ABSTRACT
Scattering resonances play a central role in collision processes in physics and chemistry. They help build an intuitive understanding of the collision dynamics due to the spatial localization of the scattering wavefunctions. For resonances that are localized in the reaction region, located at short separation behind the centrifugal barrier, sharp peaks in the reaction rates are the characteristic signature, observed recently with state-of-the-art experiments in low-energy collisions. If, however, the localization occurs outside of the reaction region, mostly the elastic scattering is modified. This may occur due to above-barrier resonances, the quantum analogue of classical orbiting. By probing both elastic and inelastic scattering of metastable helium with deuterium molecules in merged-beam experiments, we differentiate between the nature of quantum resonances-tunnelling resonances versus above-barrier resonances-and corroborate our findings by calculating the corresponding scattering wavefunctions.
ABSTRACT
The laser-induced blackbody-assisted rotational cooling of a linear polyatomic ion, C2H2(+), in its (2)Π ground electronic state in the presence of the blackbody radiation field at 300 K and 77 K is investigated theoretically using a rate-equations model. Although pure rotational transitions are forbidden in this non-polar species, the ν5 cis-bending mode is infrared active and the (1-0) band of this mode strongly overlaps the 300 K blackbody spectrum. Hence the lifetimes of state-selected rotational levels are found to be short compared to the typical timescale of ion trapping experiments. The ν5 (1-0) transition is split by the Renner-Teller coupling of vibrational and electronic angular momentum, and by the spin-orbit coupling, into six principal components and these effects are included in the calculations. In this paper, a rotational-cooling scheme is proposed that involves simultaneous pumping of a set of closely spaced Q-branch transitions on the (2)Δ5/2 - (2)Π3/2 band together with two Q-branch lines in the (2)Σ(+) - (2)Π1/2 band. It is shown that this should lead to >70% of total population in the lowest rotational level at 300 K and over 99% at 77 K. In principle, the multiple Q-branch lines could be pumped with just two broad-band (â¼Δν = 0.4-3 cm(-1)) infrared lasers.
ABSTRACT
Ensembles of ultra-cold atoms, molecules and ions (both atomic and molecular) can be held in traps for increasingly long periods of time. While these trapped species remain translationally cold, for molecules the absorption of ambient black-body radiation can result in rapid thermalisation of the rotational (and vibrational) degrees of freedom. At 300 K, internal state purity is lost typically on the order of tens of seconds, inhibiting the study of quantum state selected reactions. In this paper a theoretical model is used to investigate laser-driven, blackbody-mediated, rotational cooling schemes for several (1)Σ and (2)Π diatomic species. The rotational cooling is particularly effective for DCl(+) and HCl(+), for which 92% and >99% (respectively) of the population can be driven into the rovibrational ground state. For the other systems a broadband optical pumping source (simultaneously exciting up to four transitions) is found to enhance the population that can be accumulated in the rovibrational ground state by up to 29% over that achieved when exciting a single transition. The influence of the rotational constant, dipole moments and electronic state of the diatomics on the rotational cooling achievable is also considered. An extension to polyatomic species is discussed and a combination of cold trap environments (at 77 K) and optical pumping schemes is proposed.
