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Two‐Photon Voltmeter for Measuring a Molecular Electric Field
Author(s) -
Rebane Aleksander,
Wicks Geoffrey,
Drobizhev Mikhail,
Cooper Thomas,
Trummal Aleksander,
Uudsemaa Merle
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201502157
Subject(s) - chromophore , polarizability , chemistry , excited state , dipole , dielectric , electric field , oscillator strength , solvatochromism , molecular orbital , two photon absorption , chemical physics , photochemistry , computational chemistry , molecular physics , solvent , atomic physics , materials science , molecule , optoelectronics , organic chemistry , physics , optics , quantum mechanics , spectral line , laser
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, 0–10 7 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.