Using ion imaging to analyze higher-order moments of the angular distributions of photofragments

We investigate the effect of the hexadecapole (K=4) polarization moment on the spatial distributions of angular momenta for atoms produced during the photodissociation of diatomic or triatomic molecules by polarized radiation. We derive general expressions for the angular distributions of the atomic density matrix for K = 2, 4 and expressions for the corresponding anisotropy parameters that contain all information on the photodissociation dynamics. We show that these anisotropy parameters can be experimentally determined by using ion imaging. We consider oxygen atoms in the ¹ D ₂ state aligned with respect to the orbital angular momentum as an example and provide ion images of the signals that correspond to the population of the atomic magnetic sublevels ¦m¦ = 0, 1, 2. We show the contributions from the second-and fourth-rank state multipoles to the angular distributions of the atomic density matrix to be comparable in magnitude and significantly different in form.     

Theoretical insights into the host–guest interactions between [6]cycloparaphenyleneacetylene and its anthracene‐containing derivative and fullerene C70

The host–guest complexes formed with [6]cycloparaphenyleneacetylene ([6]CPPA) and its anthracene‐containing derivative ([6]CPPAs) hosts and fullerene C₇₀ guest were explored by density functional calculations. Besides two previously reported configurations in which C₇₀ guest is standing or lying in the cavity of the host, we found a new kind of configuration in which C₇₀ guest is half‐lying in the cavity of the host. More interestingly, the calculated results revealed that the fine‐tuning deformations occur readily during the formations of the complexes, suggesting that both [6]CPPA and [6]CPPAs are highly elastic host molecules. The large host–guest binding energies indicate that both two host molecules, [6]CPPA and [6]CPPAs, have excellent encapsulation ability for C₇₀ guest, and the [6]CPPAs even has much better encapsulation ability for C₇₀ than [6]CPPA. Furthermore, the host–guest interactions regions were detected and visualized in real space based on the electron density and reduced density gradient. Additionally, ¹H NMR spectra of those three different kinds of configurations mentioned earlier have been calculated with gage‐independent atomic orbital method, which may be helpful for further experimental characterizations in future. Copyright © 2014 John Wiley & Sons, Ltd.     

Ab-initio molecular dynamical study of a single transition metal atom on fullerene C<Subscript>60</Subscript>: the case of Ta

We report the first-principles Car-Parrinello molecular dynamics study of the behaviour of a single transition metal Ta atom on fullerene C₆₀, at different temperatures, and for both neutral and charged clusters. We seek to characterise the motion of the lone Ta metal atom on the C₆₀ surface, contrasting its behaviour both with that of three Ta atoms, as well as with a single alkali metal atom on the cage surface. Our earlier simulations on C₆₀Ta₃ had revealed that the Ta atoms on the surface of the fullerene are affected by a rather high mobility, and that the motion of these atoms is highly correlated due to Ta-atom-Ta-atom attraction. Earlier, experimental studies of a single metal atom (K, Rb) on the surface of a C₆₀ molecule had led to the inference that at room temperature the metal atom skates freely over the surface, the first direct evidence for which was presented by us in earlier first principles molecular dynamical simulations.     

Propagation properties of electromagnetic fields in elliptic dielectric hollow fibres and their applications

We numerically calculate and analyse the electromagnetic fields, optical intensity distributions, polarization states and orbital angular momentum of some elliptic hollow modes in an elliptic dielectric hollow fiber (EDHF) by using Mathieu functions, and also calculate the optical potential of the blue-detuned _eHE₁₁ mode evanescent-light wave for ⁸⁵Rb atoms, including the position-dependent van der Waals potential, and discuss briefly some potential applications of our EDHF in atom and molecule optics, etc. Our study shows that the vector electric field distributions of the odd modes in the cross section of the EDHF are the same as that of the even modes and with different boundary ellipses by rotating an angle of π/2, and the orbital angular momentum (OAM) of single HE (EH) mode is exactly equal to zero, while that of dual-mode in the EDHF is fractional in h, and has a sinusoidal oscillation as z varies. The EDHF can be used to produce various elliptic hollow beams, even to generate and study various atomic vortices with a fractional charge and its fractional quantum Hall effect in atomic Bose--Einstein condensate, and so on.     

Orbital angular momentum exchange in the interaction of twisted light with molecules

In the interaction of molecules with light endowed with orbital angular momentum, an exchange of orbital angular momentum in an electric dipole transition occurs only between the light and the center of mass motion; i.e., internal "electronic-type" motion does not participate in any exchange of orbital angular momentum in a dipole transition. A quadrupole transition is the lowest electric multipolar process in which an exchange of orbital angular momentum can occur between the light, the internal motion, and the center of mass motion. This rules out experiments seeking to observe exchange of orbital angular momentum between light beams and the internal motion in electric dipole transitions.     

Reactive scattering of a supersonic oxygen atom beam O+ICl

Reactive scattering of O atoms with ICl molecules has been studied at an initial translational energy E = 40 kJ mol^-1 using a supersonic beam of O atoms seeded in He and at E = 15 kJ mol^-1 using O atoms seeded in Ne. Velocity distributions of OI product were measured by cross-correlation time-of-flight analysis. Full contour maps of the differential reaction cross-section have been obtained which show peaking almost equally in the forward and backward directions at both initial translational energies. The product translational energy distributions are consistent with a long-lived O-I-Cl collision complex dissociating via a loose transition state. The stability of the O-I-Cl complex is attributed to the low electronegativity of the central I atom compared with the peripheral atoms. This electronegativity ordering rule also determines the stability of the intermediates in the other reactions of oxygen atoms with halogen molecules. The mild peaking of the product angular distributions for O + ICl and IBr indicates that collision complexes have quite modest collision angular momenta L ～ 40 ? corresponding to impact parameters b ～ 1·4 Å and that the angular momentum of the OI molecule in the loose transition state may be approximately half the product orbital angular momentum.     

Theoretical study of the toroidal forms of carbon and related endohedral complexes with lithium

The atomic and electron structures of toroidal carbon molecules (C₂₄₀ and two C₁₂₀ isomers) and related endohedral complexes with lithium (Li₂@C_n and Li₄@C_n) were theoretically studied using both nonempirical (3–21G basis set) and semiempirical (MNDO) calculation schemes. For the metal-containing compounds, the behavior of lithium atoms embedded into internal cavities of the carbon framework was studied using methods of molecular dynamics. It is demonstrated that the structure of electron levels of metal-containing carbon complexes exhibits an embedded state in the forbidden band, which appears due to the presence of electrons accepted from metal atoms. The position of this embedded state and the bandgap width depend both on the initial carbon structure and on the amount of metal atoms incorporated.     

Slow light in ultra-cold atomic gases

We investigate the influence of slow light with an orbital angular momentum on the mechanical motion of ultra-cold atomic gases including both the atomic Bose–Einstein condensates and degenerate Fermi gases. We present a microscopic analysis of the interplay between light and matter and show how slow light can provide an effective magnetic field acting on the electrically neutral atoms.     

Structure and electronic properties of Hn@C20 molecule

Density functional theory has been employed to optimize the structure of endohedral doped C₂₀ fullerene. We have also investigated electronic properties. We have found that C₂₀ cage can accommodate up to 8 hydrogen atoms. Some hydrogen atoms get chemisorbed on the inner surface of C₂₀ cage and form C-H bond. Structural deformation is found to increase with increase in H-atoms. From the analysis of electronic properties, we observe that due to endohedral doping of hydrogen atoms inside C₂₀, H-atoms acquire net negative charge by accepting electrons and fullerene molecules acquire positive charge by donating electrons to H-atoms. For endohedral complexes where H₃ triangular molecule formation takes place, the nature of net charge transfer changes, i.e. fractional electronic charge is transferred from H-atoms to fullerene. C₂₀ doped with odd number of H-atoms should be more reactive compared to the even number case. Most of the present results are similar to those of endohedral C₆₀.     

Study of the Initial Stage of Fluorinated C<Subscript>60</Subscript>F<Subscript>18</Subscript> Fullerene Adsorption on the Cu(001) Surface

The dynamics of the adsorption and evolution of fluorinated C₆₀F₁₈ fullerene molecules on the Cu(001) surface are studied by real-time ultra-high vacuum scanning tunneling microscopy. Fluorinated fullerene molecules are shown to decompose with time on the Cu(001) surface transforming to C₆₀ molecules. The decay rate depends on the initial molecular coverage. The rapid decay of fluorinated fullerene molecules is observed when the coverage is no higher than 0.2 single layers. As a result, two-dimensional islands consisting of pure C₆₀ molecules are formed on the Cu(001) surface. 2D islands consisting of fluorinated fullerene molecules are formed when the initial molecular coverage is higher than 0.5 single layers. The molecules inside these islands also tend to decompose with time. It is found experimentally that fluorine atoms are removed completely from the initial C₆₀F₁₈ molecules adsorbed on the Cu(001) surface after 250 h when the initial molecular coverage is 0.6 single layers.     

Formation of an alignment in collisions of laser excited sodium with xenon atoms

By photon absorption from a monomode dye-laser beam a spatially ordered velocity distribution (‘atomic beam’) of sodium atoms excited to the 3p ² P _1/2-state, is created. It is predicted theoretically that in collisions of these atoms with atoms of a heavy foreign gas an alignment of the electronic orbital angular momentum is produced. This alignment leads to the appearance of a linear polarization in the sensitizedD ₂-fluorescent light. This polarization is verified experimentally and interpreted in terms of a simplifiedT-operator. It turns out that the scattering distribution for sensitizing collision is of the wide-angle type.     

The effect of alignment of the exotic atom orbital angular momentum on depolarization of negative muons

The theory of cascade depolarization of negative muons is generalized to the case where the orbital angular momentum of a meson becomes aligned as a result of its atomic capture. An explanation of the experimental data on the residual polarization of ^– in helium is proposed on the basis of the developed theory and available arguments in favour of the possible existence of alignment of the orbital angular momentum in the lightes exotic atoms. An angular distribution and linear polarization of muonic X-rays is considered. The connection between these characteristics and the depolarization factor due to the alignment of the orbital angular momentum enables one to make a direct experimental test of the proposed explanation of the residual polarization of muons in helium.     

Relative intensities in photoelectron spectroscopy of atoms and molecules

The relative intensities of photoelectron lines is discussed. The relationship of observed intensities to angle of observation is considered as are the errors introduced by ignoring the fact that different lines may have different angular distributions. Tables of theoretical results for the angular distribution asymmetry parameter, β, are presented for incident Al K_α, Mg K_α, and Zr M_ζ radiation for all atomic ground state subshells of non-zero angular momentum. The application of these results to molecules is discussed.     

Molecular dynamics simulation of the low-energy interaction between Cu<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>@C<Subscript>60</Subscript> endofullerenes and the surface of a copper crystal

A molecular dynamics simulation of the low-energy interaction of C₆₀ fullerenes and Cu₁@C₆₀, Cu₆@C₆₀, and Cu₁₃@C₆₀ endofullerenes with a Cu(100) surface was performed. The effects of a copper cluster encapsulated in a fullerene and of a fullerene’s translational motion and rotation energy on its penetration into a surface were investigated. It was shown that the presence of an encapsulated cluster has a positive effect on fullerene penetration into a surface with preservation of the fullerene’s structure. The optimal conditions for fullerene penetration into a copper crystal surface were determined.     

Possible scheme of synthesis-assembling of fullerenes

A new scheme of fullerene formation is proposed on the basis of the similarity between the experimentally detected carbon structures. According to experimental data, the microclusters of C₂ and C₁₀ are synthesized first and then either an intermediate nucleus cluster or an obtainable lower fullerene is assembled from them. A high-symmetry fullerene can be assembled with a high probability from a nucleus cluster with a “good” symmetry. The atomic and electronic structures of molecules such as C₃₆, C₆₀, C₇₀, and C₇₆ are analyzed. For C₃₆, the NMR spectra are calculated and compared with the experimental data.     

Polarizability exaltation of endofullerenes X@C<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript> (<Emphasis Type="Italic">n</Emphasis> = 20, 24, 28, 36, 50, and 60; X is a noble gas atom)

The polarizability exaltation in molecules of endohedral complexes of C₂₀, C₂₄, C₂₈, C₃₆, C₅₀, and C₆₀ fullerenes with He, Ne, Ar, and Kr noble gas atoms has been revealed and studied by the density functional theory method. It has been found that the sign of the Δα polarizability exaltation depends on the number of atoms in a fullerene molecule.     

Efficient and accurate modeling of electron photoemission in nanostructures with TDDFT

We derive and extend the time-dependent surface-flux method introduced in [L. Tao, A. Scrinzi, New J. Phys. 14, 013021 (2012)] within a time-dependent density-functional theory (TDDFT) formalism and use it to calculate photoelectron spectra and angular distributions of atoms and molecules when excited by laser pulses. We present other, existing computational TDDFT methods that are suitable for the calculation of electron emission in compact spatial regions, and compare their results. We illustrate the performance of the new method by simulating strong-field ionization of C₆₀ fullerene and discuss final state effects in the orbital reconstruction of planar organic molecules.     

Ab initio modeling of the electronic and spin properties of the [NV]<Superscript>−</Superscript> centers in diamond nanocrystals

The electronic and spin properties of different nanocrystals of carbon are studied. The properties of these cluster systems are modeled in terms of the ab initio (Hartree-Fock) and semiempirical (PM3, AM1) quantum-chemical methods. The calculations are performed for different carbon nanocluster systems: defect-free and with [NV]^? centers, hydrogen passivated (C₃₈H₄₂, C₇₁H₈₄, C₈₆H₇₈), and with a free (unpassivated) surface (C₃₈, C₇₁, C₈₆). The spin properties of unhydrated nanoclusters were studied for the first time. The structure of all the clusters under study was optimized using the total energy minimization principle. It is shown that, in the case of hydrated carbon nanocrystals passivated by hydrogen atoms, diamond-like clusters are formed. The atomic structure of an unpassivated nanocrystal depends on the number of atoms in the cluster, as well as on its initial geometrical parameters. In some cases, clusters with a fullerene-like surface are formed. In hydrogenpassivated diamond nanocrystals with [NV]^? centers, the spin density is localized at the nuclei of C atoms nearest to the center vacancies. For the unpassivated counterparts, the spin density is localized at the nuclei of C atoms forming the surface of the corresponding nanocrystal.     

Zeeman effect on holes in the <Emphasis Type="Italic">Q</Emphasis> bands in the absorption spectra of molecules of phthalocyanine metal complexes in amorphous polymer glasses

The effect of magnetic fields up to 140 kOe on holes in inhomogeneously broadened absorption spectra of molecules of phthalocyanine complexes with aluminum and zinc in disordered polymer matrices of polyvinyl butyral was investigated experimentally. The effective values of the projections of the orbital angular momentum on the symmetry axis of the molecules studied are obtained in the S₁ excited state, and the parameters characterizing the specific features of the manifestation of the Jahn–Teller dynamic effect and the crystal field effect in the systems under consideration are determined.     

Atomic level analysis of biomolecules by the scanning atom probe

Utilizing the unique features of the scanning atom probe (SAP) the binding states of the biomolecules, leucine and methionine, are investigated at atomic level. The molecules are mass analyzed by detecting a single atom and/or clustering atoms field evaporated from a specimen surface. Since the field evaporation is a static process, the evaporated clustering atoms are closely related with the binding between atoms forming the molecules. For example, many thiophene radicals are detected when polythiophene is mass analyzed by the SAP. In the present study the specimens are prepared by immersing a micro cotton ball of single walled carbon nanotubes (SWCNT) in the leucine or methionine solution. The mass spectra obtained by analyzing the cotton balls exhibit singly and doubly ionized carbon ions of SWCNT and the characteristic fragments of the molecules, CH₃, CHCH₃, C₄H₇, CHNH₂ and COOH for leucine and CH₃, SCH₃, C₂H₄, C₄H₇, CHNH₂ and COOH for methionine.