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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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Atomic absorption spectroscopy (AAS) relies on the Beer-Lambert law, which requires that the radiation source emits a narrow range of wavelengths to match the absorption characteristics of the analyte atom. The primary criteria for choosing an appropriate radiation source in AAS is to provide a precise and intense emission at specific wavelengths that will allow accurate detection of the analyte.
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When solids, liquids, or condensed gases are heated sufficiently, they radiate some of the excess energy as light. Photons produced in this manner have a range of energies, and thereby produce a continuous spectrum in which an unbroken series of wavelengths is present.
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Inductively coupled plasma (ICP) is the most widely used plasma source in atomic emission spectroscopy (AES), also known as Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). The ICP source, or torch, consists of three concentric quartz tubes with argon gas flowing through them. A spark from a Tesla coil initiates the ionization of argon, generating a high-temperature plasma.
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Atomic Emission Spectroscopy: Overview01:20

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Atomic emission spectroscopy (AES) is an analytical technique used to determine the elemental composition of a sample by analyzing the light emitted from excited atoms. In AES, atoms in a sample are excited to higher energy levels by thermal energy from high-temperature sources, such as plasma, arcs, or sparks. When these excited atoms return to lower energy states, they emit light at specific wavelengths characteristic of each element. The resulting atomic emission spectrum, which consists of...
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Updated: Jul 18, 2025

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
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Computing photoionization spectra in Gaussian basis sets.

Ivan Duchemin1, Antoine Levitt2

  • 1Université Grenoble Alpes, CEA, IRIG-MEM-L Sim, Grenoble 38054, France.

The Journal of Chemical Physics
|August 23, 2023
PubMed
Summary
This summary is machine-generated.

We developed a new method to calculate photoionization spectra using time-dependent density functional theory. This approach accurately computes atomic and molecular spectra without artificial adjustments, offering reliable results with standard basis sets.

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Area of Science:

  • Quantum Chemistry
  • Computational Physics
  • Spectroscopy

Background:

  • Accurate computation of photoionization spectra is crucial for understanding atomic and molecular electronic structures.
  • Traditional methods often require complex approximations or extensive computational resources.

Purpose of the Study:

  • To present a novel, efficient, and accurate method for computing photoionization spectra.
  • To enable reliable spectral calculations using standard computational chemistry tools.

Main Methods:

  • Linear-response, time-dependent density functional theory (LR-TDDFT).
  • Expansion of electronic orbital variations using delocalized functions derived from the Helmholtz equation.
  • Green's function-based approach.

Main Results:

  • The method successfully reproduces photoionization spectra without artificial regularization or localization.
  • Accurate spectra were obtained for semilocal exchange-correlation functionals.
  • The approach is effective even with relatively small, standard Gaussian basis sets.

Conclusions:

  • The Green's function-based LR-TDDFT method provides a robust and accurate way to compute photoionization spectra.
  • This technique simplifies spectral calculations, making them more accessible for atoms and molecules.
  • The findings pave the way for more efficient theoretical investigations in quantum chemistry.