(2+1) REMPI PES of Gerade Rydberg states of molecular bromine in the 68000 to 73400 cm−1 region

Koenders, B.G.; Kuik, G.J.; Drabe, Karel E.; Lange, C.A. de

doi:10.1016/0009-2614(88)80239-2

Cited by 19 publications

(3 citation statements)

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“…Such behaviour is most readily explained by assuming some core-mixing in the resonance enhancing Rydberg level, as suggested previously by Koenders et al to account for the unexpected complexity of certain of their measured 2 + 1 REMPI-photoelectron spectra of Br 2 . 27 All of the peaks in the present Br + speed distributions are found to fit well to single Gaussian functions, with w 1/2 $ 4.0 pixels (FWHM). This value matches closely the FWHM used to fit the contribution from just a single parent quantum state in our earlier studies of IBr photolysis, employing the same experimental conditions, implying that the ions prepared in the present study are not just electronic, spin-orbit and vibrational state selected, but also involve a high degree of rotational state selection.…”

Section: Resultssupporting

confidence: 53%

“…26 This is important if, as here, it is intended to use one-colour 2 + 1 REMPI to prepare the parent ion, and to rely on the expected propensity for core-conserving Dv ¼ 0 transitions from the intermediate Rydberg level to ensure that these ions are formed, predominantly, in a single, well-defined electronic, spin-orbit and vibrational state. 27 Numerous previous REMPI-time-of-flight mass spectrometry (TOFMS) and REMPI-photoelectron spectroscopy (PES) studies have shown that multiphoton excitation with just l prep can often lead to fragment ion formation. 28 Such fragmentation can arise in many different ways.…”

Section: Resultsmentioning

confidence: 99%

“…Previous 2 + 1 REMPI studies of Br 2 have identified a number of resonances which result in, primarily, parent ion formation, 26 and that demonstrate the expected propensity for Dv ¼ 0 core conserving transitions in the final ionisation step. 27 The first of these studies guided our choice of a resonance associated with the [1/ 2]4d;0 g X;0 g two-photon transition. Br 2 exists in three isotopomers, however, and the respective origin bands of the [1/ 2]4d;0 g X;0 g transition of each of these overlap one another to the extent that it is not possible to excite just a single isotopomer.…”

Section: Resultsmentioning

confidence: 99%

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High resolution ion imaging studies of the photodissociation of the Br2+ cation

Beckert

Greaves

Ashfold

2002

Phys. Chem. Chem. Phys.

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We demonstrate the potential of velocity map ion imaging methods for high resolution studies of the photofragmentation of a state selected molecular ion, Br 2 + . 79 Br 2 + cations were prepared in the v + ¼ 1 levels of both spin-orbit components of the X 2 P g ground state by 2 + 1 resonance enhanced multiphoton ionisation (REMPI) of jet-cooled, isotopomer-selected 79 Br 2 molecules at an excitation wavelength of 263.012 nm. The subsequent photolysis of these state selected ions was then investigated in the wavelength range 372 < l phot < 432 nm by imaging the resulting 79 Br + ions. Use of a home-built Pockels cell assembly allowed measurement of images with and without l phot present, on successive laser shots. The resulting difference image allows clear visualisation of the parent ion fragmentation, free from unintended fragment ion signal induced by the REMPI preparation step. The images reveal participation of dissociation channels yielding Br + ions in both their ground ( 3 P 2 ) and first excited ( 3 P 1 ) spin-orbit states, together with ground state Br atoms. No fragmentation channels involving formation of spin-orbit excited Br( 2 P 1/2 ) atoms are found to be active in this range of photolysis wavelengths. Image analysis yields a precise value for the bond strength of the Br 2 + cation, in both spin-orbit components of its ground electronic state: D 0 [ 79 Br 2 + (X 2 P 1/2,g )] ¼ 23528.1 AE 0.6 cm À1 and D 0 [ 79 Br 2 + (X 2 P 3/2,g )] ¼ 26345 AE 2 cm À1 , and thus a refined measure of the spin-orbit splitting in the ground state Br 2 + cation: A ¼ 2817 AE 3 cm À1 .

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Section: Resultssupporting

confidence: 53%

Section: Resultsmentioning

confidence: 99%