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Rotational and nuclear-spin level dependent photodissociation dynamics of H₂S.

ABSTRACT: The detailed features of molecular photochemistry are key to understanding chemical processes enabled by non-adiabatic transitions between potential energy surfaces. But even in a small molecule like hydrogen sulphide (H₂S), the influence of non-adiabatic transitions is not yet well understood. Here we report high resolution translational spectroscopy measurements of the H and S(¹D) photoproducts formed following excitation of H₂S to selected quantum levels of a Rydberg state with ¹B₁ electronic symmetry at wavelengths λ ~ 139.1 nm, revealing rich photofragmentation dynamics. Analysis reveals formation of SH(X), SH(A), S(³P) and H₂ co-fragments, and in the diatomic products, inverted internal state population distributions. These nuclear dynamics are rationalised in terms of vibronic and rotational dependent predissociations, with relative probabilities depending on the parent quantum level. The study suggests likely formation routes for the S atoms attributed to solar photolysis of H₂S in the coma of comets like C/1995 O1 and C/2014 Q2.

SUBMITTER: Zhao Y

PROVIDER: S-EPMC8298612 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:We report REMPI spectra and velocity-mapped ion images of the O2(a1Δg) and (b1Σg+) fragments arising from the spin-forbidden photodissociation of O3 near 320 and 330 nm. The O2(a1Δg, v = 0) REMPI spectrum following a 320 nm dissociation shows enhanced peak intensity for the odd rotational states relative to the even states, which is the opposite of the trend observed by Gunthardt et al. ( J. Chem. Phys. 2019, 151, 224302) for spin-allowed dissociation at 266 nm but is consistent with the couplings between the B state and 3A' and 3A″ states calculated by Grebenshchikov and Rosenwaks ( J. Phys. Chem. A 2010, 114, 9809-9819). There are no significant differences between the ion image angular distributions of fragments in odd and even rotational states, which indicates a cold distribution of O3 and supports the explanation that the alternation in peak intensities results from a difference in the couplings. Quantitative analysis of the image angular distributions was limited due to the single laser polarization geometry accessible in one-color experiments. Radial distributions of the 320 nm images indicate a broad rotational distribution, evidenced in bimodal speed distributions with peaks corresponding to both high (j = 35-43) and low (j = 17-20) rotational states. The REMPI spectrum of O2(a1Δg) near 330 nm was collected, and while quantitative population analysis is difficult because of the perturbed resonant state, the spectrum clearly supports a broad rotational distribution as well, consistent with the images collected at 320 nm. A 2D-REMPI spectrum was collected following dissociation of O3 near 330 nm, which showed evidence of contributions from O2 fragments in both the a1Δg and b1Σg+ states. The rotational distribution for the O2(b1Σg+, v = 0) product peaks at j = 32 and is narrower than that of the O2(a1Δg) fragment, consistent with distributions reported by O'Keeffe et al. at longer dissociation wavelengths ( J. Chem. Phys. 2002, 117, 8705-8709). At smaller radii in the 2D-REMPI spectrum, there is additional signal assigned to v = 1-4 of O2(b1Σg+), with rotational distributions similar to v = 0. The vibrational distribution of the O2(b1Σg+) fragment peaks at v = 0, with populations monotonically decreasing with increasing vibrational state. Ion image angular distributions of the O2(b1Σg+) fragment and the corresponding anisotropy parameters are also reported.

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Rotational and nuclear-spin level dependent photodissociation dynamics of H₂S.

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