Long-lived oscillatory incoherent electron dynamics in molecules: trans-polyacetylene oligomers

We identify an intriguing feature of the electron-vibrational dynamics of molecular systems via a computational examination of trans-polyacetylene oligomers. Here, via the vibronic interactions, the decay of an electron in the conduction band resonantly excites an electron in the valence band, and vice versa, leading to oscillatory exchange of electronic population between two distinct electronic states that lives for up to tens of picoseconds. The oscillatory structure is reminiscent of beating patterns between quantum states and is strongly suggestive of the presence of long-lived molecular electronic coherence. Significantly, however, a detailed analysis of the electronic coherence properties shows that the oscillatory structure arises from a purely incoherent process. These results were obtained by propagating the coupled dynamics of electronic and vibrational degrees of freedom in a mixed quantum-classical study of the Su-Schrieffer-Heeger Hamiltonian for polyacetylene. The incoherent process is shown to occur between degenerate electronic states with distinct electronic configurations that are indirectly coupled via a third auxiliary state by vibronic interactions. A discussion of how to construct electronic superposition states in molecules that are truly robust to decoherence is also presented

Design and synthesis of quasi-diastereomeric molecules with unchanging central, regenerating axial and switchable helical chirality via cleavage and formation of Ni(II)–O and Ni(II)–N coordination bonds

9 p.

Spin-helical Dirac states in graphene induced by polar-substrate surfaces with giant spin-orbit interaction: a new platform for spintronics

Spintronics, or spin electronics, is aimed at efficient control and manipulation of spin degrees of freedom in electron systems. To comply with demands of nowaday spintronics, the studies of electron systems hosting giant spin-orbit-split electron states have become one of the most important problems providing us with a basis for desirable spintronics devices. In construction of such devices, it is also tempting to involve graphene, which has attracted great attention because of its unique and remarkable electronic properties and was recognized as a viable replacement for silicon in electronics. In this case, a challenging goal is to lift spin degeneracy of graphene Dirac states. Here, we propose a novel pathway to achieve this goal by means of coupling of graphene and polar-substrate surface states with giant Rashba-type spin-splitting. We theoretically demonstrate it by constructing the graphene@BiTeCl system, which appears to possess spin-helical graphene Dirac states caused by the strong interaction of Dirac and Rashba electrons. We anticipate that our findings will stimulate rapid growth in theoretical and experimental investigations of graphene Dirac states with real spin-momentum locking, which can revolutionize the graphene spintronics and become a reliable base for prospective spintronics applications.

Coordination and crystallisation molecules: Their interactions affecting the dimensionality of metalloporphyrinic SCFs

Synthetic metalloporphyrin complexes are often used as analogues of natural systems, and they can be used for the preparation of new Solid Coordination Frameworks (SCFs). In this work, a series of six metalloporphyrinic compounds constructed from different meso substituted metalloporphyrins (phenyl, carboxyphenyl and sulfonatophenyl) have been structurally characterized by means of single crystal X-ray diffraction, IR spectroscopy and elemental analysis. The compounds were classified considering the dimensionality of the crystal array, referred just to coordination bonds, into 0D, 1D and 2D compounds. This way, the structural features and relationships of those crystal structures were analyzed, in order to extract conclusions not only about the dimensionality of the networks but also about possible applications of the as-obtained compounds, focusing the interest on the interactions of coordination and crystallization molecules. These interactions provide the coordination bonds and the cohesion forces which produce SCFs with different dimensionalities.

Spectroscopic analysis of atoms and molecules

151 p.

Quantum ricochets: surface capture, release and energy loss of fast ions hitting a polar surface at grazing incidence

A diffraction mechanism is proposed for the capture, multiple bouncing and final escape of a fast ion (keV) impinging on the surface of a polarizable material at grazing incidence. Capture and escape are effected by elastic quantum diffraction consisting of the exchange of a parallel surface wave vector G= 2p/ a between the ion parallel momentum and the surface periodic potential of period a. Diffraction- assisted capture becomes possible for glancing angles F smaller than a critical value given by Fc 2- 2./ a-| Vim|/ E, where E is the kinetic energy of the ion,. = h/ Mv its de Broglie wavelength and Vim its average electronic image potential at the distance from the surface where diffraction takes place. For F< Fc, the ion can fall into a selected capture state in the quasi- continuous spectrum of its image potential and execute one or several ricochets before being released by the time reversed diffraction process. The capture, ricochet and escape are accompanied by a large, periodic energy loss of several tens of eV in the forward motion caused by the coherent emission of a giant number of quanta h. of Fuchs- Kliewer surface phonons characteristic of the polar material. An analytical calculation of the energy loss spectrum, based on the proposed diffraction process and using a model ion-phonon coupling developed earlier (Lucas et al 2013 J. Phys.: Condens. Matter 25 355009), is presented, which fully explains the experimental spectrum of Villette et al (2000 Phys. Rev. Lett. 85 3137) for Ne+ ions ricocheting on a LiF(001) surface.