Linking Electronic Relaxation Dynamics and Ionic Photofragmentation Patterns for the Deprotonated UV Filter Benzophenone-4

Natalie Wong; Conor Rankine; Caroline Elizabeth Helen Dessent

doi:10.1021/acs.jpclett.1c00423

Linking Electronic Relaxation Dynamics and Ionic Photofragmentation Patterns for the Deprotonated UV Filter Benzophenone-4

Natalie Wong, Conor Rankine, Caroline Elizabeth Helen Dessent

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

Understanding how deprotonation impacts on the photophysics of UV filters is critical to better characterize how they behave in key alkaline environments including surface waters and coral reefs. Using anion photodissociation spectroscopy, we have measured the intrinsic absorption electronic spectroscopy (400-214 nm) and numerous accompanying ionic photofragmentation pathways of the benzophenone-4 anion ([BP4–H]–). Relative ion yield plots reveal the locations of the bright S1 and S3 excited states. For the first time for an ionic UV filter, ab initio potential energy surfaces are presented to provide new insight into how the photofragment identity maps the relaxation pathways. These calculations reveal that [BP4–H]– undergoes excited-state decay consistent with a statistical fragmentation process where the anion breaks down on the ground state after non-radiative relaxation. The broader relevance of the results in providing a basis for interpreting the relaxation dynamics of a wide range ionic systems is discussed.

Original language	English
Pages (from-to)	2831-2836
Number of pages	6
Journal	JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume	12
Issue number	11
Early online date	2 Mar 2021
DOIs	https://doi.org/10.1021/acs.jpclett.1c00423
Publication status	Published - 15 Mar 2021

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acs.jpclett.1c00423
© 2021 The Authors. Published by American Chemical Society
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Cite this

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title = "Linking Electronic Relaxation Dynamics and Ionic Photofragmentation Patterns for the Deprotonated UV Filter Benzophenone-4",

abstract = "Understanding how deprotonation impacts on the photophysics of UV filters is critical to better characterize how they behave in key alkaline environments including surface waters and coral reefs. Using anion photodissociation spectroscopy, we have measured the intrinsic absorption electronic spectroscopy (400-214 nm) and numerous accompanying ionic photofragmentation pathways of the benzophenone-4 anion ([BP4–H]–). Relative ion yield plots reveal the locations of the bright S1 and S3 excited states. For the first time for an ionic UV filter, ab initio potential energy surfaces are presented to provide new insight into how the photofragment identity maps the relaxation pathways. These calculations reveal that [BP4–H]– undergoes excited-state decay consistent with a statistical fragmentation process where the anion breaks down on the ground state after non-radiative relaxation. The broader relevance of the results in providing a basis for interpreting the relaxation dynamics of a wide range ionic systems is discussed.",

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AU - Dessent, Caroline Elizabeth Helen

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N2 - Understanding how deprotonation impacts on the photophysics of UV filters is critical to better characterize how they behave in key alkaline environments including surface waters and coral reefs. Using anion photodissociation spectroscopy, we have measured the intrinsic absorption electronic spectroscopy (400-214 nm) and numerous accompanying ionic photofragmentation pathways of the benzophenone-4 anion ([BP4–H]–). Relative ion yield plots reveal the locations of the bright S1 and S3 excited states. For the first time for an ionic UV filter, ab initio potential energy surfaces are presented to provide new insight into how the photofragment identity maps the relaxation pathways. These calculations reveal that [BP4–H]– undergoes excited-state decay consistent with a statistical fragmentation process where the anion breaks down on the ground state after non-radiative relaxation. The broader relevance of the results in providing a basis for interpreting the relaxation dynamics of a wide range ionic systems is discussed.

AB - Understanding how deprotonation impacts on the photophysics of UV filters is critical to better characterize how they behave in key alkaline environments including surface waters and coral reefs. Using anion photodissociation spectroscopy, we have measured the intrinsic absorption electronic spectroscopy (400-214 nm) and numerous accompanying ionic photofragmentation pathways of the benzophenone-4 anion ([BP4–H]–). Relative ion yield plots reveal the locations of the bright S1 and S3 excited states. For the first time for an ionic UV filter, ab initio potential energy surfaces are presented to provide new insight into how the photofragment identity maps the relaxation pathways. These calculations reveal that [BP4–H]– undergoes excited-state decay consistent with a statistical fragmentation process where the anion breaks down on the ground state after non-radiative relaxation. The broader relevance of the results in providing a basis for interpreting the relaxation dynamics of a wide range ionic systems is discussed.

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