A Divide and Conquer Approach to the Response Properties of Biomolecules: Electron Transfer Reactions, Raman Spectroscopy, and Spectroscopic Probes of Chirality

David Beratan获得了理论与计算化学项目的资助，研究生物分子的响应特性，包括电子转移反应和手性拉曼光谱探针。这项工作的目标是开发一种通用的新工具，通过利用化学相互作用的局部性质，对生化结构-功能和反应性关系进行理论探索。提出了一种从头开始的分治法，专门用于描述大分子的电子和振动响应特性。这些方法将以这样一种方式发展，它们可以用于：1)在蛋白质和DNA中建立3D结构和电子转移速率之间的联系；2)协助将分子结构与药物发现和蛋白质结构确定中至关重要的热学性质联系起来，3)通过拉曼光谱扩展蛋白质的结构-性质解释。该策略的实际实施涉及到使用有效的哈密顿量和格林函数理论来确定相关的响应函数。生物功能的定量分子水平描述将从大分子电子和振动结构的详细描述中产生。然而，可靠的电子结构计算是可能的系统只有适度的规模。Beratan的研究计划将使生物化学结构-功能和反应性关系的理论探索在分子水平上的生物大分子系统的兴趣。

David Beratan is supported by a grant from the Theoretical and Computational Chemistry Program to study response properties of biomolecules including electron transfer reactions and Raman spectroscopic probes of chirality. The goal of the proposed work is to develop a general new tool that will enable the theoretical exploration of biochemical structure-function and reactivity relations by exploiting the local nature of chemical interactions. An ab initio divide-and-conquer method is proposed, tailored to describe the electronic and vibronic response properties of macromolecules. The methods will be developed in such a way that they can be used to: 1) establish a link between 3D structure and electron transfer rates in proteins and DNA; 2) assist in relating molecular structure to chiroptical properties critical for drug discovery and protein structure determination, and 3) expand the structure-property interpretations of proteins available via Raman spectroscopy. The actual implementation of this strategy involves the use of an effective Hamiltonian, and Greens function theory to determine the relevant response function. A quantitative molecular-level description of biological function will arise from a detailed description of macromolecular electronic and vibronic structure. Yet, reliable electronic structure calculations are possible on systems of only modest size. Beratan's research program will enable the theoretical exploration of biochemical structure-function and reactivity relations at the molecular level for macromolecular systems of biological interest.