The definition of the spectra in quantum mechanics

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SUMMARY

The spectrum in quantum mechanics is defined as the set of all eigenvalues of the Schrödinger equation, which can be calculated by solving the energy eigenvalue problem for a system. Spectral lines correspond to electromagnetic radiation emitted during transitions from higher to lower energy states, with frequencies determined by the energy differences, expressed as ##\hbar \omega_{\gamma}=E_n-E_m##. The discussion emphasizes the complexity of spectroscopy, noting that various types of spectra—such as atomic emission, absorption, and fluorescence—require consideration of multiple factors, including relaxation processes and interactions. It asserts that while computational techniques like DFT can approximate outcomes, they cannot fully define a spectrum.

PREREQUISITES
  • Understanding of the Schrödinger equation
  • Familiarity with energy eigenvalues and eigenstates
  • Knowledge of quantum mechanics fundamentals
  • Basic concepts of spectroscopy techniques
NEXT STEPS
  • Study the principles of quantum mechanics using "Introduction to Quantum Mechanics" by David J. Griffiths
  • Explore first-order perturbation theory and its applications in quantum systems
  • Learn about different types of spectroscopy, including atomic emission and absorption spectroscopy
  • Investigate the role of computational techniques like Density Functional Theory (DFT) in predicting spectral properties
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Undergraduate students in physics, researchers in quantum mechanics, and professionals in spectroscopy who seek to deepen their understanding of spectral definitions and calculations.

Asmaa
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I have read that "The spectrum of a substance (gas, liquid or solid) can be defined as the set of all eigenvalues of the Schrodinger equation"

please, Can anyone explain this?
for undergraduate students how to explain this?
 
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The sentence is not entirely correct.

You can calculate the spectrum by first solving for the energy eigenvalue problem for the system. Then the spectral lines, i.e., the electromagnetic radiation emitted when the system undergoes transitions from states of higher energy to lower. In first-order perturbation theory what you get are the dipole transitions, and the frequencies of the radiation are given by the energy-differences: ##\hbar \omega_{\gamma}=E_n-E_m##, where ##E_j## are the bound-state energies of the system.
 
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Can you be more specific about what is unclear? Which of these terms do you not understand?

spectrum

eigenvalues

Schrödinger equation
 
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Also,

"Spectrum" is quite vague. What kind of spectra? Atomic emission, absorption, fluorescence, inelastic scattering? There are many things to consider in some of these techniques, such as the probability of several relaxation processes, intermolecular and intramolecular interactions, solvents.

Spectroscopy is a messy thing. If we could simply use DFT and other computational techniques to define everything, then spectroscopists would be out of a job, and monkeys could do the work.

You can get close to predicting what might happen when light interacts with matter, but there is no theory that can define a "spectrum".
 
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