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A new type of reaction pathway which involves a nontotally symmetric trifurcation was found and investigated for a typical SN2‐type reaction, NC‐ + CH3X → NCCH3 + X‐ (X = F, Cl). A nontotally symmetric valley‐ridge inflection (VRI) point was located along the C3v reaction path. For X = F, the minimum energy path (MEP) starting from the transition state (TS) leads to a second‐order saddle point with...
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