CONTRIBUTION OF ELECTRON CORRELATION TO H-BONDS

分子之间的相互作用导致了各种不同的 生物现象包括蛋白质结构、DNA碱基配对和 疏水效应。然而氢键的基本性质是， 也许最具生物相关性的生物，仍然没有完全被理解， 主要基于20世纪70年代开发和应用的分解方法， 使用了不太适合这类研究的基组。此外， 早期的工作仅限于SCF级别，完全忽略了 现在已知的电子关联的影响是深远的。这个 本项目旨在剖析对氢的关联贡献。 绑定到多个组件；SCF组件也将 计算比过去可靠得多。这些组件将是 通过一种新的混合程序进行评估，该程序结合了 分子间微扰理论和Moller-Plesset超分子微扰理论。这个 将对每个组件的行为进行多项研究 通常存在于生物分子中的不同化学基团 不同几何图形的范围。项目的最终目标是一个基本的 了解氢键的性质。模型势将是 用于在不可行的情况下协助从头计算 显式计算关联效应。这些潜力也会得到利用。 水中生物分子的动力学和蒙特卡罗模拟 环境。

Interactions between molecules are responsible for a wide diversity of biological phenomena including protein structure, DNA base pairing, and the hydrophobic effect. Yet the fundamental nature of the hydrogen bond, perhaps the most biologically relevant, remains incompletely understood, based largely on decomposition methods developed and applied in the 1970s, using basis sets that were not well-suited to such studies. Moreover, the earlier work was restricted to the SCF level, neglecting completely the effects of electron correlation which are now known to be profound. The present project aims to dissect the correlation contribution to hydrogen bonding into a number of components; the SCF components will also be computed much more reliably than in the past. These components will be evaluated by a new hybrid procedure which combines the best features of intermolecular and Moller-Plesset supermolecular perturbation theory. The behavior of each of the components will be studied for a number of different chemical groups which commonly occur in biomolecules and for a range of different geometries. The ultimate goal of the project is a basic understanding of the nature of the H-bond. Model potentials will be developed to assist in ab initio calculations where it is not feasible to calculate correlation effects explicitly. The potentials will also find use in dynamics and Monte Carlo simulations of biomolecules in aqueous environment.