The symmetry-broken wave function can transform the 1 Σg + state of C2 from the classic double bonding to the quadruple bonding, where the transformed wave functions of ϕ L and ϕ R are singly occupied by two opposite-spinning electrons. In this article, the effective bond order (EBO) contribution of the fourth bond in C2 is assessed through the overlap integral between ϕ L and ϕ R , namely the value (0.60) is the EBO contribution of the fourth bond in the transformed scheme. Hence, the new EBO is 3.36, which is more equitable than the original EBO (2.15) in the traditional scheme. In addition, the singlet diradical character of the linear polyacetylenic C4 and C6 in the 1 Σg + state is addressed for the first time. No spin-polarized bonding exists in other linear C2n clusters, because the ionic interaction in the polyacetylenic 1 Σg + state of C4 is negligible. Moreover, the coupling energy between α and β single electrons in C4 is only 4.0 kcal mol-1 based on the electron spin-flip energy. © 2019 Wiley Periodicals, Inc.