A theoretical study of the reaction of Ti+ with ethane

Abstract

The doublet and quartet potential energy surfaces for the Ti++C2H6→TiC2H+4+H2 and Ti++C2H6→TiCH+2+CH4reactions are studied using density functional theory(DFT) with the B3LYP functional and ab initiocoupled cluster CCSD(T) methods with high quality basis sets. Structures have been optimized at the DFT level and the minima connected to each transition state (TS) by following the intrinsic reaction coordinate (IRC). Relative energies are calculated both at the DFT and coupled-cluster levels of theory. The relevant parts of the potential energy surface, especially key transition states, are also studied using multireference wave functions with the final energetics obtained with multireference second-order perturbation theory. The doublet and quartet potential energy surfaces for the Ti ϩ ϩC 2 H 6 →TiC 2 H 4 ϩ ϩH 2 and Ti ϩ ϩC 2 H 6 →TiCH 2 ϩ ϩCH 4 reactions are studied using density functional theory ͑DFT͒ with the B3LYP functional and ab initio coupled cluster CCSD͑T͒ methods with high quality basis sets. Structures have been optimized at the DFT level and the minima connected to each transition state ͑TS͒ by following the intrinsic reaction coordinate ͑IRC͒. Relative energies are calculated both at the DFT and coupled-cluster levels of theory. The relevant parts of the potential energy surface, especially key transition states, are also studied using multireference wave functions with the final energetics obtained with multireference second-order perturbation theory.

Theoretical study of the reaction of titanium ion with ethane — Structure, mechanism, and potential energy surface

“…On the theoretical side, several outstanding works have also been conducted in the recent years by using ab initio and density function calculations (15)(16)(17)(18)(19), and the relevant results have provided some important information on the potential energy surfaces (PESs). The most detailed computational results for the reaction of Ti + with methane have been reported by Sililia and Russo (18).…”

Why is Pt4+ the Least Efficient Cationic Cluster in Activating the C−H Bond in Methane? Two-State Reaction Computational Investigation

“…A large number of recent studies, both experimental and theoretical, have been devoted to reactions of gas-phase transition metal atoms or ions with CH 4 . For example, the first- and secondrow M + (M = Ti, V, Cr, Fe, Co, Ni, Mo, and Nb) and third-row M + (M = W, Os, Ir, and Pt) − have all been studied experimentally and/or theoretically.…”

C–H Bond Activation by the Excited Zinc Atom: Gas-Phase Formation of Methylzinc Hydride (HZnCH3) Based on Multireference Second-Order Perturbation Theory and Coupled Cluster Calculations

“…The performance of these various SOC computing procedures was evaluated through calculation of the spin–orbit splittings in the 3 P state of atomic zinc (Table ), which shows that the MCSCF­(2,4)/SBKJC ECP and DK-MCSCF­(2,4)/aug-cc-pVTZ-DK (cc-pVTZ-DK) results are in reasonable agreement with those obtained by the DK-MRCI­(2,4)/aug-cc-pwCVTZ-DK (cc-pwCVTZ-DK) approach and experiment . The magnitude of the calculated SOC constant at the MEX is strongly dependent on the Zn–C distance. That is, at the MCSCF geometry, the SOC constant is found to be in the range of 1.05–1.83 cm –1 with the MCSCF­(2,4)/SBKJC ECP and DK-MCSCF­(2,4)/aug-cc-pVTZ-DK procedures and at the B3LYP geometry, it is predicted to be 28.56 cm –1 (MCSCF­(2,4)/SBKJC ECP) and 38.73 cm –1 (DK-MCSCF­(2,4)/aug-cc-pVTZ-DK).…”

“…This is due to insufficient dynamic correlation in the MCSCF method, which has implications for the location of the system’s MEX ( s ) . The rate of intersystem crossing is known to depend on the SOC . To compute the SOC matrix element at the MEX , we first applied the approximate one-electron Breit–Pauli spin–orbit operator combined with the effective nuclear charge approach along with state-averaged MCSCF wave functions employing the relativistic Stevens–Basch–Krauss–Jasien–Cundari (SBKJC) effective core potentials and associated basis sets (MCSCF/SBKJC ECP) .…”