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Catastrophic brittle failure of ductile materials by liquid metal embrittlement (LME) is a widely documented phenomenon but the fundamentals of its initiation mechanism are poorly understood. The widespread use of Zn-coated advanced high strength steels in the automotive industry has been plagued by Zn-induced LME which is frequently observed in high-temperature forming and welding applications. In this study, numerical modeling and an atomic-scale experimental investigation are used in order to gain insight into the atomistic events that lead to the onset of LME cracking. The results showed that the formation of a stress-induced diffusion wedge (SIDW) at the exposed grain boundary (GB) due to the interdiffusion of Zn-embrittler atoms was the trigger for LME. The formation of the SIDW facilitated the diffusion of the Zn-embrittler atoms into the GBs, which compromised their mechanical integrity. The results show that LME initiation entails several steps: (i) solid-state GB diffusion, (ii) formation of the SIDW, (iii) eventual melting of the SIDW, and (iv) opening of the liquid wedge due to interdiffusion and the application of externally applied stresses. [ABSTRACT FROM AUTHOR]