Dynamics in supercritical fluids studied using ultrafast pulse laser spectroscopy

Noritsugu Kometani, Yuji Hoshihara, Mark Maroncelli

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

Solvation dynamics and rotational relaxation in supercritical fluids have been examined using the techniques of the subpicosecond laser spectroscopy. The fluorescence up-conversion technique has been employed to detect the fluorescence anisotropy decay of coumarin 153 in supercritical CO 2 (310 K) and CHF 3 (302, 310 K) over a wide density range. The rotational correlation times in supercritical CHF 3 exhibit the remarkable increase at 0.6 0.7 times ρ c, which implies that the local solvent density augmentation slows down the rotational dynamics in supercritical fluids. This conclusion is supported by computer simulations based on a 2-site model of fluoroform. The solvation dynamics of the probe 4-dimethylamino-4′-cyanostilbene have been measured in supercritical CHF 3 at 310 K using the optical Kerrgated emission technique, which appears to have captured most (∼90%) of the dynamics occurring over the accessible density range between 1.4-2.0ρ c. The measured spectral response exhibits a bimodal decay with ∼0.6 ps and ∼9 ps components and only a modest density dependence.

Original languageEnglish (US)
Pages (from-to)113-119
Number of pages7
JournalReview of High Pressure Science and Technology/Koatsuryoku No Kagaku To Gijutsu
Volume16
Issue number2
DOIs
StatePublished - Jun 22 2006

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Laser spectroscopy
Supercritical fluids
supercritical fluids
laser spectroscopy
Laser pulses
Solvation
pulses
solvation
Fluorescence
fluorescence
decay
Carbon Monoxide
spectral sensitivity
light emission
Anisotropy
computerized simulation
anisotropy
augmentation
probes
Computer simulation

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

Cite this

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title = "Dynamics in supercritical fluids studied using ultrafast pulse laser spectroscopy",
abstract = "Solvation dynamics and rotational relaxation in supercritical fluids have been examined using the techniques of the subpicosecond laser spectroscopy. The fluorescence up-conversion technique has been employed to detect the fluorescence anisotropy decay of coumarin 153 in supercritical CO 2 (310 K) and CHF 3 (302, 310 K) over a wide density range. The rotational correlation times in supercritical CHF 3 exhibit the remarkable increase at 0.6 0.7 times ρ c, which implies that the local solvent density augmentation slows down the rotational dynamics in supercritical fluids. This conclusion is supported by computer simulations based on a 2-site model of fluoroform. The solvation dynamics of the probe 4-dimethylamino-4′-cyanostilbene have been measured in supercritical CHF 3 at 310 K using the optical Kerrgated emission technique, which appears to have captured most (∼90{\%}) of the dynamics occurring over the accessible density range between 1.4-2.0ρ c. The measured spectral response exhibits a bimodal decay with ∼0.6 ps and ∼9 ps components and only a modest density dependence.",
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Dynamics in supercritical fluids studied using ultrafast pulse laser spectroscopy. / Kometani, Noritsugu; Hoshihara, Yuji; Maroncelli, Mark.

In: Review of High Pressure Science and Technology/Koatsuryoku No Kagaku To Gijutsu, Vol. 16, No. 2, 22.06.2006, p. 113-119.

Research output: Contribution to journalArticle

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AU - Maroncelli, Mark

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