| Autor: |
Golubeva, Elena N., Zubanova, Ekaterina M., Melnikov, Michail Ya., Gostev, Fedor E., Shelaev, Ivan V., Nadtochenko, Victor A. |
| Předmět: |
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| Zdroj: |
Dalton Transactions: An International Journal of Inorganic Chemistry; 2014, Vol. 43 Issue 47, p17820-17827, 8p |
| Abstrakt: |
Photoinduced processes of tetrahexylammonium tetrachlorocuprate [(C6H13)4N]2CuIICl4 in chloroorganic solvents were investigated by steady state photolysis and femtosecond transient absorption spectroscopy. The quantum yield of photoreduction of CuCl42- was estimated to be about 1%; the process resulted in the formation of the copper(I) chlorocomplex Cu¹Cl32- and a chlorine atom. Femtosecond laser photolysis with a 422 nm, 40 fs pulse revealed a three-exponential decay of the LMCT excited state of [(C6H13)4N]2CuCl4. A global fitting SVD analysis of the femtosecond transient spectra suggested three relaxation times, ~400 fs, ~1.4 ps and ~5.8 ps. Oscillations in transient absorption kinetic traces were documented for CuCl42- solutions in 2-chlorobutane. The oscillation Fourier transform analysis of the oscillations and linear predictive singular value decomposition revealed peaks at 283 cm-1 (damping time ~600 fs) and 181 cm-1 (damping time ~400 fs). These peaks can be tentatively attributed to vs(Cu-Cl) symmetric stretching frequency A1 and T2 reflecting excited state vibrational coherence. Quantum chemical calculations suggest a possible scheme for relaxation pathways in CuCl42-. The observed transient excited state absorption bands agree semiquantitatively with the calculated transition bands of CuCl42-. [ABSTRACT FROM AUTHOR] |
| Databáze: |
Complementary Index |
| Externí odkaz: |
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