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Molecular Spectroscopy: Absorption and Emission01:14

Molecular Spectroscopy: Absorption and Emission

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Molecules possess discrete energy levels called quantum states. Unlike atoms, which have simpler energy levels, molecules possess additional rotational and vibrational energy levels.  Each energy level is separated by an energy gap, with the gaps between adjacent electronic, vibrational, and rotational levels varying significantly. The three types of energy levels in a diatomic molecule are shown in Figure 1.
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sp3d and sp3d 2 Hybridization
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UV–Vis Spectroscopy: Molecular Electronic Transitions01:16

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In Ultraviolet–Visible (UV–Vis) spectroscopy, the absorption of electromagnetic radiation is used to probe the electronic structure of molecules. This technique provides insights into molecular electronic transitions, particularly the movement of electrons between different molecular orbitals. Radiation is absorbed if the energy of the electromagnetic radiation passing through the molecule is precisely equal to the energy difference between the excited and ground states. During this...
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An applied magnetic field causes loosely bound π-electrons in organic molecules to circulate, producing a local or induced diamagnetic field over a large spatial volume. As the molecules tumble in solution, the field generated by π-electrons in spherical substituents results in a zero net field. However, the net field generated by π-electrons in non-spherical substituents is not zero. The effect of this induced field depends on the orientation of the molecule with respect to B0,...
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Atomic spectroscopy is a vital tool in elemental analysis, both qualitatively and quantitatively. It can be broadly divided into optical spectroscopy, mass spectroscopy, and X-ray spectroscopy methods. The optical spectroscopic methods are atomic absorption spectroscopy (AAS), atomic emission spectroscopy (AES), and atomic fluorescence spectroscopy (AFS). The first step in all three methods is atomization, where the solid, liquid, or solution-phase samples are converted into gas-phase atoms and...
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Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
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超越探索的功能:两个光子吸收的计算之旅

Ismael A Elayan1, Laura Rib1, Rodrigo A Mendes1,2

  • 1Department of Chemistry, University of Alberta, Edmonton, Alberta T6G 2G2, Canada.

Journal of chemical theory and computation
|April 22, 2024
PubMed
概括

本研究评估了19种密度函数理论 (DFT) 方法,用于计算两光子吸收 (2PA) 截面. 距离分离的混合功能,特别是那些具有短距离和长距离校正的功能,对氨酸染料表现出优越的性能.

科学领域:

  • 计算化学的计算化学
  • 量子化学 是一个量子化学.
  • 频谱学是一种光谱学.

背景情况:

  • 精确计算两光子吸收 (2PA) 截面对于理解分子的光物理性质至关重要.
  • 密度函数理论 (DFT) 函数为预测2PA提供了一个计算效率高的高水平相关方法的替代方案.
  • 对于2PA计算的各种DFT函数的性能,特别是对于氨酸染料,需要进行系统的评估.

研究的目的:

  • 综合评估 19 个 DFT 函数的准确性,用于计算 2PA 截面 (σ2PA) 和相关的二极极矩.
  • 为了比较不同DFT功能类的性能,包括LDA,GGA,H-GGA,RSH-GGA,M-GGA和HM-GGA.
  • 确定新的,高性能的DFT函数来预测氨酸染料的2PA特性,与RI-CC2结果进行基准测试.

主要方法:

  • 使用 19 个 DFT 函数,对氨酸染料的 2PA 截面和二极矩进行气相计算.
  • 使用RI-CC2方法进行的参考计算.
  • 基于类别的功能性能的系统分析:LDA,GGA,H-GGA,RSH-GGA,M-GGA和HM-GGA.

主要成果:

  • 包含短距离 (SR) 和长距离 (LR) 校正的函数式,特别是RSH-GGA和HM-GGA类型,表现出卓越的性能.

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  • 在改善2PA预测方面,区间分离策略比变化的Hartree-Fock交换百分比更有影响力.
  • 性能最好的函数 (M11,QTP变体,oB97X,oB97X-V,M06-2X) 之前没有被识别为2PA计算,并且表现优于常用的函数,如CAM-B3LYP.
  • 结论:

    • 具有SR/LR校正的特定RSH-GGA和HM-GGA函数为计算氨酸染料2PA截面提供了更高的准确性.
    • 这些发现挑战了2PA计算的传统选择,突出了较少探索的DFT函数的潜力.
    • 这项研究为选择适当的DFT方法提供了宝贵的指导,以准确预测分子2PA特性.