Ionization energy

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In physics and chemistry, ionization energy (IE) is the minimum energy required to remove the most loosely bound electron of an isolated gaseous atom, positive ion, or molecule.^[1] The first ionization energy is quantitatively expressed as

X(g) + energy ⟶ X⁺(g) + e⁻

where X is any atom or molecule, X⁺ is the resultant ion when the original atom was stripped of a single electron, and e⁻ is the removed electron.^[2] Ionization energy is positive for neutral atoms, meaning that the ionization is an endothermic process. Roughly speaking, the closer the outermost electrons are to the nucleus of the atom, the higher the atom's ionization energy.

In physics, ionization energy is usually expressed in electronvolts (eV) or joules (J). In chemistry, it is expressed as the energy to ionize a mole of atoms or molecules, usually as kilojoules per mole (kJ/mol) or kilocalories per mole (kcal/mol).^[3]

Comparison of ionization energies of atoms in the periodic table reveals two periodic trends which follow the rules of Coulombic attraction:^[4]

1. Ionization energy generally increases from left to right within a given period (that is, row).
2. Ionization energy generally decreases from top to bottom in a given group (that is, column).

The latter trend results from the outer electron shell being progressively farther from the nucleus, with the addition of one inner shell per row as one moves down the column.

The nth ionization energy refers to the amount of energy required to remove the most loosely bound electron from the species having a positive charge of (n − 1). For example, the first three ionization energies are defined as follows:

1st ionization energy is the energy that enables the reaction X ⟶ X⁺ + e⁻

2nd ionization energy is the energy that enables the reaction X⁺ ⟶ X²⁺ + e⁻

3rd ionization energy is the energy that enables the reaction X²⁺ ⟶ X³⁺ + e⁻

The most notable influences that determine ionization energy include:

• Electron configuration: This accounts for most elements' IE, as all of their chemical and physical characteristics can be ascertained just by determining their respective electron configuration.
• Nuclear charge: If the nuclear charge (atomic number) is greater, the electrons are held more tightly by the nucleus and hence the ionization energy will be greater (leading to the mentioned trend 1 within a given period).
• Number of electron shells: If the size of the atom is greater due to the presence of more shells, the electrons are held less tightly by the nucleus and the ionization energy will be smaller.
• Effective nuclear charge (Z_eff): If the magnitude of electron shielding and penetration are greater, the electrons are held less tightly by the nucleus, the Z_eff of the electron and the ionization energy is smaller.^[5]
• Stability: An atom having a more stable electronic configuration has a reduced tendency to lose electrons and consequently has a higher ionization energy.

Minor influences include:

• Relativistic effects: Heavier elements (especially those whose atomic number is greater than about 70) are affected by these as their electrons are approaching the speed of light. They therefore have smaller atomic radii and higher ionization energies.
• Lanthanide and actinide contraction (and scandide contraction): The shrinking of the elements affects the ionization energy, as the net charge of the nucleus is more strongly felt.
• Electron pairing energies: Half-filled subshells usually result in higher ionization energies.

The term ionization potential is an older and obsolete term^[6] for ionization energy,^[7] because the oldest method of measuring ionization energy was based on ionizing a sample and accelerating the electron removed using an electrostatic potential.