Resonance-enhanced multiphoton ionization photoelectron spectroscopy of Rydberg states of N2O below the X 2Π ionization limit

Abstract

Resonance-enhanced multiphoton ionization photoelectron spectroscopy of Rydberg states of N2O below the X ionization limit Scheper, C.R.; Kuijt, J.; Buma, W.J.; de Lange, C.A. 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. A three-photon resonance-enhanced multiphoton ionization spectroscopic study on N 2 O is carried out in the spectral range from 80 000 cm Ϫ1 up to the lowest ionization limit at 103 963 cm Ϫ1. High-resolution photoelectron spectroscopy is used to identify and characterize the observed excited states. Eighteen origins are reported which have either not been assigned before or are reassigned now. Moreover, the photoelectron spectra taken at higher-lying resonances often show extensive vibronic coupling with the near-resonant vibronic manifolds built on lower-lying origins.

Laser photoelectron spectroscopy: spectroscopy and dynamics of excited states in small and medium‐sized molecules

“…This spectrum was obtained by monitoring the N 2 0 + mass channel. As can be seen from the proposed assignments, indicated by (Reproduced with permission from [42], copyright 1998 American Institute of Physics.) combs above the spectra, the experimental bands can be arranged into well-defined series, split by N 134cm-', and converging upon the two spinorbit components of the ground-state ion.…”

“…In N 2 0 a (3 + 1) REMPI-PES study was performed in the spectral range from 80,00Ocm-' up to the lowest ionization limit of 103,963 cm-'. Rydberg states of the type [X2FI]nsc3 (1'3n), (1,3C+), and [A2C +]nso ( ' X ' ) , were observed and characterized [42]. In Section V.B the [X211g3pI/2]nf (n = 4-10) complexes of CS2 will be treated as an example.…”

“…In molecules larger than diatomics the mechanism of vibronic coupling, rather than being an exception, appears to be omnipresent. In Section IV.C, we shall treat illustrative examples taken from laser PES of CS2 [48] and N 2 0 [42].…”

“…Extensive Rydberg structure has been observed, especially above 80,000 cm-'. For the present discussion, we shall focus on our (3 + 1) REMPI-PES results obtained for N 2 0 in the energy range 1~0,800-104,200cm~' [42]. In this range, [X2113/2,1/2]nso ( n = 7-1 1) C~C X C+ and [X2113/2,1/2]npa (n = 8-9) +++ X'X+ transitions were observed, as shown in Figure 38.…”

“…Simihr to the situation with conventional PES where molecular orbitals became experimentally accessible in a direct way 127-341, laser PES has now developed to the point where orbital interactions between orbitals with different cores can be made experimentally "visible" for the first time. Many examples exist to date in systems as diverse as N [35] and S atoms [36,37], the NH radical [38,39], the SH radical [40,41], N20 [42], NH3 [43,441, methanethiol [45], and dimethyl sulfide [46]. The role of orbital interactions in laser PES will prove to be one of the key elements of the research described in this contribution.…”