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Contents

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Atomic Structures

 

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Atom

1.1 .

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1.1.1

The concept of “atom” .

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1.1.2

The structure of the atom

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1.1.3

Atomic Number, Mass Number, and Isotopes

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1.1.4

Periodic Table

 

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1.2 Electron Configuration .

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1.2.1 Atomic spectrum of hydrogen .

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1.2.2 Quantum mechanics

 

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1.2.3 Atomic Orbitals

 

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1.2.3.1 solution of Schr¨odinger equation for hydrogenic atoms

 

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1.2.3.2 Shells, subshells, and orbitals .

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1.2.3.3 The radial variation of atomic orbitals .

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1.2.3.4 The angular variation of atomic orbitals

 

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1.2.3.5 The other quantum numbers – Electron spin

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1.2.4 The Build-up Principle

 

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1.2.4.1 Penetration and shielding

 

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1.2.4.2 Build-up Principle

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1.3 Atomic parameters

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1.3.1 Atomic and ionic radii

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1.3.2 Ionization Energy

 

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1.3.3 Electron Affinity

 

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1.3.4 Electronegativity

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1.3.5 Polarizability

 

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1.4 Homework questions I (from Atkins book):

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1

Chapter 1

Atomic Structures

1.1

Atom

1.1.1

The concept of “atom”

In the 5th century B.C., Greek philosopher Democritus: all matter consists of very small, indivisible particles – atomos.

In 1808, John Dalton atomic theory (marked the beginning of the modern era of chemistry)

Elements are composed of extremely small particles called atoms.

All atoms of a given element are identical, having the same size, mass, and chemical properties. The atoms of one element are different from the atoms of all other elements.

Compounds are composed of atoms of more than one element. In any com- pound, the ratio of the numbers of atoms of any two of the elements present is either an integer or a simple fraction.

A chemical reaction involves only the separation, combination, or rearrange- ment of atoms. It does not result in their creation or destruction.

An atom is the basic unit of an element that can retain the chemical properties and involve in chemical reaction.

1.1.2 The structure of the atom

The electron: discovered by J. J. Thomson using cathode ray tubes in 1897. Elec- trons are negatively charge particles, and e/m ratio is -1.76 × 10 8 C/g.

charge particles, and e/m ratio is -1.76 × 10 8 C/g. • Protons and nucleus discovered

Protons and nucleus discovered by Rutherford in 1910

2

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CHAPTER 1. ATOMIC STRUCTURES 3 • Neutrons: James Chadwick 1932. • Rutherford’s atomic model • The

Neutrons: James Chadwick 1932.

Rutherford’s atomic model

James Chadwick 1932. • Rutherford’s atomic model • The main subatomic particles: Charge Particle Mass

The main subatomic particles:

Charge

Particle

Mass (g)

Coulomb

Charge Unit

Electron

9.10939 × 10 28 1.67262×10 24

-1.6022 × 10 19 +1.6022 ×

-1

Proton

+1

 

10

19

Neutron

1.672493×10 24

0

0

1.1.3 Atomic Number, Mass Number, and Isotopes

The identification of an element is determined by the number of protons in the atom.

Atomic number (Z) = number of protons in nucleus.

Mass number (A) = number of protons + number of neutrons=atomic number (Z) + number of neutrons.

The same element has the same atomic number (i.e. number of protons), but can have different numbers of neutrons (isotope).

For example: 1 1 H, 2 H (D), 3 H (T),

235

92

U,

238

92

U

1

1

1.1.4 Periodic Table

More than half of the elements known today were discovered between 1800 and 1900. With many elements discovered, scientist started to recognize the periodic regularities in physical and chemical properties. (see figure below) The observation of periodicity among elements led to the development of a periodic table, a table in which the elements are grouped and arranged according to their chemical and physical properties.

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CHAPTER 1. ATOMIC STRUCTURES 4 • Classification of elements – Metallic elements: lustrous, malleable, ductile,

Classification of elements

Metallic elements: lustrous, malleable, ductile, and electrically conducting

Nonmetals: gases, liquids, or solids that do not conduct electricity.

Metalloids: silicon

First periodic table, Dmitri Mendeleev, 1869. Arranged the known elements in order of increasing atomic weight (molar mass) The arrangement led to group the elements with similar chemical properties into a group. For example, C, Si, Ge, and Sn.

At the same time, Lothar Meyer in Germany arranged the elements according to their physical properties. (see above figure)

Using Periodic table to predict or rationalize trends in the physical and chemical

properties. For example, R 2 C=CR 2 suggests the R 2 Si=SiR 2 , and was isolated in

1981.

Modern periodic table: arranged according to the atomic number (Z); periods, groups; main-group (representative) elements (s- and p-blocks), transition metal elements (d-block), Lanthanides (f-block, lighter), and actinides (f-block, heavier)

(s- and p-blocks), transition metal elements (d-block), Lanthanides (f-block, lighter), and actinides (f-block, heavier)

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CHAPTER 1. ATOMIC STRUCTURES 5 1.2 Electron Configuration According to Rutherford’s experiment, the center of the

1.2 Electron Configuration

According to Rutherford’s experiment, the center of the atom is composed of nucleus (protons + neutrons). The volume of the nucleus is very tiny, and the rest of the atom is pretty much empty space. The electrons are wondering around the empty space in an atom. When chemical reaction occurs, different atoms interact with each other, and we can image the interactions start with the electrons of different atoms. It is important to know how the electrons move in an atom, or how do we describe the electrons in the atom. Modern quantum mechanics provide a way to answer the question. We will start with hydrogen spectrum.

1.2.1 Atomic spectrum of hydrogen

Hydrogenic atoms: hydrogen-like atoms (or ions) that have only one electron, so free of the complicating effects of e-e repulsion.

hydrogen-like atoms (or ions) that have only one electron , so free of the complicating effects

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In the emission spectrum of hydrogen gas, the emission is found to consist of a series of discrete lines in the UV, visible, and IR regions.

Johann Rydberg equation:

1 2 ), where R is the Rydberg constant

1

λ

=

R(

1

n

2

1

n

2

(=1.097×10 7 m 1 )

Lyman series: n 1 =1; Balmer series: n 1 =2; Paschen series: (n 1 =3); Brackett series:

n 1 =4.

Bohr’s atomic model

Key assumption: electrons can only have specific (quantized) energy values at

discrete radius (called orbits). E n = R(

1 2 )

n

Light is emitted as e moves from one energy level to a lower energy level

Bohr’s atomic model explains the hydrogen atomic spectrum well, but failed to explain the spectra of elements with more than one electrons.

1.2.2 Quantum mechanics

Bohr’s atomic model of electrons with discrete orbits surrounding the nucleus could not explain the atomic spectrum of many elements, and eventually replaced by the quantum mechanics developed by Erwin Schr¨odinger and Werner Heisenberg in 1926. Here are several concepts related to quantum mechanics.

The quantum of energy: Energy is discrete, and quantum is the smallest quantity of energy. E = hv = hc/λ (Planck’s constant =6.63× 10 34 J·s)

The dual nature of the electron: (De Broglie, 1926) Electron has both wave and

mu h . The diffraction pattern of the electrons (Thomson and

Davisson) is explained by the possibility of finding an electrons with certain energy, i.e. the wave of electron is a possibility wave associated with energy.

Example 1: An electron has a mass of 9.11 × 10 31 kg and a charge of 1.602 ×10 19 C. Calculate the de Broglie wavelength of an electron that has been accelerated by a potential of 50 V.

particle properties. λ =

the de Broglie wavelength of an electron that has been accelerated by a potential of 50

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In the quantum world, it is not possible to know simultaneously both the momen- tum p (mv) and the position of a particle with certainty (Heisenberg uncertainty principle). In other words, classic mechanics can not be used to describe the world of an atom. According to Heisenberg uncertainty principle, the electrons does not orbit the nucleus in well-defined path. ∆xp

Schr¨odinger equation.

h

4π

wavefunction, Ψ, is a mathematical function of the position coordinates, and is used to describe the behavior of an electron in an atom.

+

h 2 m 2 + V (x, y, z) Ψ(x, y, z)

8π 2

EΨ(x, y, z), i.e.,

2 Ψ ∂x 2

+ 2 Ψ + 2 Ψ

∂y 2

∂y 2

=

8π 2 m

h 2

(E V (x, y, z))Ψ = 0

In the Schr¨odinger equation, the physically acceptable solutions exist only for certain value of E, i.e., quantization of energy.

Probability density Ψ 2 : proportional to the probability of finding an electron at a given location. i.e., theΨ 2 2 dxdydz is proportional to the probability of finding the electron in that volume .

probability of finding the electron in that volume dτ . Wavefunction has regions of positive and

Wavefunction has regions of positive and negative amplitude, or sign. The inte- ractions between wavefunctions can be constructive interference or destructive interference.

amplitude, or sign. The inte- ractions between wavefunctions can be constructive interference or destructive interference.

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1.2.3 Atomic Orbitals

The wavefunction of an electron in Schr¨odinger equation is called atomic orbital. In chemistry, we use the visual representation of the wavefunction (i.e. atomic orbital). Here, we discuss briefly the mathematics forms of the wavefunction.

1.2.3.1 solution of Schro¨dinger equation for hydrogenic atoms

Since the potential in hydrogenic atom is spherically symmetric (Z/r), the solution is expressed in terms of the spherical polar coordinates, as shown below.

in terms of the spherical polar coordinates, as shown below. • In these coordinates, the orbitals

of the spherical polar coordinates, as shown below. • In these coordinates, the orbitals (wavefunctions) all

In these coordinates, the orbitals (wavefunctions) all have the form Ψ nlm l = R nl (r)Y lm l (θ, φ)

The allowed energies are given by

E n = hcRZ 2

n

2

, with n = 1, 2, 3,

,

and R = m e e 4

8h 3

2

0

The wavefunction solution indicates that the atomic orbitals of hydrogenic atoms is uniquely labeled by a set of three integers n, l, m l , which are called quantum numbers.

n : principle quantum number, specifies the energy of the orbital

hcR=13.6 eV, and the the zero of energy corresponds to the electron and nucleus have no interaction with each other.

l: angular momentum quantum number, indicates the angular shape of orbitals

m l , magnetic quantum number, indicates the orientation of the orbital.

Electron spin, s.

1.2.3.2 Shells, subshells, and orbitals

In a hydrogenic atom, the set of orbitals with the same n have the same energy, and are said to be “in the same shell”. The principle quantum number defines a series of shells of the atom.

The orbitals belonging to each shell are classified into subshells according to the quantum number l.

 
 

The quantum number l can have the values l=0, 1,

n.

,

n-1 for a given value of

For example, for n=1, only one subshell with l=0 (s); for n=2, two subshells with l=0 (s), 1(p).

Value of l

0

1

2

3

4

   

Orbital

s

p

d

f

g

 

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Individual orbitals: a subshell with quantum number l consists of 2l+1 individual orbitals. These orbitals are distinguished by the third quantum number m l , where m l change from l to l.

Example: Identifying orbitals from quantum numbers: Which set of orbitals is defined by n=4 and l=1? How many orbitals are there in this set?

1.2.3.3 The radial variation of atomic orbitals

In the spherical polar coordinates, the orbitals have the following form for hydrogenic atom, Ψ nlm l = R nl (r)Y lm l (θ, φ) The solution indicates that the wavefunction can be written as the product of a function R(r) of the radius and a function Y (θ, φ) of the angular coordinates.

• The radial wavefunction R(r) expresses the variation of the orbital with distance from the
The radial wavefunction R(r) expresses the variation of the orbital with distance
from the nucleus.
nodes.
The location where R(r) passes through zero are called radial
The angular wavefunction expresses the orbital’s angular shape.
The planes on
which the angular wavefunction passes through zero are called nodal planes or
angular nodes.
Table: Hydrogen orbitals
The radial wavefunctions
– – All orbitals decay exponentially at sufficiently great distance from the nucleus. – An
All orbitals decay exponentially at sufficiently great distance from the nucleus.
An orbital has n − l − 1 radial nodes, i.e. the radial wavefunction crosses
zeron − l − 1 times.

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All orbitals except s orbitals are zero at the nucleus, as a consequence of the absence of orbital angular momentum.

The radial distribution function: gives the probability that an electron will be found at a given distance from the nucleus, regardless of the direction.

As we discussed earlier, Ψ 2 gives the probability density of electrons, and the

total probability of finding the electrons in space is the integral of Ψ 2 2 dθdφdr

.

The total probability of finding the electron in a spherical shell of radius r and thickness dr is the integral of Ψ 2 over all angles of θ and φ, i.e. Ψ 2 dθdφdr = θ φ r R 2 (r)Y 2 (θ, φ) = r P (r)dr.

P(r) = R 2 (r) · θ φ Y 2 (θ, φ) is called the radial distribution function, which gives the probability that an electron will be found at r from the nucleus, regardless of the direction.

In general, P (r) = r 2 R 2 (r).A radial distribution function for an orbital in a shell of principle quantum number n has n l peaks, and the outermost peak being the highest.

In hydrogenic atoms, for 1s orbital, the distance at which the electron is most likely to be found is r max = a 0 , where a 0 is Bohr radius, a 0 = ε 0 2 πm e e 2 =52.9 pm. (Figure1.13)

Example 1.3. Figure 1.14 shows the radial distribution function for 2s and 2p hydrogenic orbitals. Which orbital gives the electron a great probability of close approach to the nucleus?

Z

a great probability of close approach to the nucleus? Z 1.2.3.4 The angular variation of atomic

1.2.3.4 The angular variation of atomic orbitals

The orbital is normally represented by the boundary surface, which defines the region of space within which there is a high (typically 75%) probability of finding the electron.

s-orbital (Figure 1.15): spherical, no nodal plane.

p-orbital (Figure 1.16): 1 nodal plane, p x , p y , p z . positive (+) and negative (-).

d-orbital (Figure 1.17) and f-orbital (Figure 1.18).

In general, an orbital with the quantum number l has l nodal plane.

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CHAPTER 1. ATOMIC STRUCTURES 11 • •
CHAPTER 1. ATOMIC STRUCTURES 11 • •