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Vibrational coherence transfer in the ultrafast intersystem crossing of a diplatinum complex in solution
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SYSNO ASEP 0490769 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title Vibrational coherence transfer in the ultrafast intersystem crossing of a diplatinum complex in solution Author(s) Monni, R. (CH)
Capano, G. (CH)
Auböck, G. (CH)
Gray, H. B. (US)
Vlček, Antonín (UFCH-W) RID, ORCID
Tavernelli, I. (CH)Source Title Proceedings of the National Academy of Sciences of the United States of America. - : National Academy of Sciences - ISSN 0027-8424
Roč. 115, č. 28 (2018), E6396-E6403Number of pages 8 s. Language eng - English Country US - United States Keywords ultrafast ; intersystem crossing ; vibrational coherence Subject RIV CF - Physical ; Theoretical Chemistry OECD category Physical chemistry R&D Projects GA17-01137S GA ČR - Czech Science Foundation (CSF) Method of publishing Open access Institutional support UFCH-W - RVO:61388955 UT WOS 000438050900005 EID SCOPUS 85049629783 DOI https://doi.org/10.1073/pnas.1719899115 Annotation We investigate the ultrafast transient absorption response of tetrakis(mu-pyrophosphito) diplatinate(II), [Pt-2(mu-P2O5H2)(4)](4-) [hereafter abbreviated Pt(pop)], in acetonitrile upon excitation of its lowest singlet (1)A(2u) state. Compared with previously reported solvents [van der Veen RM, Cannizzo A, vanMourik F, Vlcek A, Jr, CherguiM(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. Workplace J. Heyrovsky Institute of Physical Chemistry Contact Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Year of Publishing 2019
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