Dynamics of ground and excited state chlorophylla molecules in pyridine solution probed by femtosecond transient absorption spectroscopy

Martinsson, Peter; Oksanen, J. A. I.; Hilgendorff, M.; Hynninen, Paavo H.; Sundström, Villy; Åkesson, Eva

doi:10.1016/s0009-2614(99)00710-1

Cited by 27 publications

(35 citation statements)

References 27 publications

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“…Early time DAS spectra at 490 nm excitation (Fig. 6Sa in ESM) show positive amplitudes (rise of ESA) around 652 nm most (Oksanen et al 1998;Martinsson et al 1999). Around 680 nm positive amplitudes (rise of Chl a bleach/stimulated emission, SE) appear at early times but turn into negative amplitudes at later times (decay of Chl a bleach/SE).…”

Section: Nm Excitationmentioning

confidence: 96%

Excitation energy transfer in the LHC-II trimer: from carotenoids to chlorophylls in space and time

et al. 2011

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Exciton model for description of experimentally determined excitation energy transfer from carotenoids to chlorophylls in the LHC-II trimer of spinach is presented. Such an approach allows connecting the excitonic states to the spatial structure of the complex and hence descriptions of advancements of the initially created excitations in space and time. Carotenoids were excited at 490 nm and at 500 nm and induced absorbance changes probed in the Chl Q(y) region to provide kinetic data that were interpreted by using the results from exciton calculations. Calculations included the 42 chlorophylls and the 12 carotenoids of the complex, Soret, Q(x) and Q(y) states of the chlorophylls, and the main absorbing S(2) state of the carotenoids. According to the calculations excitation at 500 nm populates mostly a mixed Lut S(2) Chl a Soret state, from where excitation is transferred to the Q(x) and Q(y) states of the Chl a's on the stromal side. Internal conversion of the mixed state to a mixed Lut S(1) and Chl a Q(y) state provides a channel for Lut S(1) to Chl a Q(y) energy transfer. The results from the calculations support a picture where excitation at 490 nm populates primarily a mixed neoxanthin S(2) Chl b Soret state. From this state excitation from neoxanthin is transferred to iso-energetic Chl b Soret states or via internal conversion to S(1) Chl b Q(y) states. From the Soret states excitation proceeds via internal conversion to Q(y) states of Chl b's mostly on the lumenal side. A rapid Chl b to Chl a transfer and subsequent transfer to the stromal side Chl a's and to the final state completes the process after 490 nm excitation. The interpretation is further supported by the fact that excitation energy transfer kinetics after excitation of neoxanthin at 490 nm and the Chl b Q(y) band at 647 nm (Linnanto et al., Photosynth Res 87:267-279, 2006) are very similar.

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Section: Nm Excitationmentioning

confidence: 96%

Excitation energy transfer in the LHC-II trimer: from carotenoids to chlorophylls in space and time

et al. 2011

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“…[19][20][21] A similar result was reported by Wells et al for the 2DES of Chl a in methanol and related observations were reported from hole-burning measurements by Sundstrom and coworkers. 9,12 The solvent dependence of spectral diffusion in Chl a will be investigated further below.…”

Section: B) 2des Reshapingmentioning

confidence: 99%

“…Early work by Sundstrom and co-workers revealed spectral hole burning in the Qy transition of Chl a in pyridine solution, indicating inhomogeneous broadening of this electronic transition. 9 In addition, picosecond kinetics were observed in pyridine and methanol solutions which occurred in addition to excited state population decay.…”

Section: Introductionmentioning

confidence: 99%

Two-Dimensional Electronic Spectroscopy of Chlorophyll a: Solvent Dependent Spectral Evolution

2015

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The interaction of the monomeric chlorophyll Q band electronic transition with solvents of differing physical-chemical properties is investigated through two-dimensional electronic spectroscopy (2DES). Chlorophyll constitutes the key chromophore molecule in light harvesting complexes. It is well known that the surrounding protein in the light harvesting complex fine tunes chlorophyll electronic transitions to optimize energy transfer. Therefore an understanding of the influence of the environment on the monomeric chlorophyll electronic transitions is important. The Q band 2DES are inhomogeneous at early times, particularly in hydrogen bonding polar solvents, but also in nonpolar solvents like cyclohexane. Interestingly this inhomogeneity persists for long times, even up to the nanosecond timescale in some solvents. The reshaping of the 2DES occurs over multiple timescales and was assigned mainly to spectral diffusion. At early times the reshaping is Gaussianlike, hinting at a strong solvent reorganization effect. The temporal evolution of the 2DES response was analysed in terms of a Brownian oscillator model. The spectral densities underpinning the Brownian oscillator fitting were recovered for the different solvents. The absorption spectra and Stokes shift were also properly described by this model. The extent and nature of inhomogeneous broadening was a strong function of solvent, being larger in H-bonding and viscous media and smaller in nonpolar solvents. The fastest spectral reshaping components were assigned to solvent dynamics, modified by interactions with the solute.

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“…Violaxanthin has 9 conjugated double bonds; antheraxanthin, 10; and zeaxanthin, 11. The lowest excited singlet state of violaxanthin thus lies above that of zeaxanthin by about 300 cm À1 [60][61][62]. Although the absolute energies are subject to some uncertainty, the excitation energy of violaxanthin is close to that of chlorophyll-a in its lowest excited singlet state.…”

Section: Energy Transfer To and From Carotenoids In Photosynthesismentioning

confidence: 93%

Resonance Energy Transfer

Parson

2015

Modern Optical Spectroscopy

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Dynamics of ground and excited state chlorophylla molecules in pyridine solution probed by femtosecond transient absorption spectroscopy

Cited by 27 publications

References 27 publications

Excitation energy transfer in the LHC-II trimer: from carotenoids to chlorophylls in space and time

Excitation energy transfer in the LHC-II trimer: from carotenoids to chlorophylls in space and time

Two-Dimensional Electronic Spectroscopy of Chlorophyll a: Solvent Dependent Spectral Evolution

Resonance Energy Transfer

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