Ultrafast energy transfer dynamics of a bioinspired dyad molecule

Janne Savolainen, Niels Dijkhuizen, Riccardo Fanciulli, Paul A. Liddell, Devens Gust, Thomas Moore, Ana Moore, Jürgen Hauer, Tiago Buckup, Marcus Motzkus, Jennifer L. Herek

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

A caroteno-purpurin dyad molecule was studied by steady-state and pump-probe spectroscopies to resolve the excited-state deactivation dynamics of the different energy levels as well as the connecting energy flow pathways and corresponding rate constants. The data were analyzed with a two-step multi-parameter global fitting procedure that makes use of an evolutionary algorithm. We found that following ultrafast excitation of the donor (carotenoid) chromophore to its S2 state, the energy flows via two channels: energy transfer (70%) and internal conversion (30%) with time constants of 54 and 110 fs, respectively. Additionally, some of the initial excitation is found to populate the hot ground state, revealing another limitation to the functional efficiency. At later times, a back transfer occurs from the purpurin to the carotenoid triplet state in nanosecond timescales. Details of the energy flow within the dyad as well as species associated spectra are disentangled for all excited-state and ground-state species for the first time. We also observe oscillations with the most pronounced peak on the Fourier transform spectrum having a frequency of 530 cm-1. The dyad mimics the dynamics of the natural light-harvesting complex LH2 from Rhodopseudomonas acidophila and is hence a good model system to be used in studies aimed to further explain previous work in which the branching ratio between the competing pathways of energy loss and energy transfer could be manipulated by adaptive femtosecond pulse shaping.

Original languageEnglish (US)
Pages (from-to)2678-2685
Number of pages8
JournalJournal of Physical Chemistry B
Volume112
Issue number9
DOIs
StatePublished - Mar 6 2008

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Carotenoids
Excited states
Energy transfer
Ground state
energy transfer
Pulse shaping
carotenoids
Molecules
Chromophores
Ultrashort pulses
Evolutionary algorithms
Electron energy levels
excitation
molecules
Rate constants
Energy dissipation
Fourier transforms
Pumps
Spectroscopy
ground state

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Savolainen, J., Dijkhuizen, N., Fanciulli, R., Liddell, P. A., Gust, D., Moore, T., ... Herek, J. L. (2008). Ultrafast energy transfer dynamics of a bioinspired dyad molecule. Journal of Physical Chemistry B, 112(9), 2678-2685. https://doi.org/10.1021/jp0757199

Ultrafast energy transfer dynamics of a bioinspired dyad molecule. / Savolainen, Janne; Dijkhuizen, Niels; Fanciulli, Riccardo; Liddell, Paul A.; Gust, Devens; Moore, Thomas; Moore, Ana; Hauer, Jürgen; Buckup, Tiago; Motzkus, Marcus; Herek, Jennifer L.

In: Journal of Physical Chemistry B, Vol. 112, No. 9, 06.03.2008, p. 2678-2685.

Research output: Contribution to journalArticle

Savolainen, J, Dijkhuizen, N, Fanciulli, R, Liddell, PA, Gust, D, Moore, T, Moore, A, Hauer, J, Buckup, T, Motzkus, M & Herek, JL 2008, 'Ultrafast energy transfer dynamics of a bioinspired dyad molecule', Journal of Physical Chemistry B, vol. 112, no. 9, pp. 2678-2685. https://doi.org/10.1021/jp0757199
Savolainen J, Dijkhuizen N, Fanciulli R, Liddell PA, Gust D, Moore T et al. Ultrafast energy transfer dynamics of a bioinspired dyad molecule. Journal of Physical Chemistry B. 2008 Mar 6;112(9):2678-2685. https://doi.org/10.1021/jp0757199
Savolainen, Janne ; Dijkhuizen, Niels ; Fanciulli, Riccardo ; Liddell, Paul A. ; Gust, Devens ; Moore, Thomas ; Moore, Ana ; Hauer, Jürgen ; Buckup, Tiago ; Motzkus, Marcus ; Herek, Jennifer L. / Ultrafast energy transfer dynamics of a bioinspired dyad molecule. In: Journal of Physical Chemistry B. 2008 ; Vol. 112, No. 9. pp. 2678-2685.
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