Linnett double-quartet theory

Left: The dot-and-cross diagram of the LDQ structure of ozone (O3). The nuclei are as indicated and the electrons are denoted by either dots or crosses, depending on their relative spins. Right: Simplified diagram of the LDQ structure of O3, showing electrons in non-coincident pairs using thin lines and a coincident electron pair using a thick line.

Linnett double-quartet theory (LDQ) is a method of describing the bonding in molecules which involves separating the electrons depending on their spin, placing them into separate 'spin tetrahedra' to minimise the Pauli repulsions between electrons of the same spin. Introduced by J. W. Linnett in his 1961 monograph[1] and 1964 book,[2] this method expands on the electron dot structures pioneered by G. N. Lewis. While the theory retains the requirement for fulfilling the octet rule, it dispenses with the need to force electrons into coincident pairs. Instead, the theory stipulates that the four electrons of a given spin should maximise the distances between each other, resulting in a net tetrahedral electronic arrangement that is the fundamental molecular building block of the theory.

By taking cognisance of both the charge and the spin of the electrons, the theory can describe bonding situations beyond those invoking electron pairs, for example two-centre one-electron bonds. This approach thus facilitates the generation of molecular structures which accurately reflect the physical properties of the corresponding molecules, for example molecular oxygen, benzene, nitric oxide or diborane. Additionally, the method has enjoyed some success for generating the molecular structures of excited states, radicals, and reaction intermediates. The theory has also facilitated a more complete understanding of chemical reactivity, hypervalent bonding and three-centre bonding.

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  2. ^ Cite error: The named reference :1 was invoked but never defined (see the help page).