Compared with para-substitution, substituent effects (R = NH₂, OH, CH₃, F, Cl, H, SiH₃, CHO, CN, NO₂) of meta-position effects on hydrogen-bonded complex of aniline with one water molecule are studied at B3LYP/6-311++G(d,p) level of theory. The differences in hydrogen bonding and some properties associated with the H-bond (such as bond length, vibrational frequency, binding energies, pK_a values of aniline derivatives) are discussed between meta and para substitutions. Natural bond orbital (NBO) and atoms in molecules (AIM) analysis are applied to investigate the physical origin of the differences. The results show that the differences are mainly attributed to the variations in electron delocalization from amino group to phenyl ring (reflected by interaction) induced by substituents.

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