梦幻般的兴奋状态优化结构以及在哪里找到它们
Justin J Talbot1, Juan E Arias-Martinez1,2, Stephen J Cotton1
1Department of Chemistry, University of California Berkeley, Berkeley, California 94720, USA.
The Journal of chemical physics
|November 2, 2023
概括
一些计算优化的兴奋状态在物理上并不真实,表现出不现实的频率. 这些"奇妙"的结构表明电子状态和快速衰变之间的合,可以通过量子化学计算来检测.
科学领域:
- 量子化学 是一个量子化学.
- 计算光谱学是一种计算光谱学.
- 理论化学 理论化学
背景情况:
- 对于近似电子激发状态的分析力允许探索激发状态的潜在能量表面 (PES).
- 这使得激发状态最小值和Born-Oppenheimer近似中的点的计算特征成为可能.
研究的目的:
- 为了研究计算优化的兴奋状态最小结构的物理现实.
- 在量子化学中识别非可观测的激发状态结构的诊断方法.
主要方法:
- 进行了ab initio计算来分析激发状态的潜在能量表面.
- 使用了简单的非adiabatic动力学,包括兰道-泽纳模型.
- 为了优化结构,评估了波频率和力常数.
主要成果:
- 一些激发状态最小结构是"奇幻的",只存在于计算工件中.
- 这些结构显示非物理高波频率和力常数.
- 非协作动力学表明,这些结构的寿命大约为 femtoseconds.
结论:
- 高波频率作为一个诊断非可观测的兴奋状态结构.
- 奇幻的结构来自于在形交叉点附近的电子状态之间的合.
- 这些发现突出了Born-Oppenheimer近似对于某些激发状态的局限性.
相关概念视频
Resonance and Hybrid Structures
17.0K
According to the theory of resonance, if two or more Lewis structures with the same arrangement of atoms can be written for a molecule, ion, or radical, the actual distribution of electrons is an average of that shown by the various Lewis structures.
Resonance Structures and Resonance Hybrids
The Lewis structure of a nitrite anion (NO2−) may actually be drawn in two different ways, distinguished by the locations of the N–O and N=O bonds.
Resonance Structures and Resonance Hybrids
The Lewis structure of a nitrite anion (NO2−) may actually be drawn in two different ways, distinguished by the locations of the N–O and N=O bonds.
17.0K
Stability of structures
177
In mechanical engineering, the stability of systems under various forces is critical for designing durable and efficient structures. One fundamental way to explore these concepts is by analyzing systems like two rods connected at a pivot point, O, with a torsional spring of spring constant k at the pivot point. This system is similar in appearance to a scissor jack used to change tires on a car. In this case, the arms of the linkage (equivalent to the rods in this system) are entirely vertical,...
177
Electronic Structure of Atoms
21.4K
An atom comprises protons and neutrons, which are contained inside the dense, central core called the nucleus, with electrons present around the nucleus. Taking into account the wave–particle duality of electrons and the uncertainty in position around the nucleus, quantum mechanics provides a more accurate model for the atomic structure. It describes atomic orbitals as the regions around the nucleus where electrons of discrete energy exist, characterized by four quantum...
21.4K
Energy Diagrams, Transition States, and Intermediates
16.6K
Free-energy diagrams, or reaction coordinate diagrams, are graphs showing the energy changes that occur during a chemical reaction. The reaction coordinate represented on the horizontal axis shows how far the reaction has progressed structurally. Positions along the x-axis close to the reactants have structures resembling the reactants, while positions close to the products resemble the products. Peaks on the energy diagram represent stable structures with measurable lifetimes, while...
16.6K
Structures of Solids
14.2K
Solids in which the atoms, ions, or molecules are arranged in a definite repeating pattern are known as crystalline solids. Metals and ionic compounds typically form ordered, crystalline solids. A crystalline solid has a precise melting temperature because each atom or molecule of the same type is held in place with the same forces or energy. Amorphous solids or non-crystalline solids (or, sometimes, glasses) which lack an ordered internal structure and are randomly arranged. Substances that...
14.2K
Atomic Structure
192.6K
Overview
192.6K


