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Chapter 7
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
Quantum Theory and the
Electronic Structure of Atoms
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Properties of Waves
Wavelength (l) is the distance between identical points on
successive waves.
Amplitude is the vertical distance from the midline of a
wave to the peak or trough.
Frequency (n) is the number of waves that pass through a
particular point in 1 second (Hz = 1 cycle/s).
The speed (u) of the wave = l x n
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Maxwell (1873), proposed that visible light consists of
electromagnetic waves.
Electromagnetic
radiation is the emission
and transmission of energy
in the form of
electromagnetic waves.
Speed of light (c) in vacuum = 3.00 x 108 m/s
All electromagnetic radiation
l x n = c
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l x n = c
l = c/n
l = 3.00 x 108 m/s / 6.0 x 104 Hz
l = 5.0 x 103 m
A photon has a frequency of 6.0 x 104 Hz. Convert this
frequency into wavelength (nm). Does this frequency fall in
the visible region?
l = 5.0 x 1012 nm
l
n
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Mystery #1, “Heated Solids Problem”
Solved by Planck in 1900
Energy (light) is emitted or
absorbed in discrete units
(quantum).
E = h x n
Planck’s constant (h)
h = 6.63 x 10-34 J•s
When solids are heated, they emit electromagnetic radiation
over a wide range of wavelengths.
Radiant energy emitted by an object at a certain temperature
depends on its wavelength.
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Light has both:
1. wave nature
2. particle nature
hn = KE + W
Mystery #2, “Photoelectric Effect”
Solved by Einstein in 1905
Photon is a “particle” of light
KE = hn - W
hn
KE e-
where W is the work function and
depends how strongly electrons
are held in the metal
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E = h x n
E = 6.63 x 10-34 (J•s) x 3.00 x 10 8 (m/s) / 0.154 x 10-9 (m)
E = 1.29 x 10 -15 J
E = h x c / l
When copper is bombarded with high-energy electrons, X rays
are emitted. Calculate the energy (in joules) associated with
the photons if the wavelength of the X rays is 0.154 nm.
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Line Emission Spectrum of Hydrogen Atoms
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1. e- can only have specific
(quantized) energy
values
2. light is emitted as e-
moves from one energy
level to a lower energy
level
Bohr’s Model of
the Atom (1913)
En = -RH ( )1
n2
n (principal quantum number) = 1,2,3,…
RH (Rydberg constant) = 2.18 x 10-18J
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E = hn
E = hn
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Ephoton = DE = Ef - Ei
Ef = -RH ( )1
n2f
Ei = -RH ( )1
n2i
i f
DE = RH( )1
n2
1
n2
nf = 1
ni = 2
nf = 1
ni = 3
nf = 2
ni = 3
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Ephoton = 2.18 x 10-18 J x (1/25 - 1/9)
Ephoton = DE = -1.55 x 10-19 J
l = 6.63 x 10-34 (J•s) x 3.00 x 108 (m/s)/1.55 x 10-19J
l = 1280 nm
Calculate the wavelength (in nm) of a photon emitted
by a hydrogen atom when its electron drops from the
n = 5 state to the n = 3 state.
Ephoton = h x c / l
l = h x c / Ephoton
i f
DE = RH( )1
n2
1
n2Ephoton =
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De Broglie (1924) reasoned
that e- is both particle and
wave.
Why is e- energy quantized?
u = velocity of e-
m = mass of e-
2pr = nl l = h
mu
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l = h/mu
l = 6.63 x 10-34 / (2.5 x 10-3 x 15.6)
l = 1.7 x 10-32 m = 1.7 x 10-23 nm
What is the de Broglie wavelength (in nm) associated
with a 2.5 g Ping-Pong ball traveling at 15.6 m/s?
m in kgh in J•s u in (m/s)
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Electronic
Structure
of Atoms
The Wave Nature of Matter
• Louis de Broglie positedأثبت that if light
can have material properties, matter
should exhibit wave properties.
• He demonstrated that the relationship
between mass and wavelength was
l =h
mv
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Electronic
Structure
of Atoms
The Uncertainty Principleمبدأ عدم التأكد لهايزنبيرج
• Heisenberg showed that the more precisely
the momentum of a particle is known, the less
precisely is its position known:
• In many cases, our uncertainty of the
whereabouts of an electron is greater than the
size of the atom itself!
(Dx) (Dmv) h
4p
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Electronic
Structure
of Atoms
• What does the uncertainty principle mean?
• The uncertainty principle also called the Heisenberg Uncertainty
Principle, or Indeterminacy Principle, articulated (1927) by the
German physicist Werner Heisenberg, that the position and the
velocity of an object cannot both be measured exactly, at the same
time, even in theory.
• What did the uncertainty principle state?
• The Heisenberg uncertainty principle states that it is impossible to
know simultaneously the exact position and momentum of a particle.
That is, the more exactly the position is determined, the less known the
momentum, and vice versa.
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Electronic
Structure
of Atoms
أهمنمالشكمبدأأواللايقينمبدأأوالريبةمبدأأوالتأكدعدممبدأيعتبر•1927عامهايزنبرجالألمانيالعالمصاغهأنبعدالكمنظريةفيالمبادئجملةصخوامنمقاستينخاصيتينتحديديمكنلاأنهعلىالمبدأهذاوينصقةبدالخاصيتينأحدتحديدأنأيالدقة،منمعينةحدودضمنإلاكموميةلخاصيةاقياسفيكبيرتأكدعدميستتبع(ضئيلتأكدعدمذات)متناهيةضعالموتحديدخاصيتيعلىبكثرةالمبدأهذاتطبيقويشيعالأخرى،
كلرفةمععلىقادراليسالإنسانأنمعناهالمبدأفهذا.أوليلجسيمالسرعةولاقدرهناكإنما،%100بدقةشيءكلقياسيمكنهولا.%100بدقةشيءأدناهالمكتوبةةللمعادلتخضعالطبيعيةالحقيقةوهذه.قياسهيستطيعولايعرفه.بلانكثابتhفيهايتحكموالتي
تمنعيزياءللفالأساسيةالقوانينكانتفإذاحقاً،هائلشيءالمبدأهذاونتائج•ًًأي .اتماممؤكدةمعلوماتعلىللحصولمثاليةظروفالهكانتمهماعالمالأنهتخطيه،يستطيعلاالدقةعدممنقدرعلىطبيعيايحتويبقياسهيقومفما
أنيعيستطلاأنهذلكومعنى.التأكدعدممبدأمنطقهوفهذا.طبيعيقانونمنصغيرةولوةنسبهناكتظلبلمتناهية،بدقةمستقبلاًًالأشياءبحركةيتنبألقياسافيوسائلناوتطويرالإحكامكانمهماأنهالمبدأهذاومعنى.التأكدعدم.حولنامنللطبيعةكاملةمعرفةإلىالتوصلمنذلكيمكننافلن
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Electronic
Structure
of Atoms
Schrodinger’s Wave Equation
22
2 2
8
dh EVm dx
p− + =
Equation for the
probability of a single
electron being found
along a single axis (x-axis)Erwin Schrodinger
(this slide from: J. Hushen’s presentation on Atomic Structure at
http://teachers.greenville.k12.sc.us/sites/jhushen/Pages/AP%20Chemistry.aspx)
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Schrodinger Wave Equation
In 1926 Schrodinger wrote an equation that
described both the particle and wave nature of the e-
Wave function () describes:
1. energy of e- with a given
2. probability of finding e- in a volume of space
Schrodinger’s equation can only be solved exactly
for the hydrogen atom. Must approximate its
solution for multi-electron systems.
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Schrodinger Wave Equation
is a function of four numbers called
quantum numbers (n, l, ml, ms)
principal quantum number n
n = 1, 2, 3, 4, ….
n=1 n=2 n=3
distance of e- from the nucleus
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Where 90% of the
e- density is found
for the 1s orbital
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quantum numbers: (n, l, ml, ms)
angular momentum quantum number l
for a given value of n, l = 0, 1, 2, 3, … n-1
n = 1, l = 0
n = 2, l = 0 or 1
n = 3, l = 0, 1, or 2
Shape of the “volume” of space that the e- occupies
l = 0 s orbital
l = 1 p orbital
l = 2 d orbital
l = 3 f orbital
Schrodinger Wave Equation
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l = 0 (s orbitals)
l = 1 (p orbitals)
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l = 2 (d orbitals)
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quantum numbers: (n, l, ml, ms)
magnetic quantum number ml
for a given value of l
ml = -l, …., 0, …. +l
orientation of the orbital in space
if l = 1 (p orbital), ml = -1, 0, or 1
if l = 2 (d orbital), ml = -2, -1, 0, 1, or 2
Schrodinger Wave Equation
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ml = -1, 0, or 1 3 orientations is space
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ml = -2, -1, 0, 1, or 2 5 orientations is space
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(n, l, ml, ms)
spin quantum number ms
ms = +½ or -½
Schrodinger Wave Equation
ms = -½ms = +½
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Existence (and energy) of electron in atom is described
by its unique wave function .
Pauli exclusion principle - no two electrons in an atom
can have the same four quantum numbers.
Schrodinger Wave Equation
quantum numbers: (n, l, ml, ms)
Each seat is uniquely identified (E, R12, S8)
Each seat can hold only one individual at a
time
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Schrodinger Wave Equation
quantum numbers: (n, l, ml, ms)
Shell – electrons with the same value of n
Subshell – electrons with the same values of n and l
Orbital – electrons with the same values of n, l, and ml
How many electrons can an orbital hold?
If n, l, and ml are fixed, then ms = ½ or - ½
= (n, l, ml, ½) or = (n, l, ml, -½)
An orbital can hold 2 electrons
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How many 2p orbitals are there in an atom?
2p
n=2
l = 1
If l = 1, then ml = -1, 0, or +1
3 orbitals
How many electrons can be placed in the 3d subshell?
3d
n=3
l = 2
If l = 2, then ml = -2, -1, 0, +1, or +2
5 orbitals which can hold a total of 10 e-
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Energy of orbitals in a single electron atom
Energy only depends on principal quantum number n
En = -RH ( )1
n2
n=1
n=2
n=3
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Energy of orbitals in a multi-electron atom
Energy depends on n and l
n=1 l = 0
n=2 l = 0n=2 l = 1
n=3 l = 0n=3 l = 1
n=3 l = 2
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“Fill up” electrons in lowest energy orbitals: Building – Up Principle
(Aufbau principle)
H 1 electron
H 1s1
He 2 electrons
He 1s2
Li 3 electrons
Li 1s22s1
Be 4 electrons
Be 1s22s2
B 5 electrons
B 1s22s22p1
C 6 electrons
? ?
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C 6 electrons
The most stable arrangement of electrons in
subshells is the one with the greatest number of
parallel spins (Hund’s rule).
C 1s22s22p2
N 7 electrons
N 1s22s22p3
O 8 electrons
O 1s22s22p4
F 9 electrons
F 1s22s22p5
Ne 10 electrons
Ne 1s22s22p6
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Order of orbitals (filling) in multi-electron atom
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s
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Electron configuration is how the electrons are
distributed among the various atomic orbitals in an
atom.
1s1
principal quantum
number n
angular momentum
quantum number l
number of electrons
in the orbital or subshell
Orbital diagram
H
1s1
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What is the electron configuration of Mg?
Mg 12 electrons
1s < 2s < 2p < 3s < 3p < 4s
1s22s22p63s2 2 + 2 + 6 + 2 = 12 electrons
Abbreviated as [Ne]3s2 [Ne] 1s22s22p6
What are the possible quantum numbers for the last
(outermost) electron in Cl?
Cl 17 electrons 1s < 2s < 2p < 3s < 3p < 4s
1s22s22p63s23p5 2 + 2 + 6 + 2 + 5 = 17 electrons
Last electron added to 3p orbital
n = 3 l = 1 ml = -1, 0, or +1 ms = ½ or -½
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Outermost subshell being filled with electrons
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Some Anomalies
( شذوذ عن القاعدة(
Some irregularities
occur when there
are enough
electrons to half-fill
s and d orbitals on
a given row.
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Some Anomalies
For instance, the electron
configuration for
chromium is
[Ar] 4s1 3d5
rather than the expected
[Ar] 4s2 3d4
Copper is [Ar] 4s1 3d10
rather than the expected
[Ar] 4s23d9
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Some Anomalies
• 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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Paramagnetic
unpaired electrons
2p
Diamagnetic
all electrons paired
2p
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© 2009, Prentice-Hall, Inc.
The shielding Effectتأثير الحجب في الذرات متعددة الإلكترونات
• The shielding effect describes the attraction between an electron and the nucleus in any atom with more than
one electron shell. Shielding effect can be defined as a reduction in the Effective Nuclear Charge on the electron
cloud, due to a difference in the attraction forces of the electrons on the nucleus.
• In hydrogen, or any other atom in group 1A of the periodic table (those with only one valence electron), the
force on the electron is just as large as the electromagnetic attraction from the nucleus. However, when more
electrons are involved, each electron (in the nth-shell) experiences not only the electromagnetic attraction from
the positive nucleus, but also repulsion forces from other electrons in shells from 1 to n. This causes the net
force on electrons in outer shells to be significantly smaller in magnitude; therefore, these electrons are not as
strongly bonded to the nucleus as electrons closer to the nucleus. This phenomenon is often referred to as the
orbital penetration effect. The shielding theory also contributes to the explanation of why valence -shell
electrons are more easily removed from the atom