Method Development on Valence Bond Theory and Its Applications

传统的价键理论方法较少涉及到溶液体系的理论研究及其应用，本文试图发展考虑溶剂效应的价键理论方法并将其进一步扩展到非平衡溶剂化的研究领域。另外，考虑到价键方法的研究领域仍然有限，本论文力图拓展从头算价键方法的应用研究范围。本工作主要包括以下三个方面：1．考虑溶剂效应的从头算价键方法的发展及其程序的编写第三章介绍本课题组最新发展的从头算溶剂化价键方法——VBSM方法。基本理论思路为：通过价键密度矩阵求得原子净电荷，运用Generalized-Born方程求得当前波函数下的极化溶剂化自由能。经过价键自恰场迭代，波函数和能量同时得到优化。VBSM的优点在于它不仅能够计算体系的溶剂化自由能而且能够得到该...In this paper, new Valence Bond (VB) methods for solvent effects are developed. Sequentially ab initio VB methods are applied to several chemical reactions and small molecules. There are three sections in it. 1. Development on VB methods Chapter 3 presents a VB method, called VBSM, to study free energies of solvation by VB methods. The VB calculation takes the polarization free energies which co...学位：理学博士院系专业：化学化工学院化学系_物理化学(含化学物理)学号：B20032503

Ab Initio Computational Method for Classical Valence Bond Theory

价键理论是两大现代化学键理论之一,广泛应用于化学键本质和化学反应机理的研究。由于计算困难,价键理论应用局限于定性的讨论而无法有效地开展从头计算研究。现代经典价键理论在经典价键理论的理论基础上,引入合理有效的计算方法,提高了价键计算的效率。本文回顾近年来经典价键理论从头算方法在提高计算精度和拓展研究范围方面的发展,并简要展望价键理论方法的发展趋势。In modern quantum chemistry,valence bond(VB) theory and molecular orbital(MO) theory are the two general theoretical approaches for chemical bonding.VB theory provides clear interpretation and chemical insights by employing covalent and ionic VB structures explicitly.This review focuses on the methodology development of the current modern classical VB methods in the improvement of computational accuracy and the extension of application areas.Moreover,the further development of modern classical VB methods is briefly prospected.国家自然科学基金项目(No.21120102035;21003101)资

优化资源研发具有影响力的电子结构计算软件包

理论化学的重要性和地位与日俱增,然而作为理论化学的主要研究手段,国内理论化学计算软件发展的现状却不容乐观。本文就当前理论化学国内软件开发工作面临的挑战和机遇,提出若干需要重视的问题

理论与计算化学研究进展

化学是一门有坚实理论体系的基础学科,作为其中一个分支,理论与计算化学的飞速发展使得化学成为实验与理论并重的科学.结合价键理论方法、生物体系理论模拟和激发态光化学、固体表面与纳米结构体系、复杂体系分子量子动力学和密度泛函理论方法发展和核磁共振理论研究等,简要回顾了近期本研究团队和国内外本学科的发展情况,重点介绍了厦门大学在量子化学理论计算方法发展、计算程序研发、复杂体系的动力学以及酶催化反应的计算模拟等方面的研究

Ab initio nonorthogonal valence bond methods

Ministry of Science and Technology of China [2011CB808504]; Natural Science Foundation of China [21120102035, 21003101]Modern classical valence bond (VB) methods provide clear interpretation and chemical insights by employing covalent and ionic VB structures explicitly. This review focuses on a methodical development of current modern classical VB methods. As a basic method of the classical VB theory, the VB self-consistent field (VBSCF) method provides a compact wave function, mainly containing static correlation. On the basis of the VBSCF method, the development of classical VB methods can be divided into two aspects-one focuses on improvement of computational accuracy, such as the breathing orbital VB (BOVB), VB configuration interaction (VBCI), and VB second-order perturbation theory (VBPT2) methods; the other focuses on extending VB approaches to molecules and reactions in solvated or biological environments, including the VB polarizable continuum model (VBPCM), VB solvation model (VBSM), VB effective fragment potential (VBEFP), and VB/molecular mechanics (VB/MM) methods. These improved methods have the advantage of VB theory and provide intuitive chemical insights into medium-sized chemical problems. Finally, the further development of modern classical VB methods is briefly discussed. (C) 2012 John Wiley & Sons, Ltd. How to cite this article: WIREs Comput Mol Sci 2013, 3:56-68 doi: 10.1002/wcms.110

Ab Initio Computational Method for Classical Valence Bond Theory

In modern quantum chemistry, valence bond (VB) theory and molecular orbital (MO) theory are the two general theoretical approaches for chemical bonding. VB theory provides clear interpretation and chemical insights by employing covalent and ionic VB structures explicitly. This review focuses on the methodology development of the current modern classical VB methods in the improvement of computational accuracy and the extension of application areas. Moreover, the further development of modern classical VB methods is briefly prospected

Free energy decomposition analysis of bonding and nonbonding interactions in solution

A free energy decomposition analysis algorithm for bonding and nonbonding interactions in various solvated environments, named energy decomposition analysis-polarizable continuum model (EDA-PCM), is implemented based on the localized molecular orbital-energy decomposition analysis (LMO-EDA) method, which is recently developed for interaction analysis in gas phase [P. F. Su and H. Li, J. Chem. Phys. 130, 074109 (2009)]. For single determinant wave functions, the EDA-PCM method divides the interaction energy into electrostatic, exchange, repulsion, polarization, desolvation, and dispersion terms. In the EDA-PCM scheme, the homogeneous solvated environment can be treated by the integral equation formulation of PCM (IEFPCM) or conductor-like polarizable continuum model (CPCM) method, while the heterogeneous solvated environment is handled by the Het-CPCM method. The EDA-PCM is able to obtain physically meaningful interaction analysis in different dielectric environments along the whole potential energy surfaces. Test calculations by MP2 and DFT functionals with homogeneous and heterogeneous solvation, involving hydrogen bonding, vdW interaction, metal-ligand binding, cation-pi, and ionic interaction, show the robustness and adaptability of the EDA-PCM method. The computational results stress the importance of solvation effects to the intermolecular interactions in solvated environments. c 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4736533]Ministry of Science and Technology of China [2011CB808504]; Natural Science Foundation of China [21120102035, 21003101

Internal rotation barrier of the XH3-H3(X, Y = C or Si) moleculesAn energy decomposition analysis study

In this paper, the barriers of the internal rotation in ethane, methylsilane, and disilane are investigatedby the generalized Kohn-Sham based energy decomposition analysis (GKS-EDA) scheme (P. Su, et al. J.Phys. Chem A 118 (2014) 2531). The rotation barriers and the inter-conversion energies from the threegeometrical variation processes are decomposed into the electrostatic, exchange-repulsion, polariza-tion, correlation and geometrical relaxation terms. It is concluded that the rotation barriers of the threemolecules are all dominated by exchange-repulsion (Pauli repulsion). The geometry relaxation does notmake a difference to the origin of the barrier. ? 2014 Elsevier B.V. All rights reserved

Internal rotation barrier of the XH3YH3 (X, y = C or Si) molecules An energy decomposition analysis study

In this paper, the barriers of the internal rotation in ethane, methylsilane, and disilane are investigated by the generalized Kohn-Sham based energy decomposition analysis (GKS-EDA) scheme (P. Su, et al. J. Phys. Chem A 118 (2014) 2531). The rotation barriers and the inter-conversion energies from the three geometrical variation processes are decomposed into the electrostatic, exchange-repulsion, polarization, correlation and geometrical relaxation terms. It is concluded that the rotation barriers of the three molecules are all dominated by exchange-repulsion (Pauli repulsion). The geometry relaxation does not make a difference to the origin of the barrier. ? 2014 Elsevier B.V

Energy Decomposition Scheme Based on the Generalized Kohn-Sham Scheme

Ministry of Science and Technology of China [2011CB808504]; Natural Science Foundation of China [21373165, 21273176, 21120102035]; Natural Science Foundation of Fujian Province, China [2013J01058]In this paper, a new energy decomposition analysis scheme based on the generalized Kohn-Sham (GKS) and the localized molecular orbital energy decomposition analysis (LMO-EDA) scheme, named GKS-EDA, is proposed. The GKS-EDA scheme has a wide range of DFT functional adaptability compared to LMO-EDA. In the GKS-EDA scheme, the exchange, repulsion, and polarization terms are determined by DFT orbitals; the correlation term is defined as the difference of the GKS correlation energy from monomers to supermolecule. Using the new definition, the GKS-EDA scheme avoids the error of LMO-EDA which comes from the separated treatment of E-X and E-C functionals. The scheme can perform analysis both in the gas and in the condensed phases with most of the popular DFT functionals, including LDA, GGA, meta-GGA, hybrid GGA/meta-GGA, double hybrid, range-separated (long-range correction), and dispersion correction. By the GKS-EDA scheme, the DFT functionals assessment for hydrogen bonding, vdW interaction, symmetric radical cation, charge-transfer, and metal-ligand interaction is performed