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.