Issue 40, 2022

The primary photo-dissociation dynamics of aqueous formamide and dimethylformamide

Abstract

We study the primary dissociation dynamics of aqueous formamide (HCONH2) and dimethylformamide (HCON(CH3)2) induced by photo-excitation at λ = 200 nm. The photolysis is recorded with sub-picosecond time resolution by UV pump–IR probe transient absorption spectroscopy. Formamide dissociates with a quantum yield of Φ(t = 20 ps) = 0.30 ± 0.05, t = 20 ps after the excitation. The rest of the excited formamide molecules return to the ground state within t = 1 ps and vibrationally relax towards equilibrium in t ≈ 10 ps. The only product observed is NH3. NH3 is produced with a yield of Φ(NH3) = 0.23 ± 0.10 on a timescale of τ = 3 ± 1 ps and likely constitutes the dominating product. The CO counter product to NH3 is not observed. Dimethylformamide is photolysed with a quantum yield of Φ(t = 30 ps) = 0.29 ± 0.05, t = 30 ps after the excitation. The photolysis of dimethylformamide produces CO on a time scale of τ ≈ 30 ps. The data indicate that dimethylamine and the N(CH3)2 radical are likely photoproducts.

Graphical abstract: The primary photo-dissociation dynamics of aqueous formamide and dimethylformamide

Supplementary files

Article information

Article type
Paper
Submitted
11 Jul 2022
Accepted
30 Aug 2022
First published
30 Aug 2022

Phys. Chem. Chem. Phys., 2022,24, 24695-24705

The primary photo-dissociation dynamics of aqueous formamide and dimethylformamide

J. Thøgersen, T. Weidner and F. Jensen, Phys. Chem. Chem. Phys., 2022, 24, 24695 DOI: 10.1039/D2CP03166C

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