A photoelectron spectroscopic study of low-lying Rydberg states in molecular chlorine using multiphoton ionisation

General rightsIt is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. This paper extends our knowledge of the higher excited states of the ammonia molecule by presenting detailed measurements of the 2ϩ1 resonance enhanced multiphoton ionization ͑REMPI͒ spectrum of both NH 3 and ND 3 obtained following excitation in the wavelength range 298-242 nm, i.e., at energies up to the first ionization energy. Complementary analyses of the wavelength resolved REMPI spectrum and the accompanying REMPI-photoelectron spectra leads to the identification of ten new Rydberg origins of NH 3 ͑four for ND 3 ͒ with principal quantum numbers nр8 and, in most cases, of the accompanying out-of-plane bending vibrational progression. Symmetry assignments for the various newly identified excited states are offered, based on band contour simulation and/or quantum defect considerations. Dominant amongst these are the ẼЉThe present work serves to reinforce the previously noted dominance of np←1a 2 Љ Rydberg excitations in the 2ϩ1 REMPI spectrum of ammonia. In addition, the adiabatic ionization energy of ND 3 is estimated to be 82 280Ϯ40 cm Ϫ1 based on the assumption that analogous Rydberg states of NH 3 and ND 3 will have very similar quantum defects.

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“…Both experiments have been described in detail previously 41,42 and so only brief summaries of the two experimental methods are given here.…”

Section: Methodsmentioning

confidence: 99%

“…41 An effusive beam of pure NH 3 or ND 3 vapor was crossed by the focused laser beam and photoelectrons resulting from each laser pulse were extracted into the spectrometer. The measured times of arrival of the photoelectrons at a pair of MCPs situated at the end of the 500 mm flight tube were used to determine electron kinetic energies.…”

Section: Methodsmentioning

confidence: 99%

The spectroscopy of high Rydberg states of ammonia

Langford

Orr‐Ewing

Morgan

et al. 1998

The Journal of Chemical Physics

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“…The latter experiment has been described in detail previously, [32][33][34][35] and only a cursory description is given here, but the Bristol TOF mass spectrometer is newly constructed and replaces our previous REMPI-TOF experiment, so is described in more detail.…”

Section: Methodsmentioning

confidence: 99%

Resonance enhanced multiphoton ionization spectroscopy of carbonyl sulphide

Morgan

Orr‐Ewing

Ascenzi

et al. 1996

The Journal of Chemical Physics

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Rydberg excited states of the OCS molecule in the energy range 70500-86000 cm Ϫ1 have been investigated via the two and three photon resonance enhancements they provide in the mass resolved multiphoton ionization ͑MPI͒ spectrum of a jet-cooled sample of the parent molecule. Spectral interpretation has been assisted by companion measurements of the kinetic energies of the photoelectrons that accompany the various MPI resonances. The present study supports the earlier conclusions of Weinkauf and Boesl ͓J. Chem. Phys. 98, 4459 ͑1993͔͒ regarding five Rydberg origins in the 70500-73000 cm Ϫ1 energy range, attributable to, respectively, states of 3 ⌸, 1 ⌸, 3 ⌬, 1 ⌬ and 1 ⌺ ϩ symmetry arising from the 4p←3 orbital promotion. We also identify a further 21 Rydberg origins at higher energies. These partition into clumps with quantum defects ca. 3.5 and 4.5, which we associate with the orbital promotions np←3 (nϭ5,6), and others with near integer quantum defect which are interpretable in terms of excitation to s,d and ͑possibly͒ f Rydberg orbitals. We also identify MPI resonances attributable to CO(X 1 ⌺ ϩ ) fragments and to S atoms in both their ground ( 3 P) and excited ( 1 D) electronic states. Analysis of the former resonances confirms that the CO(X) fragments resulting from one photon dissociation of OCS at excitation wavelengths ca. 230 nm are formed with a highly inverted, bimodal rotational state population distribution, whilst the latter are consistent with previous reports of the wavelength dependence for forming ground and excited state S atoms in the near uv photolysis of OCS.

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“…Both experiments have been described in detail previously [51][52][53][54] so only brief summaries of the two experimental methods are given here.…”

Section: Methodsmentioning

confidence: 99%

Resonance enhanced multiphoton ionization spectroscopy of carbon disulphide

Morgan

Baldwin

Orr‐Ewing

et al. 1996

The Journal of Chemical Physics

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Rydberg excited states of the CS 2 molecule in the energy range 56 000-81 000 cm Ϫ1 have been further investigated via the two and three photon resonance enhancements they provide in the mass resolved multiphoton ionization ͑MPI͒ spectrum of a jet-cooled sample of the parent molecule. Spectral interpretation has been aided by parallel measurements of the kinetic energies of the photoelectrons that accompany the various MPI resonances. Thus we have been able to extend, and clarify, previous analyses of the tangled spin-orbit split vibronic structure associated with the

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A photoelectron spectroscopic study of low-lying Rydberg states in molecular chlorine using multiphoton ionisation

Cited by 40 publications

References 10 publications

The spectroscopy of high Rydberg states of ammonia

The spectroscopy of high Rydberg states of ammonia

Resonance enhanced multiphoton ionization spectroscopy of carbonyl sulphide

Resonance enhanced multiphoton ionization spectroscopy of carbon disulphide

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