基于块定域化波函数的绝热表象成键分析方法的发展与应用

成键分析方法是将量子化学计算结果转译为直观化学概念的有效工具，对化学键理论的发展有重要意义。块定域化波函数（Block-localized wavefunction, BLW）方法采用严格定域的轨道和单行列式波函数，兼具价键理论的直观化学图像和分子轨道理论的计算效率，是一种特色鲜明的电子结构计算方法。本项目将发展基于BLW的绝热表象成键分析方法，进而在包含中间电子态结构驰豫的情况下描绘成键图像。此外，针对非共价键理论中亟待解决的若干问题，如分子内非共价键的分析、氢键及卤键红外光谱中振动耦合的影响等，本项目将从能量、电子密度、定域振动模式分析的角度开展绝热表象的成键分析，并重点探究电场对非共价键的调控机制，进而丰富和发展化学键理论。

Methods of Chemical bonding analysis bridge the gap between quantum chemical calculations and the insightful explanations, and is one essential subject for the development of novel chemical bonding theory. The Block-localized wavefunction (BLW) method combines the computational efficiency of MO theory, and the chemically and physically insightful feature of valence bond (VB) theory, by using a single Slater determinant wavefunction constructed with strictly localized orbitals. Methods of bonding analysis in an adiabatic picture based on BLW will be developted, in order to clarify some challenging issues in noncovalent interactions: Study of intramolecular noncovalent interactions is still triky due to the selection of referenced artificial states; Effect of vibrational mode couplings on the infrared spectroscopy of hydrogen and halogen bonds remain to be explored thoroughly, and so on. Accordingly, bonding analysis will be performed in an adiabatic picture and from multi-angles of energy, electron density and especially, localized vibrational mode. More importantly, non-covalent interaction in oriented external electric fields (OEEFs) will be inspected systematically using the proposed approaches.