CONTRIBUTION OF ELECTRON CORRELATION TO H-BONDS

电子相关性对氢键的贡献

• 批准号: 3291562
• 负责人: STEVE SCHEINER
• 金额: $ 13.36万
• 依托单位: SOUTHERN ILLINOIS UNIVERSITY CARBONDALE
• 依托单位国家: 美国
• 财政年份: 1987
• 资助国家: 美国
• 起止时间: 1987-07-01 至 1995-07-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/3291562
• 关键词: amides; amines; carbon; carbonyl group; chemical bond; chemical models; computer simulation; disulfide bond; electrical potential; electron density; electronic spectra; hydrogen bond; hydrogen sulfide; hydroxyl group; imines; methyl group; molecular energy level; molecular orbital; quantum chemistry; sulfur compounds; thermodynamics; water solution

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.

分子之间的相互作用导致了多种 生物现象，包括蛋白质结构、DNA 碱基配对和 疏水作用。然而氢键的基本性质， 也许与生物学最相关的，仍然不完全被理解， 主要基于 20 世纪 70 年代开发和应用的分解方法， 使用不太适合此类研究的基础集。此外， 早期的工作仅限于 SCF 级别，完全忽略了 现在已知电子关联的影响是深远的。这 本项目旨在剖析对氢的相关贡献 粘合成多个组件； SCF 组件也将是 计算比过去可靠得多。这些组件将是 通过新的混合程序进行评估，该程序结合了以下各项的最佳功能 分子间和Moller-Plesset 超分子微扰理论。这 每个组件的行为将被研究多个 生物分子中常见的不同化学基团 不同几何形状的范围。该项目的最终目标是基本 了解氢键的性质。模型势将是 开发用于在不可行的情况下协助从头计算 明确计算相关效应。潜力也将得到利用 水溶液中生物分子的动力学和蒙特卡罗模拟 环境。