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Observation of a substantially-bound excited-core Rydberg state in I2 by optical triple resonance
KTH, School of Engineering Sciences (SCI), Physics, Atomic and Molecular Physics.
2005 (English)In: Chemical Physics Letters, ISSN 0009-2614, E-ISSN 1873-4448, Vol. 416, no 1-3, p. 64-69Article in journal (Refereed) Published
Abstract [en]

A substantially-bound (D-e similar to 7000 cm(-1), R-e similar to 3.1 angstrom, T-e similar to 60 546 cm(-1)) 6s Rydberg state Of I-2 with 0(u)(+) symmetry based on the lowest excited state of the ion core, previously labelled a (4 Sigma(u,)(1/2)(-)), has been identified using optical triple resonance via the B(0(u)(+)) and E0(g)(+)(P-3(2)) states together with resonance ionization. The interactions with ground-core Rydberg states that the new state undergoes and the reasons why it is observed in the resonance ionization spectrum via the E0(g)(+)(P-3(2)) state, whilst the A[(2)Pi(u,1/2)](c); 6s0(u)(+) state is not, are explained in terms of its electronic configuration.

Place, publisher, year, edition, pages
2005. Vol. 416, no 1-3, p. 64-69
Keywords [en]
ion-pair states, photoelectron-spectra, field-ionization, band system, iodine, spectroscopy, energy
National Category
Physical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-6076DOI: 10.1016/j.cplett.2005.09.029ISI: 000233687000013Scopus ID: 2-s2.0-33644523061OAI: oai:DiVA.org:kth-6076DiVA, id: diva2:10681
Note
Uppdaterad från submitted till published: 20101006 QC 20101006Available from: 2005-09-13 Created: 2005-09-13 Last updated: 2017-12-14Bibliographically approved
In thesis
1. Resonant multi-photon ionisation studies of high-energy states in small molecules
Open this publication in new window or tab >>Resonant multi-photon ionisation studies of high-energy states in small molecules
2005 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

This thesis describes separate studies of high-energy Rydberg and ion-pair states in small molecules using resonant multi-photon ionisation spectroscopy.

* OODR/REMPI study of ungerade Rydberg states in O2

The energy region between 75000 and 99900 cm-1 of O2 has been studied using optical-optical double resonance (OODR) with resonance enhanced multi-photon ionisation (REMPI). Three-photon excitation via single rotational levels of the b(1Σ+g ) valence state was used to study np (n=3–10) and nf (n=4–9) Rydberg states converging on O2+X(2Π1/2,g) and X(2Π3/2,g). The excitation pathway picks out non-predissociated states that are singlet in the (Λ,S) coupling scheme – suitable for np states for n ≥8, or are linear combinations of equal weight of singlet and triplet-spin states in the (Ω,ω) coupling scheme which was found to be suitable for nf states for all values of n.

* OTR/RI study of Rydberg and ion-pair states in I2

Optical triple resonance (OTR) together with resonance ionisation (RI) has been used to study the ungerade manifold of molecular iodine between 57000 and 73000 cm-1 via the E 0g+(3P2) ion-pair state. Two 6s Rydberg states with 0 +u symmetry based on excited states of the ion core have been observed.

During this study we also observed electric-field-induced mixing of nearly isoenergetic rovibrational levels of the E0gP+(3P2) and D0u+(3P2) ion-pair states. Detectable mixing with an applied field of 1kV/cm occurs over a range of energy level separations of ≤0.3 cm-1.

* (2+1)and (3+1) REMPI study of pyrrole (C4H5N) The two- and three-photon REMPI spectra of Rydberg states of pyrrole (C4H5N) have been recorded using circularly and linearly polarised light. The spectra were compared to the single-photon absorption spectrum of pyrrole and a similar study of furan (C4H4O). Although the ionisation spectra of pyrrole were considerably weaker than corresponding furan spectra, a strong propensity for excitation of d series with two photons and p and f series with three photons was observed for both molecules. The totally symmetric nd-Rydberg series associated with the first ionisation energy, [A2]nd;A1, was identified from n=3 to n=15 and extrapolated to obtain IE1.

Place, publisher, year, edition, pages
Stockholm: KTH, 2005. p. viii, 56
Series
Trita-FYS, ISSN 0280-316X ; 2005:36
National Category
Physical Sciences
Identifiers
urn:nbn:se:kth:diva-409 (URN)91-7178-112-9 (ISBN)
Public defence
2005-09-23, Sal FA32, AlbaNova, Roslagstullsbacken 21, Stockholm, 10:00
Opponent
Supervisors
Note
QC 20101006Available from: 2005-09-13 Created: 2005-09-13 Last updated: 2010-10-06Bibliographically approved

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