Charge-transfer and impulsive electronic-to-vibrational energy conversion in ferricyanide: ultrafast photoelectron and transient infrared studies
The photophysics of ferricyanide in H O, D O and ethylene glycol was studied upon excitation of ligand-to-metal charge transfer (LMCT) transitions by combining ultrafast photoelectron spectroscopy (PES) of liquids and transient vibrational spectroscopy. Upon 400 nm excitation in water, the PES resul...
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| Vydáno v: | Physical chemistry chemical physics : PCCP Ročník 19; číslo 26; s. 17052 |
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| Hlavní autoři: | , , , , |
| Médium: | Journal Article |
| Jazyk: | angličtina |
| Vydáno: |
England
2017
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| ISSN: | 1463-9084, 1463-9084 |
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| Abstract | The photophysics of ferricyanide in H
O, D
O and ethylene glycol was studied upon excitation of ligand-to-metal charge transfer (LMCT) transitions by combining ultrafast photoelectron spectroscopy (PES) of liquids and transient vibrational spectroscopy. Upon 400 nm excitation in water, the PES results show a prompt reduction of the Fe
to Fe
and a back electron transfer in ∼0.5 ps concomitant with the appearance and decay of a strongly broadened infrared absorption at ∼2065 cm
. In ethylene glycol, the same IR absorption band decays in ∼1 ps, implying a strong dependence of the back electron transfer on the solvent. Thereafter, the ground state ferric species is left vibrationally hot with significant excitation of up to two quanta of the CN-stretch modes, which completely decay on a 10 ps time scale. Under 265 nm excitation even higher CN-stretch levels are populated. Finally, from a tiny residual transient IR signal, we deduce that less than 2% of the excited species undergo photoaquation, in line with early flash photolysis experiments. The latter is more significant at 265 nm compared to 400 nm excitation, which suggests photodissociation in this system is an unlikely statistical process related to the large excess of vibrational energy. |
|---|---|
| AbstractList | The photophysics of ferricyanide in H2O, D2O and ethylene glycol was studied upon excitation of ligand-to-metal charge transfer (LMCT) transitions by combining ultrafast photoelectron spectroscopy (PES) of liquids and transient vibrational spectroscopy. Upon 400 nm excitation in water, the PES results show a prompt reduction of the Fe3+ to Fe2+ and a back electron transfer in ∼0.5 ps concomitant with the appearance and decay of a strongly broadened infrared absorption at ∼2065 cm-1. In ethylene glycol, the same IR absorption band decays in ∼1 ps, implying a strong dependence of the back electron transfer on the solvent. Thereafter, the ground state ferric species is left vibrationally hot with significant excitation of up to two quanta of the CN-stretch modes, which completely decay on a 10 ps time scale. Under 265 nm excitation even higher CN-stretch levels are populated. Finally, from a tiny residual transient IR signal, we deduce that less than 2% of the excited species undergo photoaquation, in line with early flash photolysis experiments. The latter is more significant at 265 nm compared to 400 nm excitation, which suggests photodissociation in this system is an unlikely statistical process related to the large excess of vibrational energy.The photophysics of ferricyanide in H2O, D2O and ethylene glycol was studied upon excitation of ligand-to-metal charge transfer (LMCT) transitions by combining ultrafast photoelectron spectroscopy (PES) of liquids and transient vibrational spectroscopy. Upon 400 nm excitation in water, the PES results show a prompt reduction of the Fe3+ to Fe2+ and a back electron transfer in ∼0.5 ps concomitant with the appearance and decay of a strongly broadened infrared absorption at ∼2065 cm-1. In ethylene glycol, the same IR absorption band decays in ∼1 ps, implying a strong dependence of the back electron transfer on the solvent. Thereafter, the ground state ferric species is left vibrationally hot with significant excitation of up to two quanta of the CN-stretch modes, which completely decay on a 10 ps time scale. Under 265 nm excitation even higher CN-stretch levels are populated. Finally, from a tiny residual transient IR signal, we deduce that less than 2% of the excited species undergo photoaquation, in line with early flash photolysis experiments. The latter is more significant at 265 nm compared to 400 nm excitation, which suggests photodissociation in this system is an unlikely statistical process related to the large excess of vibrational energy. The photophysics of ferricyanide in H O, D O and ethylene glycol was studied upon excitation of ligand-to-metal charge transfer (LMCT) transitions by combining ultrafast photoelectron spectroscopy (PES) of liquids and transient vibrational spectroscopy. Upon 400 nm excitation in water, the PES results show a prompt reduction of the Fe to Fe and a back electron transfer in ∼0.5 ps concomitant with the appearance and decay of a strongly broadened infrared absorption at ∼2065 cm . In ethylene glycol, the same IR absorption band decays in ∼1 ps, implying a strong dependence of the back electron transfer on the solvent. Thereafter, the ground state ferric species is left vibrationally hot with significant excitation of up to two quanta of the CN-stretch modes, which completely decay on a 10 ps time scale. Under 265 nm excitation even higher CN-stretch levels are populated. Finally, from a tiny residual transient IR signal, we deduce that less than 2% of the excited species undergo photoaquation, in line with early flash photolysis experiments. The latter is more significant at 265 nm compared to 400 nm excitation, which suggests photodissociation in this system is an unlikely statistical process related to the large excess of vibrational energy. |
| Author | Chergui, Majed Helbing, Jan Longetti, Luca Arrell, Christopher A Ojeda, José |
| Author_xml | – sequence: 1 givenname: José surname: Ojeda fullname: Ojeda, José email: majed.chergui@epfl.ch organization: Laboratory of Ultrafast Spectroscopy, ISIC, and Lausanne Centre for Ultrafast Science (LACUS), Ecole Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland. majed.chergui@epfl.ch – sequence: 2 givenname: Christopher A surname: Arrell fullname: Arrell, Christopher A – sequence: 3 givenname: Luca surname: Longetti fullname: Longetti, Luca – sequence: 4 givenname: Majed surname: Chergui fullname: Chergui, Majed – sequence: 5 givenname: Jan surname: Helbing fullname: Helbing, Jan |
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| Snippet | The photophysics of ferricyanide in H
O, D
O and ethylene glycol was studied upon excitation of ligand-to-metal charge transfer (LMCT) transitions by combining... The photophysics of ferricyanide in H2O, D2O and ethylene glycol was studied upon excitation of ligand-to-metal charge transfer (LMCT) transitions by combining... |
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| Title | Charge-transfer and impulsive electronic-to-vibrational energy conversion in ferricyanide: ultrafast photoelectron and transient infrared studies |
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