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This work probes the role of hydrogen bonds (such as O-H ... O and N-H ... O) in some inorganic nonlinear optical (NLO) crystals, such as HIO3, NH4H2PO4 (ADP), K[B5O6(OH)(4)] . 2H(2)O (KB5) and K2La(NO3)(5) . 2H(2)O (KLN), from the chemical bond standpoint. Second order NLO behaviors of these four typical inorganic crystals have been quantitatively studied, results show hydrogen bonds play a very important role in NLO contributions to the total nonlinearity. Conclusions derived here concerning the effect of hydrogen bonds on optical nonlinearities of inorganic crystals have important implications with regard to the utilization of hydrogen bonds in the structural design of inorganic NLO crystals. (C) 1999 Elsevier Science B.V. All rights reserved.