Electronic Structure of Atoms

The Electronic Structure of Atoms
Juvinch Vicente
UPV Chemistry Department
J. Vicente (UPV) CHEM 11 lec

Electronic Structure
• refers to the arrangement of electrons in an atom.

Bohr’s Model of the Hydrogen Atom
1. Electrons in an atom can only occupy certain orbits

(corresponding to certain energies).
2. Electrons in permitted orbits have specific,

“allowed” energies; these energies will not be
radiated from the atom.
3. Energy is only absorbed or emitted in such a way as

to move an electron from one “allowed” energy
state to another.



• Bohr showed mathematically that
En=(-2.18 10-18 J)(1/n2)
• where n is the principal quantum number (i.e., n = 1,

2, 3, ….),
• The first orbit in the Bohr model has n = 1 and is

closest to the nucleus.
• The farthest orbit in the Bohr model has n→ ∞ and

corresponds to E = 0.

Quantum Mechanics and Atomic Orbitals
• Heisenberg’s uncertainty principle:

– “We cannot determine the exact position, exact direction of
motion, and exact speed of subatomic particles
simultaneously.”
• For electrons, we cannot determine their momentum

and position simultaneously.

• The Schrodinger Equation: Hψ = Eψ

– Schrödinger proposed an equation containing
both wave and particle terms.
– Solving the equation leads to wave functions, (ψ).
– The wave function gives the shape of the
electron’s orbital.

• The Schrodinger Equation: Hψ = Eψ
– The square of the wave

function, (ψ2), gives the
probability of finding the
electron.
– That is (ψ2) gives the electron
density for the atom.
– (ψ2) is called the probability
density.

Quantum Numbers
• numbers describing the atomic orbitals
1. Principal q.n.(n):
– size and energy of the orbital
2. Angular momentum q.n. (l):
– shape of atomic orbital
3. Magnetic q.n. (ml):
– spatial orientation of orbital

Quantum Numbers
Principal Quantum Number: n
• a positive integral (1,2,3…) number describing the

size and energy of an orbital.
• also referred as shells.
• as n increases:
– orbital gets larger, electron spends more time
farther from the nucleus.
– energy gets higher, electron is less tightly bound,

energy is less negative.

Quantum Numbers
Principal Quantum Number: n
• the size of an orbital increases as n increases.

• electrons staying farther from the nucleus have
higher energy

Quantum Numbers
Angular Momentum Quantum Number: l
• integral values from 0 to (n-1), related to the shapes

of the atomic orbitals
• often referred subshells
– Examples:
• n=2: l could be = 0 or 1
• n=4: l could be = 0, 1, 2, or 3
• letter assignments of l:
Value of l 0 1 2 3
Type of orbital s p d f

Quantum Numbers
Magnetic Quantum Number: ml
• integral values between -l to +l, including 0.

– Examples:
• l=1: ml= -1,0,+1
• l=2: ml= -2,-1,0,+1,+2
• related to the spatial orientation of orbitals, relative
to other orbitals in the atom
• Therefore, on any given energy level (n), there can

be up to 1 s orbital, 3 p orbitals, 5 d orbitals, 7 f
orbitals, etc.

Orbital Shapes and Orientation
The p Orbital
• (l=1)(ml=-1,0,+1)
• dumbbell-shaped: 3 possible orientations
• two lobes: one node between the lobes

The s Orbital
• (l=0)(ml=0)
• sphere-shaped, with only one

possible orientation
• we see that s orbitals possess

(n−1) nodes, or regions where
there is 0 probability of finding
an electron

The d Orbital
• (l=2)(ml=-2,-1,0,+1,+2)
• ??-shaped: 5 possible orientations
• 4 have 4 lobes: 1 resembles a p orbital with a doughnut
around the center

The f Orbital
• (l=3)(ml=-3,-2,-1,0,+1,+2,+3)
• ?????? shaped: 7 possible orientations

Quantum Numbers

Energy of Orbitals
• For a one-electron hydrogen

atom, orbitals on the same
energy level have the same
energy.
• That is, they are degenerate.

Ens = Enp = End = Enf
• Example
E4s = E4p = E4d = E4f

Energy of Orbitals
• As the number of electrons
increases, though, so does the
repulsion between them.
• In many-electron atoms,
orbitals on the same energy
level are no longer degenerate.
Ens < Enp < End < Enf
• Example
E4s < E4p < E4d < E4f

Spin Quantum Number, ms
• Two electrons in the same
orbital do not have exactly
the same energy.
• The “spin” of an electron

describes its magnetic field,
which affects its energy.
• The spin quantum number

has only 2 allowed values:
+1/2 and −1/2.

Pauli’s Exclusion Principle
• “NO two electrons in the

same atom can have exactly
the same energy”
• NO two electrons in the

same atom can have
identical sets of quantum
numbers.

Electronic Configurations
Hydrogen: 1 e- • Shows the distribution

of electrons among
1s1 various orbitals in an
Lithium: 3 e- atom.
1s22s1 • Each component consists of

a) A number denoting the
Sodium: 11 e- energy level of each orbital
b) letter describing the orbital
ls 2s 2p 3s
2 2 6 1 shape
c) a superscript denoting the
number of electrons in an
orbital

Aufbau Principle
• The “building-up”
principle
• Fill orbitals with increasing

order of energy
• Remember:
Ens < Enp < End < Enf

Orbital Diagrams
• Each box in the diagram

represents one orbital, and
half-arrows represent the
electrons.
• The direction of the arrow

represents the relative spin
of the electron.
– by convention:
– “up” = +1/2 , “down”= -1/2

Hund’s Rule
• For degenerate orbitals, the lowest energy is attained

when the number of electrons with the same spin is
maximized.
NOT

Electronic Config. and The Periodic Table
• Different blocks on the periodic table correspond to different
shapes of orbitals.

• Condensed electronic configuration

– simplify long electronic configuration by the use of the
noble gases.
• Example:
– Ti(22)
• Long: 1s22s22p63s23p64s23d2
• Condensed:[Ar] 3d24s2

• Anomalies in Electron Configurations

– Some irregularities occur when there are enough
electrons to half-fill s and d orbitals on a given row.
– E.g. Copper:
• [Ar] 4s1 3d10 rather than the expected [Ar] 4s2 3d9
– This occurs because the 4s and 3d orbitals are very close

in energy.
– These anomalies occur in f-block atoms, as well.

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The Electronic Structure of Atoms

UPV Chemistry Department

J. Vicente (UPV) CHEM 11 lec

• refers to the arrangement of electrons in an atom.

J. Vicente (UPV) CHEM 11 lec

Bohr’s Model of the Hydrogen Atom

1. Electrons in an atom can only occupy certain orbits

2. Electrons in permitted orbits have specific,

3. Energy is only absorbed or emitted in such a way as

J. Vicente (UPV) CHEM 11 lec

Bohr’s Model of the Hydrogen Atom

J. Vicente (UPV) CHEM 11 lec

Bohr’s Model of the Hydrogen Atom

• where n is the principal quantum number (i.e., n = 1,

• The first orbit in the Bohr model has n = 1 and is

• The farthest orbit in the Bohr model has n→ ∞ and

J. Vicente (UPV) CHEM 11 lec

Quantum Mechanics and Atomic Orbitals

• Heisenberg’s uncertainty principle:

• For electrons, we cannot determine their momentum

J. Vicente (UPV) CHEM 11 lec

Quantum Mechanics and Atomic Orbitals

• The Schrodinger Equation: Hψ = Eψ

J. Vicente (UPV) CHEM 11 lec

Quantum Mechanics and Atomic Orbitals

• The Schrodinger Equation: Hψ = Eψ

– The square of the wave

J. Vicente (UPV) CHEM 11 lec

• numbers describing the atomic orbitals

J. Vicente (UPV) CHEM 11 lec

Principal Quantum Number: n

• a positive integral (1,2,3…) number describing the

– energy gets higher, electron is less tightly bound,

J. Vicente (UPV) CHEM 11 lec

Principal Quantum Number: n

• the size of an orbital increases as n increases.

J. Vicente (UPV) CHEM 11 lec

Angular Momentum Quantum Number: l

• integral values from 0 to (n-1), related to the shapes

J. Vicente (UPV) CHEM 11 lec

Magnetic Quantum Number: ml

• integral values between -l to +l, including 0.

• Therefore, on any given energy level (n), there can

J. Vicente (UPV) CHEM 11 lec

J. Vicente (UPV) CHEM 11 lec

• sphere-shaped, with only one

• we see that s orbitals possess

J. Vicente (UPV) CHEM 11 lec

J. Vicente (UPV) CHEM 11 lec

J. Vicente (UPV) CHEM 11 lec

J. Vicente (UPV) CHEM 11 lec

• For a one-electron hydrogen

• That is, they are degenerate.

J. Vicente (UPV) CHEM 11 lec

Ens < Enp < End < Enf

J. Vicente (UPV) CHEM 11 lec

• The “spin” of an electron

• The spin quantum number

J. Vicente (UPV) CHEM 11 lec