Calculation of the properties of the S3− radical anion and its complexes with Cu+ in aqueous solution

Contrasting regimes of Cu, Zn and Pb transport in ore-forming hydrothermal fluids

“…The certainty of the prediction is high for Cu, because of a large amount of consistent work over a broad range of temperatures (review in Etschmann et al, 2010). We note that the presence of unconventional S-ligands, such as polysulfides, would probably only strengthen the conclusion of two modes of metal transport, since quantum chemical simulations suggest that these ligands would have similar strength as bisulfide for Cu(I) (Tossell, 2012;Mei et al, 2013b). However, the data on Zn and Pb bisulfide complexes are scarce and limited to relatively low temperatures (≤ 350°C).…”

Unravelling the Origin of the Yellow-Orange Luminescence in Natural and Synthetic Scapolites

“…For (Sn) x (n>2), the calculated distance could only be attributed to (S3) 0 trimers with interatomic distances of 1.92 Å 49 . The (S3)and (S3) 2entities are characterized by higher interatomic distances of 2.02 Å, 50 and 2.08 Å. 47 Simulations of the luminescence properties have been performed using the Adiabatic Shift Paradigm.…”

Theoretical estimates of equilibrium sulfur isotope effects among aqueous polysulfur and associated compounds with applications to authigenic pyrite formation and hydrothermal disproportionation reactions

“…7). Our recent calcula- (Otake et al, 2008;Tossell, 2012) suggest a larger fractionation factor of 1000⇥ln( 34 ↵) = 6.2-6.6 ‰ at 25 (Fig. 7).…”

“…Previous theoretical estimates for the H 2 S/HS fractionation factor (Sakai, 1968;Tossell, 2012;Otake et al, 2008;Eldridge et al, 2016) exhibit variability that arises from the di↵erent approaches taken (Fig. 7).…”

“…Polysulfur radical anions could play a role in facilitating isotope exchange between oxidized (i.e., sulfate) and reduced sulfur (i.e., sulfide) at elevated temperatures in hydrothermal fluids under some conditions (e.g., Kokh et al, 2020) but such processes are not yet understood in detail. Few studies have directly constrained the isotopic fractionations among the polysul-fur radicals and coexisting sulfur compounds such as aqueous sulfide and sulfate (i.e., limited to the theoretical calculations of Tossell, 2012). Such constraints are required to lay the groundwork for understanding the possible role these compounds may play in sulfur isotopic variability among naturally occurring phases that result from transformations related to these compounds.…”