The recently developed hierarchical equations of motion(HEOM)method is employed to study the dynamics,as well as linear and nonlinear spectra of molecular aggregates in photosynthetic systems.A brief introduction of t...
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The recently developed hierarchical equations of motion(HEOM)method is employed to study the dynamics,as well as linear and nonlinear spectra of molecular aggregates in photosynthetic systems.A brief introduction of the theoretical method and its application is first presented to show that,it is important to go beyond the commonly used second order perturbation approximation in the so called intermediate coupling *** will then focus on the recent developments in calculating the emission and pump-probe spectra,where arriving at the correct excited state equilibrium structure,and capturing the correct dynamics are both *** will also present recent works on applying the HEOM method effectively to general form of spectral densities,which opens the way to simulate a broad range of problems in condensed phase dynamics and spectroscopy.
Our density functional theory study reveals that the dehydrogenation of ethanol catalyzed by an aliphatic PNP pincer Ru complex,(PNP)Ru(H)CO{1Ru,PNP=bis[2-(diisopropylphosphino)-ethyl]amino},and its Fe analogue,(PNP)F...
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Our density functional theory study reveals that the dehydrogenation of ethanol catalyzed by an aliphatic PNP pincer Ru complex,(PNP)Ru(H)CO{1Ru,PNP=bis[2-(diisopropylphosphino)-ethyl]amino},and its Fe analogue,(PNP)Fe(H)CO(1Fe),proceed via a self-promotion mechanism that features an ethanol molecule acting as a bridge to assist the transfer of a proton from ligand nitrogen to the metal center for the formation of *** calculated total free energy barrier of ethanol dehydrogenation catalyzed by 1Fe is only 22.1 kcal/mol,which is even 0.7 kcal/mol lower than the calculated total free energy barrier of the reaction catalyzed by 1Ru(Figure 1).Therefore,the potential of 1Fe as a low-cost and high-efficiency catalyst for the production of hydrogen from ethanol is promising.1 A recent experimental study of Beller and co-workers has confirmed 1Fe is an active catalyst for the dehydrogenation of methanol under mild condition.2 In addition to the finding of above self-promoted dehydrogenation mechanism for the aliphatic pincer complexes,the very different catalytic properties between the in ruthenium complexes with aromatic and aliphatic pincer ligands are analyzed based on our calculation results.
Our density functional theory study reveals that the dehydrogenation of ethanol catalyzed by an aliphatic PNP pincer Ru complex,(PNP)Ru(H)CO {1Ru,PNP = bis[2-(diisopropylphosphino)-ethyl]amino},and its Fe analogue,(PN...
Our density functional theory study reveals that the dehydrogenation of ethanol catalyzed by an aliphatic PNP pincer Ru complex,(PNP)Ru(H)CO {1Ru,PNP = bis[2-(diisopropylphosphino)-ethyl]amino},and its Fe analogue,(PNP)Fe(H)CO(1Fe),proceed via a self-promotion mechanism that features an ethanol molecule acting as a bridge to assist the transfer of a proton from ligand nitrogen to the metal center for the formation of *** calculated total free energy barrier of ethanol dehydrogenation catalyzed by 1Fe is only 22.1 kcal/mol,which is even 0.7 kcal/mol lower than the calculated total free energy barrier of the reaction catalyzed by 1Ru(Figure 1).Therefore,the potential of 1Fe as a low-cost and high-efficiency catalyst for the production of hydrogen from ethanol is promising.1 A recent experimental study of Beller and co-workers has confirmed 1Fe is an active catalyst for the dehydrogenation of methanol under mild condition.2 In addition to the finding of above self-promoted dehydrogenation mechanism for the aliphatic pincer complexes,the very different catalytic properties between the in ruthenium complexes with aromatic and aliphatic pincer ligands are analyzed based on our calculation results.
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