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S. B. Piepho, Fall 2005

Quantum Numbers, Orbitals, and Electron Configurations Quantum Mechanics and the H Atom Bohr theory (1914) ran into problems when it was applied to atoms other than H, and was soon replaced by quantum mechanics (1926). When quantum mechanics was applied to the H atom, the same energies were calculated for the H atom energy levels as in the Bohr model,

1 En = − RH 2 n

for n = 1, 2, 3, ...

(Applies only to H atom!!)

(1)

but the method by which they were calculated was entirely different. Quantum mechanics assumes the electron is wave-like, and the planetary orbits of Bohr theory (which views the electron as a particle) are discarded. Orbitals, which give us a picture of the most probable locations for the electron in a particular energy state, replace the Bohr orbits. Since the electron is viewed as a wave, it is impossible to describe its precise location: an averaged picture is the best we can do! Another change is that while the quantum number n still plays the prominent role, it is augmented by the quantum numbers l, ml, and ms. The allowed quantum numbers for the H atom are given in the tables below. Table 1.

Quantum Number Allowed Values Name and Meaning

n l

n = 1, 2, 3, ...... l = (n-1), (n-2), ...., 0

ml ms

ml = l, (l-1), ..., 0, ..., (-l+1), -l ms = 1/2, -1/2

Principal quantum number: orbital energy and size. Azimuthal (or orbital) quantum number: orbital shape (and energy in a multi-electron atom), letter name for subshell (s, p, d, f) Magnetic quantum number: orbital orientation Electron spin quantum number: spin up ( ↑ ) or spin down ( ↓ ).

Table 2

l Value Letter Equivalent to l Value No. of Orbitals in Set Approximate Shape of Orbitals with Specific l Values

0 1 2 3 Table 3

Shell ( n) Subshell (l)

s p d f

1 3 5 7

spherical px, py, pz are dumbbells along x, y, and z axes mostly cloverleaf shapes very complicated shapes!

Orbital Name (nl)

Orientations (ml)

No. of Orbitals

n=1 n=2

l=0 l=0 l=1 l=0 l=1

1s 2s 2p 3s 3p

n=3

ml = 0 ml = 0 ml = 1, 0 -1 (or px, py, pz) ml = 0 ml = 1, 0, -1

Page 1 of 3

1 1 3 1 3

Maximum Occupancy 2 e-

2 e6 e2 e6 e-

(e) [See Table 1 for the relation between the allowed values of l and value of n] _____________________________________________________________________________ _ 3. Each orbital holds 2 electrons (Pauli Exclusion Principle). dyz. 5p (fifth row). Orbitals with a lower l value penetrate closer to the nucleus and are less shielded and have a lower energy than those with a higher l value. l = 1=p. -2 (or dxy. (d) 5p. one with spin up ( ↑ ) and one with spin down ( ↓ ). py. 0. See Table 1 on p. px. 3d. Fall 2005 5 10 e- Orbital Energies and Electron Configurations of Multi-Electron Atoms For the H atom the orbital energy depends only on n. allowed values of l are: l = 0=s. If more than one orbital has the same energy (e. 7s. (a) List all the orbitals for which n = 4.. electrons in the outer orbitals are shielded somewhat from the nucleus: they do not feel the full nuclear charge. (c). l = 2=d. 0. The order of orbital filling is easily remembered if correlated with the periodic chart. d x 2 − y 2 . (b) 1 + 3 + 5 + 7 = 16 orbitals (each holds 2 e-). and l = 3=f. 4p (fourth row). however. _____________________________________________________________________________ _ 2. py. 1. B. five 4d. -1. d z2 ) S. 2p (second row). -2. Thus we have one 4s. so all orbitals with the same value of n have the same energy. 3p (third row). 4d. Table 7. What role does the principal quantum number n play in determining your answer? Page 2 of 3 . 1.g. pz ). The result is that for a given value of n the energy order is s < p < d < f. (b) 4f. additional electrons form pairs. 2. dxz. The order is 1s (first row of chart). for any other atom! The H atom orbitals may be used to approximate the orbitals for multi-electron atoms. 5d. pz) ml = 2. p. 6s. Chapters 7. For example.Chang. 5f. 293 for atomic configurations. (e) 3f? Why not? Answer: (a).3. This is not true. 2s. once each orbital in the set contains one electron. (b) How many orbitals are there in all? Answer: (a) When n = 4. -1. 6p (sixth row). Worksheet #2 l=2 3d (or px. 8th Edition. Piepho. -3. _____________________________________________________________________________ _ 1. There are a few exceptions to these rules: see Chang. List all possible values of ml for each of the indicated subshells. 1 for the allowed ml values for each value of l. three 4p. 6d. when l = 3. But since these atoms have more than one electron. (c) 2d. ml = 3. 4f. 5s. 4s. Orbitals are filled from lowest energy to highest energy. electrons first enter different orbitals with spins parallel (Hund’s Rule). 3s. and seven 4f orbitals. Which of the following subshells cannot exist: (a) 1p.

0. 0. -3. (c) 2. Principal quantum number plays no role: answers do not depend on n _____________________________________________________________________________ _ 4. 1. (d) 3. Worksheet #2 Subshell (a) 4s (b) 2p (c) 3d (d) 5f S. (b) 1. 8th Edition. 0. B. -2. Answer: 2l +1 (why?) Page 3 of 3 . -1. Piepho. -1. 1. -1. Give the formula that relates the number of possible values of ml to the value of l. 2.Chang. Chapters 7. -2. Fall 2005 Values of ml Answer: (a) 0.

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