Observing the Fluctuation Dynamics of Dative Bonds Using Two-Dimensional Electronic Spectroscopy
Thanh Nhut Do1, Jamie Hung Ni Sim1, Hoang Long Nguyen1
1Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore 637371.
Abstract:
We perform two-dimensional electronic spectroscopy on chlorophyll (Chl) a and b molecules in aprotic solvents of different Lewis basicity. By analyzing the ultrafast spectral diffusion dynamics of the Q transition, we show that a certain timescale of the spectral diffusion dynamics is affected by the solvents' Lewis basicity. Control experiments with Chlorin-e6-a Chl molecule analog-and ab initio time-dependent density functional theory calculations confirm that we are directly probing the fluctuation dynamics of the dative bond between the solvent's lone pair and the Mg2+ center in Chls that is responsible for the Lewis basicity. The observation is indicative of dative bond length and angular fluctuations with timescales ranging between ∼30 and 150 ps and the dative bond-strength-dependent perturbation on the Q transition frequency of Chls.
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