On the properties of microsolvated molecules in the ground (S0) and excited (S1) states:: The anisole-ammonia 1:1 complex
On the properties of microsolvated molecules in the ground (S0) and excited (S1) states:: The anisole-ammonia 1:1 complex
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DOI：
10.1063/1.2767265
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发表时间：
2007-10-14
影响因子：
4.4
通讯作者：
Barone, Vincenzo
中科院分区：
文献类型：
--
作者：
Biczysko, Malgorzata;Piani, Giovanni;Barone, Vincenzo
国家的最先进的光谱和理论方法已被利用在一个共同的努力，以阐明的结构和能量的苯甲醚氨1：1复杂的，一个原型的微溶剂化过程的微妙功能。共振增强多光子电离和激光诱导荧光光谱进行了讨论和比较高层次的第一性原理理论模型，密度泛函，多体二阶微扰，耦合簇理论的基础上。在最稳定的非平面结构的配合物，氨相互作用的离域π电子密度的苯甲醚环：氢键和色散力提供了一个可比的稳定能量在基态，而在激发态的色散项是可以忽略不计的，因为电子密度从氧转移到芳环。基态和激发态的几何参数推导出的实验数据和计算的量子力学方法是在非常好的协议，使我们能够明确地确定的苯甲醚氨复合物的分子结构。(c)2007年，美国物理学会。
State-of-the-art spectroscopic and theoretical methods have been exploited in a joint effort to elucidate the subtle features of the structure and the energetics of the anisole-ammonia 1:1 complex, a prototype of microsolvation processes. Resonance enhanced multiphoton ionization and laser-induced fluorescence spectra are discussed and compared to high-level first-principles theoretical models, based on density functional, many body second order perturbation, and coupled cluster theories. In the most stable nonplanar structure of the complex, the ammonia interacts with the delocalized pi electron density of the anisole ring: hydrogen bonding and dispersive forces provide a comparable stabilization energy in the ground state, whereas in the excited state the dispersion term is negligible because of electron density transfer from the oxygen to the aromatic ring. Ground and excited state geometrical parameters deduced from experimental data and computed by quantum mechanical methods are in very good agreement and allow us to unambiguously determine the molecular structure of the anisole-ammonia complex. (c) 2007 American Institute of Physics.