Reactions in chemical processes are either unimolecular or bimolecular. The rate of a unimolecular reaction is an average over a vast ensemble of the rate coefficients for the microscopic events of collisional energy transfer and of reaction of a completely isolated molecule. Gilberts work in the field of unimolecular processes started with the development of theorems for this relationship. These theorems are elegant developments in matrix algebra, proving relations that had been previously known only for particular cases. His theorems also became the basis for numerical methods that he developed to perform the requisite calculations. For this purpose, he created a computer code, UNIMOL', which is widely used by researchers.
He developed, with Prof J Troe, easily used approximate solutions for the pressure dependence of the rate coefficient. He provided the first solutions for cases where angular momentum conservation needs to be incorporated. His methods are used by experimentalists to fit data and extrapolate to different pressure regimes, supplanting previous tools which were of dubious validity and accuracy. His coworkers and he obtained data on the collisional energy transfer process and used them to prove the conjecture that each collision involves only a small exchange of energy. He then developed the first rigorous means to calculate these quantities from basic theory, and the first physical model for the process. His work is widely used, both for basic understanding of the transition states and by atmospheric and combustion modellers. Predicting climate change and effects on the ozone layer rely critically on this modelling.