carbene ligands derived through sequential alkylation of hydrotris(1,2,4-triazolyl)borate have been investigated by density functional theory (DFT) methods. The structures of complexes of the form [Mo(L)(CO)3]- were optimized (L = [HB(1,2,4-triazolyl)n(1,2,4-triazol-5-ylidene)3-n]- (n = 0 – 3), hydrotris(pyrazolyl)borate, hydrotris(3,5-dimethylpyrazolyl)borate and hydrotris(imidazol-2-ylidene)borate) and nuCO frequencies for these complexes and partial charges of their Mo(CO)3 fragments were determined. Results show that ligand donation is highly tunable when compared to similar experimentally known ligands with a shift in the symmetric nuCO stretching mode of -39 cm -1 on going from the tris(1,2,4-triazolyl)borate complexes to that of the triscarbene hydrotris(1,2,4-triazol-5-ylidene) and an increase in partial charge (distributed multipole analysis) of the Mo(CO)3 fragment from -0.23 to -0.48
Phase Separation of Saturated and Mono-unsaturated Lipids as determined from a Microscopic Model
A molecular model is proposed of a bilayer consisting of fully saturated DPPC
and mono unsaturated DOPC. The model not only encompasses the constant density
within the hydrophobic core of the bilayer, but also the tendency of chain
segments to align. It is solved within self-consistent field theory. A model
bilayer of DPPC undergoes a main chain transition to a gel phase, while a
bilayer of DOPC does not do so above zero degrees centigrade because of the
double bond which disrupts order. We examine structural and thermodynamic
properties of these membranes and find our results in reasonable accord with
experiment. In particular, order-parameter profiles are in good agreement with
NMR experiments. A phase diagram is obtained for mixtures of these lipids in a
membrane at zero tension. The system undergoes phase separation below the
main-chain transition temperature of the saturated lipid. Extensions to the
ternary DPPC, DOPC, and cholesterol system are outlined.Comment: 29 pages, 4 figures, 1 table. revised versio
Worldwide Exposures to Cardiovascular Risk Factors and Associated Health Effects: Current Knowledge and Data Gaps.
Universal Dynamical Steps in the Exact Time-Dependent Exchange-Correlation Potential
We show that the exact exchange-correlation potential of time-dependent
density-functional theory displays dynamical step structures that have a
spatially non-local and time non-local dependence on the density. Using
one-dimensional two-electron model systems, we illustrate these steps for a
range of non-equilibrium dynamical situations relevant for modeling of
photo-chemical/physical processes: field-free evolution of a non-stationary
state, resonant local excitation, resonant complete charge-transfer, and
evolution under an arbitrary field. Lack of these steps in usual approximations
yield inaccurate dynamics, for example predicting faster dynamics and
incomplete charge transfer
U(3) and Pseudo-U(3) Symmetry of the Relativistic Harmonic Oscillator
We show that a Dirac Hamiltonian with equal scalar and vector harmonic
oscillator potentials has not only a spin symmetry but an U(3) symmetry and
that a Dirac Hamiltonian with scalar and vector harmonic oscillator potentials
equal in magnitude but opposite in sign has not only a pseudospin symmetry but
a pseudo-U(3) symmetry. We derive the generators of the symmetry for each case.Comment: 8 pages, 0 figures, pusblished in Physical Review Letters 95, 252501
(2005
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