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Chemistry · Ch 2 — Quantum Mechanical Model of Atom

Quantum numbers

2.5

Quantum numbers

A single electron inside an atom is fully characterised by a set of four quantum numbers: the principal quantum number nn, the azimuthal (subsidiary) quantum number ll, the magnetic quantum number mm, and the spin quantum number ss. It's worth noting where each of these actually comes from mathematically: solving the Schrödinger equation for a wavefunction Ψ\Psi naturally produces the first three - nn, ll and mm - as the parameters needed to specify a valid solution. The fourth quantum number, spin, does not come out of that same spatial wave equation at all; it arises separately, from the fact that the electron itself spins about its own axis. (That said, picturing this literally as a tiny sphere physically spinning like a top is misleading and not to be taken as a literal classical picture - "spin" is a genuinely quantum property that simply behaves, in some ways, analogously to classical spinning.)

Principal quantum number (nn). This number specifies which energy shell the electron occupies - the shell it "revolves" in - and is denoted by the letter nn.

  • nn can take positive integer values 1,2,3,…1,2,3,\dots. Shells are also given letter names: n=1n=1 is called the K shell, n=2n=2 is the L shell, and n=3,4,5n=3,4,5 are the M, N and O shells respectively.
  • The maximum number of electrons a given shell can hold is 2n22n^2.
  • nn alone fixes both the electron's energy, En=−(1312.8 Z2/n2)E_n=-\left(1312.8\,Z^2/n^2\right) kJ mol−1^{-1}, and its average distance from the nucleus, rn=(0.529 n2/Z)r_n=\left(0.529\,n^2/Z\right) Å - the same formulas already met in the Bohr model, now reinterpreted as quantum-mechanical results rather than as classical orbit properties.

Azimuthal (subsidiary) quantum number (ll).

  • Denoted by the letter ll, it can take any integer value from 00 up to n−1n-1 for a given shell.
  • Each distinct value of ll defines a subshell (equivalently, describes the shape of the orbitals in that subshell): l=0,1,2,3,4l=0,1,2,3,4 correspond to the s, p, d, f and g subshells respectively.
  • The maximum number of electrons a given subshell can hold is 2(2l+1)2(2l+1).
  • ll also fixes the size of the electron's orbital angular momentum, through

angular momentum=l(l+1) h2π— eq. (2.14)\text{angular momentum}=\sqrt{l(l+1)}\,\frac{h}{2\pi}\qquad\text{— eq. (2.14)}

Magnetic quantum number (mlm_l).

  1. Denoted mlm_l, it takes integer values running from −l-l to +l+l passing through 0 - so for example if l=1l=1, then ml=−1, 0, +1m_l=-1,\,0,\,+1.
  2. For a fixed ll, each different value of mlm_l represents a different spatial orientation of that subshell's orbitals.
  3. The experimental evidence for this quantum number is the Zeeman effect - the splitting of spectral lines when an atom is placed in a magnetic field, which happens precisely because the different mlm_l orientations, ordinarily all of equal energy, are pulled apart in energy once an external field singles out a preferred direction in space.
  4. To put it another way: ll fixes the magnitude of the orbital angular momentum, while mlm_l fixes its direction.

Spin quantum number (msm_s).

  1. This quantum number represents the electron's own intrinsic spin and is denoted msm_s.
  2. Loosely, it is described as the electron spinning about its own axis either clockwise or anticlockwise - but as noted above, this literal picture is not physically accurate; spin is better understood simply as an intrinsic property that reveals itself experimentally through the electron's behaviour in a magnetic field.
  3. Correspondingly, only two values of this quantum number are possible, matching the two senses of "clockwise" and "anticlockwise." …
Table 2.1Quantum numbers and their significance
ShellPrincipal quantum number (n)Max. electrons in shell 2n22n^2Azimuthal quantum number (l)Max. electrons in a subshell 2(2l+1)2(2l+1)Magnetic quantum number (m) – orbital orientationsDesignation of orbitals in the shell
K120201s
L280202s
L2816−1, 0, +12py,2pz,2px2p_y, 2p_z, 2p_x
M3180203s
M31816−1, 0, +13py,3pz,3px3p_y, 3p_z, 3p_x
M318210−2, −1, 0, +1, +23dx2−y2,3dyz,3dz2,3dzx,3dxy3d_{x^2-y^2}, 3d_{yz}, 3d_{z^2}, 3d_{zx}, 3d_{xy}
N4320204s
N43216−1, 0, +14py,4pz,4px4p_y, 4p_z, 4p_x
N432210−2, −1, 0, +1, +24dx2−y2,4dxy,4dz2,4dyz,4dzx4d_{x^2-y^2}, 4d_{xy}, 4d_{z^2}, 4d_{yz}, 4d_{zx}
N432314−3, −2, −1, 0, +1, +2, +3seven f orbitals: fy(3x2−y2),fz(x2−y2),fyz2,fz3,fxz2,fxyz,fx(x2−3y2)f_{y(3x^2-y^2)}, f_{z(x^2-y^2)}, f_{yz^2}, f_{z^3}, f_{xz^2}, f_{xyz}, f_{x(x^2-3y^2)}