Photodissociation of acetic acid in the gas phase was investigated using ab initio molecular orbital methods. The stationary structures on the ground-state potential energy surfaces were mainly optimized at the MP2 level of theory, while those on the excited-state surfaces were determined by complete active space SCF calculations with a correlation-consistent basis set of cc-pVDZ. The reaction pathways leading to different photoproducts are characterized on the basis of the computed potential energy surfaces and surface crossing points. The calculations reproduce the experimental results well and provide additional insight into the mechanism of the ultraviolet photodissociation of acetic acid and related compounds.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/jo020356o | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Dynamics of photodissociation of nitric oxide from -nitrosylated cysteine and -acetylated cysteine derivatives in water.
Phys Chem Chem Phys
June 2021
Department of Chemistry and Chemistry Institute for Functional Materials, Pusan National University, Busan 46241, Korea.
Cysteine and N-acetylated cysteine derivatives are ubiquitous in biological systems; they have thiol groups that bind NO to form S-nitrosothiols (RSNOs) such as S-nitrosocysteine (CySNO), S-nitroso-N-acetylcysteine (NacSNO), and S-nitroso-N-acetylpenicillamine (NapSNO). Although they have been utilised as thermally or catalytically decomposing NO donors, their photochemical applications are yet to be fully explored owing to the lack of photodissociation dynamics. To this end, the photoexcitation dynamics of these RSNOs in water at 330 nm were investigated using femtosecond time-resolved infrared (TRIR) spectroscopy over a broad time range encompassing the entire reaction, which includes the primary reaction, secondary reactions of the reaction intermediates, and product formation.
View Article and Find Full Text PDFProbing Elusive Cations: Infrared Spectroscopy of Protonated Acetic Acid.
J Phys Chem Lett
May 2019
Department of Chemistry , University of Leicester , University Road, Leicester LE1 7RH , U.K.
Protonated carboxylic acids, (RCOOH)H, are the initial intermediates in acid-catalyzed (Fischer) esterification reactions. However, the identity of the isomeric form has been debated. Surprisingly, no optical spectra have been reported for any isomer of the protonated carboxylic acid monomer, despite it being a fundamental organic cation.
View Article and Find Full Text PDFThe primary photo-dissociation dynamics of carboxylate anions in aqueous solution: decarboxylation.
Phys Chem Chem Phys
April 2019
Dept. of Chemistry, Aarhus University, Langelandsgade 140, DK-8000 Aarhus C, Denmark.
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.
View Article and Find Full Text PDFUV/Nitrilotriacetic Acid Process as a Novel Strategy for Efficient Photoreductive Degradation of Perfluorooctanesulfonate.
Environ Sci Technol
March 2018
Linde-Robinson Laboratories , California Institute of Technology, Pasadena , California 91125 , United States.
Perfluorooctanesulfonate (PFOS) is a toxic, bioaccumulative, and highly persistent anthropogenic chemical. Hydrated electrons ( e) are potent nucleophiles that can effectively decompose PFOS. In previous studies, e are mainly produced by photoionization of aqueous anions or aromatic compounds.
View Article and Find Full Text PDFA Novel Triethylphosphonium Charge Tag on Peptides: Synthesis, Derivatization, and Fragmentation.
J Am Soc Mass Spectrom
September 2017
Department of Chemistry, Indiana University, 800 East Kirkwood Ave., Bloomington, IN, 47405, USA.
Charge tagging is a peptide derivatization process that commonly localizes a positive charge on the N-terminus. Upon low energy activation (e.g.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!