Excited state hydrogen transfer in fluorophenol.ammonia clusters studied by two-color REMPI spectroscopy
| Autor: | Claude Dedonder-Lardeux, Norihiro Tsuji, Christophe Jouvet, Makoto Sakai, Takayuki Ebata, Masaaki Fujii, Shun-ichi Ishiuchi |
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| Rok vydání: | 2006 |
| Předmět: |
rotational isomers
internal-rotation Hydrogen electronic-structure spectra Fluorine Compounds General Physics and Astronomy chemistry.chemical_element Color Photoionization Mass Spectrometry hypervalent molecular clusters Phenols Ammonia orbital calculations Ionization Cluster (physics) Molecule ion dip spectroscopy Physical and Theoretical Chemistry Spectroscopy pulsed-field ionization methyl-group phenol/ammonia clusters chemistry Excited state Mass spectrum Atomic physics |
| Zdroj: | Physical chemistry chemical physics : PCCP. 8(1) |
| ISSN: | 1463-9076 |
| Popis: | Two-color (1 + 1') REMPI mass spectra of o-, m- and p-fluorophenol.ammonia (1 ration) clusters were measured with a long delay time between excitation and ionization lasers. The appearance of NH(4)(NH(3))(n-1)(+) with 100 ns delay after exciting the S(1) state is a strong indication of generation of long-lived species via S(1). In analogy with the phenol.ammonia clusters, we conclude that an excited state hydrogen transfer reaction occurs in o-, m- and p-fluorophenol.ammonia clusters. The S(1)-S(0) transition of o-, m- and p-fluorophenol.ammonia (1 : 1) clusters were measured by the (1 + 1') REMPI spectra, while larger (1 ration) cluster (n = 2-4) were observed by monitoring the long-lived NH(4)(NH(3))(n-1) clusters action spectra. The vibronic structures of m- and p-fluorophenol.ammonia clusters are assigned based on vibrational calculations in S(0). The o-fluorophenol.ammonia (1 : 1) cluster shows an anharmonic progression that is analyzed by a one-dimensional internal rotational motion of the ammonia molecule. The interaction between the ammonia molecule and the fluorine atom, and its change upon electronic excitation are suggested. The broad action spectra observed for the o-fluorophenol.ammonia (1 : n) cluster (n== 2) suggest the excited state hydrogen transfer is faster than in m- and p-fluorophenol.ammonia clusters. The different reaction rates between o-, m- and p-fluorophenol.ammonia clusters are found from comparison between the REMPI and action spectra. |
| Databáze: | OpenAIRE |
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