Photoinduced Bifurcation and Multistability in the Oscillatory Briggs−Rauscher Reaction

Abstract

The effect of continuous light irradiation on the Briggs-Rauscher system has been investigated by the light intensity scanning method. A state diagram has been established in the control parameter plane spanned by the initial concentration of I -([I -] 0 ) and the light power (P). An increase of [I -] 0 leads to a transition from the large-amplitude oscillatory state (OS) to the reduced steady state (SSI), whereas an increase of P gives rise to a transition from OS to the oxidized steady state (SSII). Both transitions are accompanied by hysteresis, resulting in tristability among OS, SSI, and SSII in the overlapped part of the two hysteresis regions. In addition to the photoinhibition reported previously, the photoinduction of oscillations has been found in a certain range of [I -] 0 . In the low-[I -] 0 region, bistability between OS and another oscillatory state with small amplitude (OS′) has also been discovered. The origin of the transitions is discussed on the basis of photoinduced autocatalytic processes.

Kinetic Resonance Raman Spectroscopy of the Briggs–Rauscher Oscillator

“…The oscillating reaction was arrested by illumination of the BR reaction mixture with a green laser ( λ =514.5 nm, 100 mW), as shown for the 200–400 s time period in Figure 4. This light‐induced transition from the dark oscillatory state to the oxidised steady state occurs close to a supercritical Hopf bifurcation, as has previously been noted by others who used visible absorption spectroscopy25 and chronopotentiometry to monitor the reaction 9, 10. It is noteworthy that the formation of the starch–iodine complex is promoted by illumination with green light ( λ =514.5 nm, 100 mW), even though green light photolyses molecular iodine.…”

“…The BR reaction is a hybrid of the Belousov–Zhabotinskii8a,8b and Bray–Liebhafsky8c,8d oscillating reactions, and it exhibits a rich collection of nonlinear dynamic phenomena such as bifurcation and hysteresis, mixed‐mode oscillations and multiple stable states 9, 10. The reaction involves the acidic Mn II ‐catalysed oxidation of malonic acid by a mixture of hydrogen peroxide and iodate.…”

“…This is consistent with a reaction scheme which has been used to describe the BR reaction and involves ten reaction steps (see Table 1). 9, 21, 22 Some of these component steps, such as Reactions (6), (7), (9) and (10), involve scission of bonds to hydrogen atoms.…”

Experimental and Model Studies of Oscillations, Photoinduced Transitions, and Steady States in the Ru(bpy)32+-Catalyzed Belousov−Zhabotinsky Reaction under Different Solute Compositions

“…The optical system was set up with reference to that reported by Okazaki et al 30 The light source was a 500 mW tunable argon ion laser (Omnichrome, 543-500MA) that emits light wavelengths of mainly 488 and 514.5 nm. The laser power was set to a constant value of 350 mW maintained by an internal optical feed back circuit in the laser system.…”

Effect of Light on the Belousov−Zhabotinsky Reaction in Water-in-Oil Microemulsions of Aerosol OT in Octane

“…The effect of light on the dynamics of nonlinear chemical systems has been the subject of considerable attention of many scientists. − The use of light in controlling the system is advantageous over the other external parameters because of the feasibility of changing its intensity and wavelength. A change in the wavelength sometimes brings about a different nonlinear behavior.…”