The reaction of sulfur atoms with carbon disulfide: Potential energy surface features

Froese, Robert D. J.; Goddard, John D.
May 1992
Journal of Chemical Physics;5/15/1992, Vol. 96 Issue 10, p7449
Academic Journal
The lowest singlet and triplet potential energy surfaces of the reaction, S+CS2→CS3→CS+S2, were investigated by the 6-31G* ab initio self-consistent-field (SCF) method with the inclusion of electron correlation by Mo\ller–Plesset perturbation theory. The triplet reactants and products [S(3P)+CS2(1Σ+g),S2(3Σ-g)+CS(1Σ+)] are predicted to be more stable than their singlet counterparts [S(1D)+CS2(1Σ+g),S2(1Δg)+CS(1Σ+)] in agreement with experiment. However, the CS3 complex is more stable in its singlet as opposed to triplet state, leading to interesting surface crossings in the intermediate regions of the surfaces. The triplet surface contains shallow wells corresponding to cis- and trans-CS3 chain isomers. A low-lying singlet C2v ring structure, carbon trisulfide, was connected to a chain molecule, carbon disulfide S-sulfide, by a relatively low-lying transition state. Another transition state was found with a modest barrier, which joined the C2v ring structure to another relatively low-lying minimum, a symmetric D3h structure. Relative to the singlet ring compound, the singlet chain isomer and the D3h structure are 14.3 and 4.1 kcal/mol higher in energy, and the triplet cis and trans minima 31.2 and 34.1 kcal/mol higher in energy. At the unrestricted Hartree–Fock level (UHF or UMP2), transition states join the chain structure to both reactants and products on the singlet surface. From the experimental evidence and the predictions of this work, an intersystem crossing from the triplet potential energy surface to the singlet one is expected in the region of those transition states leading to the products, CS+S2.


Related Articles

  • An ab initio study of the reaction of atomic hydrogen with sulfur dioxide. Binns, Derk; Marshall, Paul // Journal of Chemical Physics;10/1/1991, Vol. 95 Issue 7, p4940 

    The potential energy surface for H(1 2S)+SO2 has been investigated computationally in order to study the catalytic removal of atomic hydrogen in flames by sulfur dioxide. HF/3–21G(*) and MP2/3–21G(*) levels of theory were employed to locate stationary points, which were then...

  • The Role of a Reaction of Direct Substitution for a Sulfur Atom in the CS2 Molecule in the Combustion of Carbon Disulfide with Oxygen. Azatyan, V. V. // Kinetics & Catalysis;Jul2003, Vol. 44 Issue 4, p459 

    In the combustion of carbon disulfide, the direct substitution reaction O + CS2 = OCS + S (I) was found to be the main source of atomic sulfur, which is responsible for the branching of reaction chains. As distinct from the reactions of intermediate products with each other, step (I), which is a...

  • Potential energy surfaces for Pt3+H2 and Pd3+H2 systems. Dai, Dingguo; Liao, D. W.; Balasubramanian, K. // Journal of Chemical Physics;5/15/1995, Vol. 102 Issue 19, p7530 

    Potential energy surfaces of Pt3+H2 and Pd3+H2 systems are computed for different modes of approach using the complete active space multiconfiguration self-consistent field theory (CAS-MCSCF). The equilibrium geometries and the dissociation limits were computed using multireference...

  • Converged five-dimensional quantum calculations for OH+CO→H+CO[sub 2]. McCormack, Drew A.; Kroes, Geert-Jan // Journal of Chemical Physics;3/8/2002, Vol. 116 Issue 10, p4184 

    We perform five-dimensional quantum wave packet calculations of initial-state-resolved reaction probabilities for the reaction OH+CO→H+CO[sub 2], with OH and CO initially in the rovibrational ground state, and total angular momentum J=0. In essence, the dynamics are treated exactly for...

  • A hierarchical family of global analytic Born–Oppenheimer potential energy surfaces for the H+H[sub 2] reaction ranging in quality from double-zeta to the complete basis set limit. Mielke, Steven L.; Garrett, Bruce C.; Peterson, Kirk A. // Journal of Chemical Physics;3/8/2002, Vol. 116 Issue 10, p4142 

    A hierarchical family of analytical Born–Oppenheimer potential energy surfaces has been developed for the H+H[sub 2] system. Ab initio calculations of near full configuration interaction (FCI) quality (converged to within approx. 1 μE[sub h]) were performed for a set of 4067...

  • A globally smooth ab initio potential surface of the 1 A[sup ′] state for the reaction S([sup 1]D)+H[sub 2]. Ho, Tak-San; Hollebeek, Timothy; Rabitz, Herschel; Der Chao, Sheng; Skodje, Rex T.; Zyubin, Alexander S.; Mebel, Alexander M. // Journal of Chemical Physics;3/8/2002, Vol. 116 Issue 10, p4124 

    A procedure based on the reproducing kernel Hilbert space (RKHS) interpolation method has been implemented to produce a globally smooth potential energy surface (PES) for the 1 A[sup ′] state of the S([sup 1]D)+H[sub 2] reaction from a set of accurate ab initio data, calculated at the...

  • Diatomics-in-molecules models for H2O and H2O-. II. A self-consistent description of the 1A′, 1A″, 3A′, and 3A″ states of H2O. Polak, R.; Paidarova, I.; Kuntz, P. J. // Journal of Chemical Physics;9/1/1987, Vol. 87 Issue 5, p2863 

    This paper describes a small (6 to 9 basis functions) model for the potential energy surfaces relevant to the chemical reaction O(1D)+H2→OH(X 2Π)+H. The model is optimized with respect to the 1A′ and 1A″ states correlating with the reagents and products of this reaction;...

  • An ab initio study of the O(1D)+HCl reaction. Hernandez, Maria Luz; Redondo, Carmen; Laganà, Antonio; Ochoa de Aspuru, Guillermo; Rosi, Marzio; Sgamellotti, Antonio // Journal of Chemical Physics;8/15/1996, Vol. 105 Issue 7, p2710 

    The potential energy surface of the O([SUP1]D)+HCl reaction has been calculated at an ab initio level. The calculated values have been fitted using a bond-order polynomial. On this potential energy surface quasiclassical trajectory calculations have been performed. These calculations reproduce...

  • The geometric phase effect in chemical reactions: A quasiclassical trajectory study. Adhikari, Satrajit; Billing, Gert D. // Journal of Chemical Physics;10/22/1997, Vol. 107 Issue 16, p6213 

    Focuses on the hyperspherical formulation of the vector potential arising due to the presence of a conical intersection in the adiabatic potential energy hypersurface of an A + B[sub 2] type reactive system. Difference in the absolute peak position of rotational distributions obtained by...


Read the Article


Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics