Spin-Orbit Effects in the Spectroscopy of the X2Π and a4Σ- Electronic States of Carbon Iodide, CI.

Highly correlated ab initio calculations have been performed to describe the potential energy curves (PECs) and the spectroscopic properties of the X2Π state and of the first excited state of the CI radical. Multi Reference configuration interaction calculations with Davidson correction (MRCI+Q) and relativistic effective core potential for the iodine atom have been performed. It is found that the two lowest electronic states, the X2Π and the a4Σ- states, are stable against dissociation and well separated from the other electronic states. Spectroscopic constants of these two states have been evaluated using their calculated PECs. Because of the presence of the iodine atom in this molecular system, spin-orbit (SO) interactions are playing an important role in the molecular and in the dissociation regions. The excitation energy of the a4Σ- state is calculated 1.67 eV (MRCI) above the X2Π ground state and 1.70/1.62 eV (MRCI with SO correction) for the Ω = 1/2 and 3/2 transitions, respectively. The dissociation energy D0 of the X2Π ground state is evaluated 2.66 eV (MRCI calculation) without SO correction and 2.46/2.36 eV with SO correction for the Ω = 1/2 and 3/2 components, respectively. The dissociation energy D0 of the a4Σ- state is evaluated 0.99 eV (MRCI calculation) without SO correction and 0.83/0.72 eV with SO correction for the Ω = 1/2 and 3/2 components, respectively. This work should help for the identification of this radical in laboratory and in atmospheric media.

Energetic Diagrams and Structural Properties of Monohaloacetylenes HC≡CX (X = F, Cl, Br).

Highly correlated electronic wave functions within the Multi Reference Configuration Interaction (MRCI) approach are used to study the stability and the formation processes of the monohaloacetylenes HCCX and monohalovinylidenes C2HX (X = F, Cl, Br) in their electronic ground state. These tetra-atomics can be formed through the reaction of triatomic fragments C2F, C2Cl, and C2Br with a hydrogen atom or of C2H with halogen atoms via barrierless reactions, whereas the reactions between the diatomics [C2 + HX] need to overcome barriers of 1.70, 0.89, and 0.58 eV for X = F, Cl, and Br. It is found that the linear HCCX isomers, in singlet symmetry, are more stable than the singlet C2HX iso-forms by 1.995, 2.083, and 1.958 eV for X = F, Cl, and Br. The very small isomerization barriers from iso to linear forms are calculated 0.067, 0.044, and 0.100 eV for F, Cl, and Br systems. The dissociation energies of the HCCX systems (without ZPE corrections), resulting from the breaking of the CX bond, are calculated to be 5.647, 4.691, and 4.129 eV for X = F, Cl, Br, respectively. At the equilibrium geometry of the X(1)Σ(+) state of HCCX, the vertical excitation energies in singlet and triplet symmetries are all larger than the respective dissociation energies. Stable excited states are found only as (3)A', (3)A″, and (1)A″ monohalovinylidene structures.

Reaction of CN(-) with F, Cl, O, and S Atoms: Attachment or Associative Detachment?

Highly correlated ab initio wave functions within the UCCSD(T)-F12 approach have been used to map the potential energy surfaces (PESs) describing the reactivity of the CN(-) (X(1)Σ(+)) anion with neutral atoms present in interstellar media (F, Cl, O, and S). With the H atom, for comparison, the reaction [CN(-)((1)Σ(+)) + H((2)S)] evolves along the PES of the X(2)Σ(+) electronic ground state of HCN(-) (or HNC(-)) until the crossing with the X(1)Σ(+) electronic ground state of HCN (or HNC), where electron detachment occurs. The process is rather similar to the two halogen atoms F and Cl, with some differences due to the larger electron affinity of the halogens, making possible the existence of ClCN(-) in a (2)Σ(+) state. The reaction of CN(-) with O and S atoms proceeds via a multistep mechanism. The lowest electronic state at long distance, the (3)Π state arising from the [CN(-)((1)Σ(+)) + O/S((3)P)] reaction channel, does not correlate with the X(1)Σ(+) ground state of the XCN(-) anion (X = O or S). This (3)Π state and its bent components cross at medium RXC (RXN) distances the X(1)Σ(+) ground state of XCN(-) or XNC(-), and at shorter distances the X(2)Π state of the neutral XCN or XNC where the extra electron can detach. With both O and S atoms, it is shown that the spin-orbit couplings can efficiently lead the [CN(-)((1)Σ(+)) + O/S((3)P)] reaction toward the stable X(1)Σ(+) ground state of XCN(-) and XNC(-).

Nucleophilic or electrophilic interactions of C2 with HX systems (X = F, Cl, Br).

Highly correlated ab initio wave functions within the MRCI approach are used in a comparative study of the interactions between C2 and the three hydrogen halides HX (X = F, Cl, Br). Test calculations are also presented using the UCCSD(T)-F12 approach. The asymptotic regions are investigated for different relative orientations of the two moieties. It is shown that the three systems C2 + HX are bound, for intermolecular distances close to 3 Å, through nucleophilic interactions between C2 and HX for approaches perpendicular to the C-C axis, with decreasing interaction energies from HF to HBr. For HX approaching C2 along its axis, the interactions, governed by the electrophilic character of C2 are decreasing from HBr to HF. Even though the reactions toward the molecular systems HCCX or CCHX are exothermic, activation barriers (0.58 eV and more) are calculated at short distances, preventing the direct reactions toward the corresponding tetra-atomic systems.