Hole-Burning Spectra of m-Fluorophenol/Ammonia (1:3) Clusters and Their Excited State Hydrogen Transfer Dynamics
| Autor: | Tsuji, N., Ishiuchi, Shun-ichi, Jouvet, C., Dedonder-Lardeux, C., Miyazaki, M., Sakai, M., Fujii, M. |
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| Jazyk: | angličtina |
| Rok vydání: | 2011 |
| Předmět: |
Reaction mechanism
phenol ammonia clusters Photochemistry Reaction rate ion dip spectroscopy Physical and Theoretical Chemistry Spectroscopy mass spectrometry Hydrogen bond Chemistry photodissociation dynamics Rate equation phenol/ammonia clusters Atomic and Molecular Physics and Optics proton-transfer reaction mechanisms substituted phenols molecular-orbital calculations picosecond measurements Excited state hydrogen bonds laser spectroscopy cluster compounds near-uv photolysis Atomic physics photoelectron-spectroscopy Isomerization Cis–trans isomerism |
| Zdroj: | Chemphyschem. 12(No. 10):1928-1934 |
| Popis: | Hole-burning spectra of m-fluorophenol/ammonia (1:3) clusters are measured by four-color UV-near IR-UV-UV hole-burning spectroscopy. Cis and trans isomers of the cluster are clearly distinguished in the (1:3) cluster. Picosecond time evolutions of the excited state hydrogen transfer (ESHT) reaction in the (1:3) clusters are measured by the ion depletion due to 3p-3s Rydberg transition of reaction products ⋅NH(4)(NH(3))(2) lying in the near infrared region. From the wavelength dependence of the time evolution, we have concluded 1) the initial formation of a metastable ⋅NH(4)-NH(3)-NH(3) radical and 2) successive isomerization to the most stable NH(3)-⋅NH(4) -NH(3) radical in both cis and trans isomers. The reaction lifetimes of ESHT are determined by the rate equation analysis as 32.4 and 31.8 ps for the cis and trans isomer, respectively, and the isomerization and its back-reaction lifetime of both isomers are determined to be 3.3 ps and 11.2 ps. The almost same reaction rates are consistent with the similarity of the hydrogen bond networks in both clusters. |
| Databáze: | OpenAIRE |
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