| Title: |
Transient Raman observation and bond properties of a mixed dihalide radical anion in water. |
| Authors: |
Janik, Ireneusz, Bhattacharya, Susmita, Tripathi, G. N. R. |
| Source: |
Journal of Chemical Physics; 2/21/2025, Vol. 162 Issue 7, p1-10, 10p |
| Subject Terms: |
RESONANCE Raman spectroscopy, RADICAL anions, DENSITY functionals, RADICALS (Chemistry), ENERGY levels (Quantum mechanics) |
| Abstract: |
An elusive short-lived mixed dihalide radical anion (BrCl·−), produced in water by radiation-induced reactions, has been observed and analyzed by time-resolved resonance Raman spectroscopy (TRRR) and density functional theory. The Raman spectrum of the radical consists of a prominently enhanced stretching vibration, represented by a band at 212 cm−1 and its overtones. Calculations by range-separated hybrid density functionals (ωB97x and LC-ωPBE) reproduce the experimental vibrational frequency well, with a corresponding bond length of 2.713 (±0.028) Å. A first order anharmonicity of ∼1.42 cm−1 determined for the Br–Cl stretching mode in the radical suggests a convergence of vibrational states at an energy of ∼1.01 eV, using the Birge–Sponer extrapolation. This value, estimated for the radical confined in the solvent cage, compares fairly well with the calculated gas-phase energy, 1.06 eV, required for the radical to dissociate into Br· and Cl− fragments. The Raman detection of a closely related radical, ICl·−, in water was unsuccessful. The reaction pathways and equilibria have been analyzed to discuss the observability of mixed dihalide and analogous radical species. [ABSTRACT FROM AUTHOR] |
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