The primary photo-dissociation dynamics of carboxylate anions in aqueous solution: decarboxylation

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The primary photo-dissociation dynamics of carboxylate anions in aqueous solution: decarboxylation. / Madsen, Marlene Møller; Jensen, Frank; Jensen, Svend Knak; Thøgersen, Jan.

In: Physical Chemistry Chemical Physics, Vol. 21, No. 14, 2019, p. 7358-7366.

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@article{06e40bef02d443008d17707dd6dd3118,
title = "The primary photo-dissociation dynamics of carboxylate anions in aqueous solution: decarboxylation",
abstract = "We study the primary photo-dissociation of aqueous anions of formic, acetic and propionic acids induced by photo-excitation at 200 nm. The photo-dissociation dynamics are recorded with sub-picosecond time resolution by UV pump-IR probe transient absorption spectroscopy. Hundred picoseconds after the excitation, 47 ± 5% of the excited formate anions, 35 ± 5% of the excited acetate anions and 27 ± 5% of the excited propionate anions are dissociated, while the rest of the excited molecules return to the electronic ground state of the parent anion. Photo-dissociation of the three anions produces CO 2 (aq) through a precursor with a lifetime of approximately 20 ps. The precursor is assigned to the excited state of the parent anion based on comparison with calculated IR spectra and isotope shifts. Of the molecules that remain dissociated after 100 ps, the percentage leading to the production of CO 2 (aq) is 7 ± 3%, 48 ± 20% and 92 ± 30% for formate, acetate and propionate, respectively, while photo-dissociation of formate in addition leads to formation of CO 2 - . Decarboxylation is thus the dominating reaction channel in acetate and propionate, and this suggests formation of CH 4 and C 2 H 6 when the initially formed anions are protonated by water. ",
keywords = "ACID, MOLECULES, PHOTOCHEMISTRY, SPECTRUM",
author = "Madsen, {Marlene M{\o}ller} and Frank Jensen and Jensen, {Svend Knak} and Jan Th{\o}gersen",
year = "2019",
doi = "10.1039/c8cp07621a",
language = "English",
volume = "21",
pages = "7358--7366",
journal = "Physical Chemistry Chemical Physics",
issn = "1463-9076",
publisher = "ROYAL SOC CHEMISTRY",
number = "14",

}

RIS

TY - JOUR

T1 - The primary photo-dissociation dynamics of carboxylate anions in aqueous solution: decarboxylation

AU - Madsen, Marlene Møller

AU - Jensen, Frank

AU - Jensen, Svend Knak

AU - Thøgersen, Jan

PY - 2019

Y1 - 2019

N2 - We study the primary photo-dissociation of aqueous anions of formic, acetic and propionic acids induced by photo-excitation at 200 nm. The photo-dissociation dynamics are recorded with sub-picosecond time resolution by UV pump-IR probe transient absorption spectroscopy. Hundred picoseconds after the excitation, 47 ± 5% of the excited formate anions, 35 ± 5% of the excited acetate anions and 27 ± 5% of the excited propionate anions are dissociated, while the rest of the excited molecules return to the electronic ground state of the parent anion. Photo-dissociation of the three anions produces CO 2 (aq) through a precursor with a lifetime of approximately 20 ps. The precursor is assigned to the excited state of the parent anion based on comparison with calculated IR spectra and isotope shifts. Of the molecules that remain dissociated after 100 ps, the percentage leading to the production of CO 2 (aq) is 7 ± 3%, 48 ± 20% and 92 ± 30% for formate, acetate and propionate, respectively, while photo-dissociation of formate in addition leads to formation of CO 2 - . Decarboxylation is thus the dominating reaction channel in acetate and propionate, and this suggests formation of CH 4 and C 2 H 6 when the initially formed anions are protonated by water.

AB - We study the primary photo-dissociation of aqueous anions of formic, acetic and propionic acids induced by photo-excitation at 200 nm. The photo-dissociation dynamics are recorded with sub-picosecond time resolution by UV pump-IR probe transient absorption spectroscopy. Hundred picoseconds after the excitation, 47 ± 5% of the excited formate anions, 35 ± 5% of the excited acetate anions and 27 ± 5% of the excited propionate anions are dissociated, while the rest of the excited molecules return to the electronic ground state of the parent anion. Photo-dissociation of the three anions produces CO 2 (aq) through a precursor with a lifetime of approximately 20 ps. The precursor is assigned to the excited state of the parent anion based on comparison with calculated IR spectra and isotope shifts. Of the molecules that remain dissociated after 100 ps, the percentage leading to the production of CO 2 (aq) is 7 ± 3%, 48 ± 20% and 92 ± 30% for formate, acetate and propionate, respectively, while photo-dissociation of formate in addition leads to formation of CO 2 - . Decarboxylation is thus the dominating reaction channel in acetate and propionate, and this suggests formation of CH 4 and C 2 H 6 when the initially formed anions are protonated by water.

KW - ACID

KW - MOLECULES

KW - PHOTOCHEMISTRY

KW - SPECTRUM

UR - http://www.scopus.com/inward/record.url?scp=85063996414&partnerID=8YFLogxK

U2 - 10.1039/c8cp07621a

DO - 10.1039/c8cp07621a

M3 - Journal article

C2 - 30899923

VL - 21

SP - 7358

EP - 7366

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 14

ER -