Your email was sent successfully. Check your inbox.

An error occurred while sending the email. Please try again.

Proceed reservation?

Export
Filter
Collection
Years
  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 115 (2001), S. 6418-6425 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The ∼235 nm photodissociation of CH3CFCl2 pre-excited to three, four, and five quanta of C–H methyl stretches was studied to investigate the effect of internal parent excitation on the dynamics of two- and three-body photofragmentation. The ∼235 nm photons also tagged spin-orbit ground Cl 2P3/2 [Cl] and excited Cl 2P1/2 [Cl*] state photofragments, via (2+1) resonantly enhanced multiphoton ionization in a time-of-flight mass spectrometer. Monitoring the shapes of 35Cl and 35Cl* time-of-arrival profiles revealed their energies and angular distributions and showed broad and unstructured fragment kinetic energy distributions. Although a significant amount (∼50%) of the available energy is transferred into internal energy of the CH3CFCl fragment, the spatial Cl distribution is characterized by a nonvanishing anisotropy parameter, β, which indicates at a fast dissociation of the parent molecule along the C–Cl dissociation coordinate. Moreover, β for Cl changes from a slightly positive value to a negative value, while that for Cl* increases when the pre-excitation is increased from three to five quanta of C–H methyl stretches. This is attributed to the promotion of one of the nonbonding electrons located on the Cl atoms to the σ* antibonding C–Cl orbital and involvement of several upper states with different symmetry properties. © 2001 American Institute of Physics.
    Type of Medium: Electronic Resource
    Signatur Availability
    BibTip Others were also interested in ...
  • 2
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The photodissociation dynamics of thiophosgene (CSCl2) and the respective branching ratios of both dissociation products Cl and CSCl have been studied by 3D imaging of the photodissociation product chlorine in its ground state 2P3/2[Cl] and excited spin–orbit state 2P1/2[Cl*] employing the resonance enhanced multiphoton ionization and time-of-flight technique at a dissociation wavelength of about 235 nm. A novel technique is applied where the complete three-dimensional (3D) momentum vector of a reaction product is directly determined. The kinetic energy distribution (KED) for Cl* is observed for the first time. The obtained KEDs of Cl and Cl* are different in the low kinetic energy range due to the correlating state of the partner fragment CSCl. In the case of ground state Cl the CSCl partner radical is produced in the ground X˜, A˜, and B˜ states with a contribution of 4±0.5%, 60±5%, and 36±3%, respectively. In the case of Cl* the corresponding CSCl is produced with a contribution of 7.5±0.5% in the ground X˜, 71.5±5.5% in state A˜, and 21±1.5% in state B˜. The yield of Cl*, φ(Cl*)=P(Cl*)/[P(Cl)+P(Cl*)], was found to be 0.47. No significant velocity dependence of the anisotropy parameter β could be observed. The mean value +0.03 suggests a decay on the B˜ (A1) surface. © 2002 American Institute of Physics.
    Type of Medium: Electronic Resource
    Signatur Availability
    BibTip Others were also interested in ...
  • 3
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The photodissociation dynamics of COCl2 has been studied by monitoring ground Cl(2P3/2) and spin–orbit excited Cl*(2P1/2) fragments by applying a novel technique where the three-dimensional momentum vector of a single reaction product is directly determined. The photodissociation at 235 nm produces exclusively three fragments: COCl2+hν→CO+2Cl. The kinetic energy distributions of Cl and Cl* are bimodal and exhibit a different behavior for the different spin–orbit states. Our attention was turned to the dependence of the anisotropy parameter β on the fragment velocity which was observed for the first time. For both spin–orbit states the anisotropy parameter differs clearly for slow and fast chlorine atoms, where a pronounced change from the value ∼0.7 to zero at about 20 kJ/mol is observed. Slow chlorine atoms are released isotropically and predominantly in the ground state Cl whereas fast chlorine atoms have an anisotropy parameter close to the theoretically limiting value and are distributed between ground and excited state Cl. These observations can be explained by a sequential decay where the first Cl fragment is released in a fast process characterized by the nonvanishing positive β parameter and a lifetime of ≤210 fs, whereas the second Cl fragment is released after a period which is long on a rotational time scale. A significant contribution of a symmetric mechanism can be excluded. © 2002 American Institute of Physics.
    Type of Medium: Electronic Resource
    Signatur Availability
    BibTip Others were also interested in ...
Close ⊗
This website uses cookies and the analysis tool Matomo. More information can be found here...