We report the hyperfine couplings and chemical shifts of water protons in a typical NMR-photonic dual-modality nanoprobe that consists of gadolinium oxide and gold nanoclusters surrounded by water molecules, which have been addressed through density functional theory (DFT). The DFT calculation of the ternary system provide a feasible approach not only to explore the intriguing interactions among functional components of a multimodal nanoprobe applied in aqueous environment, but also to interpret the underlying mechanism for enhancement of modality that is too complicated to be addressed by a phenomenological approach of the conventional NMR theory. (C) 2016 Elsevier B.V. All rights reserved.