Low-temperature condensed phase reactions of atomic hydrogen with closed-shell molecules have been studied in rare gas matrices as a way to generate unstable chemical intermediates and to study tunneling-driven chemistry. Although parahydrogen (pH2) matrix isolation spectroscopy allows these reactions to be studied equally well, little is known about the analogous reactions conducted in a pH2 matrix host. In this study, we present Fourier transform infrared (FTIR) spectroscopic studies of the 193 nm photoinduced chemistry of formic acid (HCOOH) isolated in a pH2 matrix over the 1.7 to 4.3 K temperature range. Upon short-term irradiation the HCOOH readily undergoes photolysis to yield CO, CO2, HOCO, HCO and H atoms. Furthermore, after photolysis at 1.9 K tunneling reactions between migrating H atoms and trapped HCOOH and CO continue to produce HOCO and HCO, respectively. A series of postphotolysis kinetic experiments at 1.9 K with varying photolysis conditions and initial HCOOH concentrations show the growth of HOCO consistently follows single exponential (k = 4.9(7)x10(-3) min(-1)) growth kinetics. The HCO growth kinetics is more complex displaying single exponential growth under certain conditions, but also biexponential growth at elevated CO concentrations and longer photolysis exposures. By varying the temperature after photolysis, we show the H atom reaction kinetics qualitatively change at ∼2.7 K; the reaction that produces HOCO stops at higher temperatures and is only observed at low temperature. We rationalize these results using a kinetic mechanism that involves formation of an H···HCOOH prereactive complex. This study clearly identifies anomalous temperature effects in the reaction kinetics of H atoms with HCOOH and CO in solid pH2 that deserve further study and await full quantitative theoretical modeling.

We present low temperature kinetic measurements for the H + N2O association reaction in solid parahydrogen (pH2) at liquid helium temperatures (1-5 K). We synthesize (15)N2(18)O doped pH2 solids via rapid vapor deposition onto an optical substrate attached to the cold tip of a liquid helium bath cryostat. We then subject the solids to short duration 193 nm irradiations to generate H-atoms produced as byproducts of the in situ N2O photodissociation, and monitor the subsequent reaction kinetics using rapid scan FTIR. For reactions initiated in solid pH2 at 4.3 K we observe little to no reaction; however, if we then slowly reduce the temperature of the solid we observe an abrupt onset to the H + N2O → cis-HNNO reaction at temperatures below 2.4 K. This abrupt change in the reaction kinetics is fully reversible as the temperature of the solid pH2 is repeatedly cycled. We speculate that the observed non-Arrhenius behavior (negative activation energy) is related to the stability of the pre-reactive complex between the H-atom and (15)N2(18)O reagents.

The diffusion and reactivity of hydrogen atoms in solid parahydrogen at temperatures between 1.5 K and 4.3 K are investigated by high-resolution infrared spectroscopy. Hydrogen atoms are produced within solid parahydrogen as the by-products of the 193 nm in situ photolysis of N2O, which induces a two-step tunneling reaction, H + N2O → cis-HNNO → trans-HNNO. The second-order rate constant for the first step to form cis-HNNO is found to be inversely proportional to the N2O concentration after photolysis, indicating that the hydrogen atoms move through solid parahydrogen via quantum diffusion. This reaction only readily occurs at temperatures below 2.8 K, not due to an increased rate constant for the first reaction step at low temperatures but rather due to an increased selectivity to the reaction. The rate constant for the second step of the reaction mechanism involving unimolecular isomerization is shown to be independent of the N2O concentration as expected. The inverse concentration dependence of the rate constant for the reaction step that involves the hydrogen atom demonstrates clearly that quantum diffusion influences the reactivity of the hydrogen atoms in solid parahydrogen, which does not have an analogy in classical reaction kinetics.

The in situ UV photolysis of a precursor molecule trapped in a parahydrogen (pH2) matrix is a simple method used to generate isolated radical photofragments that are well suited for infrared spectroscopic studies. However, for molecules that can dissociate via multiple pathways, little is known about how the pH2 matrix influences the branching among these open pathways. We report FTIR spectroscopic studies of the 193 nm photodecomposition of methylamine (MA, CH3NH2) isolated in pH2 quantum matrixes at 1.8 K. We observe single exponential decay of the MA precursor upon irradiation and the quantum yield for MA photodissociation is measured to be Φ = 0.26(2) consistent with a weak pH2 cage effect. By comparing to gas-phase results, we show the in situ photolysis results in greater production of molecular products (CH2═NH + H2) compared to radical products (CH3NH + H) consistent with the idea of partial caging of the H atom photofragments. The information gained in this work can be used to guide future photolysis studies in pH2 matrixes.

In 1969 A. F. Andreev and I. M. Lifshitz radically changed the way we think about diffusion in cryocrystals by predicting that at sufficiently low temperatures the probability of exchange tunneling of neighboring particles in quantum crystals becomes noticeable such that impurities can move freely through the crystal as narrow-band quasiparticles. a The term "quantum crystal" was introduced by de Boer in 1948 for substances in which the energy of the zero-point vibrations of the particles is comparable to the total energy of the crystal. b The main idea put forth by Andreev and Liftshitz is that the rate of quantum diffusion should increase with falling temperatures and should show an inverse dependence on the concentration of impurities. As we will show, the hydrogen atom (H-atom) trapped in a parahydrogen crystal is an ideal candidate for quantum diffusion owing to its small mass and neutral charge. In 2013 our group published a communication c on the kinetics of the H + N 2 O reaction in solid parahydrogen that showed an anomalous temperature dependence. In these studies we generate the H-atoms as byproducts of the in situ photodissociation of N 2 O and monitor the subsequent reaction kinetics using rapid scan FTIR. Specifically, if we photolyze N 2 O doped parahydrogen solids with 193 nm UV radiation at 4.3 K, we observe little to no reaction; however, if we then slowly reduce the temperature of the sample, we observe an abrupt onset to the reaction at temperatures below 2.4 K. In a number of studies conducted since this original work we have come to a better understanding of the effect of temperature on the reaction and will show data that the rate constant for the H + N 2 O reaction shows an inverse dependence on the N 2 O concentration. These findings support previous ESR measurements of H-atom quantum diffusion in solid parahydrogen d and more importantly illustrate how H-atom quantum diffusion impacts the kinetics of these anomalous low temperature, condensed phase reactions.