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

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

Collisional Energy Transfer from Highly Vibrationally Excited Radicals Is Very Efficient

Although highly vibrationally excited (HVE) radicals are ubiquitous in natural environments, the effect of collisional energy transfer (ET) on their reactivity has yet to be fully characterized. We have used time-resolved IR emission spectroscopy to characterize the vibrational-to-translational quenching of a small HVE radical, ketenyl (HCCO), by inert gases. Photolysis of ethyl ethynyl ether at 193 nm provides HVE HCCO in the <i>X̃</i>²A″ electronic ground-state, with a nascent internal energy of 2.2 ± 0.6 eV. IR emission is monitored as an indicator of vibrational energy, and spectral modeling allows direct determination of the average energy lost per collision as a function of the internal energy. Collisional deactivation of HVE HCCO is shown to be minimally an order of magnitude more efficient than closed-shell molecules of comparable size. Schwartz–Slawsky–Herzfeld–Tanczos (SSHT) theory, modified for HVE molecules, suggests that this ET enhancement is due to a strong attractive intermolecular interaction

Chemical Activation through Super Energy Transfer Collisions

Can a molecule be efficiently activated with a large amount of energy in a single collision with a fast atom? If so, this type of collision will greatly affect molecular reactivity and equilibrium in systems where abundant hot atoms exist. Conventional expectation of molecular energy transfer (ET) is that the probability decreases exponentially with the amount of energy transferred, hence the probability of what we label “super energy transfer” is negligible. We show, however, that in collisions between an atom and a molecule for which chemical reactions may occur, such as those between a translationally hot H atom and an ambient acetylene (HCCH) or sulfur dioxide, ET of chemically significant amounts of energy commences with surprisingly high efficiency through chemical complex formation. Time-resolved infrared emission observations are supported by quasi-classical trajectory calculations on a global ab initio potential energy surface. Results show that ∼10% of collisions between H atoms moving with ∼60 kcal/mol energy and HCCH result in transfer of up to 70% of this energy to activate internal degrees of freedom

Chemical Activation through Super Energy Transfer Collisions

Can a molecule be efficiently activated with a large amount of energy in a single collision with a fast atom? If so, this type of collision will greatly affect molecular reactivity and equilibrium in systems where abundant hot atoms exist. Conventional expectation of molecular energy transfer (ET) is that the probability decreases exponentially with the amount of energy transferred, hence the probability of what we label “super energy transfer” is negligible. We show, however, that in collisions between an atom and a molecule for which chemical reactions may occur, such as those between a translationally hot H atom and an ambient acetylene (HCCH) or sulfur dioxide, ET of chemically significant amounts of energy commences with surprisingly high efficiency through chemical complex formation. Time-resolved infrared emission observations are supported by quasi-classical trajectory calculations on a global <i>ab initio</i> potential energy surface. Results show that ∼10% of collisions between H atoms moving with ∼60 kcal/mol energy and HCCH result in transfer of up to 70% of this energy to activate internal degrees of freedom