TRANSIENT RAMAN SPECTRA, STRUCTURE AND THERMOCHEMISTRY OF THE THIOCYANATE DIMER RADICAL ANION IN WATER
| Autor: | G. N. R. Tripathi, Ian Carmichael, Ireneusz Janik |
|---|---|
| Rok vydání: | 2017 |
| Předmět: |
Thiocyanate
Dimer General Physics and Astronomy 02 engineering and technology 010402 general chemistry 021001 nanoscience & nanotechnology Photochemistry 01 natural sciences 0104 chemical sciences Ion Bond length chemistry.chemical_compound symbols.namesake Molecular geometry chemistry Radiolysis symbols Thermochemistry Physical chemistry Density functional theory Transient (oscillation) Physical and Theoretical Chemistry 0210 nano-technology Raman spectroscopy |
| Zdroj: | Proceedings of the 72nd International Symposium on Molecular Spectroscopy. |
| Popis: | Time-resolved resonance-enhanced Stokes and anti-Stokes Raman spectra of the thiocyanate dimer radical anion, (SCN)2•−, prepared by pulse radiolysis in water, have been obtained and interpreted in conjunction with theoretical calculations to provide detailed information on the molecular geometry and bond properties of the species. The structural properties of the radical are used to develop a molecular perspective on its thermochemistry in an aqueous solution. Twenty-nine Stokes Raman bands of the radical observed in the 120-4200 cm−1 region are assigned in terms of the strongly enhanced 220 cm−1 fundamental, weakly enhanced 721 cm−1, and moderately enhanced 2073 cm−1 fundamentals, their overtones, and combinations. Calculations by range-separated hybrid density functionals (ωB97x and LC-ωPBE) support the spectroscopic assignments of the 220 cm−1 vibration to a predominantly SS stretching mode and the features at 721 cm−1 and 2073 cm−1 to CS and CN symmetric stretching modes, respectively. The correspondi... |
| Databáze: | OpenAIRE |
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