Physics

The structure and the medium effects exerted on the spectral characteristics of the carbonyl group stretching vibrations in some structural fragments of poly-3-hydroxybutyrate have been analyzed. Calculations of the equilibrium configurations and IR spectra were carried out using the Gaussian program set in the approximation B3LYP/cc-pVDZ. It has been shown that typical bending of the poly-3-hydroxybutyrate chain is observed with an increase in the number of structural units. In order to explain the difference between the calculated and experimental frequencies of the C=O group stretching vibrations, the calculations of the potential energy curve associated with variations in the length of C=O bond and the subsequent numerical solution of a one-dimensional vibrational Schrödinger equation have been performed. The medium effects have been taken into account within the scope of a polarizable continuum model. Owing to the inclusion of the above-mentioned factors, which affect frequencies of the carbonyl groups stretching vibrations, correlation between the theoretical and experimental results has been improved significantly.

We study the system of two ultracold atoms in a three-dimensional (3D) or two-dimensional (2D) completely anisotropic harmonic trap. We derive the algebraic equation J_{3D}(E) = 1/a_{3D} (J_{2D}(E) = ln a_{2D}) for the eigen-energy E of this system in the 3D (2D) case, with a_{3D} and a_{2D} being the corresponding s-wave scattering lengths, and provide the analytical expressions of the functions J_{3D}(E) and J_{2D}(E). In previous researches this type of equation was obtained for spherically or axially symmetric harmonic traps (T. Busch, et. al., Found. Phys. 28, 549 (1998); Z. Idziaszek and T. Calarco, Phys. Rev. A 74, 022712 (2006)). However, for our cases with a completely anisotropic trap, only the equation for the ground-state energy of some cases has been derived (J. Liang and C. Zhang, Phys. Scr. 77, 025302 (2008)). Our results in this work are applicable for arbitrary eigen-energy of this system, and can be used for the studies of dynamics and thermal-dynamics of interacting ultracold atoms in this trap, e.g., the calculation of the 2nd virial coefficient or the evolution of two-body wave functions. In addition, our approach for the derivation of the above equations can also be used for other two-body problems of ultracold atoms.

Angle-resolved photoelectron spectroscopy of the unpaired electron in sodium-doped water, methanol, ammonia, and dimethyl ether clusters is presented. The experimental observations and the complementary calculations are consistent with surface electrons for the cluster size range studied. Evidence against internally solvated electrons is provided by the photoelectron angular distribution. The trends in the ionization energies seem mainly determined by the degree of hydrogen bonding in the solvent and the solvation of the ion core. The onset ionization energies of water and methanol clusters do not level off at small cluster sizes, but decrease slightly with increasing cluster size.

It is shown that negative ions are ejected from gas-phase water molecules when bombarded with positive ions at keV energies typical of solar-wind velocities. This finding is relevant for studies of planetary and cometary atmospheres, as well as for radiolysis and radiobiology. Emission of both H- and heavier (O- and OH-) anions, with a larger yield for H-, was observed in 6.6-keV 16O+ + H2O collisions. The ex-perimental setup allowed separate identification of anions formed in collisions with many-body dynamics from those created in hard, binary collisions. Most of the ani-ons are emitted with low kinetic energy due to many-body processes. Model calcu-lations show that both nucleus-nucleus interactions and electronic excitations con-tribute to the observed large anion emission yield.

Free energy differences ΔF:=F− F prism are computed for several isomers of water hexamer relative to the "prism" isomer using the self-consistent phonons method. % ΔF:=F−F(prism) We consider the isotope effect defined by the quantity δ F D 2 O :=Δ F D 2 O −Δ F H 2 O , and the quantum effect, δ F ℏ=0 :=Δ F ℏ=0 −Δ F H 2 O , and evaluate them using different flexible water models. While both δ F D 2 O and δ F ℏ=0 are found to be rather small for all of the potentials, they are especially small for two of the empirical models, q-TIP4P/F and TTM3-F, compared to q-SPC/Fw and the two {\it abinitio}-based models, WHBB and HBB2-pol. This qualitative difference in the properties of different water models cannot be explained by one being "more accurate" than the other. We speculate as to whether the observed anomalies are caused by the special properties of water systems, or are an artifact of either the potential energy surface form/parametrization or the numerical approximation used.

Using the evolutionary algorithm USPEX and DFT+U calculations, we predicted a high-symmetry geometric structure of bare Ti8O12 cluster composed of 8 Ti atoms forming a cube, which O atoms are at midpoints of all of its edges, in excellent agreement with experimental results. Using Natural Bond Orbital analysis, Adaptive Natural Density Partitioning algorithm, electron localization function and partial charge plots, we find the origin of the particular stability of bare Ti8O12 cluster: unique chemical bonding where eight electrons of Ti atoms interacting with each other in antiferromagnetic fashion to lower the total energy of the system. The bare Ti8O12 is thus an unusual molecule stabilized by d-orbital antiferromagnetic coupling.

The density matrix equations of motion in near-degenerate three-level V-type closed-loop atomic system are calculated numerically in Floquet frame. The dynamical behavior of atom- photon entanglement between the dressed atom and its spontaneous emission is studied in semi classical approach beyond the two-photon resonance condition in such a system. The quantum entropy of these two subsystems is investigated by using the von Neumann entropy. It is shown that, the degree of entanglement measure (DEM) can be controlled via the intensity and the detuning of coupling optical field and quantum interference induced by spontaneous emission. Moreover in the absence of quantum interference the steady state behavior of DEM can be achieved even in beyond the two- photon resonance condition. Furthermore in the absence of quantum interference for special parameters of Rabi frequency and detuning of driving laser field disentanglement can be occurred. Also the electromagnetically induced transparency condition can be obtained when the system is disentangled.

Recently we reported a series of numerical simulations proving that it is possible in principle to create an electronic wave packet and subsequent electronic motion in a neutral molecule photoexcited by a UV pump pulse within a few femtoseconds. We considered the ozone molecule: for this system the electronic wave packet leads to a dissociation process. In the present work, we investigate more specifically the time-resolved photoelectron angular distribution of the ozone molecule that provides a much more detailed description of the evolution of the electronic wave packet. We thus show that this experimental technique should be able to give access to observing in real time the creation of an electronic wave packet in a neutral molecule and its impact on a chemical process.

A nonadiabatic scheme for the description of the coupled electron and nuclear motions in the ozone molecule was proposed recently. An initial coherent nonstationary state was prepared as a superposition of the ground state and the excited Hartley band. In this situation neither the electrons nor the nuclei are in a stationary state. The multiconfiguration time dependent Hartree method was used to solve the coupled nuclear quantum dynamics in the framework of the adiabatic separation of the time-dependent Schrödinger equation. The resulting wave packet shows an oscillation of the electron density between the two chemical bonds. As a first step for probing the electronic motion we computed the time-dependent molecular dipole and the Dyson orbitals. The latter play an important role in the explanation of the photoelectron angular distribution. Calculations of the Dyson orbitals are presented both for the time-independent as well as the time-dependent situations. We limited our description of the electronic motion to the Franck-Condon region only due to the localization of the nuclear wave packets around this point during the first 5-6 fs.

The ionization dynamics of helium droplets in a wide size range from 220 to 10^6 He atoms irradiated with intense femtosecond extreme ultraviolet (XUV) pulses of 10^9 ÷ 10^{12} W/cm2 power density is investigated in detail by photoelectron spectroscopy. Helium droplets are resonantly excited in the photon energy range from ~ 21 eV (corresponding to the atomic 1s2s state) up to the atomic ionization potential (IP) at ~ 25 eV. A complex evolution of the electron spectra as a function of droplet size and XUV intensity is observed, ranging from atomic-like narrow peaks due to binary autoionization, to an unstructured feature characteristic of electron emission from a nanoplasma. The experimental results are analyzed and interpreted with the help of numerical simulations based on rate equations taking into account various processes such as multi-step ionization, interatomic Coulombic decay (ICD), secondary inelastic collisions, desorption of electronically excited atoms, collective autoionization (CAI) and further relaxation processes.