Abstract
The potential energy surface of HPS2 system containing nine isomers and fifteen transition states is obtained at MP2/6-311++G(d, p) and QCISD(t)/6-311++G(3df, 2p)(single-point) levels. On the potential energy surface, the lowest-lying trans-HSPS(E1) is found to be thermodynamically the most stable isomer followed by cis-HSPS(E2) and HP(S)S(C2v, E3) at 3.43 and 14.17 kJ/mol higher, respectively. The computed results show that species E1, E2, E3, stereo HP(S)S(Cs, E4) with PSS three-membered ring, isomers trans-HPSS(E5) and cis-HPSS(E6) which coexist with E4 are kinetically stable isomers. The products E6 and E5 in the reaction of HP with S2 can be isomerized into higher kinetic stable isomer E4 with 65.75 and 71.73 kJ/mol reaction barrier height, respectively. The predicated results may correct the possible inaccurate conclusion in that the product was experimentally assigned as isomer cis-HPSS(E6).
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References
Leung, Y. C., Wasser, J., Van Houten, S. et al., The crystal structure of P4S3, Acta Crystallogr., 1957,10: 574–582.
Griffin, A. M., Minshall, P. C., Sheldrick, G. M., Two new molecular phosphorous sulfides: α-P4S4 and β-P4S4; X-ray crystal structure of α-P4S4, J. Chem. Soc., Chem. Commun., 1976: 809–810.
Meisel, M., Grunze, H., New phosphorus sulfide phase P4S9, II. Different preparative methods, properties, and constitution of P4S9, Z. Anorg. Allg. Chem., 1970, 373:265–278.
Mielke, Z., Brabson, G. D., Andrews, L., Matrix infrared spectra of the phosphorus sulfides PS, P2S, PS2, J. Phys. Chem., 1991, 95: 75–79.
Schenk, P. W., Leutner, B., Existence of ternary compounds of phosphorus with sulfur and hydrogen, Angew. Chem. Intern. Ed. Eng., 1966, 5: 898–900.
Mielke, Z., Andrews, L., Infrared spectra of HSPH2, HPS2, and HSPS2 in solid argon, J. Phys. Chem., 1993, 97: 4313–4319.
Davies, P. B., Thrush, B. A., The reactions of atomic oxygen with phosphorus and with phosphine, Proc. Roy. Soc. A, 1968, 302: 243–252.
Withnall, R., Andrews, L., Infrared spectra of O-Atom-PH3 reaction products trapped in solid argon, J. Phys. Chem., 1988, 92: 4610–4619.
Nakamura, S., Takahashi, M., Okazaki, R. et al., An ab initio MO study of isomers of HNS2 and HNO2, J. Am. Chem. Soc., 1987,109:4142–4148.
Bell, I. S., Ahmad, I. K., Hamilton, P. A. et al., Detection of the transient molecule HOPO in the gas phase by infrared laser spectroscopy, Chem. Phys. Lett., 2000, 320: 311–315.
Lohr, L. L., Boehm, R. C., Ab initio study of the gaseous oxyacids of phosphorus, their conjugate bases, and their corresponding neutral radicals, J. Phys. Chem., 1987, 91: 3203–3207.
Yu, H. T., Chi, Y. J., Fu, H. G. et al., The structures and stabilities of HPO2 isomers, Science in China, Series B, 2002, 45(1): 1–7.
Goumri, A., Rocha, J. D. R., Laakso, D. et al., Characterization of reaction pathways on the potential energy surfaces for H + SO2andHS + O2, J. Phys. Chem., 1999, 103: 11328–11335.
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Yu, H., Chi, Y., Fu, H. et al. Structures and stabilities of HPS2 isomers. Sc. China Ser. B-Chem. 45, 282–288 (2002). https://doi.org/10.1360/02yb9037
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DOI: https://doi.org/10.1360/02yb9037