Van der Waals surface

The Van der Waals surface of a molecule is an abstract representation or model of that molecule, illustrating where, in very rough terms, a surface might reside for the molecule based on the hard cutoffs of Van der Waals radii for individual atoms, and it represents a surface through which the molecule might be conceived as interacting with other molecules. Also referred to as a Van der Waals envelope, the Van der Waals surface is named for Johannes Diderik van der Waals, a Dutch theoretical physicist and thermodynamicist who developed theory to provide a liquid-gas equation of state that accounted for the non-zero volume of atoms and molecules, and on their exhibiting an attractive force when they interacted (theoretical constructions that also bear his name). Van der Waals surfaces are therefore a tool used in the abstract representations of molecules, whether accessed, as they were originally, via hand calculation, or via physical wood/plastic models, or now digitally, via computational chemistry software. Practically speaking, CPK models, developed by and named for Robert Corey, Linus Pauling, and Walter Koltun, were the first widely used physical molecular models based on Van der Waals radii, and allowed broad pedagogical and research use of a model showing the Van der Waals surfaces of molecules. Related to the title concept are the ideas of a Van der Waals volume, Vw, and a Van der Waals surface area, abbreviated variously as Aw, vdWSA, VSA, and WSA. A Van der Waals surface area is an abstract conception of the surface area of atoms or molecules from a mathematical estimation, either computing it from first principles or by integrating over a corresponding Van der Waals volume. In simplest case, for a spherical monatomic gas, it is simply the computed surface area of a sphere of radius equal to the Van der Waals radius of the gaseous atom: The Van der Waals volume, a type of atomic or molecular volume, is a property directly related to the Van der Waals radius, and is defined as the volume occupied by an individual atom, or in a combined sense, by all atoms of a molecule.