Photodissociation Dynamics of Benzoyl Chloride at 235 nm: Resonance-Enhanced Multiphoton Ionization Detection of Cl and HCl

Saha, Ankur; Kawade, Monali; Sengupta, S.; Upadhyaya, Hari P.; Kumar, Awadhesh; Naik, Prakash D.

doi:10.1021/jp410511c

Cited by 5 publications

(17 citation statements)

References 42 publications

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“…There are three distinct humps at ∼280 nm (S 1 ), ∼ 255 nm (S 2 ), and ∼235 nm (S 3 ) that are consistent with previous work. , The excitation wavelengths in our experiment are indicated by arrows. The nature of these states are reported to be π*(ring, CO)← n(Cl, O) (S 1 ), π*(ring, CO) ← π(ring) (S 2 ) and π*(ring, CO) ← π(ring) (S 3 ) type . All bands are structureless, which would be in agreement with a fast nonradiative relaxation.…”

Section: Resultssupporting

confidence: 92%

“…The P ( E T ) was calculated from the reconstructed 2D slice of Cl + generated by [1 + 1′] REMPI, following photodissociation. In contrast to the previous report, we observed an isotropic, unimodal energy distribution rather than a bimodal one . The calculated P ( E T ) was fitted with the empirical function (). ,, …”

Section: Resultscontrasting

confidence: 74%

“…The previous study also investigated the HCl loss from benzoyl chloride and computed possible pathways . We also detected HCl fragments in a one-color experiment at 236.00–235.07 nm.…”

Section: Resultsmentioning

confidence: 94%

“…Earlier calculations predicted the angle between transition dipole moment and the dissociating C–Cl bond to be ∼150° for the excitation to the S 3 state. In case of a fast dissociation, a β-value of ∼1.2 would be expected …”

Section: Resultsmentioning

confidence: 99%

“…The translational energy distribution was obtained by forward convolution of the experimental profile. In their one-color experiments, they found two Cl dissociation channels along with HCl formation . The fast channel was assigned to dissociation in the S 1 state, populated via S 3 → S 1 internal conversion, while the slower one was found to originate from statistical dissociation in the S 0 ground state following IC.…”

Section: Introductionmentioning

confidence: 99%

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Photodissociation of Benzoyl Chloride: A Velocity Map Imaging Study Using VUV Detection of Chlorine Atoms

2021

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UV photodissociation of benzoyl chloride, Ph−CO−Cl, is associated with the loss of a chlorine atom. Here we excite benzoyl chloride to the S 1 , S 2 , and S 3 excited states at 237, 253, 265, and 279.6 nm and detect the Cl photofragment by [1 + 1′] photoionization using 118.9 nm VUV radiation. The translational energy distribution of the Cl atom is measured by velocity map ion imaging. An isotropic image and a unimodal translational energy distribution are observed at all dissociation wavelengths, and a fraction of 18−20% of the excess energy is released into translation. The results indicate a dissociation that predominately proceeds from the vibrationally hot S 0 ground state, although the observed translational energy release deviates significantly from a prior distribution. However, the impulsive model does also not represent the translational energy release. As a Cl/Cl* branching ratio of 9:1 or more is observed in one-color experiments at 235 nm, we conclude that direct dissociation from excited electronic states contributes only to a minor extent.

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Section: Resultssupporting

confidence: 92%

Section: Resultscontrasting

confidence: 74%

“…The previous study also investigated the HCl loss from benzoyl chloride and computed possible pathways . We also detected HCl fragments in a one-color experiment at 236.00–235.07 nm.…”

Section: Resultsmentioning

confidence: 94%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Photodissociation of Benzoyl Chloride: A Velocity Map Imaging Study Using VUV Detection of Chlorine Atoms

2021

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Effect of Surfactants on the Molecular Structure of the Buried Oil/Water Interface

2021

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The oil/water interface,for instance in emulsions,is often stabilized by surfactants.H ence,t he co-existence of oil, water,and surfactant molecules at the buried oil/water interface determines macroscopic properties such as surface tension or emulsion stability.U tilizing an inherently surface sensitive spectroscopic method, sum frequency generation (SFG) spectroscopy, we showt hat adsorption of an anionic surfactant to the buried oil/water interface increases the magnitude of the interfacial electric field. Meanwhile,t he degree of ordering of the interfacial oil molecules increases with the surfactant concentration owing to the intercalation of aliphatic chains of interfacial oil and surfactant molecules.A ts ufficiently high surfactant concentrations,the interfacial charge reaches amaximum value and the interfacial oil molecules arrange in afully ordered conformation, as tate which coincides with the significant decrease in interfacial tension and increased emulsion stability.

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Concerted stereodynamics of chemical changes: The branching selectivity in the photodissociation of asymmetric‐top molecules, formic acid, and the cold reactivity of the H + H₂ exchange reaction

Che

Kawamata

Nakamura

et al. 2023

J Chinese Chemical Soc

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This review article presents our recent examples of the branching selectivity in the photodissociation of asymmetric‐top molecules, halothane CF3CHBrCl and isohaloethane CF2BrCHFCl. The former gave the unexpected branching ratio of ([Cl] + [Cl*])/([Br] + [Br*])≈2 for the Br, Br* and Cl, Cl* atom fragmentations, meaning that the strongly bounded Cl‐C bond gave twice favorable fragmentation, while the later isohaloethane gave almost the same value for all‐atom fragmentations. We interpret this result due to the curve crossing of electronically excited states and the non‐adiabatic interaction on the excited states. The bimodal vibrational distribution of the product CO fragment in the formic acid photodissociation at 193 nm evidenced a roaming signature by using the μs time‐resolved Fourier‐transform infrared emission spectra for the first time. We find the characteristic propensity rule in the time‐dependent interaction potential to judge reactivity in the H + H2 exchange reaction and the roaming‐type of trajectory at temperature 3 K, by use of the impact‐parameter dependent quasi‐classical trajectory simulation, based on the present results, we conclude that reaction dynamics proceeds not only by the prerequisite of energy conservation but also by the timing of the time‐dependent interaction potential which is very sensitive to the steric configuration of reaction intermediate, thus it may be called as the concerted stereodynamics.

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Photodissociation Dynamics of Benzoyl Chloride at 235 nm: Resonance-Enhanced Multiphoton Ionization Detection of Cl and HCl

Cited by 5 publications

References 42 publications

Photodissociation of Benzoyl Chloride: A Velocity Map Imaging Study Using VUV Detection of Chlorine Atoms

Photodissociation of Benzoyl Chloride: A Velocity Map Imaging Study Using VUV Detection of Chlorine Atoms

Effect of Surfactants on the Molecular Structure of the Buried Oil/Water Interface

Concerted stereodynamics of chemical changes: The branching selectivity in the photodissociation of asymmetric‐top molecules, formic acid, and the cold reactivity of the H + H₂ exchange reaction

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Photodissociation Dynamics of Benzoyl Chloride at 235 nm: Resonance-Enhanced Multiphoton Ionization Detection of Cl and HCl

Cited by 5 publications

References 42 publications

Photodissociation of Benzoyl Chloride: A Velocity Map Imaging Study Using VUV Detection of Chlorine Atoms

Photodissociation of Benzoyl Chloride: A Velocity Map Imaging Study Using VUV Detection of Chlorine Atoms

Effect of Surfactants on the Molecular Structure of the Buried Oil/Water Interface

Concerted stereodynamics of chemical changes: The branching selectivity in the photodissociation of asymmetric‐top molecules, formic acid, and the cold reactivity of the H + H2 exchange reaction

Contact Info

Product

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Concerted stereodynamics of chemical changes: The branching selectivity in the photodissociation of asymmetric‐top molecules, formic acid, and the cold reactivity of the H + H₂ exchange reaction