Journal of Physical Chemistry. A

Black carbon is an important constituent of atmospheric aerosol particle matter (PM) with significant effects on the global radiation budget and on human health. The soot particle aerosol mass spectrometer (SP-AMS) has been developed and deployed for real-time ambient measurements of refractory carbon particles. In the SP-AMS, black carbon or metallic particles are vaporized through absorption of 1064 nm light from a CW Nd:YAG laser. This scheme allows for continuous "soft" vaporization of both core and coating materials...

The adsorption and catalytic properties of three-dimensional zeolite UTL were investigated computationally along with properties of its two-dimensional analogue IPC-1P that can be obtained from UTL by a removal of D4R units. Adsorption properties and Lewis acidity of extra-framework Li(+) sites were investigated for both two- and three-dimensional forms of UTL using the carbon monoxide as a probe molecule. The CO adsorption enthalpies, calculated with various dispersion-corrected DFT methods, including DFT/CC, DFT-D2, and vdW-DF2, and the CO stretching frequencies obtained with the νCO/rCO correlation method are compared for corresponding Li(+) sites in 3D and 2D UTL zeolite...

We report a photoelectron-imaging investigation of the chlorocyanomethyl radical (CHClCN) and the corresponding carbene (CClCN). The results are discussed in comparison with the corresponding dichloro- and dicyano-substituted species, focusing on the divergent effects of the halogen and pseudohalogen (CN) substitutions. A cooperative (captodative) interaction of the π-donor Cl and π-acceptor cyano groups favors the increased stability of the CHClCN radical, but a competition of the two substituents is observed in the singlet-triplet splitting of the carbene...

The selective increase in the oxidation rate of certain organic compounds with permanganate in the presence of environmental "ligands" and reduced species has been ascribed to the different reactivity of the target compounds toward Mn(III), which bears striking similarities to recent independent investigations into the use of permanganate as a chemiluminescence reagent. In spite of the importance of Mn(III) in the light-producing pathway, the dependence of the oxidation mechanism for any given compound on this intermediate could not be determined solely through the emission intensity...

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Neodymium monofluoride dication was studied as a model of the Nd-F bond in NdFx. Multiconfigurational self-consistent field (MCSCF) and second order multireference quasi-degenerate perturbation theory (MCQDPT2) methods were used with a variety of active spaces to elucidate the roles of the Nd 4f, 5d, and 6s orbitals. Spin-orbit coupling calculations were performed at the SO-MCQDPT2 level, and potential energy curves were obtained for the four lowest energy quartet states as well as for the four lowest doublet states and the lowest sextet state...

In this article, we report a detailed study on halogen bonds in complexes of CHCBr, CHCCl, CH2CHBr, FBr, FCl, and ClBr with a set of Lewis bases (NH3, OH2, SH2, OCH2, OH(-), Br(-)). To obtain insight into the physical nature of these bonds, we extensively used Bader's Quantum Theory of Atoms-in-Molecules (QTAIM). With this aim, in addition to the examination of the bond critical points properties, we apply Pendás' Interacting Quantum Atoms (IQA) scheme, which enables rigorous and physical study of each interaction at work in the formation of the halogen-bonded complexes...

The trithionate-hypochlorous acid reaction has been studied by the stopped-flow technique and conventional spectrophotometry between pH = 6.59-12.2 monitoring absorbance-time profiles at 285 and 225 nm. We showed that the formal kinetic order of Cl(I) is nearly 2; however, those of hydrogen ion and trithionate are significantly lower than unity, suggesting complex kinetics. It was also demonstrated that both forms of Cl(I) are kinetically active within the concentration range studied. Simultaneous evaluation of the kinetic curves revealed that the reaction was initiated by a formal Cl(+) transfer to the partially negatively charged β-sulfur of trithionate...