Compared with O2-dependent
chemiluminescence (CL) and bioluminescence (BL), H2O2-dependent ones are far from being completely understood.
A two-step mechanism for H2O2-dependent CL production
from tetrachloro-1,4-benzoquinone (TCBQ) was proposed based on experimental
evidence of detecting the formation of several intermediates and products.
This mechanism is not yet supported by theoretical evidence, and its
details remain unknown. In the present paper, we performed multireference
and (time-dependent) density functional theory calculations on the
complete reaction process of TCBQ with H2O2 to
produce CL. The calculations reproduced the experimentally observed
two-step CL. Although the reactants are different, the first and second
CLs follow very similar reaction processes and mechanisms. First,
an anionic dioxetane is formed via five sequential reactions. The
intrinsically produced •OH is crucial for forming
dioxetane. Subsequently, the anionic dioxetane decomposes to produce
an anionic excited-state (S1) product. A conical interaction
of the ground and the S1-state potential energy surfaces
is responsible for producing the S1-state product. Finally,
the S1-state anionic product changes to its neutral form,
and the latter emits light as an actual light emitter. This mechanism
could be extended to luminescent systems of all H2O2-dependent tetrahalogenated quinoids, including acorn worms,
because TCBQ/H2O2 is a typical representative
of these luminescent systems.