Measurement of Raman χ(3) and Theoretical Estimation of DOVE Four Wave Mixing of Hydrogen Peroxide

Abstract

Hydrogen peroxide has strong infrared (IR) transitions ν(6) and its combination band ν(2)+ν(6), which may provide a unique opportunity to implement doubly vibrationally enhanced (DOVE) four wave mixing (FWM) for directly measuring hydrogen peroxide in spectrally overcrowded mixtures. In this work, the magnitude of the DOVE third-order susceptibility χ(3) was theoretically estimated. By using a FWM interferometric method, one of the strongest Raman bands, O-O stretch ν(3) Raman χ(3) of 30 wt % H(2)O(2), was first measured to be 1.2 × 10(-14) esu. The Raman χ(3) of ν(2) was then determined to be 5.3 × 10(-15) esu based on their relative Raman intensities. The resulting Raman χ(3) of ν(2) was used to calculate the DOVE χ(3) of (ν(6), ν(2)+ν(6)), together with the dipolar moments of the two IR transitions determined from IR absorption measurement. The calculated value of DOVE-IR χ(3) was 1.1 × 10(-13) esu for pure H(2)O(2), about 1.5 times larger than that of the strong ring breathing Raman band of benzene. The large DOVE χ(3) suggests the feasibility of direct measurement of hydrogen peroxide in an aqueous environment using DOVE four wave mixing.