Proton affinities of pertechnetate (TcO4−) and perrhenate (ReO4−)

文献信息

发布日期 2020-05-18
DOI 10.1039/D0CP01721C
影响因子 3.676
作者

Jiwen Jian, Elumalai Varathan, Thibault Cheisson, Tian Jian, Wayne W. Lukens, Rebecca L. Davis, Eric J. Schelter, Georg Schreckenbach, John K. Gibson


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摘要

The anions pertechnetate, TcO4−, and perrhenate, ReO4−, exhibit very similar chemical and physical properties. Revealing and understanding disparities between them enhances fundamental understanding of both. Electrospray ionization generated the gas-phase proton bound dimer (TcO4−)(H+)(ReO4−). Collision induced dissociation of the dimer yielded predominantly HTcO4 and ReO4−, which according to Cooks’ kinetic method indicates that the proton affinity (PA) of TcO4− is greater than that of ReO4−. Density functional theory computations agree with the experimental observation, providing PA[TcO4−] = 300.1 kcal mol−1 and PA[ReO4−] = 297.2 kcal mol−1. Attempts to rationalize these relative PAs based on elementary molecular parameters such as atomic charges indicate that the entirety of bond formation and concomitant bond disruption needs to be considered to understand the energies associated with such protonation processes. Although in both the gas and solution phases, TcO4− is a stronger base than ReO4−, it is noted that the significance of even such qualitative accordance is tempered by the very different natures of the underlying phenomena.

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来源期刊

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
自引率: 10.3%
年发文量: 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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