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By the end of this section, you will be able to:
  • Derive the predicted ground-state electron configurations of atoms
  • Identify and explain exceptions to predicted electron configurations for atoms and ions
  • Relate electron configurations to element classifications in the periodic table

Having introduced the basics of atomic structure and quantum mechanics, we can use our understanding of quantum numbers to determine how atomic orbitals relate to one another. This allows us to determine which orbitals are occupied by electrons in each atom. The specific arrangement of electrons in orbitals of an atom determines many of the chemical properties of that atom.

Orbital energies and atomic structure

The energy of atomic orbitals increases as the principal quantum number, n , increases. In any atom with two or more electrons, the repulsion between the electrons makes energies of subshells with different values of l differ so that the energy of the orbitals increases within a shell in the order s < p < d < f. [link] depicts how these two trends in increasing energy relate. The 1 s orbital at the bottom of the diagram is the orbital with electrons of lowest energy. The energy increases as we move up to the 2 s and then 2 p , 3 s , and 3 p orbitals, showing that the increasing n value has more influence on energy than the increasing l value for small atoms. However, this pattern does not hold for larger atoms. The 3 d orbital is higher in energy than the 4 s orbital. Such overlaps continue to occur frequently as we move up the chart.

A table entitled, “Subshell electron capacity,” is shown. Along the left side of the table, an upward pointing arrow labeled, “E,” is drawn. The table includes three columns. The first column is narrow and is labeled, “2.” The second is slightly wider and is labeled, “6.” The third is slightly wider yet and is labeled, “10.” The fourth is the widest and is labeled, “14.” The first column begins at the very bottom with a horizontal line segment labeled “1 s.” Evenly spaced line segments continue up to 7 s near the top of the column. In the second column, a horizontal dashed line segment labeled, “2 p,” appears at a level between the 2 s and 3 s levels. Similarly 3 p appears at a level between 3 s and 4 s, 4 p appears just below 5 s, 5 p appears just below 6 s, and 6 p appears just below 7 s. In the third column, a dashed line labeled, “3 d,” appears just below the level of 4 p. Similarly, 4 d appears just below 5 p and 5 d appears just below 6 p. Six d however appears above the levels of both 6 p and 7 s. The far right column entries begin with a dashed line labeled, “4 f,” positioned at a level just below 5 d. Similarly, a second dashed line segment appears just below the level of 6 d, which is labeled, “5 f.”
Generalized energy-level diagram for atomic orbitals in an atom with two or more electrons (not to scale).

Electrons in successive atoms on the periodic table tend to fill low-energy orbitals first. Thus, many students find it confusing that, for example, the 5 p orbitals fill immediately after the 4 d , and immediately before the 6 s . The filling order is based on observed experimental results, and has been confirmed by theoretical calculations. As the principal quantum number, n , increases, the size of the orbital increases and the electrons spend more time farther from the nucleus. Thus, the attraction to the nucleus is weaker and the energy associated with the orbital is higher (less stabilized). But this is not the only effect we have to take into account. Within each shell, as the value of l increases, the electrons are less penetrating (meaning there is less electron density found close to the nucleus), in the order s > p > d > f . Electrons that are closer to the nucleus slightly repel electrons that are farther out, offsetting the more dominant electron–nucleus attractions slightly (recall that all electrons have −1 charges, but nuclei have + Z charges). This phenomenon is called shielding and will be discussed in more detail in the next section. Electrons in orbitals that experience more shielding are less stabilized and thus higher in energy. For small orbitals (1 s through 3 p ), the increase in energy due to n is more significant than the increase due to l ; however, for larger orbitals the two trends are comparable and cannot be simply predicted. We will discuss methods for remembering the observed order.

Questions & Answers

what is chemistry
Terhemba Reply
what is the difference between ph and poh?
Abagaro Reply
chemical bond that results from the attractive force between shared electrons and nonmetals nucleus is what?
Abagaro
what is chemistry
Ayok
what is chemistry
ISIYAKA Reply
what is oxidation
Chidiebube Reply
calculate molarity of NaOH solution when 25.0ml of NaOH titrated with 27.2ml of 0.2m H2SO4
Gasin Reply
what's Thermochemistry
rhoda Reply
the study of the heat energy which is associated with chemical reactions
Kaddija
How was CH4 and o2 was able to produce (Co2)and (H2o
Edafe Reply
explain please
Victory
First twenty elements with their valences
Martine Reply
what is chemistry
asue Reply
what is atom
asue
what is the best way to define periodic table for jamb
Damilola Reply
what is the change of matter from one state to another
Elijah Reply
what is isolation of organic compounds
IKyernum Reply
what is atomic radius
ThankGod Reply
Read Chapter 6, section 5
Dr
Read Chapter 6, section 5
Kareem
Atomic radius is the radius of the atom and is also called the orbital radius
Kareem
atomic radius is the distance between the nucleus of an atom and its valence shell
Amos
Read Chapter 6, section 5
paulino
Bohr's model of the theory atom
Ayom Reply
is there a question?
Dr
when a gas is compressed why it becomes hot?
ATOMIC
It has no oxygen then
Goldyei
read the chapter on thermochemistry...the sections on "PV" work and the First Law of Thermodynamics should help..
Dr
Which element react with water
Mukthar Reply
Mgo
Ibeh
Practice Key Terms 7

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Source:  OpenStax, Chemistry. OpenStax CNX. May 20, 2015 Download for free at http://legacy.cnx.org/content/col11760/1.9
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