549. Excited states of acetylene. Part I. Possibilities of interaction between σ-bond hybridisation and π-electron excitation with resulting changes of shape during transitions

Ingold, C. K.; King, G.W.

doi:10.1039/jr9530002702

Cited by 148 publications

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“…At 193 nm, acetylene absorbs to v3= 10 (the C-H bending vibration) of the 'A u excited state [19]. The acetylene absorption has been studied extensively in the range 1970-2500 A and this work established that the 'A u excited state has a transbent configuration (C 2h symmetry) [20,21]. Figure 1 [9,22,23,24] shows the products that are thermodynamically possible.…”

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confidence: 99%

193 nm photodissociation of acetylene

Balko¹,

Zhang²,

Lee³

1991

The Journal of Chemical Physics

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The product translational energy distribution P(ET) for acetylene photodissociation at 193 nm was obtained from the time-of-flight spectrum of the H atom fragments. The P(ET) shows resolved structure from the vibrational and electronic excitation of the C2H fragment; comparison of the translational energy release for given excited states of C2H with the known energy levels of these states gives D0(HCC–H)=131.4±0.5 kcal/mol. This value is in agreement with that determined previously in this group from analogous studies of the C2H fragment and with the latest experimental and theoretical work. The high resolution of the experiment also reveals the nature of C2H internal excitation. A significant fraction of the H atoms detected at moderate laser power were from the secondary dissociation of C2H. The P(ET) derived for this channel indicates that most of the C2 is produced in excited electronic states.

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confidence: 99%

193 nm photodissociation of acetylene

Balko¹,

Zhang²,

Lee³

1991

The Journal of Chemical Physics

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“…Many experiments of this type have been carried out in order to characterize the higher vibrational levels of the ground state, [19][20][21][22][23][24][25][26][27][28] the Rydberg states, [29][30][31] and the ground state of the cation. [32,33] The first rotational analyses of the Ã # X system, over 50 years ago, [34][35][36] showed that C 2 H 2 , though linear in its ground electronic state, becomes trans-bent (point group C 2h ) in the Ã state. Consistent with this, the most obvious feature of the vibrational structure in absorption is a long progression in the trans-bending vibration, !…”

Section: Introductionmentioning

confidence: 99%

Stretch-bend combination polyads in the Ã1Au state of acetylene, C2H2

Steeves

Bechtel

Merer

et al. 2009

Journal of Molecular Spectroscopy

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“…Without this enhancement, the hot band-pumped IR-UV transitions to 3 3 of these transitions is easily verified as this K ′ = 3 level has been previously observed in IR-UV DR spectra via the ν ′′ 3 + ν ′′ 4 (ℓ ′′ = 1) level, where it gains intensity only through strong Coriolis coupling to the K ′ = 1 level.…”

Section: Hot Band-pumped Ir-uv Double Resonance: Proof Of Principlementioning

confidence: 77%

Probing cis-trans isomerization in the S1 state of C2H2 via H-atom action and hot band-pumped IR-UV double resonance spectroscopies

Changala

Baraban

Merer

et al. 2015

The Journal of Chemical Physics

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Articles you may be interested inVibrational energy relaxation of benzene dimer and trimer in the CH stretching region studied by picosecond time-resolved IR-UV pump-probe spectroscopy J. Chem. Phys. 136, 044304 (2012) Probing cis-trans isomerization in the S 1 state of C 2 H 2 via H-atom action and hot band-pumped IR-UV double resonance spectroscopies We report novel experimental strategies that should prove instrumental in extending the vibrational and rotational assignments of the S 1 state of acetylene, C 2 H 2 , in the region of the cis-trans isomerization barrier. At present, the assignments are essentially complete up to ∼500 cm −1 below the barrier. Two difficulties arise when the assignments are continued to higher energies. One is that predissociation into C 2 H + H sets in roughly 1100 cm −1 below the barrier; the resulting quenching of laser-induced fluorescence (LIF) reduces its value for recording spectra in this region. The other difficulty is that tunneling through the barrier causes a staggering in the K-rotational structure of isomerizing vibrational levels. The assignment of these levels requires data for K values up to at least 3. Given the rotational selection rule K ′ − ℓ ′′ = ±1, such data must be obtained via excited vibrational levels of the ground state with ℓ ′′ > 0. In this paper, high resolution H-atom resonance-enhanced multiphoton ionization spectra are demonstrated to contain predissociated bands which are almost invisible in LIF spectra, while preliminary data using a hyperthermal pulsed nozzle show that ℓ ′′ = 2 states can be selectively populated in a jet, giving access to K ′ = 3 states in IR-UV double resonance. C 2015 AIP Publishing LLC. [http://dx

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549. Excited states of acetylene. Part I. Possibilities of interaction between σ-bond hybridisation and π-electron excitation with resulting changes of shape during transitions

Cited by 148 publications

References 0 publications

193 nm photodissociation of acetylene

193 nm photodissociation of acetylene

Stretch-bend combination polyads in the Ã1Au state of acetylene, C2H2

Probing cis-trans isomerization in the S1 state of C2H2 via H-atom action and hot band-pumped IR-UV double resonance spectroscopies

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