Vibrational coherence transfer in the ultrafast intersystem crossing of a diplatinum complex in solution

Kód výsledku v 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>

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

Vibrational coherence transfer in the ultrafast intersystem crossing of a diplatinum complex in solution

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

Vibrational coherence transfer in the ultrafast intersystem crossing of a diplatinum complex in solution

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GA17-01137S" target="_blank" >GA17-01137S: Přenos elektronu v (bio)molekulárních systémech: časově rozlišená vibrační spektroskopie a teorie</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2018

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Proceedings of the National Academy of Science of the United Stated of America

ISSN

1091-6490

e-ISSN

—

Svazek periodika

115

Číslo periodika v rámci svazku

28

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

8

Strana od-do

"E6396"-"E6403"

Kód UT WoS článku

000438050900005

EID výsledku v databázi Scopus

2-s2.0-85049629783