We show that underdamped molecular vibrations fuel the efficient excitation energy transfer in the Fenna-Matthews-Olson molecular aggregate under realistic physiological conditions. By employing an environmental fluctuation spectral function derived from experiments, we obtain numerically exact results for the exciton quantum dynamics in the presence of underdamped vibrationally coherent quantum states. Assuming the prominent 180-cm(-1) vibrational mode to be underdamped, additional coherent transport channels for the excitation energy transfer open up and we observe an increase of the transfer speed towards the reaction center by up to 24%.
The excitation energy transfer dynamics in the Fenna-Matthews-Olson complex is quantified in terms of a non-Markovianity measure based on the time evolution of the trace distance of two quantum states. We use a system description derived from experiments and different environmental fluctuation spectral functions, which are obtained either from experimental data or from molecular dynamics simulations. These exhibit, in all cases, a nontrivial structure with several peaks attributed to vibrational modes of the pigment-protein complex. Such a structured environmental spectrum can, in principle, give rise to strong non-Markovian effects. We present numerically exact real-time path-integral calculations for the transfer dynamics and find, in all cases, a monotonic decrease of the trace distance with increasing time which renders a Markovian description valid.
In
this work, the effect of temperature on the electro-oxidation
of formic acid on platinum was modeled and numerically investigated.
Numerical simulations were carried out using an electrokinetic model
recently validated through voltammetric and galvanostatic experiments.
We show that the intrinsic electrocatalytic activity of the working
electrode for the overall electrochemical reaction can hardly be interpreted
from the apparent activation energy due to the complexity of the reaction
scheme. A detailed analysis is possible through the estimation of
the activation energies determined from the individual rate coefficients.
By doing so, we observed that the direct pathway, with an activation
energy of 91 kJ mol–1 at 0.40 V and 72 kJ mol–1 at 0.80 V, is the energetically easiest pathway for
the formation of CO2 in the proposed reaction scheme. Regarding
the self-organized potential oscillations under the galvanostatic
regime, our model was able to reproduce experimentally observed results
including the phenomena of temperature compensation and overcompensation.
Importantly, we have introduced a formalism to classify the elementary
steps that contribute to the increase and decrease of the oscillatory
frequency in electrochemical systems. Our results shed light on the
understanding of the temperature dependence of complex electrocatalytic
reactions, and the developed methodology was proven to be robust and
of general applicability.
A Pd(II)-catalyzed C(sp 2 /sp 3 )À H bond arylation protocol has been developed to access ortho-diaryl, ortho-mono-aryl, and biaryldiarylmethane-glycinamide derivatives bearing picolinamide as directing group. Mechanistic details of the process have been obtained by computational modelling of the activation reaction through DFT calculations.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.