Understanding Luminescence Spectra and Efficiency Using Wp and Related Functions

Struck, C. W.; Fonger, W. H.

doi:10.1007/978-3-642-48629-6

Cited by 64 publications

(53 citation statements)

References 30 publications

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“…This function accounts for the phonon-structure on an electronic transition and has been described in detail by Struck and Fonger. 7 It provides an analytic expression for the Franck-Condon intensity factors for displaced harmonic oscillators by assuming dominant coupling from a single phonon mode with a frequency ប . The value of ប is taken to be the average of the fundamental frequencies for the ground and excited electronic states coupled in the transition.…”

Section: B Lineshape Analysis Of the Mn A A 6 D J ] A 6 S Excitationmentioning

confidence: 99%

Crystal field splitting on D↔S transitions of atomic manganese isolated in solid krypton

Byrne

Collier

Ryan

et al. 2010

Low Temperature Physics

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Narrow excitation features present on the ͓Ar͔3d 6 4s 1 a 6 D ͑J=9/2−1/2͒ ← ͓Ar͔3d 5 4s 2 a 6 S 1/2 transitions of manganese atoms isolated in solid Kr are analyzed within the framework of weak crystal field splitting. Use of the W p optical lineshape function allowed identification of multiple zero-phonon lines for individual spin-orbit J states of the a a 6 D ← a 6 S transition recorded with laser-induced excitation spectroscopy. Excellent agreement exists between the predicted crystal field splitting patterns for the J levels of the a 6 D state isolated in the «red» tetravacancy site of solid Kr. The tetrahedral crystal field of the «red» trapping site splits J Ͼ 3 / 2 levels of the a 6 D J and a 4 D 7/2 states by approximately 30 cm −1 . This report represents the first definitive evidence of crystal field splitting, induced by the weak van der Waals interactions between a neutral metal atom and the rare gas atoms surrounding it in a well-defined solid-state site.

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Section: B Lineshape Analysis Of the Mn A A 6 D J ] A 6 S Excitationmentioning

confidence: 99%

Crystal field splitting on D↔S transitions of atomic manganese isolated in solid krypton

Byrne

Collier

Ryan

et al. 2010

Low Temperature Physics

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“…This function was given originally by Huang and Rhys 15 described in detail by Struck and Fonger 16 as…”

Section: B Hg 3 P 0 \ 1 S 0 Emission Spectramentioning

confidence: 99%

Luminescence spectroscopy of P13 and P3 state atomic mercury isolated in solid Ar, Kr, and Xe

Collier¹,

McCaffrey²

2003

The Journal of Chemical Physics

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Multicomponent emission bands are recorded for the 3 P 1 → 1 S 0 transition of atomic mercury isolated at single sites in solid Ar, Kr, and Xe matrices. A blueshift observed at elevated temperatures on the 273 nm emission of Hg/Xe is identified in line shape analysis as arising from decreasing intensity of the central component in the band profile. The origin of the multiple components in the emission bands is ascribed to the existence of several vibronic modes which lead to excited state stabilization in the Hg( 3 P 1 )/RG matrix systems. A detailed description of these modes and their energetics is presented in the paper directly following. Photoexcitation of the 3 P 1 state also yields small amounts of 3 P 0 state emission. Hg atom 3 P 1 to 3 P 0 state intramultiplet relaxation ͑IMR͒ is most efficient in Hg/Xe where the ratio of this relaxation channel to 3 P 1 state radiative decay is 1/200 as established in time-integrated emission spectra. Despite the weakness of IMR, pulsed laser excitation combined with photon counting detection provide time-gated 3 P 0 state emission spectra largely free of the more intense 3 P 1 state emission. Such emission spectra recorded under high resolution for the 3 P 0 → 1 S 0 transition of atomic mercury isolated in solid Xe provide the first example of the occurrence of a zero-phonon lines for a metal atom isolated in a rare gas matrix. Wp line shape analysis conducted on the emission bands recorded at specific temperatures, confirm this assignment. The electron-phonon coupling strength ͑Huang-Rhys, S factor͒ extracted in the line shape fits for the Hg/Xe transition is 1.3. Slightly stronger coupling is identified in Kr (S ϭ2.2) and stronger still in Ar (Sϭ3.3). Analysis of the diatomic Hg•RG potential energy curves reveal that the origin of the weak electron-phonon coupling lies primarily in the similarity in the ground and excited states, but also indicates the site size offered by the host solid plays a role.

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“…Excited state lifetime measurements, made with pulsed laser excitation, are used to assign the recorded emission bands to transitions of atomic manganese. Lineshape analyses conducted with the optical W p function 17 …”

Section: Introductionmentioning

confidence: 99%

Luminescence spectroscopy of matrix-isolated atomic manganese: Site size and orbital occupancy dependence of crystal field splitting

Collier

Byrne

Murray

et al. 2010

The Journal of Chemical Physics

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Narrow linewidth emission features observed in the near-UV following y 6 P state excitation of atomic manganese isolated in the solid rare gases are assigned to b 4 D and a 4 P states. These states arise from the 3d 5 4s 2 electronic configuration, identical to that of the 6 S ground state, and the origin of the narrow linewidths. Two thermally stable sites, labeled blue and red on the basis of their position in absorption spectra, are occupied by atomic Mn in Ar and Kr while a single site is present in Xe. The red site produces a single, narrow line emission for the b 4 D state at 329 nm. In contrast, a lineshape analysis of the complex blue site b 4 D state emission between 331 and 332 nm reveals the occurrence of three zero phonon lines ͑ZPLs͒. Millisecond emission decay curves recorded for these features are found to be complex, requiring double and triple exponential fit functions. The origins of the complex decays and multiple ZPLs are shown to arise from weak crystal field splitting ͑CFS͒ of the J = 7 / 2 spin-orbit level of the b 4 D state of atomic Mn isolated in the blue site of the solid rare gases. Fields of cubic symmetry are capable of inducing splitting for J Ͼ 3 / 2 so atoms isolated in both single vacancy and tetravacancy sites in the fcc lattices of the solid rare gases are prone to this effect. b 4 D state emission is also produced following y 6 P excitation for Mn atoms occupying the red sites in Ar and Kr. However, Mn atoms isolated in the larger tetravacancy sites have small matrix shifts and do not exhibit any CFS. The magnitudes of the weak CF splittings are shown to depend on both the excited state electronic configurations 3d 5 4s 2 b 4 D and 3d 6 4s 1 a 4 D states and the size of the matrix site occupied by atomic Mn.

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Understanding Luminescence Spectra and Efficiency Using Wp and Related Functions

Cited by 64 publications

References 30 publications

Crystal field splitting on D↔S transitions of atomic manganese isolated in solid krypton

Crystal field splitting on D↔S transitions of atomic manganese isolated in solid krypton

Luminescence spectroscopy of P13 and P3 state atomic mercury isolated in solid Ar, Kr, and Xe

Luminescence spectroscopy of matrix-isolated atomic manganese: Site size and orbital occupancy dependence of crystal field splitting

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