Nonadiabatic Couplings Can Speed Up Quantum Tunneling Transition Path Times.

Quantum tunneling is known to play an important role in the dynamics of systems with nonadiabatic couplings. However, until recently, the time-domain properties of nonadiabatic scattering have been severely under-explored. Using numerically exact quantum methods, we study the impact that nonadiabatic couplings have on the time it takes to tunnel through a barrier. We find that the Wigner phase time is the appropriate measure to use when determining the tunneling flight time also when considering nonadiabatic systems. The central result of the present study is that in an avoided crossing system in one dimension, the nonadiabatic couplings speed up the tunneling event, relative to the adiabatic case in which all nonadiabatic coupling is ignored. This has implications for both the study of quantum tunneling times and for the field of nonadiabatic scattering and chemistry.

Transition Path Flight Times and Nonadiabatic Electronic Transitions.

Transition path flight times are studied for scattering on two electronic surfaces with a single crossing. These flight times reveal nontrivial quantum effects such as resonance lifetimes and nonclassical passage times and reveal that nonadiabatic effects often increase flight times. The flight times are computed using numerically exact time propagation and compared with results obtained from the Fewest Switches Surface Hopping (FSSH) method. Comparison of the two methods shows that the FSSH method is reliable for transition path times only when the scattering is classically allowed on the relevant adiabatic surfaces. However, where quantum effects such as tunneling and resonances dominate, the FSSH method is not adequate to accurately predict the correct times and transition probabilities. These results highlight limitations in methods which do not account for quantum interference effects, and suggest that measuring flight times is important for obtaining insights from the time-domain into quantum effects in nonadiabatic scattering.

The Influence of the Symmetry of Identical Particles on Flight Times.

In this work, our purpose is to show how the symmetry of identical particles can influence the time evolution of free particles in the nonrelativistic and relativistic domains as well as in the scattering by a potential δ-barrier. For this goal, we consider a system of either two distinguishable or indistinguishable (bosons and fermions) particles. Two sets of initial conditions have been studied: different initial locations with the same momenta, and the same locations with different momenta. The flight time distribution of particles arriving at a 'screen' is calculated in each case from the density and flux. Fermions display broader distributions as compared with either distinguishable particles or bosons, leading to earlier and later arrivals for all the cases analyzed here. The symmetry of the wave function seems to speed up or slow down the propagation of particles. Due to the cross terms, certain initial conditions lead to bimodality in the fermionic case. Within the nonrelativistic domain, and when the short-time survival probability is analyzed, if the cross term becomes important, one finds that the decay of the overlap of fermions is faster than for distinguishable particles which in turn is faster than for bosons. These results are of interest in the short time limit since they imply that the well-known quantum Zeno effect would be stronger for bosons than for fermions. Fermions also arrive earlier and later than bosons when they are scattered by a δ-barrier. Although the particle symmetry does affect the mean tunneling flight time, in the limit of narrow in momentum initial Gaussian wave functions, the mean times are not affected by symmetry but tend to the phase time for distinguishable particles.

Low-temperature chemistry using the R-matrix method.

Techniques for producing cold and ultracold molecules are enabling the study of chemical reactions and scattering at the quantum scattering limit, with only a few partial waves contributing to the incident channel, leading to the observation and even full control of state-to-state collisions in this regime. A new R-matrix formalism is presented for tackling problems involving low- and ultra-low energy collisions. This general formalism is particularly appropriate for slow collisions occurring on potential energy surfaces with deep wells. The many resonance states make such systems hard to treat theoretically but offer the best prospects for novel physics: resonances are already being widely used to control diatomic systems and should provide the route to steering ultracold reactions. Our R-matrix-based formalism builds on the progress made in variational calculations of molecular spectra by using these methods to provide wavefunctions for the whole system at short internuclear distances, (a regime known as the inner region). These wavefunctions are used to construct collision energy-dependent R-matrices which can then be propagated to give cross sections at each collision energy. The method is formulated for ultracold collision systems with differing numbers of atoms.