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The main quantum number, n, determines the energy of the state (exactly in the
case of hydrogen-like atoms; with minor corrections involving the other quantum numbers for multi-electron
atoms). It also determines the size of the spherical envelope of the wave function: The higher n,
the further the probability cloud stretches out into space. Possible values of n are positive
integer numbers.
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The angular momentum quantum number, l, governs the ellipticity of the probability cloud
and the number of planar nodes going through the nucleus. In the Fig., red and blue areas indicate regions
with opposite sign of the wave function and the black dot represents the position of the nucleus.
For a given n, the possible values are integers from 0 up to n-1.
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The magnetic quantum number, m, is related to the magnetic moment of any non-spherical
electron (probability) distribution. Therefore, the different m states relate to differently
orientated orbitals. Which one is which depends on the preferential axis, i.e. the orientation of
an external field, if any. All (n,l) states with different m look the same. In the Fig.,
the third one is the same shape as the others but orientated perpendicular to the screen. The values of
m for a given (n,l) range from -l to +l.
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The spin (quantum number), s, is similar to l in that it refers to an angular
momentum component. It can be visualised as the rotation of the electron, thought of as a particle,
around its own axis rather than around the nucleus. This is, however, a bit of a crutch because the
electron's behaviour has both aspects of particle (such as scattering) and wave (such as diffraction),
and if carried through quantitatively doesn't give accurate results. The possible values of the spin
quantum number are -½ and +½ for electrons.
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The uncertainty principle applies to all products of observables whose units combine to [J s] =
[kg m2 s-1], i.e.
the dimension of Planck's constant. The best-known uncertainty principle is the one linking the
uncertainties of position, x, and momentum, p. We have also used the energy-time
uncertainty principle when discussing energy bands.
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Angular momentum is a vector defined by the cross product
. Judging by its units,
[kg][m]×[m s-1]=[kg m2 s-1], the complementary uncertainty
should be dimensionless. It is in fact the uncertainty of the angle of rotation, phi.
The uncertainty of the angle must be limited to 2pi - the angular momentum has to point somewhere
on a circular orbit. Therefore, the uncertainty of the component of the angular momentum perpendicular
to the direction of motion must be of the order of Planck's constant. We may therefore conclude that
values of Lz are quantised in multiples of h/2pi.
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There are 2l+1 possible orientations of the angular momentum,
,
and two possible orientations of the spin,
, of an electron. The Fig. shows the situation for
the spin: The spin aligns at an angle with the z axis (which could be a preferential axis generated by
applying a magnetic field or by a chemical bond). There are two possible orientations (these are
often called parallel or up and anti-parallel or down although
that's exactly what they are not!). The angle with the z axis is given by the need to distribute
the 2l+1 states uniformly over the whole angular range from the +z to the -z direction. For example,
in the case of an l=1 angular momentum state, there are three possible orientations, one of which
is perpendicular to the z axis, and the other two are 45o of the positive and negative z axis,
respectively. In no case is the angular momentum vector exactly (anti-)parallel to the z axis. If it was,
we would know both the angular momentum and the angle precisely, which would defy the uncertainty
principle.
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