Low-Lying Electronic States of the Nickel Dimer

The generalized Van Vleck second order multireference perturbation theory (GVVPT2) method was used to investigate the low-lying electronic states of Ni2. Because the nickel atom has an excitation energy of only 0.025 eV to its first excited state (the least in the first row of transition elements), Ni2 has a particularly large number of low-lying states. Full potential energy curves (PECs) of more than a dozen low-lying electronic states of Ni2, resulting from the atomic combinations 3F4 + 3F4 and 3D3 + 3D3, were computed. In agreement with previous theoretical studies, we found the lowest lying states of Ni2 to correlate with the 3D3 + 3D3 dissociation limit, and the holes in the d-subshells were in the subspace of delta orbitals (i.e., the so-dubbed δδ-states). In particular, the ground state was determined as X 1Γg and had spectroscopic constants: bond length (Re) = 2.26 Å, harmonic frequency (ωe) = 276.0 cm−1, and binding energy (De) = 1.75 eV; whereas the 1 1Σg+ excited state (with spectroscopic constants: Re = 2.26 Å, ωe = 276.8 cm−1, and De = 1.75) of the 3D3 + 3D3 dissociation channel lay at only 16.4 cm−1 (0.002 eV) above the ground state at the equilibrium geometry. Inclusion of scalar relativistic effects through the spin-free exact two component (sf-X2C) method reduced the bond lengths of both of these two states to 2.20 Å, and increased their binding energies to 1.95 eV and harmonic frequencies to 296.0 cm−1 for X 1Γg and 297.0 cm−1 for 1 1Σg+. These values are in good agreement with experimental values of Re = 2.1545 ± 0.0004 Å, ωe = 280 ± 20 cm−1, and D0 = 2.042 ± 0.002 eV for the ground state. All states considered within the 3F4 + 3F4 dissociation channel proved to be energetically high-lying and van der Waals-like in nature. In contrast to most previous theoretical studies of Ni2, full PECs of all considered electronic states of the molecule were produced.

Breakdown curves of CH2(+), CH3(+), and CH4(+) molecules

Aims. The aim of this work is to furnish branching ratios (BRs) to the kinetic databases used in astrochemistry such as the KInetic Database for Astrochemistry (KIDA). This concerns CHy(+) species (y = 2–4) excited by cosmic rays, electrons and photons, or the intermediate excited complexes CHy(+) resulting from a chemical reaction. Methods. The full set of fragmentation branching ratios following CHy(+) (y = 2,4) of constant velocity (250 keV uma−1) colliding with He atoms has been measured with the multidetector AGAT. Kinetic energy distributions of neutral fragments produced in each dissociation channel have been also measured. With these experimental inputs, and theoretical dissociation energies, semiempirical breakdown curves (BDCs) have been constructed. Results. Prediction of BRs with the present BDCs is found to agree with available BR measurements for electronic dissociative recombination, collision with fast electron and photodissociation. Dependence of BRs with the various UV fields relevant to interstellar medium and planetary atmospheres is predicted.

Calculation of anharmonic effects for the unimolecular dissociation of CH3OOH and its deuterated species CD3OOD using the Rice–Ramsperger–Kassel–Marcus theory

Anharmonic and harmonic rate constants for the unimolecular dissociation of CH3OOH and CD3OOD were calculated using the Rice–Ramsperger–Kassel–Marcus (RRKM) theory at the MP2/6-311++G(3df,3pd) level of theory. The anharmonic effect of the reactions was investigated. Comparison of results for the decompositions of CH3OOH and CD3OOD shows that the direct bond dissociation channel, CH3 (D3) O + OH (D), is the most dominant reaction. The anharmonic effect plays an important role in the unimolecular dissociation of both CH3OOH and CD3OOD. For channels CH3 (D3) O + OH (D) and CH3 (D3) + H (D) O2, the anharmonic effect of the unimolecular dissociation of CD3OOD is more pronounced than that of the unimolecular dissociation of CH3OOH. For channel H2 (D2) CO + H2 (D2) O, the anharmonic effect of the unimolecular dissociation of CH3OOH is more pronounced than that of the unimolecular dissociation of CD3OOD. The isotope effect is more distinct in the anharmonic oscillator model.

The triplet-charge annihilation in copolymer-based organic light emitting diodes: through the “Scattering Channel” or the “Dissociation Channel”?

Organic magneto-current of OLEDs reveals that 3LE and 3CT are participants in the “Scattering Channel” and the “Dissociation Channel” of triplet-charge annihilation, respectively.