Spectroscopy and relaxation dynamics of metastable electronically excited states of iodine in rare gas matrices

Macler, Michel; Heaven, Michael C.

doi:10.1016/0301-0104(91)80103-o

Cited by 42 publications

(31 citation statements)

References 31 publications

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“…41 This structure was previously attributed to the formation of I 2 -Kr charge-transfer exciplex observed also in solid Kr. 23 When Xe is used for cluster formation instead of Kr, similar quenching of the D-state and population of the D -state is observed for the low Xe pressures, but for the higher Xe pressures all of the first IP tier emissions are efficiently quenched implying enhancement of non-radiative decay channel similar to our Xe doped matrices. Partly this effect has been attributed in the gas-phase to the reactive quenching and formation of XeI* (emission at 253 nm) excimer by absorption of two 193 nm photons.…”

Section: B Emissionsupporting

confidence: 65%

“…The main emission band structure at ∼26 000-23 000 cm −1 has an intense central peak at 24 000 cm −1 and distinctive shoulder at 24 900 cm −1 , more clearly resolved at T = 5 K (not shown). Observed emissions in krypton have been previously characterized as transitions originating from the two lowest ion-pair tiers to various valence states of I 2 , and have been tentatively assigned 5,10,23,24 in the Figure 3. Exciting the I 2 /Kr matrix with ArF laser results also in a weak emission in the UVregion at 31 200 cm −1 , now assigned as F → a transition.…”

Section: B Emissionmentioning

confidence: 93%

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Electronic spectroscopy of I2–Xe complexes in solid Krypton

Hulkko

Ahokas

Myllyperkiö

et al. 2012

The Journal of Chemical Physics

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Articles you may be interested inIn the present work, we have studied ion-pair states of matrix-isolated I 2 with vacuum-UV absorption and UV-vis-NIR emission, where the matrix environment is systematically changed by mixing Kr with Xe, from pure Kr to a more polarizable Xe host. Particular emphasis is put on low doping levels of Xe that yield a binary complex I 2 -Xe, as verified by coherent anti-Stokes Raman scattering (CARS) measurements. Associated with interaction of I 2 with Xe we can observe strong new absorption in vacuum-UV, redshifted 2400 cm −1 from the X → D transition of I 2 . Observed redshift can be explained by symmetry breaking of ion-pair states within the I 2 -Xe complex. Systematic Xe doping of Kr matrices shows that at low doping levels, positions of I 2 ion-pair emissions are not significantly affected by complexation with Xe, but simultaneous increase of emissions from doubly spin-excited states indicates non-radiative relaxation to valence states. At intermediate doping levels ion-pair emissions shift systematically to red due to change in the average polarizability of the environment. We have conducted spectrally resolved ultrafast pump-probe ion-pair emission studies with pure and Xe doped Kr matrices, in order to reveal the influence of Xe to I 2 dynamics in solid Kr. Strikingly, relaxed emission from the ion-pair states shows no indication of complex presence. It further indicates that the complex escapes detection due to a non-radiative relaxation.

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Section: B Emissionsupporting

confidence: 65%

Section: B Emissionmentioning

confidence: 93%

Electronic spectroscopy of I2–Xe complexes in solid Krypton

Hulkko

Ahokas

Myllyperkiö

et al. 2012

The Journal of Chemical Physics

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“…A very large body of work including both time independent, and time resolved spectroscopic experiments, as well as analytic theories and molecular dynamics simulations [1][2][3][4][5][6][7] ͓see Ref. ͑1͒ for other references to this theoretical and computational work͔, has been devoted to the study of diatomic molecular photodissociation, in particular the photodissociation of I 2 , in clusters, [8][9][10][11][12][13] solids, [14][15][16] liquids, 1,[17][18][19][20][21][22][23][24] and high pressure gases [25][26][27][28][29] composed of nonpolar molecules ranging from simple rare gas atoms to more complex polyatomic solvents such as cyclohexane and benzene. 30 The interpretation of much of this work is complicated by two related issues: First, despite the fact that many of the gas phase potential surfaces for I 2 are known quite accurately, the perturbation of these surfaces due to the presence of the solvent environment has only recently become ammenable to detailed study through the application of semiempirical electronic structure methods to these complex manybody interactions.…”

Section: Introductionmentioning

confidence: 99%

Nonadiabatic molecular dynamics simulation of ultrafast pump-probe experiments on I2 in solid rare gases

Batista

Coker

1997

The Journal of Chemical Physics

113

103

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Recent experimental studies of both A and B state photoexcitation of I 2 and the ensuing many-body dynamics in rare gas matrices by Apkarian and co-workers are simulated using the methods we presented in an earlier work combining nonadiabatic molecular dynamics with semiempirical diatomics-in-molecules ͑DIM͒ excited state electronic structure techniques. We extend our DIM methods to compute the ion pair states of the I 2-rare gas crystal system and use these states together with a model of the configurational dependence of the electronic dipole operator matrix elements to calculate the time resolved probe absorption signals in these pump-probe experiments using a simple golden rule result. Our computed signals are in remarkable agreement with experiments and we use our calculations to provide a detailed microscopic analysis of the channels to predissociation and recombination underlying these experiments.

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“…As a result of collision-induced quenching the lower lying ion-pair states become populated and the fluorescence originating from them dominates the emission spectra. The direct study on the I þ I À states in Ar and Kr solids carried out by Heaven and co-workers [4,5] established a redshift of 2900 cm À1 for the D 0 ð2 g Þ ! A 0 ð2 u Þ emission in Ar compared to the gas phase, which gives rise to a bright feature at 380 nm.…”

Section: Introductionmentioning

confidence: 99%

“…The description of the molecular deformation, environmental accommodation and relative solvation of the valence and ion-pair states of an I 2 molecule in a cryogenic rare gas matrix is an interesting model problem that has received considerable experimental attention [1][2][3][4][5]. The interpretation of some of the spectral features observed in these condensed phase experiments is ambiguous and the aim of this paper is to extend existing theoretical models [6] to develop a complete and consistent picture of how such states are influenced by environment.…”

Section: Introductionmentioning

confidence: 99%

Ion pair state emission from I₂in rare gas matrices: effects of solvent induced symmetry breaking

Yu¹,

Coker²

2004

Molecular Physics

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In this paper, we employ a diabatic model Hamiltonian based on the DIM (diatomics-inmolecules) and DIIS (diatomics-in-ionic-systems) methods to describe the valence and ion-pair states of the iodine molecule, with the objective of characterizing the influence of Ar and Kr rare gas matrices on the ion-pair states. In particular, we combined this model Hamiltonian with classical simulations to calculate the shifts of the ion-pair state emission spectra due to solvation environment. The computed main emission peaks in Ar and Kr solids appear at 378 and 417 nm, in excellent agreement with the experimental emission peaks of 380 and 418 nm recently observed by Chergui et al. with the identical transition assignments. Our study also shows that these calculated bands correspond to redshifts from the gas phase of 2600 and 5100 cm À1 , compared with shifts of 2900 and 4700 cm À1 , respectively, observed in experiments, and the equilibrium bond lengths of the D 0 ð2 g Þ state in Ar and Kr extend to 3.70 and 3.75 Å compared to the gas-phase value of 3.594 Å , consistent with experimental implications. Emission bands originating from the ð2 u Þ state are also computed, as well as the counterparts of these bands in the visible region and the results are shown to be in reasonable agreement with experiments. We present a detailed study of the ion-pair state symmetry breaking which mixes the symmetrical gas-phase states resulting in charge localization, and the establishment of permanent molecular dipole moments in these solvated ion-pair state molecules due to local distortion of the polarizable matrix. Finally we use our calculations to explore model defect solvation sites in solid Ar which have been proposed as the source of various ambiguous emission bands in experimental spectra.

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Spectroscopy and relaxation dynamics of metastable electronically excited states of iodine in rare gas matrices

Cited by 42 publications

References 31 publications

Electronic spectroscopy of I2–Xe complexes in solid Krypton

Electronic spectroscopy of I2–Xe complexes in solid Krypton

Nonadiabatic molecular dynamics simulation of ultrafast pump-probe experiments on I2 in solid rare gases

Ion pair state emission from I₂in rare gas matrices: effects of solvent induced symmetry breaking

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Spectroscopy and relaxation dynamics of metastable electronically excited states of iodine in rare gas matrices

Cited by 42 publications

References 31 publications

Electronic spectroscopy of I2–Xe complexes in solid Krypton

Electronic spectroscopy of I2–Xe complexes in solid Krypton

Nonadiabatic molecular dynamics simulation of ultrafast pump-probe experiments on I2 in solid rare gases

Ion pair state emission from I2in rare gas matrices: effects of solvent induced symmetry breaking

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Ion pair state emission from I₂in rare gas matrices: effects of solvent induced symmetry breaking