Noncovalently bound molecular complexes beyond diatom–diatom systems: full-dimensional, fully coupled quantum calculations of rovibrational states
Noncovalently bound molecular complexes beyond diatom–diatom systems: full-dimensional, fully coupled quantum calculations of rovibrational states
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硅藻-硅藻系统之外的非共价键合分子复合物：振动态的全维、全耦合量子计算
DOI：
10.1039/d2cp04005k
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发表时间：
2022
影响因子：
3.3
通讯作者：
Bačić, Zlatko
中科院分区：
文献类型：
--
作者：
Felker, Peter M.;Bačić, Zlatko
近年来取得的方法的进步显着扩大了非共价键，氢键和货车范德华，分子复合物的范围和维度，其振转态的全维和完全耦合的量子计算是可行的。他们利用了意想不到的含义，即弱耦合之间的分子间和分子内的振转自由度（DOFs）的配合物，便于计算后者的高能量本征态。这是非常有效地做到这一点，通过使用收缩的本征态基，以涵盖内和分子间的自由度。因此，现在可以严格计算所有的分子内振转基本原理，连同低的分子间振转态，涉及两个小分子的复合物，超越了双金属，二元多原子分子-大（刚性）分子复合物，和轻多原子分子的内笼复合物（刚性）富勒烯笼。在这个角度来看，这些进展进行了相当深入的审查。一些有代表性的应用说明了由于它们而取得的进展。只要有可能，直接比较与现有的红外，远红外和微波光谱数据。
The methodological advances made in recent years have significantly extended the range and dimensionality of noncovalently bound, hydrogen-bonded and van der Waals, molecular complexes for which full-dimensional and fully coupled quantum calculations of their rovibrational states are feasible. They exploit the unexpected implication that the weak coupling between the inter- and intramolecular rovibrational degrees of freedom (DOFs) of the complexes has for the ease of computing the high-energy eigenstates of the latter. This is done very effectively by using contracted eigenstate bases to cover both intra- and intermolecular DOFs. As a result, it is now possible to calculate rigorously all intramolecular rovibrational fundamentals, together with the low-lying intermolecular rovibrational states, of complexes involving two small molecules beyond diatomics, binary polyatomic molecule-large (rigid) molecule complexes, and endohedral complexes of light polyatomic molecules confined inside (rigid) fullerene cages. In this Perspective these advances are reviewed in considerable depth. The progress made thanks to them is illustrated by a number of representative applications. Whenever possible, direct comparison is made with the available infrared, far-infrared, and microwave spectroscopic data.