CH1 introduction to inorganic chemistry

atomic orbital
- Bohr’s model has some limitation -> wave property of atoms ->
orbital

Instead of precise orbits of e-, we can only describe orbitals, regions

that describe the probable locations of e-
The probability of finding the e-, e- density can be calculated.
Orbital 전자의 위치를 알려누는 지도같은 의미

De broglie equation for particle-energy duality

- very light particles like e- have observable wave properties

이 방정식을 통하여 움직이는 입자는 wave로 표현가능함을 알게 되었다. 다만 크기가 크고 질

량이 큰 입자의 경우 파장이 매우 작아서 wave임을 알기 힘들다. 하지만, e-와 같이 작고
가벼운 경우에는 파장임을 관찰할 수 있다

Heisenberg’s uncertainty principle

CH2 atomic structure
- there is a relationship bt inherent uncertainties in the location &
momentum of e-

With high precision in momentum, there is a large uncertainty in the

location of e-

*the schrodinger equation

- describes the wave properties of e-

- the wave functions describes an e- wave in space

- the hamiltonian operator includes derivatives that operate on the
wave function
- the operation gives the result of constant(E) times wave function

- the potential E, V, is result of electrostatic attraction bt e- and nucleus.

Attractive forces are defined as a - potential e
- for e- at infinite distance, V is 0
- probability of finding e- at a given point in space is proportional to
 The particle in a box
Quantum Numbers and atomic wave function
Atomic orbitals are solutions of 3D schrodinger eqn

Spherical coordinate is useful in describing wave functions

_ The squared wave faction(sine functions) are the probability densities

Wavefunction can be factored into radial component&2 angular components

The wave equations of p and d orbitals contain i and thus linear

combination of wave equation is necessary.

Hydrogen electron
2) quantum numbers and atomic wave functions
- radial factor R(r) is determined by 2 QNs, n and l

- radial distribution function

Nodal surface
- a surface with 0 electron density
- node is a surface where the wave function is 0 as it changes sign
- the lowest energy orbitals of each classification have no radial
nodes. n-1 = n-l-1(radial) + l(angular)

같은 수의 전자를 같고 있는 이온 혹은 원자의 오비탈 크기를 비교하는 경우

보통 핵전하량이 크면, 당기는 힘이 강해서 오비탈의 크기가 작다

3) Aufbau principle
The buildup of electrons in atoms results from continually increasing QN.
1. Aufbau principle: Electrons are placed in orbitals to give the lowest
total energy to the atom. The lowest values of n and l are filled first.
2. Pauli exclusion principle requires that each electron in an atom have a
unique set of QN.
3. Hund’s rule of maximum multiplicity requires that electrons be placed
in orbitals so as to give the maximum total spin possible.

Hunt's rule: rule of maximum multiplicity

Multiplicity: The number of unpaired e+1

Hund’s rule
1. Maximizes the number of unpaired electrons
2. Maximizes spin multiplicity (2s+1)
: Reduction of electron-electron repulsion & gain of exchange energy. orbitals)
Energy level splitting and overlap
- The orbital energies of many-electron system depend not only on n
but also on l, due to the shielding effect.
Shielding effect
- Effective nuclear charge Z* = Z – S
- The order of stability: s > p > d > f
- n + l rule: penetration effect vs. principal QN
1s > 2s > 2p > 3s > 3p > 4s ~ 3d > 4p > 5s ~ 4d > 5p …….
Aufbau Principle : for many electron-system, orbitals are filled
sequentially in the order given above.
- 24Cr : 3d54s1 and 29Cu : 3d104s1 (Extra stability of half-filled or filled
- Ionization of transition metal begins with the removal of s electrons.

Shielding effect: An electron in one orbitals partially shields electrons

of other orbitals.
Degenerate: have the same energy

Slater's rule for shielding Periodic properties of Atoms

1. As atomic number increases, the energy of given type of orbital
becomes more negative (increase of stability). Enhanced electrostatic
interaction
2. Going across the period, the Z* increase. Incomplete shielding to
compensate the increase of nuclear charge.
3. There are some exceptions to the general order of orbital stability.
4. The removal of electron reduces the shielding, resulting in increased
stability for the valence orbitals. The reverse is observed for the
addition of electron.

Ionization energy: required to remove e- from a gaseous atom or ion

Electron affinity: e required to remove an e from - ion

- Most elements have positive first EA.

Exception: Groups 2 & 18.
- Second EA and beyond are always endothermic.
- EA tends to increase going across a period and decrease going
down a family.
- There are some exceptions EA(Cl) > EA(F).

Variation of atomic size in the periodic table

1. As the nuclear charge increases, the electrons are pulled in toward
the center of the atom, leading to the decrease of atomic size.
2. As the nuclear charge increases, more electrons are added to the
atom and their mutual repulsion keeps the outer orbitals large.
3. Size tends to decrease going across a period due to incomplete
shielding.
4. Going down a family, size increases because of the added shell.
5. For a given nuclear charge, size increases with the number of
electrons. M2+< M+ < M0 < M- < M2- …
6. For a given number of electrons, size decreases as the nuclear
charge increases. S2- >Cl1- > Ar0 > K+ > Ca2+ (18 electrons)
7. The decrease of size within a period is severe for transition
metal, anthanides, and actinides (poor shielding of d and f orbitals). -
Lanthanide contraction

- The radius decreases as nuclear charge increases for ions with the
same electronic structure.
- Within a group, the ionic radius increases as Z increases.
- The ionic radius decreases with increasing charge on the cation.