Abstract
The reaction mechanism of sulfur vapor (S) with nitrite ion (NO2 −) has been investigated theoretically on the triplet and singlet potential energy surfaces (PESs). All stationary points for the title reaction have been optimized at the B3LYP/6-311+G(3df) level. The energetic data have been obtained at the CCSD(T)//B3LYP level employing the 6-311+G(3df) basis set. Five stable collision complexes, 3IN1 (S–ONO−), 3IN2 (cyclic SONO−), 1IN1 (cis S–ONO−), 1IN2 (S–NO2 −), and 1IN3 (trans S–ONO−), have been considered on the triplet and singlet PESs through barrier-less and exothermic processes. By starting from these complexes, a simple mechanism has been obtained on the triplet PES while a complex mechanism has been considered on the singlet PES. The calculated results show that there are no favorable paths for the reaction of S with NO2 − on the singlet PES. Therefore, the S + NO2 − reaction proceeds only on the triplet PES to produce 3SO + 3NO− as main products. The results from the comparative study of S + NO2 − reaction mechanism with S + O3 (as isoelectronic and isostructure reactions) on the singlet PES show similarities in the overall trend of reaction mechanism and atom connectivity and differences in the stability of intermediates and the energy barriers of transition states.
Similar content being viewed by others
References
Ferguson EE, Arnold F (1981) Acct Chem Res 14:327
Narcisi RS, Bailey AD (1965) J Geophys Res 70:3687
Ferguson EE, Fehsenfeld FC, Albritton DL (1979) In: Bowers MT (ed) Gas phase ion chemistry, vol 1, Academic Press, New York
Fehsenfeld FC, Howard CJ, Schmeltekopf AL (1975) J Chem Phys 63:2835
Amelynck C, Stépien C, Schoon N, Catoire V, Labonnette D, Arijs E, Poulet G (2001) Int J Mass Spectrom 207:205
Fehsenfeld FC, Ferguson EE (1968) Planet Space Sci 16:701
Narcisi RS, Bailey AD, Della Lucca L, Sherman C, Thomas DM (1971) J Atmos Terr Phys 33:1147
Pelc A, Sailer W, Matejcik S, Scheier P, Märk TD (2003) J Chem Phys 119:7887
Compton RN, Carman HS, Desfrancois C, Abdoul-Carmine H, Schermann JP, Hendricks JH, Lyapustina SA, Bowen KH (1996) J Chem Phys 105:3472
Stockdale JA, Davis FJ, Compton RN, Klots CE (1974) J Chem Phys 60:4279
Wincel H (2004) Int J Mass Spectrom 232:185
Wincel H (2003) Int J Mass Spectrom 226:341
Lias SG, Bartmess JE, Liebman JF, Holmes JL, Levin RD, Mallard WG (1988) J Phys Chem Ref Data 17 (Suppl 1)
Schalley CA, Schröder D, Schwarz H, Möbus K, Boche G (1997) Chem Ber 130:1085
Huey LG, Hanson DR, Howard CJ (1995) J Phys Chem 99:5001
Mallard WG, Linstrom PJ (2000) (eds.) By taking into account the heats of formation of the reactants and products as reported in NIST Chemistry Web Book, NIST Standard Reference Database Number 69. National Institute of Standards and Technology, Gaithersburg (http://webbook.nist.gov)
Davidson JA, Viggiano AA, Howard CJ, Dotan I, Fehsenfeld FC, Albritton DL, Ferguson EE (1978) J Chem Phys 68:2085
Dotan I, Albritton DL, Fehsenfeld FC, Streit GE, Ferguson EE (1978) J Chem Phys 68:5414
Turco RP (1977) J Geophcys Res 82:3585
Arnold F, Krankowsky D (1971) J Atmos Terr Phys 33:1693
Ferguson EE, Dunkin DB, Fehsenfeld FC (1972) J Chem Phys 57:1459
Van Doren JM, Viggiano AA, Morris RA, Miller TM (1995) J Chem Phys 103:10806
Goodarzi M, Vahedpour M, Nazari F (2010) J Mol Struct Theochem 944:110
Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Zakrzewski VG, Montgomery JA, Stratmann RE, Burant JC, Dapprich S, Millam JM, Daniels AD, Kudin KN, Strain MC, Farkas O, Tomasi J, Barone V, Cossi M, Cammi R, Mennucci B, Pomelli C, Adamo C, Clifford S, Ochterski J, Petersson GA, Ayala PY, Cui Q, Morokuma K, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Cioslowski J, Ortiz JV, Baboul AG, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Gomperts R, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Gonzalez C, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Andres JL, Gonzalez C, Head-Gordon M, Replogle ES, Pople JA (1998) Gaussian 98 (revision A.7 ). Gaussian Inc., Pittsburgh
Becke AD (1993) J Chem Phys 98:5648
Lee C, Yang W, Parr RG (1988) Phys Rev 37:785
Raghavachair K, Trucks GW, Pople JA, Head-Gordon M (1989) Chem Phys Lett 157:479
Gonzalez C, Schlegel HB (1989) J Chem Phys 90:2154
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
Goodarzi, M., Vahedpour, M. & Solimannejad, M. Computational study on the reaction mechanism of the gas-phase atom-negative ion of S + NO2 −: comparative study of mechanism with S + O3 reaction as isoelectronic and isostructure systems. Struct Chem 23, 381–392 (2012). https://doi.org/10.1007/s11224-011-9880-2
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11224-011-9880-2