A Comprehensive Sulfur Chemistry Network Including Excited S(1D) and SO(1Δ) for the XODIAC Photochemical Model: Accounting for Missing Sulfur Processes in Venus and Exo-Venus Analogs

Abstract

Sulfur chemistry plays a central role in controlling the atmospheric structure, cloud formation, and composition of Venus and Venus-like exoplanets. However, key reactions involving ground- and excited-state sulfur species remain poorly constrained, and existing photochemical models often rely on incomplete or uncertain kinetic data under high-temperature, CO2-rich conditions. In this work, we compute kinetic parameters for reactions of ground-state S(3P) and excited-state S(1D) with CO2 under Venus-like conditions, forming SO(3Sigma), SO(1Delta), and CO. We characterize the underlying potential energy surfaces, identify intermediate complexes, and derive temperature-dependent rate coefficients using a master-equation framework based on the chemically significant eigenvalue method. We also provide NASA 7-term polynomial coefficients for S and SO in both ground and excited states to enable consistent incorporation into photochemical models. Incorporating these reactions into the one-dimensional photochemical model XODIAC for Venus produces only minor effects above 60 km due to competing pathways. While the model reproduces most observed sulfur species, discrepancies remain for S3 and S4. Introducing a 1 ppm near-surface atomic sulfur source, representing unresolved deep-atmosphere or surface processes, enhances S3 and S4 abundances by 1-2 orders of magnitude and improves agreement with observations. For exo-Venus analogs, the updated chemistry produces modest changes under isothermal conditions. In contrast, in strongly irradiated atmospheres with a high-altitude isotherm and a near-surface sulfur source, it leads to pronounced changes in most sulfur-bearing species, along with significant enhancements in S(1D) and SO(1Delta). These results highlight missing sulfur pathways, including excited states and deep sources, and potential implications for shaping Venus and exo-Venus atmospheres.