Potential energy surfaces governing chemical reactions involving carbon, oxygen and hydrogen

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Xantheas, Sotiris
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Klaus Ruedenberg
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The lowest singlet states of O[subscript]3 in C[subscript] 2v are studied in the Full Optimized Reaction Space (FORS) MCSCF level of theory with an extended atomic basis set plus polarization functions. The [superscript]1A' ground state potential energy surface contains two minima. The upper minimum lies 29.8 kcal/mole above the ground state minimum and most importantly above the O[subscript]2([superscript]3[sigma][subscript]g[superscript]-) + O([superscript]3P) dissociation limit. It resembles a ring structure having D[subscript] 3h symmetry. The potential energy surface governing the C[subscript] 2v restricted ring opening of the cyclic O[subscript]3 to the ground state is also computed. A conical intersection is found between the 1-[superscript]1A[subscript]1 and 2-[superscript]1A[subscript]1 potential energy surfaces. This first case of an intersection of two states of the same symmetry in a real system is definitively proved by monitoring the sign of the wavefunction on a closed loop around it;Ab-initio calculations elucidating the structure, the ring opening and the dissociation process of the cyclic CO[subscript]2 isomer are reported. The optimal isosceles-triangle (C[subscript] 2v) geometries corresponding to the C[subscript] 2v constraint dissociation OCO → C + O[subscript]2 are determined. The entire C[subscript] 2v surface is computed, revealing the existence of a metastable cyclic carbene-type species corresponding to a local minimum 137.6 kcal/mole above the linear total minimum. Finally, energies are determined for various relevant cross sections with lower symmetry (C[subscript] s), i.e. for asymmetric bond lengths;Extended basis set calculations for the key regions of the ground state [superscript]1A[subscript]1 cyclopropylidene (C[subscript] 2v) to allene (D[subscript] 2d) ring opening reaction surface are performed within the FORS MCSCF framework. Optimized geometries of the reactant, product, transition state and allene isomerization transition state as well as the barrier for the ring opening and the allene isomerization together with the overall exothermicity are reported in the various levels of MCSCF approximation incorporating FORS spaces ranging from 20 to 1764 configurations. The reaction path from the transition state passes from a point where the two surfaces corresponding to the [superscript]1A' and [superscript]1A'' states intersect each other. Explanations for the various features of the potential energy surface governing the ring opening of cyclopropylidene to allene are obtained through localized quasi-atomic FORS MO's. ftn*Performed under Contract No. W-7405-Eng-82 for the U.S. Dept. of Energy

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Tue Jan 01 00:00:00 UTC 1991