Yrurtj

The IUPAC Gold Book definition of chemical decomposition is:

The breakdown of a single entity (normal molecule, reaction intermediate, etc.) into two or more fragments.

That is a very general definition, but I am not sure if it is supposed to be this inclusive. For example, think of a diamond crystal. It is a single entity. Now if chemical decomposition occurs, it can break down into multiple fragments. These fragments are not defined more closely, so it could be that the fragments are single C atoms, polyatomic C molecules... or even diamond fragments again.

In this sense, simply cutting or polishing a diamond would be a special case of chemical decomposition. This seems quite absurd to me. So the question is: Is chemical decomposition really that broad, or is there some better definition that is more commonly used in chemistry? It seems to me that the intuitive definition of chemical decomposition would be that a molecule is broken into smaller fragments, while a crystal or an amorphous solid would need to be broken into non-crystalline (non-amorphous) fragments in order for it to be considered chemical decomposition. Otherwise it's just cutting!

The question is relevant to me because I am writing my PhD thesis on laser-induced breakdown spectroscopy. The "breakdown" in the name of the technique refers to a chemical breakdown, which is the same as chemical decomposition. Usually, solid samples are analyzed, in which case some material from the sample surface is removed by laser ablation. Laser ablation is basically the same as laser-induced breakdown, if you look at the definitions. So there is some confusion on the terminology in general, and I want to unravel it as good as possible in my theory chapter.

Thank you very much for your input!

(Note: By the way, some non-IUPAC definitions I have found for chemical decomposition also confusingly define it as relating to compounds. As far as I know, the definition of a compound excludes crystals and amorphous solids, but it also excludes homonuclear molecules. So this definition seems way too exclusive, because it makes sense that decomposition can also occur for homonuclear molecules.)

When it comes to non-molecular solids such as glass, metal or diamond, "a single entity" is in fact the formula unit, the concept identical to a "molecule" for, well, molecular compounds. Both formula unit and molecule are the smallest portion of a substance that preserves its chemical properties. As long as the formula unit remains the same, there is no chemical decomposition to speak of.

However, this doesn't mean that there is no chemical processes that can be initiated mechanically. An entire branch, mechanochemistry deals with them. As for laser ablation, I think you are basically introducing a secondary phase, a thin film of another substance (for example, metal oxide) on the surface.

One more practical example I can think of: for a single-crystal diffraction experiment one has to use a 3D crystal (in a sense that it shouldn't be a 2D plate for the proper absorpton correction) with linear dimensions not exceeding fractions of a millimeter. For the probe preparation a crystallographer often has to literally cut the crystals with a special scalpel under the microscope. However, the resulting crystal structure doesn't depend on how many cuts and in what direction the crystallographer did. The x-rays though, can alter the structure of some sensitive molecular crystals (often biological samples, proteins), but this is another story.