Abstract
Hydrogen polyoxides are important species in atmospheric chemistry, advanced oxidation processes for wastewater treatment, and biological processes, among other fields. However, the electronic structure and chemical properties of the largest synthesized members of this chemical family remain poorly understood. In the present work, we have carried out a detailed theoretical study of hydrogen tetroxide (HO4H), which is a reaction intermediate of the hydroperoxyl radical (HO2) self-reaction. We have considered the molecule in gas phase, in microhydrated environments, in bulk water solution, and at the air–water interface. Very high level ab initio calculations have been carried out to describe the isolated molecule and the water complexes. Combined QM/MM molecular dynamics simulations have been performed to describe the system in liquid water and at the water surface. We show that the interactions with water strongly stabilize the tetraoxide adduct with respect to the (HO2)2 dimer. The chemical process leading to hydrogen tetroxide from two separated hydroperoxyl radicals is predicted to be an exothermic and exergonic reaction at 298 K in all the studied media, with the reaction free energy being slightly smaller (in absolute value) in the condensed phase with respect to the gas phase. An estimation of the pKa of hydrogen tetroxide has been reported (7.3), which suggests that this species is less acidic than previously thought.
Similar content being viewed by others
References
Levanov AV, Isaykina OY, Antipenko EE, Lunin VV (2015) Chem Phys 447:10–14
Denis PA, Huelmo CP (2014) Mol Phys 112:3047–3056
Levanov AV, Isaikina OY, Antipenko EE, Lunin VV (2014) Russ J Phys Chem A 88:1488–1492
Levanov AV, Isaykina OY, Antipenko EE, Lunin VV (2014) J Phys Chem A 118:62–69
Denis PA (2013) Int J Quantum Chem 113:2206–2212
Seo H-I, Bahng J-A, Kim Y-C, Kim S-J (2012) Bull Korean Chem Soc 33:3017–3024
Levanov AV, Sakharov DV, Dashkova AV, Antipenko EE, Lunin VV (2011) Eur J Inorg Chem 2011(33):5144–5150
Martins-Costa M, Anglada JM, Ruiz-Lopez MF (2011) Int J Quantum Chem 111:1543–1554
Martins-Costa M, Anglada JM, Ruiz-Lopez MF (2009) Chem Phys Lett 481:180–182
Denis PA, Ornellas FR (2009) J Phys Chem A 113:499–506
Kovacic S, Koller J, Cerkovnik J, Tuttle T, Plesnicar B (2008) J Phys Chem A 112:8129–8135
Plesnicar B (2005) Acta Chim Slov 52:1–12
Cerkovnik J, Erzen E, Koller J, Plesnicar B (2002) J Am Chem Soc 124:404–409
McKay DJ, Wright JS (1998) J Am Chem Soc 120:1003–1013
Khursan SL, Shereshovets VV (1996) Russ Chem Bull 45:1286–1291
Cerkovnik J, Plesnicar B (1993) J Am Chem Soc 115:12169–12170
Arnau JL, Giguere PA (1974) J Chem Phys 60:270–273
Plesnicar B, Kaiser S, Azman A (1973) J Am Chem Soc 95:5476–5477
Benson SW (1960) J Chem Phys 33:306–307
Anglada JM, Martins-Costa M, Francisco JS, Ruiz-Lopez MF (2015) Acc Chem Res 48:575–583
Anglada JM, Olivella S, Solé A (2007) J Phys Chem A 111:1695–1704
Zhang Y, Zhang T, Wang W (2011) Int J Quantum Chem 111:3029–3039
Zhu RS, Lin MC (2001) PhysChemComm 4:106–111
Zhou DDY, Han K, Zhang P, Harding LB, Davis MJ, Skodje RT (2012) J Phys Chem A 116:2089–2100
Christensen LE, Okumura M, Sander SP, Salawitch RJ, Toon GC, Sen B, Blavier JF, Jucks KW (2002) Geophys Res Lett 29:13-1–13-4
Stockwell WR (1995) J Geophys Res D 100:11695–11698
Hippler H, Troe J, Willner J (1990) J Chem Phys 93:1755–1760
Lightfoot PD, Veyret B, Lesclaux R (1988) Chem Phys Lett 150:120–126
Takacs GA, Howard CJ (1986) J Phys Chem 90:687–690
Patrick R, Barker JR, Golden DM (1984) J Phys Chem 88:128–136
Takacs GA, Howard CJ (1984) J Phys Chem 88:2110–2116
Sander SP (1984) J Phys Chem 88:6018–6021
Patrick R, Pilling MJ (1982) Chem Phys Lett 91:343–347
Sander SP, Peterson M, Watson RT, Patrick R (1982) J Phys Chem 86:1236–1240
Simonaitis R, Heicklen J (1982) J Phys Chem 86:3416–3418
Merenyi G, Lind J, Naumov S, von Sonntag C (2010) Chem Eur J 16:1372–1377
Anglada JM, Torrent-Sucarrat M, Ruiz-Lopez MF, Martins-Costa M (2012) Chem Eur J 18:13435–13445
Aloisio S, Francisco JS (2000) J Phys Chem A 104:6597
Kanno N, Tonokura K, Tezaki A, Koshi M (2005) J Phys Chem A 109:3153–3158
Aloisio S, Francisco JS (1998) J Phys Chem A 102:1899–1902
Lendvay G (2001) Z Phys Chem 215:377–392
Zhu RS, Lin MC (2002) Chem Phys Lett 354:217–226
Zhu RS, Lin MC (2003) PhysChemComm 6:51–54
Vácha R, Slavíček P, Mucha M, Finlayson-Pitts BJ, Jungwirth P (2004) J Phys Chem A 108:11573–11579
Martins-Costa MTC, Anglada JM, Francisco JS, Ruiz-Lopez M (2012) Angew Chem Int Edit 51:5413–5417
Anglada JM, Martins-Costa M, Ruiz-Lopez MF, Francisco JS (2014) Proc Natl Acad Sci USA 111:11618–11623
Becke AD (1993) J Chem Phys 98:5648
Frisch MJ, Pople JA, Binkley JS (1984) J Chem Phys 80:3265–3269
Hehre WJ, Radom L, Schleyer PVR, Pople JA (1986) Ab initio molecular orbital theory. Wiley, New York, pp 86–87
Pople JA, Head-Gordon M, Raghavachari K (1987) J Chem Phys 87:5968–5975
Pople JA, Krishnan R, Schlegel B, Binkley JS (1978) Int J Quantum Chem 14:545–560
Cizek J (1969) Adv Chem Phys 14:35
Barlett RJ (1989) J Phys Chem 93:1963
Raghavachari K, Trucks GW, Pople JA, Head-Gordon M (1989) Chem Phys Lett 157:479
Dunning THJ (1989) J Chem Phys 90:1007
Kendall RA, Dunning TH, Harrison RJ (1992) J Chem Phys 96:6796
Bak KL, Gauss J, Jorgensen P, Olsen J, Helgaker T, Stanton JF (2001) J Chem Phys 114:6548–6556
Graefenstein J, Kraka E, Filatov M, Cremer D (2002) Int J Mol Sci 3:360–394
Lee TJ, Taylor PR (1989) Int J Quantum Chem Symp 23:199
Rienstra-Kiracofe JC, Allen WD, Schaefer HF III (2000) J Phys Chem A 104:9823–9840
Jorgensen WL, Chandrashekar J, Madura JD, Impey WR, Klein ML (1983) J Chem Phys 79:926–935
Luque FJ, Reuter N, Cartier A, Ruiz-López MF (2000) J Phys Chem A 104:10923
Torrie GM, Valleau JP (1977) J Comput Phys 23:187
Kumar S, Rosenberg JM, Bouzida D, Swendsen RH, Kollman PA (1992) J Comput Chem 13:1011
Roux B (1995) Comput Phys Commun 91:275
Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA Jr, Peralta JE, Ogliaro F, Bearpark MJ, Heyd J, Brothers EN, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell AP, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam NJ, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas Ö, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) Gaussian 09. Gaussian Inc, Wallingford
Ponder JW (2004) TINKER: software tools for molecular design. Washington University School of Medicine, Saint Louis
Martins-Costa MTC (2014) A Gaussian 09/Tinker 4.2 interface for hybrid QM/MM applications. University of Lorraine—CNRS, Nancy
Wu A, Cremer D, Gauss J (2003) J Phys Chem A 107:8737
Martins-Costa M, Anglada JM, Ruiz-López MF (2009) Chem Phys Lett 481:180
Zhang TL, Wang WL, Zhang P, Lu J, Zhang Y (2011) Phys Chem Chem Phys 13:20794–20805
Chalmet S, Ruiz-López MF (2006) J Chem Phys 124:194502
Bielski BH, Schwarz HA (1968) J Phys Chem 72:3836–3841
Tissandier MD, Cowen KA, Feng WY, Gundlach E, Cohen MH, Earhart AD, Coe JV, Tuttle TR (1998) J Phys Chem A 102:7787–7794
Acknowledgments
JMA thanks the Spanish Secretaria de Estado de Investigación, Desarrollo e Innovación (CTQ2014-59768-P), and the Generalitat de Catalunya (Grant 2014SGR139) for financial support and the Consorci de Serveis Universitaris de Catalunya (CSUC) for providing computational resources. MTCMC and MFRL acknowledge the French CINES for providing computing time (Project Code lct2550).
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Martins-Costa, M.T.C., Anglada, J.M. & Ruiz-López, M.F. Structure of hydrogen tetroxide in gas phase and in aqueous environments: relationship to the hydroperoxyl radical self-reaction. Struct Chem 27, 231–242 (2016). https://doi.org/10.1007/s11224-015-0717-2
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11224-015-0717-2