AbstractThe Molecular Orbital‐Valence Bond (MOVB) method is briefly outlined and it is subsequently applied to the problem of geometric isomerism of molecules having eight and ten sigma valence electrons such as bent HC≡CH and HN=≡NH. It is shown that orbital symmetry dictates a trans bending tendency for HCCH and in the hypothetical absence of nonbonded repulsion, a cis geometry for XNNY and