Energetics of a model NH-π interaction:: the gas phase benzene-NH3 complex

被引：49

作者：

Mons, M ^{[1
]}

Dimicoli, I ^{[1
]}

Tardivel, B ^{[1
]}

Piuzzi, F ^{[1
]}

Brenner, V ^{[1
]}

Millié, P ^{[1
]}

机构：

[1] Ctr Etud Saclay, Serv Photons Atomes & Mol, Lab Francis Perrin, FRE CEA CNRS 2298, F-91191 Gif Sur Yvette, France

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2002年 / 4卷 / 04期

关键词：

D O I：

10.1039/b108146m

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The dissociation energy of the benzene ammonia complex formed in a supersonic expansion has been determined (D-0 = 1.84 +/- 0.12 kcal mol(-1)) from the features of its photoionisation curve as obtained by mass-resolved two-color resonant two-photon ionisation. The complex structure, stabilised by a pi-type hydrogen bond between the benzene ring and the ammonia molecule located above, has also been obtained by a semi-empirical model. The neutral structure found is in good agreement with experiment and the best ab initio calculations in the literature. The ionic structures calculated enable us to interpret the slowly increasing photoionisation curve as a consequence of a large equilibrium geometry change between neutral and ion. The present study also shows that the benzene ammonia complex is less bound than its homologue with water by ca. 0.6 kcal mol(-1). However, the value found indicates that the NH-pi interaction can be taken into account when modelling the structure of biological systems.

引用

页码：571 / 576

页数：6

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