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Origins of Optical Spectra

With gas phase atoms or ions, there are no vibrational or rotational energy states. This means that only electronic transitions occur. Thus, atomic emission, absorption, and fluorescence spectra are made up of a limited number of narrow spectral lines. Emission Spectra In atomic emission spectroscopy, analyte atoms are excited by external energy in the form of heat or electrical energy. The energy typically is supplied by plasma, a flame, a low-pressure discharge, or a high-powered laser. Three sodium emission lines (pg 840) Before the external energy source is applied, the sodium atoms are usually in their lowest energy or ground state. The applied energy then causes the atoms to be momentarily in a higher energy or excited state. With the sodium atoms in the ground state, the single valence electrons are in the 3s orbital. External energy promotes the outer electrons from their ground state 3s orbitals to 3p, 4p, or 5p excited-state orbitals. After a few nanoseconds, the excited atoms relax to the ground state, giving up their energy as photons of visible or ultraviolet radiation. A transition to or from the ground state is called a resonance transition, and the resulting spectral line is called a resonance line. Absorption Spectra In atomic absorption, an external source of radiation impinges on the analyte vapor. If the external source radiation is of the appropriate frequency (wavelength), it can be absorbed by the analyte atoms and promote them to excited-states. The absorption and emission spectra for sodium are fairly simple and consist of relatively few lines. For elements that have several outer electrons that can be excited, absorption and emission spectra may be more complex. Widths of Atomic Spectral Lines Atomic spectral lines have finite widths. With ordinary measuring spectrometers, the observed line widths are determined not by the atomic system but by the spectrometer properties. Natural broadening

Skoog, West et al, Fundamentals of analytical chemistry, 8th ed, ISBN-13: 978-0-03-035523-3

The natural line width of an atomic spectral line is determined by the lifetime of the excited state and Heisenberg's uncertainty principle. The shorter the lifetime of the excited-state, the broader the line. Collisional Broadening Collisions between atoms and molecules in the gas phase lead to deactivation of the excited state and thus broadening of the spectral line. The amount of broadening increases with the concentration (pressure) of the collision partners. As a result, collisional broadening is sometimes called pressure broadening. Pressure broadening increases with temperature. Doppler broadening Doppler broadening results from the rapid motion of atoms as they emit or absorb radiation. Atoms moving towards the detector emit wavelengths that are slightly shorter than the wavelengths emitted by atoms moving at right angles to the detector.

Skoog, West et al, Fundamentals of analytical chemistry, 8th ed, ISBN-13: 978-0-03-035523-3