The substituent effects in aerogen bond interactions between ZO 3 (Z 5 Kr, Xe) and different nitrogen bases are studied at the MP2/aug-cc-pVTZ level of theory. The nitrogen bases include the sp bases NCH, NCF, NCCl, NCBr, NCCN, NCOH, NCCH 3 and the sp 3 bases NH 3 , NH 2 F, NH 2 Cl, NH 2 Br, NH 2 CN, NH 2 OH, and NH 2 CH 3 . The nature of aerogen bonds in these complexes is analyzed by means of molecular electrostatic potential, electron localization function, quantum theory atoms in molecules, non- covalent interaction index, and natural bond orbital analyses. The interaction energy (E int ) ranges from 24.59 to 29.65 kcal/mol in the O 3 ZNCX complexes and from 25.30 to 213.57 kcal/mol in the O 3 ZNH 2 X ones. The dominant charge-transfer interaction in these complexes occurs across the aerogen bond from the nitrogen lone-pair (n N ) of the Lewis base to the r* Z-O antibonding orbital of the ZO 3 . Besides, the formation of aero- gen bond tends to decrease the 83 Kr or 131 Xe chemical shielding values in these complexes. VC 2016 Wiley Periodicals, Inc.
