Rotation of CN in solid rare gases

Schallmoser, Günter; Thoma, A.; Wurfel, Brent E.; Bondybey, V. E.

doi:10.1016/0009-2614(94)00066-2

Cited by 20 publications

(24 citation statements)

References 34 publications

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“…The number results from line widths of the infrared emission spectrum that belongs to the X 2 state v = 1-3 transitions. Observations 21 of the weak Q branch due to a rotational barrier, and the related shift of the rotational constant (B e ≈ 1.6 cm −1 ) due to an induced Xe matrix inertia, are bypassed at the present account.…”

Section: Implementation Methodsmentioning

confidence: 86%

“…The rotational superposition appears purely as a phase evolution, where the relative timing among the packet depends on delay times. A decay of coherence can be introduced by multiplying the polarization P 21 have estimated a rotational relaxation rate of about 100 GHz for CN in solid Xe, which we shall use in Sec. III B.…”

Section: Implementation Methodsmentioning

confidence: 99%

“…(1) The overall brightness of the signal can be accessed by the use of common nodal structure [Eq. (21)] in the oscillation pattern. (2) Suppression or enhancement of individual spectral components and their associated interferences in a signal obtains by tuning into half revivals [Eqs.…”

Section: Controlling the Interferogramsmentioning

confidence: 99%

“…Applying the preparation, interrogation, and manipulation procedures presented in this paper for a matrixisolated CN rotor would contribute to the research field of coherent control of rotational degrees of freedom in condensed phase systems. Several studies [20][21][22][23][24] have shown that CN radicals are relatively free rotors when trapped in solid Xe matrices, despite the pronounced, ∼1000 cm −1 red shift of the electronic B ← X transition band. The preserved high symmetry of the cavity renders an effectively isotropic interaction potential and decoupling between the impurity and its environment.…”

Section: Introductionmentioning

confidence: 99%

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Rotational coherence imaging and control for CN molecules through time-frequency resolved coherent anti-Stokes Raman scattering

Hulkko

Pettersson

Kiljunen

2011

The Journal of Chemical Physics

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states. Due to the large energy separation of vibrational states, the wave packets are superpositions of rotational states only. This allows for a specially detailed inspection of the secondand third-order coherences by a two-dimensional imaging approach. We present the time-frequency domain images to illustrate the intra-and intermolecular interferences, and discuss the procedure to rationally control and experimentally detect the interferograms in solid Xe environment.

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Section: Implementation Methodsmentioning

confidence: 86%

Section: Implementation Methodsmentioning

confidence: 99%

Section: Controlling the Interferogramsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Rotational coherence imaging and control for CN molecules through time-frequency resolved coherent anti-Stokes Raman scattering

Hulkko

Pettersson

Kiljunen

2011

The Journal of Chemical Physics

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“…Very little is known about the orientational dynamics of molecules inside the rare gas matrices and analyzing this dynamics is the purpose of the present study. Small molecules ͑H 2 O, HCl, CN, and NH 3 ͒ may rotate essentially freely in certain rare gas matrices, 6,7 as seen from rovibrational sidebands in the IR spectrum. However, somewhat larger molecules of the size of, for example, CH 3 , rotate in a thermally activated, diffusive manner, a process that has been studied by electron paramagnetic resonance, [8][9][10] as well as by IR hole burning.…”

Section: Introductionmentioning

confidence: 99%

Rotational dynamics of nitrous acid (HONO) in Kr matrix

Botan

Hamm

2008

The Journal of Chemical Physics

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With the help of ultrafast time-resolved infrared spectroscopy, we investigate rotational diffusion of cisand trans-nitrous acid (HONO) in solid Kr at 30 K, as well as its reorientation upon the IR-driven cis -> trans isomerization. We find different mobilities for the two isomers: cis-HONO is pinned to the matrix with no decay of the anisotropy on the 100 ns time scale, whereas trans-HONO rotates around its long axis, reducing its anisotropy partially on that time scale. The long axis itself, defined by the terminal oxygen and hydrogen atoms of HONO, stays fixed on even a minute time scale. Accompanying molecular dynamics simulations reproduce the anisotropic rotational diffusion of trans-HONO correctly, although on a completely wrong time scale, whereas they would predict complete reorientation of cis-HONO within approximate to 10 ps, in harsh disagreement with the experiment. We attribute the mismatch of orientational time scales to either too soft interaction potentials or to the fact that HONO occupies an interstitial rather than a monosubstitutional matrix site. The experiments furthermore show that the direction of the OH bond hardly changes during the IR-driven cis -> trans isomerization, in contrast to the intuitive picture that it is mostly the light hydrogen which moves. Rather, it is the two central nitrogen and oxygen atoms that are removed during isomerization in a hula hoop fashion, whereas the terminal atoms are still pinned to the matrix cage. With the help of ultrafast time-resolved infrared spectroscopy, we investigate rotational diffusion of cis-and trans-nitrous acid ͑HONO͒ in solid Kr at 30 K, as well as its reorientation upon the IR-driven cis → trans isomerization. We find different mobilities for the two isomers: cis-HONO is pinned to the matrix with no decay of the anisotropy on the 100 ns time scale, whereas trans-HONO rotates around its long axis, reducing its anisotropy partially on that time scale. The long axis itself, defined by the terminal oxygen and hydrogen atoms of HONO, stays fixed on even a minute time scale. Accompanying molecular dynamics simulations reproduce the anisotropic rotational diffusion of trans-HONO correctly, although on a completely wrong time scale, whereas they would predict complete reorientation of cis-HONO within Ϸ10 ps, in harsh disagreement with the experiment. We attribute the mismatch of orientational time scales to either too soft interaction potentials or to the fact that HONO occupies an interstitial rather than a monosubstitutional matrix site. The experiments furthermore show that the direction of the OH bond hardly changes during the IR-driven cis → trans isomerization, in contrast to the intuitive picture that it is mostly the light hydrogen which moves. Rather, it is the two central nitrogen and oxygen atoms that are removed during isomerization in a hula hoop fashion, whereas the terminal atoms are still pinned to the matrix cage. Rotational dynamics of nitrous acid "HONO… in Kr matrix

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