Absorption spectrum of Kr2F(4 2Γ) in the near ultraviolet and visible (335≤λ≤600 nm): Comparison with Kr 2+(1(1/2)u) measurements

D. B. Geohegan, James Gary Eden

Research output: Contribution to journalReview article

Abstract

Absolute photoabsorption cross sections for the lowest excited state (4 2Γ of Kr2F and the ground state (1(1/2)u) of Kr2+ have been measured in the visible and ultraviolet (Kr2F: 248, 308, 335-600 nm; Kr2+ : 360-500 nm). As predicted by theory, the Kr2F spectrum is dominated by the 9 2Γ ← 4 2Γ band which peaks below 340 nm and correlates with the Kr2+ 2(1/2)g ← 1 (1/2)u transition. However, Kr2F(4 2Γ) and Kr2+ (1 (1/2)u) both absorb more strongly for wavelengths beyond ∼450 nm than expected, apparently owing to a nonthennalized Kr2+ vibrational distribution. Despite interference from Kr2F stimulated emission between ∼350 and 460 nm, the experimental results show the Kr2F(4 2Γ) and Kr2+ absorption profiles to be similar for λ≥460 nm but diverging rapidly as λ increases from 335 to 360 nm. At 360 nm, the absorption cross sections differ by a factor of 3. Contrary to theoretical expectations, the Kr2F absolute absorption cross section is consistently smaller (typically < 40%) than that for Kr 2+ which suggests that the impact of F- on the Kr2+ oscillator strengths is significant.

Original languageEnglish (US)
Pages (from-to)3410-3427
Number of pages18
JournalThe Journal of Chemical Physics
Volume89
Issue number6
DOIs
StatePublished - Jan 1 1988

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Stimulated emission
Excited states
absorption cross sections
Ground state
Absorption spectra
absorption spectra
Wavelength
photoabsorption
stimulated emission
oscillator strengths
interference
ground state
cross sections
profiles
wavelengths
excitation

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Absorption spectrum of Kr2F(4 2Γ) in the near ultraviolet and visible (335≤λ≤600 nm) : Comparison with Kr 2+(1(1/2)u) measurements. / Geohegan, D. B.; Eden, James Gary.

In: The Journal of Chemical Physics, Vol. 89, No. 6, 01.01.1988, p. 3410-3427.

Research output: Contribution to journalReview article

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abstract = "Absolute photoabsorption cross sections for the lowest excited state (4 2Γ of Kr2F and the ground state (1(1/2)u) of Kr2+ have been measured in the visible and ultraviolet (Kr2F: 248, 308, 335-600 nm; Kr2+ : 360-500 nm). As predicted by theory, the Kr2F spectrum is dominated by the 9 2Γ ← 4 2Γ band which peaks below 340 nm and correlates with the Kr2+ 2(1/2)g ← 1 (1/2)u transition. However, Kr2F(4 2Γ) and Kr2+ (1 (1/2)u) both absorb more strongly for wavelengths beyond ∼450 nm than expected, apparently owing to a nonthennalized Kr2+ vibrational distribution. Despite interference from Kr2F stimulated emission between ∼350 and 460 nm, the experimental results show the Kr2F(4 2Γ) and Kr2+ absorption profiles to be similar for λ≥460 nm but diverging rapidly as λ increases from 335 to 360 nm. At 360 nm, the absorption cross sections differ by a factor of 3. Contrary to theoretical expectations, the Kr2F absolute absorption cross section is consistently smaller (typically < 40{\%}) than that for Kr 2+ which suggests that the impact of F- on the Kr2+ oscillator strengths is significant.",
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AU - Eden, James Gary

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N2 - Absolute photoabsorption cross sections for the lowest excited state (4 2Γ of Kr2F and the ground state (1(1/2)u) of Kr2+ have been measured in the visible and ultraviolet (Kr2F: 248, 308, 335-600 nm; Kr2+ : 360-500 nm). As predicted by theory, the Kr2F spectrum is dominated by the 9 2Γ ← 4 2Γ band which peaks below 340 nm and correlates with the Kr2+ 2(1/2)g ← 1 (1/2)u transition. However, Kr2F(4 2Γ) and Kr2+ (1 (1/2)u) both absorb more strongly for wavelengths beyond ∼450 nm than expected, apparently owing to a nonthennalized Kr2+ vibrational distribution. Despite interference from Kr2F stimulated emission between ∼350 and 460 nm, the experimental results show the Kr2F(4 2Γ) and Kr2+ absorption profiles to be similar for λ≥460 nm but diverging rapidly as λ increases from 335 to 360 nm. At 360 nm, the absorption cross sections differ by a factor of 3. Contrary to theoretical expectations, the Kr2F absolute absorption cross section is consistently smaller (typically < 40%) than that for Kr 2+ which suggests that the impact of F- on the Kr2+ oscillator strengths is significant.

AB - Absolute photoabsorption cross sections for the lowest excited state (4 2Γ of Kr2F and the ground state (1(1/2)u) of Kr2+ have been measured in the visible and ultraviolet (Kr2F: 248, 308, 335-600 nm; Kr2+ : 360-500 nm). As predicted by theory, the Kr2F spectrum is dominated by the 9 2Γ ← 4 2Γ band which peaks below 340 nm and correlates with the Kr2+ 2(1/2)g ← 1 (1/2)u transition. However, Kr2F(4 2Γ) and Kr2+ (1 (1/2)u) both absorb more strongly for wavelengths beyond ∼450 nm than expected, apparently owing to a nonthennalized Kr2+ vibrational distribution. Despite interference from Kr2F stimulated emission between ∼350 and 460 nm, the experimental results show the Kr2F(4 2Γ) and Kr2+ absorption profiles to be similar for λ≥460 nm but diverging rapidly as λ increases from 335 to 360 nm. At 360 nm, the absorption cross sections differ by a factor of 3. Contrary to theoretical expectations, the Kr2F absolute absorption cross section is consistently smaller (typically < 40%) than that for Kr 2+ which suggests that the impact of F- on the Kr2+ oscillator strengths is significant.

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