title: Experimental, numerical, and mechanistic analysis of the nonmonotonic relationship between oscillatory frequency and photointensity for the photosensitive Belousov-Zhabotinsky oscillator.
abstract: The oscillation frequency of a nonlinear reaction system acts as a key factor for interaction and superposition of spatiotemporal patterns. To control and design spatiotemporal patterns in oscillatory media, it is important to establish the dominant frequency-related mechanism and the effects of external forces and species concentrations on oscillatory frequency. In the Ru(bipy)3(2+)-catalyzed Belousov-Zhabotinsky oscillator, a nonmonotonic relationship exists between light intensity and oscillatory frequency (I-F relationship), which is composed of fast photopromotion and slow photoinhibition regions in the oscillation frequency curve. In this work, we identify the essential mechanistic step of the I-F relationship: the previously proposed photoreaction Ru(II)* + Ru(II) + BrO3(-) + 3H(+) → HBrO2 + 2Ru(III) + H2O, which has both effects of frequency-shortening and frequency-lengthening. The concentrations of species can shift the light intensity that produces the maximum frequency, which we simulate and explain with a mechanistic model. This result will benefit studies of pattern formation and biomimetic movement of oscillating polymer gels.
authors.affiliation: College of Chemical Engineering, China University of Mining and Technology, Xuzhou 221008, China.
authors.forename: Lin
authors.initials: L
authors.lastname: Ren
authors.affiliation: College of Chemical Engineering, China University of Mining and Technology, Xuzhou 221008, China.
authors.forename: Bowen
authors.initials: B
authors.lastname: Fan
authors.affiliation: College of Chemical Engineering, China University of Mining and Technology, Xuzhou 221008, China.
authors.forename: Qingyu
authors.initials: Q
authors.lastname: Gao
authors.affiliation: College of Chemical Engineering, China University of Mining and Technology, Xuzhou 221008, China.
authors.forename: Yuemin
authors.initials: Y
authors.lastname: Zhao
authors.affiliation: College of Chemical Engineering, China University of Mining and Technology, Xuzhou 221008, China.
authors.forename: Hainan
authors.initials: H
authors.lastname: Luo
authors.affiliation: College of Chemical Engineering, China University of Mining and Technology, Xuzhou 221008, China.
authors.forename: Yahui
authors.initials: Y
authors.lastname: Xia
authors.affiliation: College of Chemical Engineering, China University of Mining and Technology, Xuzhou 221008, China.
authors.forename: Xingjie
authors.initials: X
authors.lastname: Lu
authors.affiliation: Department of Chemistry and Volen Center for Complex Systems, MS 015, Brandeis University, Waltham, Massachusetts 02454-9110, USA.
authors.forename: Irving R
authors.initials: IR
authors.lastname: Epstein