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Photosensitized renoxification of HNO is found to produce HONO in an unexpectedly high yield, which has been considered an important source for atmospheric HONO. Conventionally, the production of HONO is ascribed to the secondary photolysis of the primarily formed NO. In this study, by using humic acid (HA) as a model environmental photosensitizer, we provide evidence of the direct formation of NO in its electronic excited state (NO*) as a key intermediate during the photosensitizing renoxification of HNO. Moreover, the high HONO yield originates from the heterogeneous reaction of the primarily formed NO* with the co-adsorbed water molecules on HA. Such a mechanism is supported by the increase of the product selectivity of HONO with relative humidity. Further luminescence measurements demonstrate clearly the occurrence of an electronic excited state (NO*) from photolysis of adsorbed HNO on HA. This work deepens our understanding of the formation of atmospheric HONO and gives insight into the transformation of RNS.
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http://dx.doi.org/10.1021/acs.est.3c01342 | DOI Listing |
Inorg Chem
September 2025
Laboratoire de Chimie Physique Matière et Rayonnement (LCPMR), CNRS UMR 7614, Sorbonne Université (SU), 4 place Jussieu, Paris 75005, France.
The one-photon KV X-ray photoelectron spectra of Na and its hydrated clusters [Na(HO)] ( = 1-6) are dominated by the unusual 1s → 1s3s transition. KV spectroscopy also reveals a pronounced redistribution of the 1s → 1s3p transition cross sections, directly correlated with hydration number and molecular arrangement. Its intrinsic two-step nature, involving simultaneous core ionization and core excitation, enables detailed investigation of solvation-induced electronic structure changes, including dipole-forbidden excitations, core-valence charge transfer, and subtle 1s → V energy shifts.
View Article and Find Full Text PDFPhys Chem Chem Phys
September 2025
School of Chemistry and Chemical Engineering, Key Laboratory of Theoretical Organic Chemistry and Function Molecule of Ministry of Education, Hunan University of Science and Technology, Xiangtan, 411201, P. R. China.
Additive assisted strategies play a crucial role in optimizing the morphology and improving the performance of organic solar cells (OSCs), yet the molecular-level mechanisms remain unclear. Here, we employ molecular dynamics (AIMD) and density functional theory (DFT) to elucidate the influence of typical additives of 1,8-diiodooctane (DIO) and 3,5-dichlorobromobenzene (DCBB) on molecular packing, electronic structures, and charge transport. It can be observed that both additives can enhance the stacking properties of the donor and acceptor materials, yet they have different effects on the local electrostatic environment.
View Article and Find Full Text PDFDalton Trans
September 2025
Department of Chemistry and Protein Research Center for Bio-Industry, Hankuk University of Foreign Studies, Yongin 17035, Republic of Korea.
The nanoscale environment within the void spaces of metal-organic frameworks (MOFs) can significantly influence the photoredox catalytic activity of encapsulated visible-light photoredox catalysts (PCs). To compare two isostructural PC@In-MOF systems, three cationic Ru(II) polypyridine complexes were successfully encapsulated within the mesoscale channels of the anionic framework of InTATB (HTATB = 4,4',4''--triazine-2,4,6-triyltribenzoic acid), which features a doubly interpenetrated framework structure. This encapsulation yielded three heterogenized visible-light PCs, RuL@InTATB, where L = 2,2'-bipyridine (bpy), 1,10-phenanthroline (phen), or 2,2'-bipyrazine (bpz).
View Article and Find Full Text PDFChem Asian J
September 2025
School of Chemistry and Chemical Engineering, Hainan University, Haikou, 570228, China.
Molecules that exhibit excited-state intramolecular proton transfer (ESIPT) have demonstrated great promise in fluorescent probes. The electronic effect of substituents has an important influence on the ESIPT process. In this study, we investigated the effects of substituents on the ESIPT mechanism and the photophysical behavior of single-benzene fluorophore (SBF) derivatives with computational chemistry methods.
View Article and Find Full Text PDFJ Phys Chem Lett
September 2025
Faculty of Chemistry, Wrocław University of Science and Technology, Wyb. Wyspiańskiego 27, PL-50370 Wrocław, Poland.
Computer simulations play an essential role in the interpretation of experimental multiphoton absorption spectra. In addition, models derived from theory allow for the establishment of "structure-property" relationships. This work contributes to these efforts and presents the results of an analysis of two- and three-photon absorptions for a set comprising 450 conjugated molecules performed at the CAM-B3LYP/aug-cc-pVDZ level.
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