Modelling non-adiabatic processes using correlated electron-ion dynamics

Here we survey the theory and applications of a family of methods (correlated electron-ion dynamics, or CEID) that can be applied to a diverse range of problems involving the non-adiabatic exchange of energy between electrons and nuclei. The simplest method, which is a paradigm for the others, is Ehrenfest Dynamics. This is applied to radiation damage in metals and the evolution of excited states in conjugated polymers. It is unable to reproduce the correct heating of nuclei by current carrying electrons, so we introduce a moment expansion that allows us to restore the spontaneous emission of phonons. Because of the widespread use of Non-Equilibrium Green's Functions for computing electric currents in nanoscale systems, we present a comparison of this formalism with that of CEID with open boundaries. When there is strong coupling between electrons and nuclei, the moment expansion does not converge. We thus conclude with a reworking of the CEID formalism that converges systematically and in a stable manner.

Nonadiabatic forces in ion-solid interactions:The initial stages of radiation damage

The Born-Oppenheimer approximation is the keystone for molecular dynamics simulations of radiation damage processes; however, actual materials response involves nonadiabatic energy exchange between nuclei and electrons. In this work, time dependent density functional theory is used to calculate the electronic excitations produced by energetic protons in Al. We study the influence of these electronic excitations on the interatomic forces and find that they differ substantially from the adiabatic case, revealing a nontrivial connection between electronic and nuclear stopping that is absent in the adiabatic case. These results unveil new effects in the early stages of radiation damage cascades.

Ultracold, radiative charge transfer in hybrid Yb ion – Rb atom traps

Ultracold hybrid ion–atom traps offer the possibility of microscopic manipulation of quantum coherences in the gas using the ion as a probe. However, inelastic processes, particularly charge transfer can be a significant process of ion loss and has been measured experimentally for the ${\rm Y}{{{\rm b}}^{+}}$ ion immersed in a Rb vapour. We use first-principles quantum chemistry codes to obtain the potential energy curves and dipole moments for the lowest-lying energy states of this complex. Calculations for the radiative decay processes cross sections and rate coefficients are presented for the total decay processes; ${\rm Y}{{{\rm b}}^{+}}(6{\rm s}{{\;}^{2}}{\rm S})+{\rm Rb}(5{\rm s}{{\;}^{2}}{\rm S})\to {\rm Yb}(6{{{\rm s}}^{2}}{{\;}^{1}}{\rm S})+{\rm R}{{{\rm b}}^{+}}(4{{{\rm p}}^{6}}{{\;}^{1}}{\rm S})+h\nu $ and ${\rm Y}{{{\rm b}}^{+}}(6{\rm s}{{\;}^{2}}{\rm S})+{\rm Rb}(5{\rm s}{{\;}^{2}}{\rm S})\to {\rm YbR}{{{\rm b}}^{+}}({{X}^{1}}{{\Sigma }^{+}})+h\nu $. Comparing the semi-classical Langevin approximation with the quantum approach, we find it provides a very good estimate of the background at higher energies. The results demonstrate that radiative decay mechanisms are important over the energy and temperature region considered. In fact, the Langevin process of ion–atom collisions dominates cold ion–atom collisions. For spin-dependent processes [1] the anisotropic magnetic dipole–dipole interaction and the second-order spin–orbit coupling can play important roles, inducing coupling between the spin and the orbital motion. They measured the spin-relaxing collision rate to be approximately five orders of magnitude higher than the charge-exchange collision rate [1]. Regarding the measured radiative charge transfer collision rate, we find that our calculation is in very good agreement with experiment and with previous calculations. Nonetheless, we find no broad resonances features that might underly a strong isotope effect. In conclusion, we find, in agreement with previous theory that the isotope anomaly observed in experiment remains an open question.

PALLADIUM CATALYZED TANDEM CYCLIZATION-ANION CAPTURE PROCESSES .1. BACKGROUND AND HYDRIDE ION CAPTURE BY ALKYL-PALLADIUM AND PI-ALLYL-PALLADIUM SPECIES

A new, wide ranging, synthetically powerful, catalytic tandem cyclisation-anion capture process is proposed which depends on the rate of cyclisation of an organopalladium specifies (RPdX) onto a proximate alkene or diene being significantly faster than anion exchange and reductive elimination in the sequence RPdX --> RPdY --> RY + Pd(0). The catalytic cyclisation - anion capture sequence is illustrated for hydride capture by a wide variety of substrates giving rise to fused- and spiro-, carbo- and hetero-cyclic systems, regio- and stereo-specifically.

New source of MeV negative ion and neutral atom beams

The scenario of "electron-capture and -loss" was recently proposed for the formation of negative ion and neutral atom beams with MeV kinetic energies. However, it does not explain why the formation of negative ions in a liquid spray is much more efficient than with an isolated atom. The role of atomic excited states in the charge-exchange processes is considered, and it is shown that it cannot account for the observed phenomena. The processes are more complex than the single electron-capture and -loss approach. It is suggested that the shell effects in the electronic structure of the projectile ion and/or target atoms may influence the capture/loss probabilities.

A disappearing act performed by magnesium: the nucleotide exchange mechanism of Ran GTPase by Quantum mechanics/Molecular mechanics studies

The Ran GTPase protein is a guanine nucleotide-binding protein (GNBP) with an acknowledged profile in cancer onset, progression and metastases. The complex mechanism adopted by GNBPs in exchanging GDP for GTP is an intriguing process and crucial for Ran viability. The successful completion of the process is a fundamental aspect of propagating downstream signalling events. QM/MM molecular dynamics simulations were employed in this study to provide a deeper mechanistic understanding of the initiation of nucleotide exchange in Ran. Results indicate significant disruption of the metal-binding site upon interaction with RCC1 (the Ran guanine nucleotide exchange factor), overall culminating in the prominent shift of the divalent magnesium ion. The observed ion drifting is reasoned to occur as a consequence of the complex formation between Ran and RCC1 and is postulated to be a critical factor in the exchange process adopted by Ran. This is the first report to observe and detail such intricate dynamics for a protein in Ras superfamily.