Nuclear spin dependence of the reaction of H(3)+ with H2. II. Experimental measurements.

The nuclear spin dependence of the chemical reaction H(3)(+)+ H(2) → H(2) + H(3)(+) has been studied in a hollow cathode plasma cell. Multipass infrared direct absorption spectroscopy has been employed to monitor the populations of several low-energy rotational levels of ortho- and para-H(3)(+) (o-H(3)(+) and p-H(3)(+)) in hydrogenic plasmas of varying para-H(2) (p-H(2)) enrichment. The ratio of the rates of the proton hop (k(H)) and hydrogen exchange (k(E)) reactions α ≡ k(H)/k(E) is inferred from the observed p-H(3)(+) fraction as a function of p-H(2) fraction using steady-state chemical models.

Nuclear spin dependence of the reaction of H(3)+ with H2. I. Kinetics and modeling.

The chemical reaction H(3)(+) + H(2) → H(2) + H(3)(+) is the simplest bimolecular reaction involving a polyatomic, yet is complex enough that exact quantum mechanical calculations to adequately model its dynamics are still unfeasible. In particular, the branching fractions for the "identity," "proton hop," and "hydrogen exchange" reaction pathways are unknown, and to date, experimental measurements of this process have been limited. In this work, the nuclear-spin-dependent steady-state kinetics of the H(3)(+) + H(2) reaction is examined in detail, and employed to generate models of the ortho:para ratio of H(3)(+) formed in plasmas of varying ortho:para H(2) ratios.

Refractive index measurements of solid parahydrogen.

Solid para-H2 is a promising gain medium for stimulated Raman scattering, due to its high number density and narrow Raman linewidth. In preparation for the design of a cw solid hydrogen Raman laser, we have made the first measurements, to our knowledge, of the index of refraction of a solid para-H2 crystal, in the wavelength range of 430-1100 nm. For a crystal stabilized at 4.

Communications: Development and characterization of a source of rotationally cold, enriched para-H3+.

In an effort to develop a source of H(3)(+) that is almost entirely in a single quantum state (J=K=1), we have successfully generated a plasma that is enriched to approximately 83% in para-H(3)(+) at a rotational temperature of 80 K. This enrichment is a result of the nuclear spin selection rules at work in hydrogenic plasmas, which dictate that only para-H(3)(+) will form from para-H(2), and that para-H(3)(+) can be converted to ortho-H(3)(+) by subsequent reaction with H(2). This is the first experimental study in which the H(2) and H(3) (+) nuclear spin selection rules have been observed at cold temperatures.

Producing and quantifying enriched para-H2.

The production of enriched para-H(2) is useful for many scientific applications, but the technology for producing and measuring para-H(2) is not yet widespread. In this note and in the accompanying auxiliary material, we describe the design, construction, and use of a versatile standalone converter that is capable of producing para-H(2) enrichments of up to > or = 99.99% at continuous flow rates of up to 0.

Dissociative recombination of highly enriched para-H3+.

The determination of the dissociative recombination rate coefficient of H(3) (+) has had a turbulent history, but both experiment and theory have recently converged to a common value. Despite this convergence, it has not been clear if there should be a difference between the rate coefficients for ortho-H(3) (+) and para-H(3) (+). A difference has been predicted theoretically and could conceivably impact the ortho:para ratio of H(3) (+) in the diffuse interstellar medium, where H(3) (+) has been widely observed.