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 and 1964 book, 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.
Historical background
The cornerstone of classical bonding theories is the Lewis structure, published by G. N. Lewis in 1916 and continuing to be widely taught and disseminated to this day. In this theory, the electrons in bonds are believed to pair up, forming electron pairs which result in the binding of nuclei. While Lewis’ model could explain the structures of many molecules, Lewis himself could not rationalise why electrons, negatively-charged particles which should repel, were able to form electron pairs in molecules or even why electrons can form a bond between atoms.
Lewis’ theory has been seminal in the understanding of the chemical bond. Yet despite this, it was formulated before the discovery of electron spin, a key intrinsic property of electrons which manifests itself through inter-electronic interactions. While spin was known about ever since the publication of Stern and Gerlach's results in 1922, with the Pauli exclusion principle being formulated in 1925, the importance of 'spin correlation' for understanding when and why electrons form pairs in molecules was not understood until the work of Lennard-Jones in the 1950s. During the latter decade, J. W. Linnett and his students began to explicitly study the role of spin in determining the electronic structures of various molecules. This resulted in Linnett's landmark 1961 publication, and subsequent 1964 book, in which he outlined what became known as “Linnett double-quartet” theory.
Linnett continued to expand on his theory through a number of publications until his death in 1975. In these writings, Linnett recognised the continued importance of the Lewis model of bonding and the importance of satisfying the octet rule. However, he also argued that this view overemphasises the importance of electron pairing in the formation of chemical bonds. Hence, his theory sought to introduce spin into the conventional model of bonding and hence rectify some of the problems associated with Lewis’ theory. While LDQ theory is a relatively simple extension of Lewis’ bonding theory, the additional freedom of the electrons to separate into two sets, differentiated by their spins, has bestowed upon the theory exquisite agreement with the results of many experiments.
In its nascent years, LDQ theory attracted the interest of many researchers, furnishing greater insights into the structures of many molecules. However, LDQ theory began to fade from the spotlight in the 1970s and was mostly abandoned by researchers in the United States, Great Britain and Europe by the mid-1980s.
Formulation of Linnett double-quartet theory
Basic principles
A key trait of LDQ theory that is shared with Lewis theory is the importance of using formal charges to determine the most important electronic structure. LDQ theory produces the spatial distributions of the electrons by considering the two fundamental physical properties of said electrons: