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Exploring nonlinear optical (NLO) functional motifs (FM, the structural origin of NLO efficiency) is vital for the rational design of NLO materials. Normal spectrum techniques applied in studying photon exciting materials are invalid for NLO materials, in which electrons are not excited substantially but only distorted under laser. A general strategy of determining NLO FM is proposed by comparative studies of experimental electron density (ED) without and under the laser. The in situ experimental ED and wavefunction of typical NLO materia

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