Wydział Chemii

Jerzy Moc

2021

ACS Omega

6

24280-24288

10.1021/acsomega.1c04531

Naukowa

Angielski

Artykuł

The pioneering spectroscopic observations of themethylzinc hydride [HZnCH3(X1A1)] molecule were reportedpreviously by the Ziurys group [J. Am. Chem. Soc.2010, 132,17186−17192], and the possible formation mechanisms weresuggested therein, including those with the participation of excitedzinc atoms in reaction with methane. Herein, the ground singlet stateand the lowest excited triplet state potential energy surfaces of the Zn+CH4reaction have been explored using high-level electronicstructure calculations with multireference second-order perturbationtheory and coupled cluster singles and doubles with perturbativetriples (CCSD(T)) methods in conjunction with all-electron basissets (up to aug-cc-pV5Z) and scalar relativistic effects incorporatedvia the second-order Douglas−Kroll−Hess (DK) method. Based onthe ab initio results, a plausible scenario for the formation ofHZnCH3(X1A1) is proposed involving the activation of the C−H bond of methane by the lowest excited3P state atomic zinc.Calculations also highlight the importance of an agostic-like Zn···H−C interactions in the pre-activation complex and goodagreement between the structure of the HZnCH3(X1A1) molecule predicted at the DK-CCSD(T)/aug-cc-pVQZ-DK level of theoryand that derived from rotational spectroscopy, as well as the discrepancies between the ab initio and density functional theorypredictions.

Zinc, Hydrocarbons, Chemical reactions, Quantum mechanics, Potential energy

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http://dx.doi.org/10.1021/acsomega.1c04531

https://www.acs.org/content/acs/en.html