Two photon sequential absorption spectroscopy of the iodine molecule

Danyluk, M.; King, G.W.

doi:10.1016/0301-0104(77)85208-7

Cited by 64 publications

(7 citation statements)

References 25 publications

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“…"AS defined in eq. [5]. All parameters for upper state fixed externally except R,, P, and b, which were obtained from condition equations for the energy, slope, and curvature of the potential at R:.…”

Section: Table 2 Spectroscopic Parameters (Cm-i) For 2880mentioning

confidence: 99%

“…Among the players in the former arena was Gerry King, who with his research colleagues published ground-breaking papers on the high-resolution multiphoton excitation of ion-pair electronic states in I2 (4)(5)(6). About the same time I published a new interpretation of the strong emission band systems responsible for the lasing in I2 and Br, (7), according to which the emission in both molecules originated from the lowest 2, ion-pair state and terminated on the first excited valence state, 2, (311), neither of which had been identified previously for either molecule.…”

Section: Introductionmentioning

confidence: 99%

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High-resolution spectroscopy with a CCD array detector: application to the 2880 Å emission band system in I₂

Tellinghuisen¹

1993

Can. J. Chem.

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The 2880 A system in the Tesla discharge spectrum of I? in Ar is reexamined using a CCD array detector to record spectra for both " ' I, and '191?. This charge-transfer transition terminates on a weakly bound valence state, giving a highly congested spectrum with fine violet-degraded band structure barely perceivable on a pseudocontinuous background. The superior signal-to-noise capabilities of the array detector permit a great improvement in the precision and number of measured bandheads, as compared with previous results obtained from photographically recorded spectra. The new data span a larger range of vibrational levels in the lower state and lead to a change in the previous u" numbering by -3 units. Both states can now be located precisely on the absolute energy axis through least-squares fits in which the lower state energy is represented as a near-dissociation expansion. The primary spectroscopic constants (cm-') are Tl = 47 084, wl = 103.93, w,xl = 0.14, T: = 12 260, w: = 18.6, w,x: = 0.21. The lower state has a dissociation energy of 287.5 cm-' and supports 35 bound levels, subject, however, to possible further revision due to a remaining uncertainty of I unit in the u" numbering. The previous tentative electronic assignment of this system remains in effect: The upper alors que I'Ctat le plus bas est la composante 0; du multiplet 3rI, de la valence la plus basse.[Traduit par la rCdaction]

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Section: Table 2 Spectroscopic Parameters (Cm-i) For 2880mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

High-resolution spectroscopy with a CCD array detector: application to the 2880 Å emission band system in I₂

Tellinghuisen¹

1993

Can. J. Chem.

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“…The B state fluorescence lifetime around 532 nm is ~1 (20). Several two-photon absorption studies have been carried out on I2 (21)(22)(23), but we are unable to assign the intermediate state.…”

Section: Resultsmentioning

confidence: 82%

Isotopic analysis of iodine by multiphoton ionization

Lubman¹,

Zare²

1982

Anal. Chem.

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“…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. In the gas phase, the ion-pair excitation and emission spectra have been measured by King and co-workers [1,2], which led to the determination of the spectroscopic constants of all the lowest-tier and several second lowest-tier ion-pair states of I 2 . In another study by Lawly et al [3], which focused on the gas-phase emission spectra, the electronic transition moments associated with the most important fluorescence transitions were thoroughly investigated.…”

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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Two photon sequential absorption spectroscopy of the iodine molecule

Cited by 64 publications

References 25 publications

High-resolution spectroscopy with a CCD array detector: application to the 2880 Å emission band system in I₂

High-resolution spectroscopy with a CCD array detector: application to the 2880 Å emission band system in I₂

Isotopic analysis of iodine by multiphoton ionization

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

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Two photon sequential absorption spectroscopy of the iodine molecule

Cited by 64 publications

References 25 publications

High-resolution spectroscopy with a CCD array detector: application to the 2880 Å emission band system in I2

High-resolution spectroscopy with a CCD array detector: application to the 2880 Å emission band system in I2

Isotopic analysis of iodine by multiphoton ionization

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

Contact Info

Product

Resources

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High-resolution spectroscopy with a CCD array detector: application to the 2880 Å emission band system in I₂

High-resolution spectroscopy with a CCD array detector: application to the 2880 Å emission band system in I₂

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