Photodissociation of phenol at 248 nm was studied using multimass ion imaging techniques. Photofragment translational energy distribution of H atom elimination was measured. The results demonstrate that H atom elimination occurs on the pi sigma(*) excited state which has repulsive potential-energy functions with respect to the stretching of OH bond. It supports the recent ab initio calculation.
The photodissociation of phenol at 193 and 248 nm was studied using multimass ion-imaging techniques and step-scan time-resolved Fourier-transform spectroscopy. The major dissociation channels at 193 nm include cleavage of the OH bond, elimination of CO, and elimination of H(2)O. Only the former two channels are observed at 248 nm. The translational energy distribution shows that H-atom elimination occurs in both the electronically excited and ground states, but elimination of CO or H(2)O occurs in the electronic ground state. Rotationally resolved emission spectra of CO (1
Several Rhodopseudomonas palustris strains have been isolated from rice paddy fields in Taiwan by combining the Winogradsky column method and molecular marker detection. These isolates were initially screened by employing seed germination and seedling vigor assays to evaluate their potential as inoculants. To fulfill the demand in the present farming system for reducing the application of chemical fertilizers, we assessed the plant growth-promoting effects of the R. palustris YSC3, YSC4, and PS3 inoculants on Brassica rapa chinensis (Chinese cabbage) cultivated under a half quantity of fertilizer. The results obtained showed that supplementation with approximately 4.0×106 CFU g−1 soil of the PS3 inoculant at half the amount of fertilizer consistently produced the same plant growth potential as 100% fertility, and also increased the nitrogen use efficiency of the applied fertilizer nutrients. Furthermore, we noted that the plant growth-promotion rate elicited by PS3 was markedly higher with old seeds than with new seeds, suggesting it has the potential to boost the development of seedlings that were germinated from carry-over seeds of poor quality. These beneficial traits suggest that the PS3 isolate may serve as a potential PGPR inoculant for integrated nutrient management in agriculture.
Photodissociation of pyridine, 2,6-d2-pyridine, and d5-pyridine at 193 and 248 nm was investigated separately using multimass ion imaging techniques. Six dissociation channels were observed at 193 nm, including C5NH5 --> C5NH4 + H (10%) and five ring opening dissociation channels, C5NH5 --> C4H4 + HCN, C5NH5 --> C3H3 + C2NH2, C5NH5 --> C2H4 +C3NH, C5NH5 --> C4NH2 + CH3 (14%), and C5NH5 --> C2H2 + C3NH3. Extensive H and D atom exchanges of 2,6-d2-pyridine prior to dissociation were observed. Photofragment translational energy distributions and dissociation rates indicate that dissociation occurs in the ground electronic state after internal conversion. The dissociation rate of pyridine excited by 248-nm photons was too slow to be measured, and the upper limit of the dissociation rate was estimated to be 2x10(3) s(-1). Comparisons with potential energies obtained from ab initio calculations and dissociation rates obtained from the Rice-Ramsperger-Kassel-Marcus theory have been made.
Photodissociation experiments employing molecular beams of N-methylindole, N-methylpyrrole, and anisole at 193 and 248 nm, respectively, have been conducted using multimass ion imaging techniques. We find that CH3 elimination is the sole dissociation channel for the studied molecules at both 193 and 248 nm. The photofragment translational energy distribution of anisole is found to contain both fast and slow components at the two wavelengths. On the other hand, a fast component (large recoil velocity) is dominant for N-methylindole at 248 nm, and a slow component (small recoil velocity) is dominant at 193 nm. The absorption coefficient of N-methylpyrrole is too weak for study at 248 nm. The photofragment translational energy distribution at 193 nm includes a large portion of the slow component and a small portion of the fast component. The findings indicate that the fast component corresponds to dissociation from the repulsive excited state and the slow component corresponding to dissociation from the ground electronic state. A comparison with the photodissociation dynamics of phenol, pyrrole, and indole suggests that replacement of the H atom by CH3 does not change the dissociation channels on the excited state. However, the respective dissociation channels for anisole and N-methylpyrrole on the ground state differ significantly from that for phenol and pyrrole.
Photoelectron spectroscopy has been performed to study the multiphoton double ionization of Ar in an intense extreme ultraviolet laser field (hν ∼ 21 eV, ∼ 5 TW/cm²), by using a free electron laser (FEL). Three distinct peaks identified in the observed photoelectron spectra clearly show that the double ionization proceeds sequentially via the formation of Ar(+): Ar+hν→Ar (+) + e⁻ and Ar²(+) + 2hν→Ar(+) + e⁻. Shot-by-shot recording of the photoelectron spectra allows simultaneous monitoring of FEL spectrum and the multiphoton process for each FEL pulse, revealing that the two-photon ionization from Ar(+) is significantly enhanced by intermediate resonances in Ar(+).
The photodissociation of p-methylphenol, p-ethylphenol, and p-(2-aminoethyl)phenol, chromophores of the amino acid tyrosine, was studied separately for each compound in a molecular beam at 248 nm using multimass ion imaging techniques. They show interesting side-chain size-dependent dissociation properties. Only one dissociation channel, that is, H atom elimination, was observed for both p-methylphenol and p-ethylphenol. The photofragment translational energy distributions and potential energy surfaces from ab initio calculation suggest that H atom elimination occurs from a repulsive excited state. On the other hand, the H atom elimination channel is quenched completely by internal conversion and/or intersystem crossing in p-(2-aminoethyl)phenol. Only C-C bond cleavage was observed from p-(2-aminoethyl)phenol. The photofragment translational energy distribution shows a slow component and a fast component. The fast component results from dissociation on an electronic excited state, but the slow component occurs only after the internal conversion to the ground electronic state. Comparison with the photodissociation of phenol and ethylbenzene is made.
The photodissociation dynamics of various aromatic molecules, studied using multimass ion imaging techniques, is reviewed. The experimental data reveals new isomerization and dissociation mechanisms. Our investigation of benzene, pyridine, and pyrimidine finds that H-atom elimination thresholds remain the same for the three molecules. We also notice that ring-opening dissociation thresholds decrease rapidly with the increase of the number of nitrogen atoms in the aromatic ring. Hydrogen atom elimination is the sole dissociation channel for benzene at 193 nm. Along with H-atom elimination, we observe five distinct ring-opening dissociation channels for pyridine at 193 nm. No dissociation channels were observed for benzene and pyridine at 248 nm. Ring-opening dissociation channels are the major channels for pyrimidine, which dissociates at 193 nm and also at 248 nm. A six-membered to seven-membered ring isomerization was observed for photodissociation processes involving toluene, m-xylene, aniline, 4-methylpyridine, alpha-fluorotoluene, and 4-fluorotoluene, indicating a general isomerization mechanism for all such aromatic molecules. What is significant, is that during the isomerization, atoms (i.e., carbon, nitrogen, fluorine, and hydrogen) belonging to respective alkyl or amino groups are involved in an exchange with atoms within the aromatic ring. This type of isomerization is not observed in other aromatic isomerization mechanisms. For small tyrosine chromophores, such as phenol, 4-methylphenol, and 4-ethylphenol, H-atom elimination from a repulsive excited state plays a key role. However, dissociation is quenched in large chromophores like 4-(2-aminoethyl)-phenol. Our work demonstrates the capability and high sensitivity of multimass ion imaging techniques in the study of aromatic compounds.
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