Hund's rule of maximum multiplicity

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Overview

Hund's rule of maximum multiplicity is an observational rule of atomic chemistry discovered by Friedrich Hund, which is one of a set of rules referred to collectively as Hund's rules. They are important for spectroscopy and quantum chemistry.

Hund's rule of maximum multiplicity is a principle (1925) of atomic chemistry which states that a greater total spin state usually makes the resulting atom more stable, most commonly manifested in a lower energy state, because it forces the unpaired electrons to reside in different spatial orbitals. A commonly given reason for the increased stability of high multiplicity states is that the different occupied spatial orbitals create a larger average distance between electrons, reducing electron-electron repulsion energy. In reality, it has been shown that the actual reason behind the increased stability is a decrease in the screening of electron-nuclear attractions. Total spin state is calculated as the total number of unpaired electrons + 1, or twice the total spin + 1 written as 2s+1.

As a result of Hund's rule, constraints are placed on the way atomic orbitals are filled using the Aufbau principle. Before any two electrons occupy an orbital in a subshell, other orbitals in the same subshell must first each contain one electron. Also, the electrons filling a subshell will have parallel spin before the shell starts filling up with the opposite spin electrons (after the first orbital gains a second electron). As a result, when filling up atomic orbitals, the maximum number of unpaired electrons (and hence maximum total spin state) is assured.

In 2004, researchers reported the synthesis of 5-dehydro-m-xylylene (DMX), the first organic molecule known to violate Hund's rule.[1]

See also

List of Hund's rules

It is general rule that if a group of n or fewer electrons occupy a set of n degenerate orbitals, they will spread themselves out among the orbitals and give n unpaired spins. This is Hund's Rule or The Rule Of Maximum Multiplicity. It means that pairing of electrons is an unfavorable process; energy must be expended in order to make it occur.

External links

References

  1. L Slipchenko; et al. (2004). "5-Dehydro-1,3-quinodimethane: A Hydrocarbon with an Open-Shell Doublet Ground State". Angewandte Chemie International Edition. 43: 742. doi:10.1002/anie.200352990.

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