摘要： The non-radiative deactivation of O2(a1(cid:2)g) and O2(b1(cid:3) + g) by solvent molecules has been a topic of intense and extensive research for almost half a century. The seminal interest derived in part from an unusually large effect of solvent and solvent deuteration on the lifetime of O2(a1(cid:2)g). The lifetime of O2(a1(cid:2)g), τ (cid:2), varies by 5 orders of magnitude in different solvents, and differences between H/D-isotopologues of the same solvent often exceed a factor of 20. The early reports on the subject were based on indirect probe-based measurements of τ (cid:2). Therefore, the interpretations were often misguided and afforded considerable controversy. With the advent of fast near-IR sensitive detectors in the late 1970s, it became possible to detect O2(a1(cid:2)g) phosphorescence with time-resolution. This facilitated the recording of an increasingly accurate set of data, which in turn, led to the development of ever more sophisticated theories. This effort culminated in the 1990’s with the development of an empirical model of electronic-to-vibrational (e-to-v) energy transfer. This model, which by now is widely accepted, focusses on the solvent as a “vibrational energy sink” that accept the excitation energy of O2(a1(cid:2)g) and O2(b1(cid:3) + g). In particular, the model accounts nicely for H/D solvent isotope effects on τ (cid:2) that are signi?cantly different from those observed on τ (cid:3). Nevertheless, as we shall see in the present chapter, it still has some important limitations.