Structure and Kinetics of Organic Acid Radicals Formed in Reaction with •OH Radicals.

The study investigated •OH-derived radicals from certain organic acids employed in nuclear fuel processing and separation using EPR spectroscopy and quantum chemistry methods. Hydroxyl radicals were generated through a Fenton-like reaction within the EPR resonator under both acidic and basic conditions, allowing for the detection of neutral and radical anions, respectively. The spectral assignment and analysis were conducted using a combination of literature data and quantum chemical calculations employing DFT theory with B3LYP or LPBE functionals and the L2a_3 basis set. The reaction of the •OH radical with lactic and glycolic acids yielded primary C-centered radicals through hydrogen abstraction from these acids. In contrast, the •OH radical exclusively generated secondary radicals from oxalic acid, whereas for citric acid, it resulted in both primary and secondary species induced by decarboxylation. The EPR spectrum of acetohydroxamic acid, upon reaction with the •OH radical, displayed a complex pattern featuring primary •N-type and N-O•-type radicals. The decay pathways of the generated radicals were primarily attributed to radical-radical reactions, with the extracted reaction rate constants generally falling within the typical range observed for such reactions. The EPR parameters calculated for potential radicals using B3LYP and LPBE functionals with L2a_3 basis set demonstrated good accuracy for neutral radicals, albeit requiring minor adjustments for radical anions.

Radicals from tributyl phosphate decomposition: a combined electron paramagnetic resonance spectroscopic and computational chemistry investigation.

The radiation- and chemically-induced radicals from tributyl phosphate (TBP) have been characterized by EPR spectroscopy and theoretical calculations. The yield of X-ray-generated TBP radicals measured by a PBN spin trap is 0.22 µmol J-1 (2.1 radicals/100 eV) at room temperature (298 K). The EPR spectra obtained by irradiating TBP with an electron beam at 77 K are in close agreement with literature data for samples irradiated with gamma- and X-rays [https://doi.org/10.1007/BF02165504, https://doi.org/10.1016/1359-0197(89)90319-6]. Possible conformers of alkyl-type, TBP-derived radicals were analyzed by Density Functional Theory calculations. The main contribution to the experimental spectrum at 77 K is shown to be made by a conformer of the CH3˙CHCH2-radical, which contains all carbon atoms of the butyl group in the same plane. The EPR spectra of TBP radicals induced by the OH radical in aqueous solution were measured for the first time using a continuous flow system. The formation of the alkyl-type TBP radicals CH3˙CHCH2-, ˙CH2CH2-, and -CH2˙CHO- in the ratio of 5/4/1 was detected; their spectral assignment was based on quantum chemical calculations with rotational averaging of HFC constants for the corresponding beta- and alpha-protons.

Reactions of oxygen atoms with fluoroform and its radiolysis products: matrix isolation and ab initio study.

The investigation of the reactions of oxygen atoms with fluoroform (CHF3) molecules and products of their degradation present significant interest for better understanding of the impact of chemically inert fluorinated compounds on atmospheric chemistry and may provide a deeper insight into mechanisms of chemical processes occurring under the action of hard UV and ionizing radiation. In the present study we applied a matrix isolation technique with FTIR spectroscopic detection combined with ab initio calculations to address this issue. It was found that the reactions of "hot" (translationally excited) O(1D) atoms produced by X-ray or UV radiation from appropriate precursors (N2O or H2O) resulted in the formation of carbonyl fluoride (COF2) and its complex with HF. The complex was detected and characterized for the first time. Singlet oxygen atoms also probably react with the products of radiation-induced degradation of fluoroform (CF3 and CF2). Additionally, the reaction of "hot" O(3P) atoms with fluoroform may occur to a certain extent yielding the CF3 radical. No evidence for the reactions of thermal O(3P) atoms with CHF3 or products of its degradation was found under the experimental conditions used. The implications of the results of this model study for understanding the evolution of fluoroform in the upper layers of the stratosphere and ionosphere are discussed.

A hydrogen-bonded CHF⋯HF complex: IR spectra and unusual photochemistry.

A hydrogen-bonded CHF⋯HF complex was characterized by FTIR matrix isolation spectroscopy and ab initio calculations. Three possible structures of this complex were found at the coupled-cluster with single, double, and perturbative triple excitations [CCSD(T)/L3a_3] level of theory. The comparison between the experiment and theory reveals that the most stable structure with the binding energy of 6.48 kcal/mol is formed upon x-ray irradiation of isolated CH2F2 molecules in noble gas matrices (Ne, Ar, Xe). This species appears to be the first known intermolecular complex of monofluorocarbene, and its identification was unambiguously proved by IR absorptions corresponding to HF deformation (libration), CF stretching, H-C-F bending, and CH and HF stretching modes. It is worth noting that the corresponding spectral features in an argon matrix were previously tentatively ascribed to CH2F2 +· and HF⋯CHF-· [L. Andrews and F. T. Prochaska, J. Chem. Phys. 70, 4714 (1979)], but the calculations performed in the present study definitely support the re-assignment. The observed CHF⋯HF complex can be converted to the parent CH2F2 under the action of light with λ < 525 nm. The plausible mechanism of this conversion using the conical intersection concept is discussed.

Radiation-Induced Transformation of CHF3···CO to the CF3···CO Complex: Matrix Isolation and Ab Initio Study.

The X-ray-induced transformations of CHF3/CO/Ar and CHF3/CO/Kr systems were investigated by Fourier transform infrared (FTIR) matrix isolation spectroscopy at 6 K. It was found that addition of CO suppressed decomposition of fluoroform in an Ar matrix, probably because of trapping of matrix holes by CO and CHF3···CO complexes. Considerable increase of the CF3/CF2 ratio with increasing CO content in the matrix was attributed to stabilization of the CF3 radical with respect to further radiation-induced fragmentation because of its complexation with the CO molecule. The CF3···CO complex generated from the CHF3···CO precursor complex was characterized by FTIR spectroscopy and ab initio calculations at the CCSD(T) and MP2 levels of theory. To the best of our knowledge, it is the first experimentally observed complex of the CF3 radical. The computed interaction energy was found to be 0.35 kcal/mol at the CCSD(T)/L2a_3 level (0.36 kcal/mol at the MP2/L2a_3 level), taking into account zero-point energy and basis set superposition error corrections. Despite the very weak intermolecular bonding, the complex is characterized by distinct features in the regions of C-F symmetric and antisymmetric stretching (CF3) and CO stretching (the latter one was observed only in a krypton matrix). The geometrical structure of the radical-molecule complex is close to that of its molecular precursor.

Matrix Isolation and Ab Initio Study on the CHF3···CO Complex.

Intermolecular complexes between CHF3 and CO have been studied by ab initio calculations and IR matrix isolation spectroscopy. The computations at the MP2 and CCSD(T) levels of theory indicated five minima on the potential energy surface (PES). The most energetically favorable structure is the C(CO)-H(CHF3) coordinated complex ( Cs symmetry) with the stabilization energy of 0.84 kcal/mol as computed at the CCSD(T) level (with ZPVE and BSSE corrections). This is the only structure experimentally found in argon and krypton matrixes, whereas the weaker non-hydrogen-bonded complexes predicted by theory were not detected. The vibrational spectrum of this complex is characterized by a red-shift of the CF3 asymmetric stretching, splitting of the C-H bending mode, and blue-shifts of the C-H and C-O stretching vibrations as compared to the monomer molecules. The observed complexation-induced shifts of CHF3 and CO fundamentals are in good agreement with the computational predictions. It was shown that both MP2 and CCSD(T) calculations generally provided a reasonable description of the vibrational properties for the weak intermolecular complexes of fluoroform.

Communication: A hydrogen-bonded difluorocarbene complex: Ab initio and matrix isolation study.

Structure and spectroscopic features of the CF2⋯HF complexes were studied by ab initio calculations at the CCSD(T) level and matrix isolation FTIR spectroscopy. The calculations predict three stable structures. The most energetically favorable structure corresponds to hydrogen bonding of HF to the lone pair of the C atom (the interaction energy of 3.58 kcal/mol), whereas two less stable structures are the H⋯F bonded complexes (the interaction energies of 0.30 and 0.24 kcal/mol). The former species was unambiguously characterized by the absorptions in the FTIR spectra observed after X-ray irradiation of fluoroform in a xenon matrix at 5 K. The corresponding features appear at 3471 (H-F stretching), 1270 (C-F symmetric stretching, shoulder), 1175 (antisymmetric C-F stretching), and 630 (libration) cm-1, in agreement with the computational predictions. To our knowledge, it is the first hydrogen-bonded complex of dihalocarbene. Possible weaker manifestations of the H⋯F bonded complexes were also found in the C-F stretching region; however, their assignment is tentative. The H⋯C bonded complex is protected from reaction yielding a fluoroform molecule by a remarkably high energy barrier (23.85 kcal/mol), so it may be involved in various chemical reactions.

Spectroscopy and radiation-induced chemistry of an atmospherically relevant CH2F2 H2O complex: Evidence for the formation of CF2 H2O complex as revealed by FTIR matrix isolation and ab initio study.

Difluoromethane is considered among the environment friendly alternatives to the ozone depleting chlorofluorocarbons. Due to its chemical inertness and lack of UV absorption above 200 nm, this compound can easily come to the upper layers forming complexes with widely abundant atmospheric components, such as water. The radiation-induced degradation of this compound and its complexes may be significant for reliable prediction of its long-term evolution in the environment as well as for development of new ways for its removal. In this work we have studied the vibrational spectroscopic properties and mechanisms of the radiation-induced decay of the CH2F2⋯H2O under the action of X-rays using matrix isolation FTIR spectroscopy and ab initio calculations. The IR spectrum of the complex in an argon matrix was characterized for the first time and assigned to a hydrogen-bonded structure with a binding energy of 11.1 kJ/mol (2.65 kcal/mol) (CCSD(T)/CBS level of theory). Complexation with water leads to a certain suppression of the efficiency of the radiation-induced decomposition of difluoromethane. The obtained results provide evidence for the radiation-induced formation of previously unreported CF2⋯H2O complex (in addition to other oxygen containing molecules, such as COF2 and CO). As demonstrated by calculations, the new difluorocarbene complex reveals a hydrogen bond and it is characterized by a binding energy of 5.73 kJ/mol (1.37 kcal/mol) (CCSD(T)/CBS level of theory).