Two‐Photon Voltmeter for Measuring a Molecular Electric Field |
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| Authors: | Dr. Aleksander Rebane Geoffrey Wicks Dr. Mikhail Drobizhev Dr. Thomas Cooper Aleksander Trummal Dr. Merle Uudsemaa |
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| Affiliation: | 1. Deptartment of Physics, Montana State University, 264 EPS, Bozeman, MT 59717 (USA);2. National Institute of Chemical Physics and Biophysics, Tallinn (Estonia);3. Air Force Research Lab, Wright Patterson Air Force Base, Dayton, OH (USA);4. Tallinn Institute of Technology, Tallinn (Estonia) |
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| Abstract: | We present a new approach for determining the strength of the dipolar solute‐induced reaction field, along with the ground‐ and excited‐state electrostatic dipole moments and polarizability of a solvated chromophore, using exclusively one‐photon and two‐photon absorption measurements. We verify the approach on two benchmark chromophores N,N‐dimethyl‐6‐propionyl‐2‐naphthylamine (prodan) and coumarin 153 (C153) in a series of toluene/dimethyl sulfoxide (DMSO) mixtures and find that the experimental values show good quantitative agreement with literature and our quantum‐chemical calculations. Our results indicate that the reaction field varies in a surprisingly broad range, 0–107 V cm?1, and that at close proximity, on the order of the chromophore radius, the effective dielectric constant of the solute–solvent system displays a unique functional dependence on the bulk dielectric constant, offering new insight into the close‐range molecular interaction. |
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| Keywords: | intramolecular charge transfer molecular reaction field solvatochromism solvent effects two‐photon absorption spectroscopy |
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