Relativistic DFT study on the reaction mechanism of second-row transition metal Ru with CO2

To estimate the importance of relativistic effects on the reaction mechanisms between Ru and CO2, the potential energy surfaces have been performed in the triplet and quintet electronic states using quasi-relativistic (Pauli), zero-order regularly approximated (ZORA), and nonrelativistic (NR) density functional theory (DFT) at the PW91/TZP level. The results demonstrate that there are two rival reaction mechanisms: one is an addition mechanism and the other is an insertion mechanism in the triplet state. The only mechanism in the quintet state is the insertion mechanism. The most favored reaction mechanism in Ru + CO2 is that the Ru atom in its ground state first attacks the CO bond of CO2, forming q-Ru(CO)O (5A') with the insertion mechanism, and then undergoes an intersystem crossing to t-Ru(CO)O (3A'). Then it crosses t-TS3 to produce t-ORuCO molecule. The relativistic effects are important for reactivity of the second-row transition metal to CO2. In the key step of t-Ru(CO)O via t-TS3 to t-ORuCO, relativistic effects reduce the barrier energy by 10.3 kcal/mol, which is nearly half the nonrelativistic barrier energy.