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Lecture 3 Alkali-Spectra

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33 views12 pages

Lecture 3 Alkali-Spectra

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anshitajain195
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Alkali Spectra

Introduction
• Alkali metals are from group 1 in the periodic table
• The 6 elements from the Alkali Metals group are Lithium (Li), Sodium (Na),
Potassium (K), Rubidium (Rb), Cesium (Cs), Francium (Fr).
• The alkali atoms have a weakly bound outer electron, the so-called valence
electron, and all other (Z-1) electrons are in closed shells.
Alkali-Spectra
• The comparison of Alkali-spectra with H-atom shows that in
the alkali atoms, the l degeneracy is lifted.
• States with the same principal quantum number n and
different orbital angular momentum quantum numbers l have
different energies.
• Relative to the terms of the hydrogen atom, states of the
alkalis lie lower - this means a larger (negative) binding
energy - and this shift increases, the smaller l is.
• For larger principal quantum numbers, i.e. greater orbital
radii, the terms are only slightly different from those of
hydrogen.
• Here also, however, electrons with small l are more strongly
bound and their terms lie lower in the term diagram.
• This effect becomes stronger with increasing Z.
Simplified term diagrams for the alkali metal atoms. For comparison, the
levels of the H atom are given on the right
Screening Effects
• The probability density of the electrons
in the neighbourhood of the nucleus
decreases in the order l = 0,1,2,... .
• The s electrons are thus most strongly
affected by the unscreened field of the
nucleus.
• For a given principal quantum number
n, the energy terms of the s electrons
are therefore shifted the most strongly
to negative values relative to the H
atom
Optical Spectra
of Alkali Atoms:
Quantum Defect

Principal Series: p → s transition

Sharp Series: s → p transition

Diffuse Series: d → p transition

Fundamental Series: d → p transition


Or Bergmann Series
Na- Spectra
• Optical spectra are determined by excitations of the
outermost 3s electron.
• The energy of each (n; l) term of the valence electron is
given
•

• Where n≥3 , 𝑛𝑒𝑓𝑓 = 𝑛 − ∆(𝑛, 𝑙) is the quantum defect


which was introduced empirically to account for the
optical spectra, it was found experimentally it depend
mainly on l as given in the following table.
• The dependency of quantum defect on l can be
understood from the radial probability density of
hydrogenic atom with Z=1.
• An individual electron in sodium atom experiences an
electrostatic potential due to the Coulomb repulsion
from all the other electrons in the atom. Ten out of
eleven electrons are in closed sub-shells, which have
spherically-symmetric charge clouds. The off-radial
forces from electrons in these closed shells cancel
because of the spherical symmetry.
Reasonable approximation: single valence electron of sodium

• Hydrogen radial probability distribution (fig.) is


expected to be a reasonable approximation for the
single valence electron of sodium.

• Both the 3s and 3p orbitals penetrate the inner shells,


and that this penetration is much greater for the 3s
electron.

• The electron will therefore see a larger effective


nuclear charge for part of its orbit and this will have
the effect of reducing the energies.

• The energy reduction is largest for the 3s electron due


to its larger core penetration

• The effect of this penetration results in the shift of


energy levels.
Continue…
• The shift of energy levels in comparison with the hydrogen energy level is shown in
figure

D-line

• Energy levels with different l have different energies, In other words degeneracy
removed.

• From the hydrogen atom energy levels, it cannot be described, because energy
depends only on ‘n’.

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