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

文献信息

发布日期 2002-01-15
DOI 10.1039/B108146M
影响因子 3.676
作者

Michel Mons, Iliana Dimicoli, Benjamin Tardivel, François Piuzzi, Valérie Brenner, Philippe Millié


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摘要

The dissociation energy of the benzene–ammonia complex formed in a supersonic expansion has been determined (D0 = 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 π-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–π interaction can be taken into account when modelling the structure of biological systems.

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来源期刊

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
自引率: 10.3%
年发文量: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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