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Using fast off-lattice Monte Carlo simulations with experimentally accessiblefluctuations, we report the first systematic study unambiguously quantifyingthe shift of the order-disorder transition (ODT) $\chi^*$ of symmetric diblockcopolymers from the mean-field prediction $\chi^*_{\rm MF}$. Our simulationsare performed in a canonical ensemble with variable box lengths to eliminatethe restriction of periodic boundary conditions on the lamellar period. Exactlythe same model system (Hamiltonian) is used in both our simulations andmean-field theory; the ODT shift is therefore due to thefluctuations/correlations neglected by the latter. While $\chi^* / \chi^*_{\rmMF} - 1 \propto \bar{\mathcal{N}}^{-k}$ is found with $\bar{\mathcal{N}}$denoting the invariant degree of polymerization, $k$ decreases around the$\bar{\mathcal{N}}$-value corresponding to the close packing of polymersegments as hard spheres, indicating the short-range correlation effects.

Quantifying Fluctuation/Correlation Effects on the Order-Disorder Transition of Symmetric Diblock Copolymers