New variational method for the ab initio study in valence coordinates of the Renner-Teller effect in tetra-atomic systems

Abstract : A new variational methodology for the treatment of the Renner Teller effect in tetraatomic molecules has been developed in valence coordinates. The kinetic-energy operator of Bramley et al. [Mol. Phys. 1991, 73, 1183] for any sequentially bonded four-atom molecule, A B C D, in the singlet nondegenerate electronic state has been adapted to the Renner Teller and spin couplings by modifying the expression of the nuclear angular momentum. The total Schrodinger equation is solved by diagonalizing the Hamiltonian matrix in a three-step contraction scheme. The main advantage of this new theoretical development is the possibility of studying different isotopomers using the same potential-energy surfaces. This procedure has been tested on HCCH(+) and its deuterated derivatives DCCD(+) and DCCH(+). The calculated rovibronic band origins were compared with previous data deduced from the Jacobi coordinates methodology, dimensionality reduced variational treatment, and photoelectron spectra with a good global agreement. Rotational structures for these systems are also tackled.
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L. Jutier, Céline Léonard. New variational method for the ab initio study in valence coordinates of the Renner-Teller effect in tetra-atomic systems. Journal of Chemical Theory and Computation, American Chemical Society, 2010, 6 (5), pp.1565-1579. ⟨10.1021/ct100071d⟩. ⟨hal-00692868⟩

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