6 research outputs found
CO diffusion and desorption kinetics in CO ices
Diffusion of species in icy dust grain mantles is a fundamental process that
shapes the chemistry of interstellar regions; yet measurements of diffusion in
interstellar ice analogs are scarce. Here we present measurements of CO
diffusion into CO ice at low temperatures (T=11--23~K) using CO
longitudinal optical (LO) phonon modes to monitor the level of mixing of
initially layered ices. We model the diffusion kinetics using Fick's second law
and find the temperature dependent diffusion coefficients are well fit by an
Arrhenius equation giving a diffusion barrier of 300 40 K. The low
barrier along with the diffusion kinetics through isotopically labeled layers
suggest that CO diffuses through CO along pore surfaces rather than through
bulk diffusion. In complementary experiments, we measure the desorption energy
of CO from CO ices deposited at 11-50 K by temperature-programmed
desorption (TPD) and find that the desorption barrier ranges from 1240 90
K to 1410 70 K depending on the CO deposition temperature and
resultant ice porosity. The measured CO-CO desorption barriers demonstrate
that CO binds equally well to CO and HO ices when both are compact. The
CO-CO diffusion-desorption barrier ratio ranges from 0.21-0.24 dependent on
the binding environment during diffusion. The diffusion-desorption ratio is
consistent with the above hypothesis that the observed diffusion is a surface
process and adds to previous experimental evidence on diffusion in water ice
that suggests surface diffusion is important to the mobility of molecules
within interstellar ices
Electron-Induced Radiolysis of Astrochemically Relevant Ammonia Ices
We elucidate mechanisms of electron-induced radiolysis in cosmic (interstellar, planetary, and cometary) ice analogs of ammonia (NH3), likely the most abundant nitrogen-containing compound in the interstellar medium (ISM). Astrochemical processes were simulated under ultrahigh vacuum conditions by high-energy (1 keV) and low-energy (7 eV) electron-irradiation of nanoscale thin films of ammonia deposited on cryogenically cooled metal substrates. Irradiated films were analyzed by temperature-programmed desorption (TPD). Experiments with ammonia isotopologues provide convincing evidence for the electron-induced formation of hydrazine (N2H4) and diazene (N2H2) from condensed NH3. To understand the dynamics of ammonia radiolysis, the dependence of hydrazine and diazene yields on incident electron energy, electron flux, electron fluence, film thickness, and ice temperature were investigated. Radiolysis yield measurements versus (1) irradiation time and (2) film thickness are semiquantitatively consistent with a reaction mechanism that involves a bimolecular step for the formation of hydrazine and diazene from the dimerization of amidogen (NH2) and imine (NH) radicals, respectively. The apparent decrease in radiolysis yield of hydrazine and diazene with decreasing electron flux at constant fluence may be due to the competing desorption of these radicals at 90 K under low incident electron flux conditions. The production of hydrazine at electron energies as low as 7 eV and an ice temperature of 22 K is consistent with condensed phase radiolysis being mediated by low-energy secondary electrons produced by the interaction of high-energy radiation with matter. These results provide a basis from which we can begin to understand the mechanisms by which ammonia can form more complex species in cosmic ices
Condensed-Phase Photochemistry in the Absence of Radiation Chemistry
We report post-irradiation photochemistry studies of condensed ammonia using photons of energies below condensed ammonia’s ionization threshold of ~ 9 eV. Hydrazine (N2H4), diazene (also known as diimide and diimine) (N2H2), triazane (N3H5), and one or more isomers of N3H3 are detected as photochemistry products during temperature-programmed desorption. Product yields increase monotonically with (1) photon fluence and (2) film thickness. In the studies reported herein, the energies of photons responsible for product formation are constrained to less than 7.4 eV. Previous post-irradiation photochemistry studies of condensed ammonia employed photons sufficiently energetic to ionize condensed ammonia and initiate radiation chemistry. Such studies typically involve ion-molecule reactions and electron-induced reactions in addition to photochemistry. Although photochemistry is cited as a dominant mechanism for the synthesis of prebiotic molecules in interstellar ices, to the best of our knowledge, ours is one of the first astrochemically-relevant studies that has found unambiguous evidence for condensed-phase chemical synthesis induced by photons in the absence of ionization
The Use of Automated Pupillometry in the Treatment of Opioid Addiction
The goal of opioid agonist therapy in addiction treatment is to control a patient's withdrawal symptoms without causing excess sedation. Tolerance to opioid medication is variable and dosage decisions are based on a combination of a patient's reported symptoms and clinically observed signs of withdrawal, including a rough estimate of pupil size that is prone to interobserver variability. The goal of this study was to determine whether more precise measurements of pupil size and reactivity, obtained using automated infrared pupillometry, might aid in the dosing of opioid agonist therapy