Sulfur-Containing Radical Anions Formed by Photolysis of Thiosulfate: Quantum-Chemical Analysis.

The photochemistry of sodium thiosulfate (S2O32-) in aqueous solutions is rather complicated. Several sulfur-containing radical anions are formed upon photoexcitation. Any of them are rather common (SO3•-, SO2•-, and SO5•-); others are rare (S2O3•-, •S4O63-, and S•-) or never documented (S2O5•-). In order to support the identification of intermediate radical anions, quantum-chemical (QM─quantum mechanical) calculations of the geometric and electronic structures of S2O3•-, S2O5•-, and •S4O63- were performed. Two different approaches, time-dependent density functional theory and complete active space self-consistent field, were applied to identify the method optimal for the reproduction of the experimental electronic absorption spectra. Several of the most commonly used functionals were considered. The best agreement with the experimentally observed spectra of reference compounds (common sulfur-containing anions and radical anions) was achieved for the WB97X-D3 functional. Using this approach, satisfactory agreement between experimental and calculated spectra of S2O3•-, S2O5•-, and •S4O63- was achieved. It was shown that S2O5•- and •S4O63- can exist in two isomeric forms with different spectral properties. These isomers are S2O3O2•-; SO3SO2•- for the case of S2O5•- and (S2O3)2•3-; (S3O32-...SO3•-) for the case of •S4O63-.

[1]  I. Pozdnyakov,et al.  Photochemistry of Sodium Thiosulfate in Aqueous Solutions Revisited , 2022, Journal of Photochemistry and Photobiology A: Chemistry.

[2]  Feng Wu,et al.  Probing reactions between imipramine and hydroxyl radical with the photolysis of iron(III) oxalate: Implications for the indirect photooxidation of tricyclic antidepressants in waters , 2022, Journal of Photochemistry and Photobiology A: Chemistry.

[3]  Feng Wu,et al.  Synergetic effect of potassium persulfate on photodegradation of para-arsanilic acid in Fe(III) oxalate system , 2021 .

[4]  L. M. Jones,et al.  Evaluating the Sulfate Radical Anion as a New Reagent for In-Cell Fast Photochemical Oxidation of Proteins. , 2021, Journal of the American Society for Mass Spectrometry.

[5]  Guangshan Zhang,et al.  A Review Study on Sulfate-Radical-Based Advanced Oxidation Processes for Domestic/Industrial Wastewater Treatment: Degradation, Efficiency, and Mechanism , 2020, Frontiers in Chemistry.

[6]  Xianjia Peng,et al.  Specific H2S Release from Thiosulfate Promoted by UV Irradiation for Removal of Arsenic and Heavy Metals from Strongly Acidic Wastewater. , 2020, Environmental science & technology.

[7]  U. von Gunten,et al.  Persulfate-based Advanced Oxidation: Critical Assessment of Opportunities and Roadblocks. , 2020, Environmental science & technology.

[8]  A. Boldyrev,et al.  Hydrated Sulfate Clusters SO42-(H2O) n ( n = 1-40): Charge Distribution Through Solvation Shells and Stabilization. , 2019, The journal of physical chemistry. B.

[9]  L. Wojnárovits,et al.  Rate constants of sulfate radical anion reactions with organic molecules: A review. , 2019, Chemosphere.

[10]  Zizheng Liu,et al.  Photooxidation of p-Arsanilic Acid in Aqueous Solution by UV/Persulfate Process , 2018 .

[11]  P. Schreiner,et al.  Atmospherically Relevant Radicals Derived from the Oxidation of Dimethyl Sulfide. , 2018, Accounts of chemical research.

[12]  T. Schmidt,et al.  Degradation of perfluorinated compounds by sulfate radicals - New mechanistic aspects and economical considerations. , 2018, Water research.

[13]  A. Affoune,et al.  Electrodeposition and characterization of Cu2O thin films using sodium thiosulfate as an additive for photovoltaic solar cells , 2017 .

[14]  F. Spiegelman,et al.  Structural Characterization of Sulfur-Containing Water Clusters Using a Density-Functional Based Tight-Binding Approach. , 2016, The journal of physical chemistry. A.

[15]  Mark T. Oakley,et al.  Structures and Energy Landscapes of Hydrated Sulfate Clusters. , 2015, Journal of chemical theory and computation.

[16]  F. Ahmad,et al.  Studies on the Oxidative Removal of Sodium Thiosulfate from Aqueous Solution , 2015 .

[17]  B. A. Lindquist,et al.  The nature of the SO bond of chlorinated sulfur–oxygen compounds , 2014, Theoretical Chemistry Accounts.

[18]  B. A. Lindquist,et al.  Bonding in Sulfur-Oxygen Compounds-HSO/SOH and SOO/OSO: An Example of Recoupled Pair π Bonding. , 2013, Journal of chemical theory and computation.

[19]  M. Head‐Gordon,et al.  The Performance of Density Functionals for Sulfate-Water Clusters. , 2013, Journal of chemical theory and computation.

[20]  Jeng-Da Chai,et al.  Long-Range Corrected Hybrid Density Functionals with Improved Dispersion Corrections. , 2012, Journal of chemical theory and computation.

[21]  M. Head‐Gordon,et al.  Refined energetic ordering for sulphate–water (n = 3–6) clusters using high-level electronic structure calculations , 2012 .

[22]  G. Galli,et al.  Solvation properties of microhydrated sulfate anion clusters: insights from ab initio calculations. , 2012, The journal of physical chemistry. B.

[23]  G. Helz,et al.  What regulates rhenium deposition in euxinic basins , 2012 .

[24]  R. Mason,et al.  Formation of reactive sulfite-derived free radicals by the activation of human neutrophils: an ESR study. , 2012, Free radical biology & medicine.

[25]  M. Gross,et al.  Sulfate radical anion as a new reagent for fast photochemical oxidation of proteins. , 2010, Analytical chemistry.

[26]  D. Dixon,et al.  Heats of formation of the H1,2OmSn (m, n = 0-3) molecules from electronic structure calculations. , 2009, The journal of physical chemistry. A.

[27]  R. Mason,et al.  New insights into the detection of sulfur trioxide anion radical by spin trapping: radical trapping versus nucleophilic addition. , 2009, Free radical biology & medicine.

[28]  N. Wong,et al.  The adiabatic electron affinities (EAs) for the heteroatomic molecule SO4: An MP2/CBS study , 2009 .

[29]  David A Dixon,et al.  Bond dissociation energies in second-row compounds. , 2008, The journal of physical chemistry. A.

[30]  D. Truhlar,et al.  The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals , 2008 .

[31]  J. Harkless,et al.  Coupled-cluster study of the electronic structure and energetics of tetrasulfur, S4. , 2007, The Journal of chemical physics.

[32]  D. Dixon,et al.  Coupled cluster study of the energetic properties of S2x (x=0,+1,1). , 2007, The Journal of chemical physics.

[33]  P. Glarborg,et al.  Reactions of SO3 with the O/H radical pool under combustion conditions. , 2007, The journal of physical chemistry. A.

[34]  Arnim Hellweg,et al.  Optimized accurate auxiliary basis sets for RI-MP2 and RI-CC2 calculations for the atoms Rb to Rn , 2007 .

[35]  S. Grimme.  Semiempirical hybrid density functional with perturbative second-order correlation. , 2006, The Journal of chemical physics.

[36]  J. Tomasi,et al.  Quantum mechanical continuum solvation models. , 2005, Chemical reviews.

[37]  B. Gao,et al.  A first principles study on the solvation and structure of SO4 2- (H2O)n, n=6-12. , 2004, The Journal of chemical physics.

[38]  N. Handy,et al.  A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP) , 2004 .

[39]  I. Shkrob,et al.  Electron photodetachment from aqueous anions. 1. Quantum yields for generation of hydrated electron by 193 and 248 nm laser photoexcitation of miscellaneous inorganic anions , 2004, physics/0401080.

[40]  A. Nishimoto,et al.  Hypervalency in sulfur? ab initio and DFT studies of the structures of thiosulfate and related sulfur oxyanions , 2003 .

[41]  C. Zhan,et al.  Theoretical Studies of Photoelectron Spectra of SO42-(H2O)n Clusters and the Extrapolation to Bulk Solution , 2003 .

[42]  J. Banfield,et al.  Kinetics and Mechanism of Trithionate and Tetrathionate Oxidation at Low pH by Hydroxyl Radicals , 2003 .

[43]  Giovanni Scalmani,et al.  Energies, structures, and electronic properties of molecules in solution with the C‐PCM solvation model , 2003, J. Comput. Chem..

[44]  I. Epstein,et al.  Oscillatory photochemical decomposition of tetrathionate ion. , 2002, Journal of the American Chemical Society.

[45]  Giovanni Scalmani,et al.  New developments in the polarizable continuum model for quantum mechanical and classical calculations on molecules in solution , 2002 .

[46]  J. Boily.  Intramolecular bonding and charge distributions in XO4 (X = Si, P, S, Cl and Ge, As, Se, Br) oxyanions from topological analyses of the electron density , 2002 .

[47]  F. Weigend,et al.  Efficient use of the correlation consistent basis sets in resolution of the identity MP2 calculations , 2002 .

[48]  J. Simons,et al.  Stabilization calculation of the energy and lifetime of metastable SO42 , 2002 .

[49]  T. N. Das.  Reactivity and Role of SO5•- Radical in Aqueous Medium Chain Oxidation of Sulfite to Sulfate and Atmospheric Sulfuric Acid Generation , 2001 .

[50]  Celestino Angeli,et al.  Introduction of n-electron valence states for multireference perturbation theory , 2001 .

[51]  B. Boo,et al.  Photoelectron Spectroscopy of SO3- at 355 and 266 nm , 2000 .

[52]  M. Jacox,et al.  The vibrational spectra of molecular ions isolated in solid neon. XVI. SO2+, SO2−, and (SO2)2− , 2000 .

[53]  P. Neta,et al.  Reduction Potentials of SO3•-, SO5•-, and S4O6•3- Radicals in Aqueous Solution , 1999 .

[54]  A. Horváth,et al.  Kinetics and Mechanism of the Reaction between Thiosulfate and Chlorine Dioxide , 1998 .

[55]  V. Barone,et al.  Quantum Calculation of Molecular Energies and Energy Gradients in Solution by a Conductor Solvent Model , 1998 .

[56]  Jacopo Tomasi,et al.  A new definition of cavities for the computation of solvation free energies by the polarizable continuum model , 1997 .

[57]  M. Mckee.  Computational Study of the Mono- and Dianions of SO2, SO3, SO4, S2O3, S2O4, S2O6, and S2O8 , 1996 .

[58]  I. Demachy,et al.  Ab initio study of the electronic structure of the (SO2)(SO−2) dimer. A one-electron SS bond formation? , 1994 .

[59]  J. Simons,et al.  Isolated SO42- and PO43- Anions Do Not Exist , 1994 .

[60]  M. Mckee.  Computational studies on sulfur oxides (SO4 and S2O3) , 1993 .

[61]  T. Dunning,et al.  Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions , 1992 .

[62]  D. Dixon,et al.  An ab initio study of the structures, vibrational spectra, and energetics of the homocyclic sulfur molecules Sn, n = 4-8 , 1990 .

[63]  R. Steudel,et al.  The Molecular Composition of Hydrophilic Sulfur Sols Prepared by Acid Decomposition of Thiosulfate [1] , 1988 .

[64]  Z. Kafafi,et al.  AB initio calculations and matrix ftir studies of the sulfur trioxide radical anion , 1986 .

[65]  K. Hirao.  SAC‐CI calculations of the electron affinity of SO2 , 1985 .

[66]  M. Grätzel,et al.  Photoreduction of thiosulfate in semiconductor dispersions , 1983 .

[67]  M. Schöneshöfer.  Pulsradiolytische untersuchung über das S4O63−-radikal als zwischenprodukt der thiosulfatoxidation und tetrathionatreduktion , 1973 .

[68]  R. W. Fessenden,et al.  Investigation of radicals produced in the photolysis of thiosulfate solutions by electron spin resonance , 1971 .

[69]  L. Dogliotti,et al.  Flash photolysis study of sulfite, thiocyanate, and thiosulfate ions in solution , 1968 .

[70]  A. Treinin,et al.  Charge-Transfer-to-Solvent Spectra of Polyvalent Anions. II. The Electronic Spectrum of S2O3-2 , 1964 .

[71]  R. Davis.  Displacement Reactions at the Sulfur Atom. I. An Interpretation of the Decomposition of Acidified Thiosulfate , 1958 .

[72]  Frank Neese,et al.  Software update: the ORCA program system, version 4.0 , 2018 .

[73]  David,et al.  Gaussian basis sets for use in correlated molecular calculations . Ill . The atoms aluminum through argon , 1999 .

[74]  R. Huie,et al.  A pulse radiolysis and flash photolysis study of the radicals SO-2, SO-3, SO-4 and SO-5 , 1989 .

[75]  O. Brede,et al.  Pulse radiolysis of aqueous solutions of thiosulphate , 1984 .

[76]  P. Neta,et al.  Rate Constants for Reactions of Inorganic Radicals in Aqueous Solution , 1979 .

[77]  E. Hayon,et al.  Electronic spectra, photochemistry, and autoxidation mechanism of the sulfite-bisulfite-pyrosulfite systems. SO2-, SO3-, SO4-, and SO5- radicals , 1972 .