Molecular hyperpolarisability as a screening descriptor for second-order nonlinear optics in ferroelectric nematic...

Ferroelectric nematic liquid crystals combine fluidity with macroscopic polar order. Although the archetypal N_F material RM734 exhibits large nonlinear optical coefficients, most known ferroelectric nematics were designed without consideration of optical nonlinearity. Here, we assess whether electronic-structure calculations can be used to identify promising nonlinear optical candidates within known polar liquid-crystal materials. Frequency-dependent molecular hyperpolarisability tensors were calculated using a range of DFT methods and basis sets, then converted to macroscopic d-coefficients using an oriented-gas model with empirical 〈P₁〉 and 〈P₃〉 values. Calculated values were benchmarked against available experimental d₃₃, d₁₅, and d₁₃/d₃₁ coefficients for representative materials. We find that absolute values depend strongly on method and bulk-parameter assumptions, whereas relative trends are more useful for screening. Explicit conformer averaging does not consistently improve agreement with experiment. Applying the best-performing single-conformer protocols to a broader polar liquid-crystal dataset identifies candidate materials with enhanced predicted nonlinear optical response and reveals simple design rules based on donor-acceptor asymmetry, conjugation length, and linker choice.