Relaxation within and from the (31/214151) and (3141/214251) Fermi dyads in acetylene: Vibrational energy transfer in collisions with C2H2, N2 and H2

Henton, Sarah; Islam, Meez; Smith, Ian W. M.

doi:10.1039/a805621h

Cited by 14 publications

(12 citation statements)

References 9 publications

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“…This initial interpretation [58] was qualitatively correct, but it has been treated more rigorously by Henton et al [343,344]. They extended Frost's original RET and intradyad V-V transfer measurements by J-resolved IR-UV DR studies with an IR PUMP pulse exciting the J init ¼ 10 level of its ( 3 / 2 þ 4 þ 5 ) II manifold of C 2 H 2 with G v ¼ 3 281.90 cm À1 .…”

Section: Ir-uvmentioning

confidence: 90%

“…They have also made parallel studies of the ( 3 þ 4 / 2 þ 2 4 þ 5 ) Fermi-type dyad of C 2 H 2 at $3890 cm À1 [343,344]. 5.2.3.…”

Section: Ir-uvmentioning

confidence: 97%

“…IR-UV DR spectroscopy of rovibrational energy transfer in the CH manifold of C 2 H 2 , centred at $3 288 cm À1 [58,60,123], has been highly productive for Smith, Frost, and coworkers [339][340][341][342][343][344]. Frost's early UV-scanned, LIF-detected IR-UV DR experiments [340] have yielded insight into ways in which intramolecular perturbations, such as the Fermi-type coupling in the ( 3 / 2 þ 4 þ 5 ) dyad of C 2 H 2 (as introduced in section 3.3 above), can influence rotationally resolved propensities and cross-sections for collision-induced intramolecular V-V transfer between the ( 3 / 2 þ 4 þ 5 ) I and ( 3 / 2 þ 4 þ 5 ) II sub-manifolds, compared to RET within either of the dyad components.…”

Section: Ir-uvmentioning

confidence: 99%

“…Smith and coworkers have performed numerous other IR-UV DR experiments on intramolecular and intermolecular V-V transfer within the CH manifold of C 2 H 2 at $3288 cm À1 , both in self-collisions [339][340][341][342][343][344] and with foreign-gas collision partners (notably He, Ar, H 2 , and N 2 ) [339,343,344]. They have also made parallel studies of the ( 3 þ 4 / 2 þ 2 4 þ 5 ) Fermi-type dyad of C 2 H 2 at $3890 cm À1 [343,344].…”

Section: Ir-uvmentioning

confidence: 99%

“…Relevant IR-UV DR spectroscopic experiments range from low-energy bending levels of C 2 D 2 [51,57] and C 2 HD [57], through the fundamental CH-stretching ( CH ) region of C 2 H 2 [339][340][341][342][343][344], and on to higher-energy overtone and combination levels of C 2 H 2 [55, 60-69, 131, 165, 338, 345-350]. Figure 1, introduced briefly in sections 3.1 and 3.6, is a generic excitation scheme for time-resolved, LIF-detected IR-UV DR spectroscopy of C 2 H 2 .…”

Section: Infrared-ultraviolet Double-resonance Spectroscopy Of Acetylenementioning

confidence: 99%

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Spectroscopy and energetics of the acetylene molecule: dynamical complexity alongside structural simplicity

Orr

2006

International Reviews in Physical Chemistry

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Section: Ir-uvmentioning

confidence: 90%

“…They have also made parallel studies of the ( 3 þ 4 / 2 þ 2 4 þ 5 ) Fermi-type dyad of C 2 H 2 at $3890 cm À1 [343,344]. 5.2.3.…”

Section: Ir-uvmentioning

confidence: 97%

Section: Ir-uvmentioning

confidence: 99%

Section: Ir-uvmentioning

confidence: 99%

Section: Infrared-ultraviolet Double-resonance Spectroscopy Of Acetylenementioning

confidence: 99%

See 3 more Smart Citations

Spectroscopy and energetics of the acetylene molecule: dynamical complexity alongside structural simplicity

Orr

2006

International Reviews in Physical Chemistry

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Symmetry-breaking collisional energy transfer in the 4νCH rovibrational manifold of acetylene: spectroscopic evidence of a quasi-continuum of background states

Payne

Milce

Frost

et al. 2000

Chemical Physics Letters

163

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Collisional Relaxation of Highly Vibrationally Excited Acetylene Mediated by the Vinylidene Isomer

Smith,

Nikow,

Wilhelm

et al. 2023

J. Phys. Chem. A

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Collisional relaxation of highly vibrationally excited acetylene, generated from the 193 nm photolysis of vinyl bromide with roughly 23,000 cm −1 of nascent vibrational energy, is studied via submicrosecond time-resolved Fourier transform infrared (FTIR) emission spectroscopy. IR emission from vibrationally hot acetylene during collisional relaxation by helium, neon, argon, and krypton rare-gas colliders is recorded and analyzed to deduce the acetylene energy content as a function of time. The average energy lost per collision, ⟨ΔE⟩, is computed using the Lennard-Jones collision frequency. Two distinct vibrational-to-translational (V−T) energy transfer regimes in terms of the acetylene energy are identified. At vibrational energies below 10,000−14,000 cm −1 , energy transfer efficiency increases linearly with molecular energy content and is in line with typical V−T behavior in quantity. In contrast, above 10,000−14,000 cm −1 , the V−T energy transfer efficiency displays a dramatic and rapid increase. This increase is nearly coincident with the acetylene-vinylidene isomerization limit, which occurs nearly 15,000 cm −1 above the acetylene zero-point energy. Combined quasi-classical trajectory calculations and Schwartz-Slawsky-Herzfeld-Tanczos theory point to a vinylidene contribution being responsible for the large enhancement. This observation illustrates the influence of energetically accessible structural isomers to greatly enhance the energy transfer rates of highly vibrationally excited molecules.

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Relaxation within and from the (31/214151) and (3141/214251) Fermi dyads in acetylene: Vibrational energy transfer in collisions with C2H2, N2 and H2

Cited by 14 publications

References 9 publications

Spectroscopy and energetics of the acetylene molecule: dynamical complexity alongside structural simplicity

Spectroscopy and energetics of the acetylene molecule: dynamical complexity alongside structural simplicity

Symmetry-breaking collisional energy transfer in the 4νCH rovibrational manifold of acetylene: spectroscopic evidence of a quasi-continuum of background states

Collisional Relaxation of Highly Vibrationally Excited Acetylene Mediated by the Vinylidene Isomer

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