Static and dynamic scavenging of ammoniated electrons by nitromethane

Literature Information

Publication Date 2019-09-16
DOI 10.1039/C9CP03342D
Impact Factor 3.676
Authors

Nicolás Rivas, Germán Sciaini, Ernesto Marceca


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Abstract

We studied the time-resolved scavenging efficiency of nitromethane for transient electron species in liquid ammonia, at a temperature of 298 K. UV excitation of iodide ions produced fully solvated electrons, as well as transient (I, e−) and (counterion, e−) pairs, the overall concentration of which was monitored by NIR absorption with subpicosecond time resolution. After the UV pulse, the solution absorbance decays almost completely in a few hundreds of picoseconds due to geminate electron–iodine atom recombination and a competitive annihilation channel involving the scavenger. Recombination of transient (I, e−) pairs follows the well-known kinetic model, while the electron–nitromethane reaction proceeds by two distinct mechanisms: static scavenging (interpreted in terms of the encounter complex model), with a characteristic time shorter than the temporal resolution of the apparatus, or via a diffusion-limited bimolecular reaction, with a rate constant of 1.1 × 1011 M−1 s−1.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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