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Chemistry · Ch 2 — Quantum Mechanical Model of Atom

Electronic configuration of atoms

2.6.4

Electronic configuration of atoms

The complete distribution of an atom's electrons among its various orbitals is called its electronic configuration. Once the Aufbau, Pauli and Hund rules are all in hand, writing it down for any atom is mechanical.

Notation. An electronic configuration is written using the shorthand nlxnl^x, where nn is the principal quantum number of the shell, ll is written using the subshell's LETTER designation rather than its numeric value (ss for l=0l=0, pp for l=1l=1, dd for l=2l=2, ff for l=3l=3), and xx is the number of electrons actually occupying that subshell. For hydrogen's single electron, which by the Aufbau principle occupies the lowest-energy orbital available (1s), this gives n=1n=1, subshell letter ss, and x=1x=1 - so the configuration is written 1s11s^1 and read aloud as "one-ess-one." Its orbital-box diagram is a single box containing one upward arrow, labelled 1s11s^1.

Building up to neon. Table 2.4 works through every element from hydrogen (Z=1Z=1) to neon (Z=10Z=10), applying the three rules in combination at each step: the shells fill 1s1s then 2s2s then 2p2p in that order (Aufbau); each orbital box takes a maximum of two electrons of opposite spin before the next orbital is touched (Pauli); and within the three 2p orbitals, each gets one electron before any of them gets a second (Hund's rule) - visible in the table as boron through nitrogen picking up one 2p electron at a time in three separate orbitals, before oxygen through neon start pairing those same three orbitals up. …

Table 2.4Electronic configuration and orbital diagrams for the first 10 elements
ElementElectronic ConfigurationOrbital diagram (1s, 2s, 2px2p_x, 2py2p_y, 2pz2p_z)
1_1H1s11s^1⬎
2_2He1s21s^2↿⇂
3_3Li1s2 2s11s^2\,2s^1↿⇂ │ ↿
4_4Be1s2 2s21s^2\,2s^2↿⇂ │ ↿⇂
5_5B1s2 2s2 2p11s^2\,2s^2\,2p^1↿⇂ │ ↿⇂ │ ↿, –, –
6_6C1s2 2s2 2p21s^2\,2s^2\,2p^2↿⇂ │ ↿⇂ │ ↿, ↿, –
7_7N1s2 2s2 2p31s^2\,2s^2\,2p^3↿⇂ │ ↿⇂ │ ↿, ↿, ↿
8_8O1s2 2s2 2p41s^2\,2s^2\,2p^4↿⇂ │ ↿⇂ │ ↿⇂, ↿, ↿
9_9F1s2 2s2 2p51s^2\,2s^2\,2p^5↿⇂ │ ↿⇂ │ ↿⇂, ↿⇂, ↿
10_{10}Ne1s2 2s2 2p61s^2\,2s^2\,2p^6↿⇂ │ ↿⇂ │ ↿⇂, ↿⇂, ↿⇂
Misc 2.6.4-cr-cuThe chromium and copper exceptions

Worked out. The textbook states the 'expected' Aufbau configurations and the actual observed ones side by side. For chromium (Z = 24), the expected configuration 1s2 2s2 2p6 3s2 3p6 3d4 4s21s^2\,2s^2\,2p^6\,3s^2\,3p^6\,3d^4\,4s^2 is NOT what is observed; the actual configuration is 1s2 2s2 2p6 3s2 3p6 3d5 4s11s^2\,2s^2\,2p^6\,3s^2\,3p^6\,3d^5\,4s^1, with one 4s electron shifted into 3d to make the d subshell exactly half filled. For copper (Z = 29), the expected configuration 1s2 2s2 2p6 3s2 3p6 3d9 4s21s^2\,2s^2\,2p^6\,3s^2\,3p^6\,3d^9\,4s^2 is likewise not observed; the actual configuration is 1s2 2s2 2p6 3s2 3p6 3d10 4s11s^2\,2s^2\,2p^6\,3s^2\,3p^6\,3d^{10}\,4s^1, with one 4s electron shifted into 3d to make the d subshell exactly completely filled. Both shifts happen because fully-filled and half-filled configurations (p3,p6,d5,d10,f7,f14p^3,p^6,d^5,d^{10},f^7,f^{14}) carry extra sta …