No abstract

aThe fundamental origins surrounding the dynamics of disordered solids near their characteristic glass transitions continue to be fiercely debated, even though a vast number of materials can form amorphous solids, including small-molecule organic, inorganic, covalent, metallic, and even large biological systems.The glass-transition temperature, T g , can be readily detected by a diverse set of techniques, but given that these measurement modalities probe vastly different processes, there has been significant debate regarding the question of why T g can be detected across all of them. Here we show clear experimental and computational evidence in support of a theory that proposes that the shape and structure of the potentialenergy surface (PES) is the fundamental factor underlying the glass-transition processes, regardless of the frequency that experimental methods probe. Whilst this has been proposed previously, we demonstrate, using ab initio molecular-dynamics (AIMD) simulations, that it is of critical importance to carefully consider the complete PES -both the intra-molecular and inter-molecular features -in order to fully understand the entire range of atomic-dynamical processes in disordered solids. Finally, we show that it is possible to utilise this dependence to directly manipulate and harness amorphous dynamics in order to control the behaviour of such solids by using high-powered terahertz pulses to induce crystallisation and preferential crystal-polymorph growth in glasses. Combined, these findings provide compelling evidence that the PES landscape, and the corresponding energy barriers, are the ultimate controlling feature behind the atomic and molecular dynamics of disordered solids, regardless of the frequency at which they occur.

Rotationally resolved electronic spectra of the vibrationless origin and of eight vibronic bands of 5-methoxyindole (5MOI) have been measured and analyzed using an evolutionary strategy approach. The experimental results are compared to the results of ab initio calculations. All vibronic bands can be explained by absorption of a single conformer, which unambiguously has been shown to be the anti-conformer from its rotational constants and excitation energy. For both anti- and syn-conformers, a (1)L(a)/(1)L(b) gap larger than 4000 cm(-1) is calculated, making the vibronic coupling between both states very small, thereby explaining why the spectrum of 5MOI is very different from that of the parent molecule, indole.

Velocity map imaging was implemented at the free electron laser in Hamburg to image atomic and molecular photoionization processes at a photon energy of 45.55 eV. High quality momentum distributions were recorded for a range of rare gases (He, Ne, Ar, Kr and Xe) and small molecules (H2, D2, O2, N2, CO2). This proof-of-principle experiment illustrates the potential for using velocity map imaging in order to study non-linear ionization and/or dissociation processes.

To better understand the propensity for the three-body breakup in dissociative recombination (DR) of dihydrides ( H(3)(+), NH(2)(+), CH(2)(+), and H(2)O(+)), we undertook a study of the dynamics of this process. A study of DR of H(2)O(+) to give O + H + H was carried out at the CRYRING Heavy-Ion Storage Ring in Stockholm. With the stored beam energy of 4.5 MeV, we separated the O signal from the H signals with a differential absorber, thus reducing the problem to a sum of two two-body problems. Results included (1) the ratio of O((3)P) to O((1)D) product, (2) the distribution of recoil-kinetic energy between the two hydrogen atoms, (3) the angular distribution between the hydrogen atoms in the O((3)P) channel and in the O((1)D) channel.