5.111 Principles of Chemical Science: Mit Opencourseware
5.111 Principles of Chemical Science: Mit Opencourseware
5.111 Principles of Chemical Science: Mit Opencourseware
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5.111 Lecture Summary #8
Readings for today: Section 1.12 (1.11 in 3rd ed) – Orbital Energies (of many-electron
atoms), Section 1.13 (1.12 in 3rd ed) – The Building-Up Principle.
Read for Lecture #9: Section 1.14 (1.13 in 3rd ed) – Electronic Structure and the
Periodic Table, Section 1.15, 1.16, 1.17, 1.18, and 1.20 (1.14, 1.15, 1.16, 1.17, and
1.19 in 3rd ed) - The Periodicity of Atomic Properties.
_______________________________________________________________________________
The Schrödinger equation correctly describes the electronic structure for all atoms,
Hartree orbitals: Assume we can write a multi-electron Ψ as the product of 1-electron Ψs:
H 1s1
He 1s2
Li 1s22s1
Be ____________ B _____________
WAVEFUNCTIONS?
• The nodal structure is the same (nodes occur at values of r, θ and Φ which give
Ψ and Ψ2 = 0).
Why? Stronger pull from the nucleus with higher Z (Z=18 for Ar , Z=1 for H).
• In multi-electron atoms, orbital energy depends on both the shell (n) and the
subshell (l).
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The lower energy results in multi-electron atoms results from a higher Z--- a stronger
pull from the nucleus.
The principal quantum number, n, is no longer the sole determining factor for the
orbital energies of multi-electron atoms. Energy now depends on n and ____.
Where Zeff is the effective charge experienced by the electron in the n,l state.
Zeff _______ the same as Z for the nucleus. Zeff differs from Z because of ___________.
To illustrate the effect of shielding, consider the two extreme shielding situations
possible for the He atom (Z = 2).
EXTREME CASE A: electron #1 is very far from nucleus; electron #2 close to nucleus
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EXTREME CASE B: electron #1 close to nucleus; electron #2 very far from nucleus
Note: Our calculated Zeff is a reasonable value, since it falls between ___ (total shielding) and ___
(no shielding).
Why is E2s < (more negative than) E2p and E3s < E3p < E3d
For a given n state (shell), electrons in orbitals with lower values of l ______________
closer to the nucleus (even though rmp decreases with increasing l!).
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This means (for the same n):
Consider why the electron configuration for Li is 1s2 2s1 and not 1s2 2p1.
The s-orbital is less shielded. Averaging over the RPD yields ________ < ________ .
AUFBAU PRINCIPLE
Fill energy states (which depend on ___ and ___) one electron at a time, starting with
the lowest energy state and following:
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Third Period: Na to Ar Fourth Period: K to Kr
K � [Ar] 4s1
Na � 1s2 2s2 2p6 3s1 Ca � [Ar] 4s2
Sc � [Ar] 4s23d1
________ electrons Ti � [Ar] 4s23d2
___________ electron V � [Ar] 4s23d3
Cr � [Ar] 4s13d5 exception to Aufbau*
Mn � [Ar] 4s23d5
Fe � [Ar] 4s23d6
Na � [Ne] 3s1 Co � [Ar] 4s23d7
Mg � [Ne] 3s2 Ni � [Ar] 4s23d8
Al � [Ne] 3s23p1 Cu � [Ar] 4s13d10 exception to Aufbau*
. Zn � [Ar] 4s23d10
. Ga � [Ar] 4s23d104p1
Ar � [Ne] 3s23p6 .
Kr � [Ar] 4s23d104p6
* Exceptions to the Aufbau principle: filled (____) and half-filled (____) d-orbitals
have lower energy than simple theory predicts.
Valence electrons: electrons in the outer most shell. Valence electrons are the
exciting ones- in general, only the valence electrons participate in chemical reactions.
Using this chart, we can write out the correct order of orbitals with
increasing energy from left to right
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p