A quantitative model of charge injection by ruthenium chromophores connecting femtosecond to continuous irradiance conditions

Cheshire, Thomas P.; Boodry, Jéa; Kober, Erin A.; Brennaman, M. Kyle; Giokas, Paul G.; Zigler, David F.; Moran, Andrew M.; Papanikolas, John M.; Meyer, Gerald J.; Meyer, Thomas J.; Houle, Frances A.

doi:10.1063/5.0127852

A quantitative model of charge injection by ruthenium chromophores connecting femtosecond to continuous irradiance conditions

Journal Article · Tue Dec 27 00:00:00 EST 2022 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/5.0127852· OSTI ID:1961826

^[1]; Boodry, Jéa ^[2]; Kober, Erin A. ^[3]; ^[3]; Giokas, Paul G. ^[4]; ^[5]; ^[3]; Papanikolas, John M. ^[3]; ^[3]; ^[3]; ^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Univ. of North Carolina, Chapel Hill, NC (United States)
Coherent Inc., Santa Clara, CA (United States)
California Polytechnic State Univ. (CalPoly), San Luis Obispo, CA (United States)

A kinetic framework for the ultrafast photophysics of tris(2,2-bipyridine)ruthenium(II) phosphonated and methyl-phosphonated derivatives is used as a basis for modeling charge injection by ruthenium dyes into a semiconductor substrate. By including the effects of light scattering, dye diffusion, and adsorption kinetics during sample preparation and the optical response of oxidized dyes, quantitative agreement with multiple transient absorption datasets is achieved on timescales spanning femtoseconds to nanoseconds. In particular, quantitative agreement with important spectroscopic handles—the decay of an excited state absorption signal component associated with charge injection in the UV region of the spectrum and the dynamical redshift of a ~500 nm isosbestic point—validates our kinetic model. Pseudo-first-order rate coefficients for charge injection are estimated in this work, with an order of magnitude ranging from 10¹¹ to 10¹² s^–1. The model makes the minimalist assumption that all excited states of a particular dye have the same charge injection coefficient, an assumption that would benefit from additional theoretical and experimental exploration. Here, we have adapted this kinetic model to predict charge injection under continuous solar irradiation and find that as many as 68 electron transfer events per dye per second take place, significantly more than prior estimates in the literature.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-05CH11231; SC0001011; SC0013461

OSTI ID:: 1961826

Alternate ID(s):: OSTI ID: 1906875

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 24 Vol. 157; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
adsorption
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stochastic simulations
thin films
transient absorption
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A quantitative model of charge injection by ruthenium chromophores connecting femtosecond to continuous irradiance conditions

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