UCL Discovery
UCL home » Library Services » Electronic resources » UCL Discovery

Unraveling the Ultrafast Photochemical Dynamics of Nitrobenzene in Aqueous Solution

Lau, Nicholas A; Ghosh, Deborin; Bourne-Worster, Susannah; Kumar, Rhea; Whitaker, William A; Heitland, Jonas; Davies, Julia A; ... Fielding, Helen H; + view all (2024) Unraveling the Ultrafast Photochemical Dynamics of Nitrobenzene in Aqueous Solution. Journal of the American Chemical Society 10.1021/jacs.3c13826. (In press). Green open access

[thumbnail of Published article]
Preview
Text (Published article)
lau-et-al-2024-unraveling-the-ultrafast-photochemical-dynamics-of-nitrobenzene-in-aqueous-solution.pdf

Download (2MB) | Preview
[thumbnail of Supporting information]
Preview
Text (Supporting information)
NB-SI-final.pdf - Accepted Version

Download (30MB) | Preview

Abstract

Nitroaromatic compounds are major constituents of the brown carbon aerosol particles in the troposphere that absorb near-ultraviolet (UV) and visible solar radiation and have a profound effect on the Earth’s climate. The primary sources of brown carbon include biomass burning, forest fires, and residential burning of biofuels, and an important secondary source is photochemistry in aqueous cloud and fog droplets. Nitrobenzene is the smallest nitroaromatic molecule and a model for the photochemical behavior of larger nitroaromatic compounds. Despite the obvious importance of its droplet photochemistry to the atmospheric environment, there have not been any detailed studies of the ultrafast photochemical dynamics of nitrobenzene in aqueous solution. Here, we combine femtosecond transient absorption spectroscopy, time-resolved infrared spectroscopy, and quantum chemistry calculations to investigate the primary steps following the near-UV (λ ≥ 340 nm) photoexcitation of aqueous nitrobenzene. To understand the role of the surrounding water molecules in the photochemical dynamics of nitrobenzene, we compare the results of these investigations with analogous measurements in solutions of methanol, acetonitrile, and cyclohexane. We find that vibrational energy transfer to the aqueous environment quenches internal excitation, and therefore, unlike the gas phase, we do not observe any evidence for formation of photoproducts on timescales up to 500 ns. We also find that hydrogen bonding between nitrobenzene and surrounding water molecules slows the S1/S0 internal conversion process.

Type: Article
Title: Unraveling the Ultrafast Photochemical Dynamics of Nitrobenzene in Aqueous Solution
Open access status: An open access version is available from UCL Discovery
DOI: 10.1021/jacs.3c13826
Publisher version: http://dx.doi.org/10.1021/jacs.3c13826
Language: English
Additional information: Copyright © 2024 The Authors. This publication is licensed under CC-BY 4.0.
UCL classification: UCL
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry
URI: https://discovery.ucl.ac.uk/id/eprint/10190358
Downloads since deposit
Loading...
55Downloads
Download activity - last month
Loading...
Download activity - last 12 months
Loading...
Downloads by country - last 12 months
Loading...

Archive Staff Only

View Item View Item