DFT-NEW教学文稿.pptxVIP

铁电体的微观理论振动-电子理论 Vibronic theory第一性原理计算在铁电材料中的应用第一性原理计算First Principle Calculationsab initio (从头算)量子化学，理论和应用应用量子力学，只借助基本常量（如Plank常量和电子电荷）和某些合理的近似，而不依赖于所研究材料的实验数据所进行的计算vibronic and DFT求解多粒子体系的Schrodinger方程，得到总能量，能级(能带)，态密度，电子密度等物理量，然后可以得到其它物理性质这一方法应用于铁电材料：把铁电体作为电子和原子核组成的多粒子体系。确定体系的基态结构，并进一步计算在有限温度下的各种性质比较系统深入的研究开始于九十年代初，R E Cohen, Nature 258 (1992) 136vibronic and DFT背景和动机传统理论:朗道理论、软模概念、横场Ising模型、计算机模拟；仅考虑离子实，忽略了电子的影响。振动电子理论: Vibronic theory 适用于窄能带铁电材料，铁电半导体材料；Shell Model电子以及电子和晶格振动对铁电体物理性质的影响？?第一性原理计算的研究vibronic and DFT研究现状主要问题：铁电材料结构复杂，而且多含有重元素。较精确的结果，计算量一般比较大。所能得到的直接结果是电子态密度、电子密度分布、能级或能带结构，基态结构；已经出现理论可以计算极化强度和压电性。进一步可以得到光学性质和介电常数等物理特性；进行蒙特卡罗方法可以进行铁电相变性质的模拟。vibronic and DFT振动电子理论 Vibronic theoryThe term “vibronic” originates from the concatenation of the terms “vibrational” and “electronic”. The Jahn-Teller Theorem was published in 1937 and states: any non-linear molecular system in a degenerate electronic state will be unstable and will undergo distortion to form a system of lower symmetry and lower energy thereby removing the degeneracyvibronic and DFTThe Jahn-Teller TheoremThe Jahn-Teller effect is most important for metal ions with octahedral geometries and their eg orbitals (the ones which lie axially) are occupied unequallyElongation is more common as there is an increased stability to the moleculevibronic and DFTThe Jahn-Teller TheoremCrystal splittingΔoctBoth distortions lower the energies of two electrons in the eg subshell, while raising the energy of only one.vibronic and DFTThe Dynamic Jahn-Teller EffectThe tetragonal distortion is occurring but the molecule is fluctuating between the z-axis being compressed and elongated. It is moving randomly so quickly that neither form can be seen spectroscopically. So, overall an undistorted molecule (or a molecule with negligible distortion) will be seen. The energy difference of the complexes eg and t2g orbitals is so neglibile that they can switch positions easily, and do, to give the dynamic effect.vibronic and