Conical intersection-regulated intermediates in bimolecular reactions: Insights from C(¹D) + HD dynamics.

ABSTRACT: The importance of conical intersections (CIs) in electronically nonadiabatic processes is well known, but their influence on adiabatic dynamics has been underestimated. Here, through combined experimental and theoretical studies, we show that CIs induce a barrier and regulate conversion from a precursor metastable intermediate (CI-R) to a deep well one. This results in bond-selective activation, influencing the adiabatic dynamics markedly in the C(¹D) + HD reaction. Theory is validated by experiment; quantum dynamics calculations on highly accurate ab initio potential energy surfaces yield rate coefficients and product branching ratios in excellent agreement with the experiment. Quasi-classical trajectory calculations reveal that the CI-R intermediate leads to unusual reaction m

SUBMITTER: Wu Y 

PROVIDER: S-EPMC6486230 | biostudies-literature | 2019 Apr

REPOSITORIES: biostudies-literature