Context. Carbonic acid (H2CO3) is a weak acid relevant to astrobiology which, to date, remains undetected in space. Experimental work has shown that the β-polymorph of H2CO3 forms under space relevant conditions through energetic (UV photon, electron, and cosmic ray) processing of CO2- and H2O-rich ices. Although its α-polymorph ice has been recently reassigned to the monomethyl ester of carbonic acid, a different form of H2CO3 ice may exist and is synthesized without irradiation through surface reactions involving CO molecules and OH radicals, that is to say γ-H2CO3. Aims. We aim to provide a systematic set of vacuum ultraviolet (VUV) photoabsorption spectroscopic data of pure carbonic acid that formed and was destroyed under conditions relevant to space in support of its future identification on the surface of icy objects in the Solar System by the upcoming Jupiter ICy moons Explorer mission and on interstellar dust by the James Webb Space Telescope spacecraft. Methods. We present VUV photoabsorption spectra of pure and mixed CO2 and H2O ices exposed to 1 keV electrons at 20 and 80 K to simulate different interstellar and Solar System environments. Ices were then annealed to obtain a layer of pure H2CO3 which was further exposed to 1 keV electrons at 20 and 80 K to monitor its destruction pathway. Fourier-transform infrared (FT-IR) spectroscopy was used as a secondary probe providing complementary information on the physicochemical changes within an ice. Results. Our laboratory work shows that the formation of solid H2CO3, CO, and O3 upon the energetic processing of CO2:H2O ice mixtures is temperature-dependent in the range between 20 and 80 K. The amorphous to crystalline phase transition of H2CO3 ice is investigated for the first time in the VUV spectral range by annealing the ice at 200 and 225 K. We have detected two photoabsorption bands at 139 and 200 nm, and we assigned them to β-H2CO3 and γ-H2CO3, respectively. We present VUV spectra of the electron irradiation of annealed H2CO3 ice at different temperatures leading to its decomposition into CO2, H2O, and CO ice. Laboratory results are compared to Cassini UltraViolet Imaging Spectrograph observations of the 70−90 K ice surface of Saturn’s satellites Enceladus, Dione, and Rhea.
The UV-photofragmentation spectra of cold Cytosine-M + complexes (M + : Na + , K + , Ag+) were recorded and analyzed through comparison with geometry optimizations and frequency calculations of the ground and excited states at the SCS-CC2/Def2-SVPD level of theory. While in all complexes, the ground state minimum geometry is planar (Cs symmetry), the * state minimum geometry has the NH2 group slightly twisted and an out-of-plane metal cation. This was confirmed by comparing the simulated * Franck-Condon spectra with the vibrationally resolved photofragmentation spectra of CytNa + and CytK + . Vertical excitation transitions were also calculated to evaluate the energies of the CT states involving the transfer of an electron from the Cyt moiety to M + . For both CytK + and CytNa + complexes, the first CT state corresponds to an electron transfer from the cytosine aromatic ring to the antibonding * orbital centered on the alkali cation. This * state is predicted to lie much higher in energy (> 6 V) than the band origin of the * electronic transition (around 4.3 eV) unlike what is observed for CytAg + complex for which the first excited state has a nO* electronic configuration. This is the reason for the absence of the Cyt + + M charge transfer fragmentation channel for CytK + and CytNa + complexes.
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