Search results for "Photodissociation"
showing 10 items of 90 documents
Matrix isolation and quantum chemical studies on the H2O2–SO2complex
2004
Complexation and photochemical reactions of hydrogen peroxide and sulfur dioxide have been studied in solid Ar, Kr and Xe. Complexes between H2O2 and SO2 are characterized using Fourier transform infrared spectroscopy and ab initio calculations. In solid Ar, the H2O2–SO2 complex absorptions are found at wavenumbers of 3572.8, 3518.7, 3511.2, 3504.3, 1340.3, 1280.2 and 1149.9 cm−1. In Kr and Xe matrices, the bonded OH stretching frequencies deviate from the values in Ar, and we propose that the matrix surrounding influences the structure of the H2O2–SO2 complex. UV photolysis of the H2O2–SO2 was also studied in solid Ar, Kr and Xe. This photolysis produces mainly a complex between sulfur tri…
Photolysis of Tertiary Amines in the Presence of CO2: The Paths to Formic Acid, α-Amino Acids, and 1,2-Diamines
2017
The photolysis of triethylamine (1a) in the presence of carbon dioxide leads to the hydrogenation of CO2, the α-C-C coupling of triethylamine (1a), and the CO2-insertion into the α-C-H σ-bond of amine 1a. This reaction is proposed to proceed through the radical ion pair [R3N·+·CO2·-] generated by the photoionization of amine 1a and the electron capture by CO2. The presence of lithium tetrafluoroborate in the reaction medium promotes the efficient and stereoselective α-C-C coupling of 1a by enhancing the production of α-dialkylamino radicals and the isomerization of N,N,N',N'-tetraethylbutane-2,3-diamine (4a).
Photoreduction of gaseous oxidized mercury changes global atmospheric mercury speciation, transport and deposition
2018
9 pags, 8 figs. -- Correction autor: https://doi.org/10.1038/s41467-022-28455-w http://hdl.handle.net/10261/268181
Synthesis and antiproliferative mechanism of action of pyrrolo[3′,2′:6,7] cyclohepta[1,2-d]pyrimidin-2-amines as singlet oxygen photosensitizers
2016
A new series of pyrrolo[3′,2′:6,7]cyclohepta[1,2-d]pyrimidin-2-amines, was conveniently prepared using a versatile and high yielding multistep sequence. A good number of derivatives was obtained and the cellular photocytotoxicity was evaluated in vitro against three different human tumor cell lines with EC50 (0.08–4.96 μM) values reaching the nanomolar level. Selected compounds were investigated by laser flash photolysis. The most photocytotoxic derivative, exhibiting a fairly long-lived triplet state (τ ∼ 7 μs) and absorbance in the UV–Vis, was tested in the photo-oxidations of 9,10-anthracenedipropionic acid (ADPA) by singlet oxygen. The photosentizing properties are responsible for the c…
A machine learning examination of hydroxyl radical differences among model simulations for CCMI-1
2020
The hydroxyl radical (OH) plays critical roles within the troposphere, such as determining the lifetime of methane (CH4), yet is challenging to model due to its fast cycling and dependence on a multitude of sources and sinks. As a result, the reasons for variations in OH and the resulting methane lifetime (τCH4), both between models and in time, are difficult to diagnose. We apply a neural network (NN) approach to address this issue within a group of models that participated in the Chemistry-Climate Model Initiative (CCMI). Analysis of the historical specified dynamics simulations performed for CCMI indicates that the primary drivers of τCH4 differences among 10 models are the flux of UV li…
In situ detection of atomic and molecular iodine using resonance and off-resonance fluorescence by lamp excitation: ROFLEX
2018
17 pags, 11 figs, 4 tabs
Measurement report: Photochemical production and loss rates of formaldehyde and ozone across Europe
2021
Various atmospheric sources and sinks regulate the abundance of tropospheric formaldehyde (HCHO), which is an important trace gas impacting the HOx (≡ HO2 + OH) budget and the concentration of ozone (O3). In this study, we present the formation and destruction terms of ambient HCHO and O3 calculated from in situ observations of various atmospheric trace gases measured at three different sites across Europe during summertime. These include a coastal site in Cyprus, in the scope of the Cyprus Photochemistry Experiment (CYPHEX) in 2014, a mountain site in southern Germany, as part of the Hohenpeißenberg Photochemistry Experiment (HOPE) in 2012, and a forested site in Finland, where measurement…
Photochemistry of 7-acetoxybenzopyran derivatives. Synthesis of eupatoriochromene and encecalin
1989
Abstract The photolysis of the 7-acetoxybenzopyran derivatives 1a-5a has been carried out. Chromene 1a was found to undergo extensive photopolymerization. Chromanone 2a underwent a rather inefficient photo-Fries rearrangement to the 6 - and 8 - acetyl derivatives 2b and 2c . Diacetoxychromene 3a gave the unsaturated ketone 8 as the main product, besides its deacetylation analogue 9 and chromanone 11 . Diacetoxychroman 4a afforded a mixture of four C-acetyl products: 1b, 1c, 2b and 2c , together with Chromene 1a and chromanone 2a. Finally, irradiation of chroman 5a gave rise to a mixture of the two possible photo-Fries products 5b (43%) and 5c (52%). The mechanistic implications of the above…
Shaping of a ground state rotational wavepacket by frequency-chirped pulses
2001
0953-4075; A coherent rotational superposition state is produced in the ground vibronic level of N2 through the interaction of the molecule with the electric field vector of a nonresonant laser pulse. This rotational wavepacket is shaped with a linear frequency chirp of the laser field. The structural shape of the rotational coherences shows a strong dependence with the frequency-chirp amplitude. A comparison with a theoretical model allows the interpretation of the observed effects in terms of dephasing of the wavepacket induced by the laser phase distortion. Application of the presented results to the phase characterization of short XUV pulses is suggested.
Controlling molecular alignment rephasing through interference of Raman-induced rotational coherence
2000
0021-9606; Quantum control over molecular alignment rephasing is experimentally investigated in gaseous CO2. The control process is achieved by illuminating the medium with a pair of pump-pulses separated in time by approximately an integer value of T0=1/8B(0), where B(0) is the rotational constant. Through a Raman-type process, each pulse alone produces rotational coherence leading to a periodic orientational anisotropy. It is the combination of the two pulses that yields to quantum interference, resulting in a modification of this anisotropy probed by a third delayed pulse. The effect is accurately analyzed for different time delays between the two pulses. A theoretical analysis supplies …