Plackett, E;
Robertson, C;
De Matos Loja, A;
McGhee, H;
Karras, G;
Sazanovich, IV;
Ingle, RA;
... Minns, RS; + view all
(2024)
Structural dynamics around a hydrogen bond: Investigating the effect of hydrogen bond strengths on the excited state dynamics of carboxylic acid dimers.
The Journal of Chemical Physics
, 160
(12)
, Article 124311. 10.1063/5.0192407.
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Abstract
The photochemical dynamics of the acetic acid and trifluoro-acetic acid dimers in hexane are studied using time-resolved infrared absorption spectroscopy and ab initio electronic structure calculations. The different hydrogen bond strengths of the two systems lead to changes in the character of the accessed excited states and in the timescales of the initial structural rearrangement that define the early time dynamics following UV excitation. The much stronger hydrogen bonding in the acetic acid dimer stabilizes the system against dissociation. Ground state recovery is mediated by a structural buckling around the hydrogen bond itself with no evidence for excited state proton transfer processes that are usually considered to drive ultrafast relaxation processes in hydrogen bonded systems. The buckling of the ring leads to relaxation through two conical intersections and the eventual reformation of the electronic and vibrational ground states on a few picosecond timescale. In trifluoro-acetic acid, the weaker hydrogen bonding interaction means that the dimer dissociates under similar irradiation conditions. The surrounding solvent cage restricts the full separation of the monomer components, meaning that the dimer is reformed and returns to the ground state structure via a similar buckled structure but over a much longer, ∼100 ps, timescale.
| Type: | Article |
|---|---|
| Title: | Structural dynamics around a hydrogen bond: Investigating the effect of hydrogen bond strengths on the excited state dynamics of carboxylic acid dimers |
| Location: | United States |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1063/5.0192407 |
| Publisher version: | http://dx.doi.org/10.1063/5.0192407 |
| Language: | English |
| Additional information: | This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third-party material in this article are included in the Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/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-pp.ucl.ac.uk/id/eprint/10190109 |
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