Vibrational coherence transfer in the ultrafast intersystem crossing of a diplatinum complex in solution
We investigate the ultrafast transient absorption response of tetrakis(μ-pyrophosphito)diplatinate(II), [Pt (μ-P O H ) ] [hereafter abbreviated Pt(pop)], in acetonitrile upon excitation of its lowest singlet A state. Compared with previously reported solvents [van der Veen RM, Cannizzo A, van Mourik...
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| Vydáno v: | Proceedings of the National Academy of Sciences - PNAS Ročník 115; číslo 28; s. E6396 |
|---|---|
| Hlavní autoři: | , , , , , , |
| Médium: | Journal Article |
| Jazyk: | angličtina |
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United States
10.07.2018
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| ISSN: | 1091-6490, 1091-6490 |
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| Abstract | We investigate the ultrafast transient absorption response of tetrakis(μ-pyrophosphito)diplatinate(II), [Pt
(μ-P
O
H
)
]
[hereafter abbreviated Pt(pop)], in acetonitrile upon excitation of its lowest singlet
A
state. Compared with previously reported solvents [van der Veen RM, Cannizzo A, van Mourik F, Vlček A, Jr, Chergui M (2011)
133:305-315], a significant shortening of the intersystem crossing (ISC) time (<1 ps) from the lowest singlet to the lowest triplet state is found, allowing for a transfer of vibrational coherence, observed in the course of an ISC in a polyatomic molecule in solution. Density functional theory (DFT) quantum mechanical/molecular mechanical (QM/MM) simulations of Pt(pop) in acetonitrile and ethanol show that high-lying, mostly triplet, states are strongly mixed and shifted to lower energies due to interactions with the solvent, providing an intermediate state (or manifold of states) for the ISC. This suggests that the larger the solvation energies of the intermediate state(s), the shorter the ISC time. Because the latter is smaller than the pure dephasing time of the vibrational wave packet, coherence is conserved during the spin transition. These results underscore the crucial role of the solvent in directing pathways of intramolecular energy flow. |
|---|---|
| AbstractList | We investigate the ultrafast transient absorption response of tetrakis(μ-pyrophosphito)diplatinate(II), [Pt2(μ-P2O5H2)4]4- [hereafter abbreviated Pt(pop)], in acetonitrile upon excitation of its lowest singlet 1A2u state. Compared with previously reported solvents [van der Veen RM, Cannizzo A, van Mourik F, Vlček A, Jr, Chergui M (2011) J Am Chem Soc 133:305-315], a significant shortening of the intersystem crossing (ISC) time (<1 ps) from the lowest singlet to the lowest triplet state is found, allowing for a transfer of vibrational coherence, observed in the course of an ISC in a polyatomic molecule in solution. Density functional theory (DFT) quantum mechanical/molecular mechanical (QM/MM) simulations of Pt(pop) in acetonitrile and ethanol show that high-lying, mostly triplet, states are strongly mixed and shifted to lower energies due to interactions with the solvent, providing an intermediate state (or manifold of states) for the ISC. This suggests that the larger the solvation energies of the intermediate state(s), the shorter the ISC time. Because the latter is smaller than the pure dephasing time of the vibrational wave packet, coherence is conserved during the spin transition. These results underscore the crucial role of the solvent in directing pathways of intramolecular energy flow.We investigate the ultrafast transient absorption response of tetrakis(μ-pyrophosphito)diplatinate(II), [Pt2(μ-P2O5H2)4]4- [hereafter abbreviated Pt(pop)], in acetonitrile upon excitation of its lowest singlet 1A2u state. Compared with previously reported solvents [van der Veen RM, Cannizzo A, van Mourik F, Vlček A, Jr, Chergui M (2011) J Am Chem Soc 133:305-315], a significant shortening of the intersystem crossing (ISC) time (<1 ps) from the lowest singlet to the lowest triplet state is found, allowing for a transfer of vibrational coherence, observed in the course of an ISC in a polyatomic molecule in solution. Density functional theory (DFT) quantum mechanical/molecular mechanical (QM/MM) simulations of Pt(pop) in acetonitrile and ethanol show that high-lying, mostly triplet, states are strongly mixed and shifted to lower energies due to interactions with the solvent, providing an intermediate state (or manifold of states) for the ISC. This suggests that the larger the solvation energies of the intermediate state(s), the shorter the ISC time. Because the latter is smaller than the pure dephasing time of the vibrational wave packet, coherence is conserved during the spin transition. These results underscore the crucial role of the solvent in directing pathways of intramolecular energy flow. We investigate the ultrafast transient absorption response of tetrakis(μ-pyrophosphito)diplatinate(II), [Pt (μ-P O H ) ] [hereafter abbreviated Pt(pop)], in acetonitrile upon excitation of its lowest singlet A state. Compared with previously reported solvents [van der Veen RM, Cannizzo A, van Mourik F, Vlček A, Jr, Chergui M (2011) 133:305-315], a significant shortening of the intersystem crossing (ISC) time (<1 ps) from the lowest singlet to the lowest triplet state is found, allowing for a transfer of vibrational coherence, observed in the course of an ISC in a polyatomic molecule in solution. Density functional theory (DFT) quantum mechanical/molecular mechanical (QM/MM) simulations of Pt(pop) in acetonitrile and ethanol show that high-lying, mostly triplet, states are strongly mixed and shifted to lower energies due to interactions with the solvent, providing an intermediate state (or manifold of states) for the ISC. This suggests that the larger the solvation energies of the intermediate state(s), the shorter the ISC time. Because the latter is smaller than the pure dephasing time of the vibrational wave packet, coherence is conserved during the spin transition. These results underscore the crucial role of the solvent in directing pathways of intramolecular energy flow. |
| Author | Capano, Gloria Chergui, Majed Monni, Roberto Gray, Harry B Auböck, Gerald Tavernelli, Ivano Vlček, Antonín |
| Author_xml | – sequence: 1 givenname: Roberto surname: Monni fullname: Monni, Roberto organization: Laboratoire de Spectroscopie Ultrarapide, Lausanne Centre for Ultrafast Science, Institut des Sciences et Ingénierie Chimiques, School of Basic Sciences, Ecole Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland – sequence: 2 givenname: Gloria surname: Capano fullname: Capano, Gloria organization: Laboratoire de Spectroscopie Ultrarapide, Lausanne Centre for Ultrafast Science, Institut des Sciences et Ingénierie Chimiques, School of Basic Sciences, Ecole Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland – sequence: 3 givenname: Gerald surname: Auböck fullname: Auböck, Gerald organization: Laboratoire de Spectroscopie Ultrarapide, Lausanne Centre for Ultrafast Science, Institut des Sciences et Ingénierie Chimiques, School of Basic Sciences, Ecole Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland – sequence: 4 givenname: Harry B surname: Gray fullname: Gray, Harry B organization: Beckman Institute, California Institute of Technology, Pasadena, CA 91125 – sequence: 5 givenname: Antonín surname: Vlček fullname: Vlček, Antonín organization: J. Heyrovský Institute of Physical Chemistry, Czech Academy of Sciences, CZ-182 23 Prague, Czech Republic – sequence: 6 givenname: Ivano surname: Tavernelli fullname: Tavernelli, Ivano organization: Science & Technology Department, IBM Research GmbH, Zurich Research Laboratory, 8803 Rüschlikon, Switzerland – sequence: 7 givenname: Majed orcidid: 0000-0002-4856-226X surname: Chergui fullname: Chergui, Majed email: majed.chergui@epfl.ch organization: Laboratoire de Spectroscopie Ultrarapide, Lausanne Centre for Ultrafast Science, Institut des Sciences et Ingénierie Chimiques, School of Basic Sciences, Ecole Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland; majed.chergui@epfl.ch |
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| Keywords | intersystem crossing diplatinum complexes solvation vibrational coherence ultrafast |
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| Snippet | We investigate the ultrafast transient absorption response of tetrakis(μ-pyrophosphito)diplatinate(II), [Pt
(μ-P
O
H
)
]
[hereafter abbreviated Pt(pop)], in... We investigate the ultrafast transient absorption response of tetrakis(μ-pyrophosphito)diplatinate(II), [Pt2(μ-P2O5H2)4]4- [hereafter abbreviated Pt(pop)], in... |
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