Vibrational coherence transfer in the ultrafast intersystem crossing of a diplatinum complex in solution
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F18%3A00490769" target="_blank" >RIV/61388955:_____/18:00490769 - isvavai.cz</a>
Result on the web
<a href="http://dx.doi.org/10.1073/pnas.1719899115" target="_blank" >http://dx.doi.org/10.1073/pnas.1719899115</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1073/pnas.1719899115" target="_blank" >10.1073/pnas.1719899115</a>
Alternative languages
Result language
angličtina
Original language name
Vibrational coherence transfer in the ultrafast intersystem crossing of a diplatinum complex in solution
Original language description
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.
Czech name
—
Czech description
—
Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
—
OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
<a href="/en/project/GA17-01137S" target="_blank" >GA17-01137S: Electron Transfer in (Bio)Molecular Systems: Time-Resolved Vibrational Spectroscopy and Theory</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2018
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Proceedings of the National Academy of Science of the United Stated of America
ISSN
1091-6490
e-ISSN
—
Volume of the periodical
115
Issue of the periodical within the volume
28
Country of publishing house
US - UNITED STATES
Number of pages
8
Pages from-to
"E6396"-"E6403"
UT code for WoS article
000438050900005
EID of the result in the Scopus database
2-s2.0-85049629783