Iron(III) oxalate, Fe3+(C2O4)33–, is a photoactive metal organic complex found in natural systems and used to quantify photon flux as a result of its high absorbance and reaction quantum yield. It also serves as a model complex to understand metal carboxylate complex photolysis because the mechanism of photolysis and eventual production of CO2 is not well understood for any system. We employed pump/probe mid-infrared transient absorption spectroscopy to study the photolysis reaction of the iron(III) oxalate ion in D2O and H2O up to 3 ns following photoexcitation. We find that intramolecular electron transfer from oxalate to iron occurs on a sub-picosecond time scale, creating iron(II) complexed by one oxidized and two spectator oxalate ligands. Within 40 ps following electron transfer, the oxidized oxalate molecule dissociates to form free solvated CO2(aq) and a species inferred to be CO2• – based on the appearance of a new vibrational absorption band and ab initio simulation. This work provides direct spectroscopic evidence for the first mechanistic steps in the photolysis reaction and presents a technique to analyze other environmentally relevant metal carboxylate photolysis reactions.

David. M. Mangiante

Richard D. Schaller

Piotr Zarzycki

Jillian F. Banfield

Benjamin Gilbert

ACS Earth and Space Chemistry

ACS 地球和空间化学的范围包括应用分析、实验和理论化学来研究与地球和空间相关的研究问题。该杂志涵盖了该领域研究的高度跨学科性质，同时强调化学和化学研究工具是统一的主题。该杂志在高低温地球化学、大气化学、海洋化学、行星化学、天体化学和分析地球化学等领域广泛发表论文。 ACS EARTH AND SPACE CHEMISTRY 发表文章、信件、评论和专题文章，以提供灵活的格式来方便地交流这些领域研究的各个方面。

The scope of the journal "ACS Earth and Space Chemistry" includes the application of analytical, experimental, and theoretical chemistry to address research questions related to Earth and space. This journal emphasizes the highly interdisciplinary nature of research in this field, while highlighting chemistry and chemical research tools as a unifying theme. It publishes a wide range of papers in areas such as low- and high-temperature geochemistry, atmospheric chemistry, marine chemistry, planetary chemistry, astrochemistry, and analytical geochemistry. "ACS Earth and Space Chemistry" accepts articles, letters, reviews, and special articles to facilitate the communication of various aspects of research in these fields.

《ACS Earth and Space Chemistry》期刊的研究范围涵盖应用分析、实验和理论化学，旨在探讨与地球和空间相关的科学问题。该杂志强调该领域研究的高度跨学科特性，同时突出化学及其研究工具作为统一的主题。期刊广泛发表高低温地球化学、大气化学、海洋化学、行星化学、天体化学和分析地球化学等领域的论文。《ACS Earth and Space Chemistry》接受文章、信件、评论和专题文章，以灵活的格式促进这些领域研究的交流。

Category	Quartile
化学	3
化学, 化学综合	3
化学, 地球化学与地球物理	3

Mechanism of Ferric Oxalate Photolysis

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Journal Info

Category	Quartile
GEOCHEMISTRY & GEOPHYSICS	2