Hard Numbers for Large Molecules: Toward Exact Energetics for Supramolecular Systems
Hard Numbers for Large Molecules: Toward Exact Energetics for Supramolecular Systems
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DOI：
10.1021/jz402663k
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发表时间：
2014-03-06
影响因子：
5.7
通讯作者：
Tkatchenko, Alexandre
中科院分区：
文献类型：
--
作者：
Ambrosetti, Alberto;Alfe, Dario;Tkatchenko, Alexandre
非共价相互作用在分子和凝聚相环境中普遍存在，因此对这些基本相互作用的可靠理论描述可以为更完整地理解化学和生物学中各种系统的微观基础铺平道路。在这项工作中，我们表明，最近的算法的进步，再加上大规模的计算资源的可用性，使随机量子蒙特卡罗方法来解决薛定谔方程的最佳竞争者实现“化学精度”（1千卡/摩尔）的化学相关的超分子复合物的结合能。为了说明这一点，我们考虑了一组选定的7个主客体复合物，代表非共价相互作用的光谱，包括分散或货车德瓦尔斯力，π-π堆积，氢键，疏水相互作用和静电（离子偶极）吸引。的相互作用能的详细分析表明，一个完整的理论描述需要治疗的条款远远超出了标准的伦敦和Axilrod-Teller贡献的货车德瓦耳斯色散能。
Noncovalent interactions are ubiquitous in molecular and condensed-phase environments, and hence a reliable theoretical description of these fundamental interactions could pave the way toward a more complete understanding of the microscopic underpinnings for a diverse set of systems in chemistry and biology. In this work, we demonstrate that recent algorithmic advances coupled to the availability of large-scale computational resources make the stochastic quantum Monte Carlo approach to solving the Schrodinger equation an optimal contender for attaining "chemical accuracy" (1 kcal/mol) in the binding energies of supramolecular complexes of chemical relevance. To illustrate this point, we considered a select set of seven host-guest complexes, representing the spectrum of noncovalent interactions, including dispersion or van der Waals forces, pi-pi stacking, hydrogen bonding, hydrophobic interactions, and electrostatic (ion dipole) attraction. A detailed analysis of the interaction energies reveals that a complete theoretical description necessitates treatment of terms well beyond the standard London and Axilrod-Teller contributions to the van der Waals dispersion energy.