Detection of Cl atoms and HCl molecules by resonantly enhanced multiphoton ionization

Arepalli, Sivaram; Presser, Nathan; Robie, Daniel C.

doi:10.1016/0009-2614(85)85272-6

Cited by 139 publications

(69 citation statements)

References 25 publications

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“…Considerable information on 2 + 1 REMPI transitions in the HCl molecule is available from extensive studies by Gordon, [24][25][26] Wallace, 27,28 Chandler, 29,30 and co-workers. The most convenient transitions for REMPI detection of HCl are the strong E 1 Σ + -X 1 Σ + and F 1 ∆-X 1 Σ + band systems, which were first observed by one-photon vacuum-UV absorption spectroscopy.…”

Section: Product Internal State Distributionsmentioning

confidence: 99%

Product State Resolved Study of the Cl + (CH₃)₃CD Reaction: Comparison of the Dynamics of Abstraction of Primary versus Tertiary Hydrogens

Varley

Dagdigian

1996

J. Phys. Chem.

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The reaction of Cl atoms with the selectively deuterated isobutane, 2-methylpropane-2-d 1 , has been investigated under single-collision conditions using state-selective detection of the products by resonance-enhanced multiphoton ionization (REMPI) in a time-of-flight mass spectrometer. The reaction was initiated in a crossed, pulsed flow of the reagents by 355 nm photolysis of Cl 2 precursor. The internal state distributions of HCl and DCl products, formed by abstraction of primary and tertiary hydrogen atoms, respectively, from the hydrocarbon reagent are reported. The degree of rotational excitation of both products was found to be very low. By comparison of the intensities of the HCl and DCl REMPI signals, the ratio of the yield of HCl to DCl product was found to be 3.3 ( 0.4. With the known speed and angular distribution of the Cl reagent, it was possible to obtain information on the product center-of-mass angular distributions from measurement of the masses 37 and 38 time of arrival profiles. The DCl product is found to be mainly backward scattered with respect to the incoming Cl atom, while the HCl product is sideways peaked. Inferences on the dynamics of the two possible abstraction pathways from these results are discussed.

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Section: Product Internal State Distributionsmentioning

confidence: 99%

Product State Resolved Study of the Cl + (CH₃)₃CD Reaction: Comparison of the Dynamics of Abstraction of Primary versus Tertiary Hydrogens

Varley

Dagdigian

1996

J. Phys. Chem.

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“…33 As fig. 5 shows, both images are isotropic, though the Cl* signal is substantially weaker, and the distributions derived therefrom both peak at low TKER (~2000 cm -1 , calculated on the basis that the partner fragment has chemical formula C6H5O and a mass m = 93.11 u).…”

Section: Vmi Studies Of CL and Cl* Atom Productsmentioning

confidence: 99%

A Multipronged Comparative Study of the Ultraviolet Photochemistry of 2-, 3-, and 4-Chlorophenol in the Gas Phase

et al. 2015

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The S1( 1 *) state of the (dominant) syn-conformer of 2-chlorophenol (2-ClPhOH) in the gas phase has a sub-picosecond lifetime, whereas the corresponding S1 states of 3-and 4-ClPhOH have lifetimes that are, respectively, ~2 and ~3-orders of magnitude longer. A range of experimental techniques -electronic spectroscopy, ultrafast time-resolved photoion and photoelectron spectroscopies, H Rydberg atom photofragment translational spectroscopy, velocity map imaging and time-resolved Fourier transform infrared emission spectroscopyas well as electronic structure calculations (of key regions of the multidimensional ground (S0) state potential energy surface (PES) and selected cuts through the first few excited singlet PESs) have been used in the quest to explain these striking differences in excited state lifetime. The intramolecular OH ---Cl hydrogen bond specific to syn-2-ClPhOH is key. It encourages partial charge transfer and preferential stabilisation of the diabatic 1 * potential (relative to that of the 1 * state) upon stretching the C-Cl bond, with the result that initial C-Cl bond extension on the adiabatic S1 PES offers an essentially barrierless internal conversion pathway via regions of conical intersection with the S0 PES. Intramolecular hydrogen bonding is thus seen to facilitate the type of heterolytic dissociation more typically encountered in solution studies.3

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“…͑7͔͒ was determined for a number of excitation wave numbers by detection of the Cl spin-orbit states through 2ϩ1 resonance enhanced multiphoton ionization ͑REMPI͒. 26 These measurements were performed in a time-of-flight mass spectrometer ͑TOFMS͒, which has been described in detail previously. 27,28 The HCl reagent, prepared as a 2%-10% mixture in helium at 1-4 atm, was introduced into the ionization region as a free jet through a pulsed solenoid valve.…”

Section: A Apparatusmentioning

confidence: 99%

Spin–orbit branching in the photofragmentation of HCl at long wavelength

Lambert

Dagdigian

Alexander

1998

The Journal of Chemical Physics

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Articles you may be interested inReduced dimensionality spin-orbit dynamics of CH3 + HCl CH4 + Cl on ab initio surfaces We report a new experimental determination of the branching ratio for formation of ground state Cl( 2 P 3/2 ) and spin-orbit excited Cl( 2 P 1/2 ) fragments subsequent to excitation of the HCl molecule to the repulsive A 1 ⌸ electronic state. Our work extends previous experimental measurements well into the long-wavelength tail of the A 1 ⌸←X 1 ⌺ ϩ absorption profile. The branching into the spin-orbit excited Cl( 2 P 1/2 ) fragment is found to reach a maximum near 220 nm, before falling to zero at threshold. Our new measured branching fractions are reproduced nearly quantitatively by new calculations which supplement those reported previously ͓M. H. Alexander, B. Pouilly, and T. Duhoo, J. Chem. Phys. 99, 1752 ͑1993͔͒.

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Detection of Cl atoms and HCl molecules by resonantly enhanced multiphoton ionization

Cited by 139 publications

References 25 publications

Product State Resolved Study of the Cl + (CH₃)₃CD Reaction: Comparison of the Dynamics of Abstraction of Primary versus Tertiary Hydrogens

Product State Resolved Study of the Cl + (CH₃)₃CD Reaction: Comparison of the Dynamics of Abstraction of Primary versus Tertiary Hydrogens

A Multipronged Comparative Study of the Ultraviolet Photochemistry of 2-, 3-, and 4-Chlorophenol in the Gas Phase

Spin–orbit branching in the photofragmentation of HCl at long wavelength

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Detection of Cl atoms and HCl molecules by resonantly enhanced multiphoton ionization

Cited by 139 publications

References 25 publications

Product State Resolved Study of the Cl + (CH3)3CD Reaction: Comparison of the Dynamics of Abstraction of Primary versus Tertiary Hydrogens

Product State Resolved Study of the Cl + (CH3)3CD Reaction: Comparison of the Dynamics of Abstraction of Primary versus Tertiary Hydrogens

A Multipronged Comparative Study of the Ultraviolet Photochemistry of 2-, 3-, and 4-Chlorophenol in the Gas Phase

Spin–orbit branching in the photofragmentation of HCl at long wavelength

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Product State Resolved Study of the Cl + (CH₃)₃CD Reaction: Comparison of the Dynamics of Abstraction of Primary versus Tertiary Hydrogens

Product State Resolved Study of the Cl + (CH₃)₃CD Reaction: Comparison of the Dynamics of Abstraction of Primary versus Tertiary Hydrogens