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We report the first experimental observation of single-photon ionization transitions of the SiC radical between 8.0 and 11.0 eV performed on the DESIRS beamline at the SOLEIL synchrotron facility. The SiC radical, very difficult to synthesize in the gas phase, was produced through chemical reactions between CHx (x = 0–3) and SiHy (y = 0–3) in a continuous microwave discharge flow tube, the CHx and SiHy species being formed by successive hydrogen-atom abstractions induced by fluorine atoms on methane and silane, respectively. Mass-selected ion yield and photoelectron spectra were recorded as a function of photon energy using a double imaging photoelectron/photoion coincidence spectrometer. The photoelectron spectrum enables the first direct experimental determinations of the X+ 4Σ− ← X 3Π and 1+ 2Π ← X 3Π adiabatic ionization energies of SiC (8.978(10) eV and 10.216(24) eV, respectively). Calculated spectra based on Franck–Condon factors are compared with the experimental spectra. These spectra were obtained by solving the rovibrational Hamiltonian, using the potential energy curves calculated at the multireference single and double configuration interaction level with Davidson correction (MRCI + Q) and the aug-cc-pV5Z basis set. MRCI + Q calculations including the core and core–valence electron correlation were performed using the aug-cc-pCV6Z basis set to predict the spectroscopic properties of the six lowest electronic states of SiC+. Complete basis set extrapolations and relativistic energy corrections were also included in the determination of the energy differences characterizing the photoionization process. Using our experimental and theoretical results, we derived semi-experimental values for the five lowest ionization energies of SiC. [ABSTRACT FROM AUTHOR]

We report the first experimental observation of single-photon ionization transitions of the SiC radical between 8.0 and 11.0 eV performed on the DESIRS beamline at the SOLEIL synchrotron facility. The SiC radical, very difficult to synthesize in the gas phase, was produced through chemical reactions between CH x ( x = 0-3) and SiH y ( y = 0-3) in a continuous microwave discharge flow tube, the CH x and SiH y species being formed by successive hydrogen-atom abstractions induced by fluorine atoms on methane and silane, respectively. Mass-selected ion yield and photoelectron spectra were recorded as a function of photon energy using a double imaging photoelectron/photoion coincidence spectrometer. The photoelectron spectrum enables the first direct experimental determinations of the X + 4 Σ - ← X 3 Π and 1 + 2 Π ← X 3 Π adiabatic ionization energies of SiC (8.978(10) eV and 10.216(24) eV, respectively). Calculated spectra based on Franck-Condon factors are compared with the experimental spectra. These spectra were obtained by solving the rovibrational Hamiltonian, using the potential energy curves calculated at the multireference single and double configuration interaction level with Davidson correction (MRCI + Q) and the aug-cc-pV5Z basis set. MRCI + Q calculations including the core and core-valence electron correlation were performed using the aug-cc-pCV6Z basis set to predict the spectroscopic properties of the six lowest electronic states of SiC + . Complete basis set extrapolations and relativistic energy corrections were also included in the determination of the energy differences characterizing the photoionization process. Using our experimental and theoretical results, we derived semi-experimental values for the five lowest ionization energies of SiC.

The predissociation spectra of the 35Cl-(H2) and 35Cl-(D2) complexes are determined within an accurate quantum approach and compared to those recently measured in an ionic trap at 8 K and 22 K. The calculations are performed using an existing three-dimensional potential energy surface. A variational approach is used for the accurate quantum calculations of the rovibrational bound states. Several methods are compared for the search and the characterization of the resonant states. A good agreement between the calculated and measured spectra is obtained, despite a slight shift to the red of the calculated spectra. The comparison shows that only the ortho or para contribution is observed in the measured 35Cl-(H2) or 35Cl-(D2) spectrum, respectively. Quantum numbers are assigned to the rovibrational resonant states. It demonstrates that the main features observed in the measured predissociation spectra correspond to a progression in the intermonomer vibrational stretching mode.

Quantum tunneling is a common fundamental quantum mechanical phenomenon. The dynamics induced by this effect is closely connected to the shape of the potentials. Here we treat the CO2-N2 van der Waals complex dynamics using a first principles treatment where nuclear motions and nuclear spins are fully considered. This dimer is found to exhibit complex spectral and dynamical features that cannot be accounted for using standard experimental and theoretical models. We shed light on some aspects of its quantum tunneling dynamics that remained unexplained since its first evidence 85 years ago. CO2-N2 represents also an important prototype for studying the systematic (as in NH3) lifting of degeneracy due to tunneling effects and large amplitude motions. Vibrational memory and quantum localization effects are evidenced. Plural potential wells separated by potential barriers are commonly found for polyatomic organic and inorganic molecules (e.g., cis-trans isomerization and enol-keto tautomerism). The present findings are useful for understanding the complex quantum effects that may occur there.

Since their recent detection in the interstellar medium, anions have raised the question of their possible mechanisms of formation, destruction and excitation. This requires knowledge of their interaction with the most abundant interstellar species. In the present work, a four dimensional rigid rotor model of the potential energy surface is developed for the collision of C3N- with H2. Ab initio calculations are performed with explicitly-correlated coupled-cluster theory via CCSD(T)-F12/aug-cc-pVTZ. Two linear equilibrium structures are found, different in the orientation of C3N-. Two more equilibrium structures, symmetrically equivalent, are obtained by the permutation of H atoms. The vibrational dynamics is mainly controlled by the considerable difference between the two bending frequencies that correspond to the hindered rotations of C3N- and H2. This arises from the potential energy surface which is soft for rotation of C3N- and stiff for rotation of H2, and also from the large difference in mass between both monomers. Although a high potential barrier prevents the rotation of H2, a significant tunneling effect is observed which causes a splitting in the degenerate energy levels. On the contrary, the rotation of C3N- is allowed since the energy of the saddle points is lower than the energy of the bound states, but the wavefunctions remain localized around each linear structure unless a large excitation energy is available.

In the present study we investigate the role played by the hyperfine structure of manganese in the cooling and magnetic trapping of MnH((7)Σ(+)). The effect of the hyperfine structure of Mn on the relaxation of the magnetically trappable maximally stretched low-field seeking state of MnH((7)Σ(+)) in collisions with (3)He is deduced from comparison between the results of the present approach and our previous nuclear spin free calculations. We show that our previous results are unchanged at the temperature of the buffer gas cooling experiment but find a new resonance at very low collision energy. The role played by the different contributions to the hyperfine diatomic Hamiltonian considered in this work as well as the effect of an applied magnetic field on this resonance are also analyzed.

Methane photolysis has been performed at the two Vacuum UltraViolet (VUV) wavelengths, 121.6 nm and 118.2 nm, via a spectrally pure laser pump-probe technique. The first photon is used to dissociate methane (either at 121.6 nm or at 118.2 nm) and the second one is used to ionise the CH(2) and CH(3) fragments. The radical products, CH(3)(X), CH(2)(X), CH(2)(a) and C((1)D), have been selectively probed by mass spectrometry. In order to quantify the fragment quantum yields from the mass spectra, the photoionisation cross sections have been carefully evaluated for the CH(2) and CH(3) radicals, in two steps: first, theoretical ab initio approaches have been used in order to determine the pure electronic photoionisation cross sections of CH(2)(X) and CH(2)(a), and have been rescaled with respect to the measured absolute photoionisation cross section of the CH(3)(X) radical. In a second step, in order to take into account the substantial vibrational energy deposited in the CH(3)(X) and CH(2)(a) radicals, the variation of their cross sections near threshold has been simulated by introducing the pertinent Franck-Condon overlaps between neutral and cation species. By adding the interpolated values of CH quantum yields measured by Rebbert and Ausloos [J. Photochem., 1972, 1, 171-176], a complete set of fragment quantum yields has been derived for the methane photodissociation at 121.6 nm, with carefully evaluated 1σ uncertainties: Φ[CH(3)(X)] = 0.42 ± 0.05, Φ[CH(2)(a)] = 0.48 ± 0.05, Φ[CH(2)(X)] = 0.03 ± 0.08, Φ[CH(X)] = 0.07 ± 0.01. These new data have been measured independently of the H atom fragment quantum yield, subject to many controversies in the literature. From our results, we evaluate Φ(H) = 0.55 ± 0.17 at 121.6 nm. The quantum yields for the photolysis at 118.2 nm differ notably from those measured at 121.6 nm, with a substantial production of the CH(2)(X) fragment: Φ[CH(3)(X)] = 0.26 ± 0.04, Φ[CH(2)(a)] = 0.17 ± 0.05, Φ[CH(2)(X)] = 0.48 ± 0.06, Φ[CH(X)] = 0.09 ± 0.01, Φ(H) = 1.31 ± 0.13. These new data should bring reliable and essential inputs for the photochemical models of the Titan atmosphere.

The H + CH(+) reaction is studied by quasiclassical trajectory (QCT) calculations, along with phase space theory (PST) and quantum rigid rotor calculations, employing a global single-valued potential energy surface recently derived by our group. We report QCT total cross sections for each of the three channels, for low collision energies and different reactant rotational quantum numbers. At the lowest collision energies, all cross sections exhibit a capture-like behaviour, as expected from a barrierless reaction. At higher energies, there are important dynamical effects coming from the opening of new channels in the inelastic and reactive exchange collisions. The inelastic cross sections turn out to largely increase, while the reactive abstraction cross sections are declining faster than predicted by the capture theory. A large value of the reactant rotational quantum number tends to suppress these dynamical effects. The QCT rate coefficients are reported for a temperature range from 1-700 K. Below 20 K, the abstraction and exchange QCT rate coefficients are almost constant, as predicted by the capture theory. Above this temperature, the abstraction rate coefficient declines, while the exchange and inelastic rate coefficients are increasing, due to the opening of new channels. A good agreement is observed between the experimental abstraction rate coefficient and the QCT and PST ones. The QCT inelastic results are also compared with those obtained from rigid rotor close coupling (CCRR) calculations in order to check the ability of this approach to provide a reliable estimate of the inelastic rate coefficients for a reactive system without a barrier. The laws of variation as a function of temperature are found to be very similar and the curves are parallel above 20 K. However, reaction is not allowed in the rigid rotor approximation, therefore the CCRR results are about twice as large as their QCT counterparts.

In this paper we report the first theoretical study of the title reaction. A global, single-valued model of the ground-state potential energy surface has been obtained by fitting to an extensive set of high-level ab initio calculations. The surface is found to be attractive apart from linear geometries where energy barriers appear due to conical intersections. This model was then used to calculate the reactive reactant state selected cross sections for collision energies ranging from threshold up to 4000 cm(-1). These calculations were performed using our version of the Baer's approach of the RIOSA-NIP method which is based on the use of a negative imaginary potential. We find that the reaction probability is extremely oscillatory as a function of kinetic energy as it is a case for insertion reactions with a low exoergicity. The resulting reaction rate coefficient is found to first increase slowly as a function of temperature up to a broad maximum around 20 K and then to decrease slowly when temperature keeps increasing.