Photochemistry and radiation chemistry of interstellar ices lead to the synthesis of prebiotic molecules which may be delivered to planets by meteorites and/or comets.
The detailed features of molecular photochemistry are key to understanding chemical processes enabled by non-adiabatic transitions between potential energy surfaces. But even in a small molecule like hydrogen sulphide (H2S), the influence of non-adiabatic transitions is not yet well understood. Here we report high resolution translational spectroscopy measurements of the H and S(1D) photoproducts formed following excitation of H2S to selected quantum levels of a Rydberg state with 1B1 electronic symmetry at wavelengths λ ~ 139.1 nm, revealing rich photofragmentation dynamics. Analysis reveals formation of SH(X), SH(A), S(3P) and H2 co-fragments, and in the diatomic products, inverted internal state population distributions. These nuclear dynamics are rationalised in terms of vibronic and rotational dependent predissociations, with relative probabilities depending on the parent quantum level. The study suggests likely formation routes for the S atoms attributed to solar photolysis of H2S in the coma of comets like C/1995 O1 and C/2014 Q2.
We report postirradiation photochemistry studies of condensed ammonia using photons of energies below condensed ammonia's ionization threshold of ∼9 eV. Hydrazine (N 2 H 4 ), diazene (also known as diimide and diimine; N 2 H 2 ), triazane (N 3 H 5 ), and one or more isomers of N 3 H 3 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.
Throughout the last century, chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) were the most widely used refrigerants. However, it was discovered that they released reactive chlorine in the upper atmosphere causing the hole in the ozone layer and they were phased out by the 1987 Montreal Protocol [1]. They were replaced by hydrofluorocarbons (HFCs), which contain no chlorine and do not damage the ozone layer. However, HFCs are potent greenhouse gases and they were phased out in a 2016 amendment to the Montreal Protocol [2]. The latest evolution of these refrigerants is the hydrofluoroolefins (HFOs). These molecules have no chlorine and incorporate a carbon-carbon double bond to greatly reduce their atmospheric lifetime, and hence their contribution as a greenhouse gas. In this work, we demonstrate that one of the most important HFOs in current use ultimately decomposes partially into HFC-23 (CHF3) in the atmosphere. HFC-23 is one of the most potent greenhouse gases known, and the most potent HFC. Despite its phaseout, the observed emissions of HFC-23 have been increasing recently and were the largest in history in 2018 with no conclusive explanation [3]. This work suggests that the production of HFOs might be partially responsible.
A new technique is reported to determine absolute photodissociation quantum yields, ϕdiss, in a molecular beam. The technique relies on a molecule having two available product channels, where a species in channel A can be converted photolytically to a species in channel B. The relative decrease in the species from channel A and the relative increase in species from B provide a direct measure of the relative product yield of each channel, with no external calibration required. In the event that only channels A and B exist, or at least dominate, then the sum rule ϕA + ϕB = 1 can be used to convert relative quantum yields into absolute yields. The technique is demonstrated using the well-understood and characterized photochemistry of HCHO. Formaldehyde photolysis at wavelengths near 310 nm produces either H + HCO (channel A) or H2 + CO (channel B). HCO can then be photolyzed with high efficiency into H + CO. The product state distributions for HCO from channel A, CO from channel B, and CO from the secondary HCO photolysis event are all well-known; this is not a requirement but is utilized here to demonstrate the veracity of the technique. The zero-pressure quantum yields of HCO from HCHO photolysis via the 2341 and 2151 states of HCHO are determined to be 0.66 and 0.74, respectively, which are in excellent agreement with the established quantum yields at atmospheric pressure and support the conclusion that HCHO quantum yields at these photolysis energies are not pressure dependent.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.