Infrared fluorescence and absorption studies of CN: spectra and relaxation in solid rare gases

Wurfel, Brent E.; Schallmoser, Günter; Lask, G.; Agreiter, Jürgen; Thoma, A.; Schlachta, Richard; Bondybey, V. E.

doi:10.1016/0301-0104(93)87010-k

Cited by 24 publications

(9 citation statements)

References 34 publications

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“…A very clear picture of diatomic rotation in solid rare gases emerged from high resolution investigation of the vibrational infrared emission of CN. 15,16 While in the gas phase the Q-branch transitions are forbidden, due to the barrier to free rotation they may become weakly allowed in the matrix, and one then observes a sharp Q(0) line. As the temperature is raised, a broadened P(1) line and other transitions involving excited rotational levels may become observable.…”

Section: A Rotating Molecules In the Matrix And The Effect Of Rotatimentioning

confidence: 99%

Photodissociation of hydrogen halides in rare gas matrices, and the effect of hydrogen bonding

Lorenz

Kraus

Räsänen

et al. 2000

The Journal of Chemical Physics

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Section: A Rotating Molecules In the Matrix And The Effect Of Rotatimentioning

confidence: 99%

Photodissociation of hydrogen halides in rare gas matrices, and the effect of hydrogen bonding

Lorenz

Kraus

Räsänen

et al. 2000

The Journal of Chemical Physics

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“…18 In contrast to the observed gas-phase behavior, it is known that nonradiative relaxation of CN(A) in solid rare gas matrices is regulated by the energy gap. [19][20][21][22][23] For CN in solid Ne, Bondybey 19 showed that vibrationally excited levels of CN(A) relaxed by sequential A, v→X, vϩ⌬v→A, vϪ1 steps. The rate for each step was exponentially depen-dent on the energy gap.…”

Section: Introductionmentioning

confidence: 99%

Spectroscopy and nonadiabatic predissociation of CN–Ne

Lawrence

Chen

1997

The Journal of Chemical Physics

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Electronic spectroscopy of toluene-rare-gas clusters: The external heavy atom effect and vibrational predissociationThe spectroscopy and predissociation dynamics of CN-Ne were investigated using a variety of laser excitation techniques. Properties of the A 2 ⌸ state ͑vibrational levels vϭ2, 3, and 4͒ were characterized through studies of the A -X system. Both spin-orbit components of CN(A) -Ne were subject to predissociation. The upper component (⍀ϭ1/2) was predissociated by rapid spin-orbit relaxation ͑Ϸ6 ps, no vibrational dependence͒. The lower component (⍀ϭ3/2) was predissociated by the nonadiabatic internal conversion process, CN(A 2 ⌸ 3/2 ,v) -Ne →CN(X 2 ⌺ ϩ ,vϩ4)ϩNe. Rates for predissociation by internal conversion were found to be exponentially dependent on the energy gap between the initial and final CN levels. These rates were relatively slow, permitting observation of rotationally resolved spectra for bands associated with the monomer ⍀ϭ3/2 vϭ3 and 4 levels. Double resonance techniques were used to simplify the spectra and establish ro-vibronic assignments. Details of the intermolecular potential-energy surfaces were derived from these data. CN final state population distributions resulting from spin-orbit and internal conversion predissociation were characterized. For the former, excess energy was channeled into rotational excitation of CN, and levels ofϪparity were preferentially populated. The excess energy in predissociation by internal conversion was released primarily to translational recoil. In the accompanying paper, Yang and Alexander present ab initio potential surfaces for CN-Ne. From these surfaces they predict ro-vibronic energies and predissociation rates for levels associated with A, vϭ3. Results that depended on the A state surface alone were found to be in good agreement with experiment. Comparison of the internal conversion predissociation rates indicates that the ab initio calculations underestimated the coupling between the A and X states.

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“…27 The vibronic cascade that leads to the observation of these fluorescing states has been well analyzed and documented in Refs. [27][28][29][30]. Two other emission bands are observed to grow with irradiation.…”

Section: Resultsmentioning

confidence: 98%

“…46 This is done with the knowledge that in the tight substitutional site of both solid Kr and Xe, the CN radical undergoes free rotation. 29,47 In effect, the pair potential anisotropy is lifted by the compact site, by averaging over the twelve nearest neighbors. To simulate the angular isotropy imposed by the Nϭ0 state, to which the radical must be limited at the cryogenic temperatures of relevance, we use the rotationally averaged pair potential.…”

Section: B Fragment Energeticsmentioning

confidence: 99%