Name : Ayesha Mustafa

Registration no. : BCH172018

Class : BS Chemistry 6th (A)
Subject : Physical chemistry
Submitted to : Dr. Muhammad Khalid
Topic : Effective nuclear charge and orbital energies
EFFECTIVE NUCLEAR CHARGE
The effective nuclear (often represented by Z eff or Z*) is the net positive
charge an electron experiences in an atom with multiple electrons. The term “effective” is used
because the shielding effect of negatively charged electrons prevent higher orbital electrons from
experiencing the full nuclear charge.

The effective nuclear charge may be approximated by the equation:

Zeff = Z – S

Zeff = effective nuclear charge

Z = no. of protons (nuclear charge)

S = screening electrons (inner electrons)

Example
Oxygen: 1s22s22p4

Zeff = 8 – 2 = +6

Fluorine: 1s22s22p5

Zeff = 9 – 2 = +7

Trends in periodic table

The periodic table tendency for effective nuclear charge:

 Increase across a period (due to increasing nuclear charge with no accompanying increase
in shielding effect).
 Decrease down a group (although nuclear charge increases down a group, shielding effect
more than counters its effect).

ORBITAL ENERGIES
The energy which is essential to take an electron present in that orbital to infinity or the
release of energy when an electron from an infinity is added to that orbital is referred to as the
energy of orbitals.
Energy of orbital in hydrogen atom
(single-electron atom)
The energy of orbital in a single electron atom can be determined solely by the principle
quantum number. Thus, the order of increase in energy of various orbitals is given as,

1s < 2s = 2p < 3s = 3p = 3d < 4s = 4p = 4d = 4f

Quantum mechanics predicts that in the hydrogen atom, all the orbitals with same value
of n (e.g., the three 2p orbitals) are degenerate. The energy levels become closer and closer
together as the value of n increase, as expected because of the 1/n2 dependence of orbital
energies.

Fig 1: Energy of orbitals for hydrogen atom

The nucleus of hydrogen has charge +1, however, if the electron is bond to a nucleus of arbitrary
charge +Z, then the energy of the electron is

Z2
E=−Ry
n2

Where Ry is the Rydberg unit of energy where 1 Ry = 2.1798 × 10-18J = 13.605eV. This
expression is for single electron orbiting a single nucleus of charge +Z. From the above equation,
it is concluded that:
  As n increases (holding Z constant), then the energy increases (become less negative). In
the limit that n goes to infinity then the energy goes to zero.
 As Z increases (holding n constant), then the energy decreases (become more negative).
This makes sense, since a higher Z means a more positively charged nucleus, which holds
the electron tighter.

Energy of orbital in multi-electron atom

Unlike hydrogen (single-electron atom), multi-electron atoms tend to have a different
energy in different subshells of the same shell. The energy of orbital in these types of atoms is
dependent on both principle quantum number (n) or shell and azimuthal quantum number (l) or
subshells. That is, for a given principle quantum number let’s say 3, the different subshells 3s,3p
and 3d will have different energies.

The reason behind different energies between the various subshells of the same shell is
that there exists a mutual repulsion among the electrons in multi-electron atoms. The stability of
multi-electrons atom is due to the bigger magnitude of attractive force between nucleus and the
electrons as compared to the forces of repulsion between the electrons of the inner shell and
outer shell.

Fig 2: Energy variation for various orbitals

Factors affecting the orbital energy

  As compared to p orbital electrons, s orbital electrons will have more negative or lesser
amount of energy. Here the p orbital electrons will have lesser energy than that of d
orbital electrons
 As the extent of shielding from the nucleus is different for the electrons in different
orbitals, it leads to the splitting of energy levels that have the same principle quantum
number. Therefore, the orbital energy would depend on the values of both the principle
quantum number and azimuthal quantum number, symbolized as n and l respectively.
Hence, the lower value of (n + l) for an orbital, the lower is its energy.
 With the increase in the atomic number (Zeff),the orbital energy decreases in the same
subshell.

(n + l) rule

The (relative) energies of the orbitals can be predicted by the sum of n + l for each
orbitals, according to the following rules:

a. Orbitals are filled in order of increasing (n +l), which represents the relative energy.
b. If two orbitals have the same value of (n + l), they are filled in order of increasing n.

The order of the electron orbital energy levels, starting from least to greatest, is as follows:

1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p

References

 https://www.thoughtco.com
 https://wiki.ubc,ca
 https://byjus.com>chemistry
 https://chemdx.org
 https://chem.libretexts.org
 https://grandinetti.org