Ab initio rovibronic states of the thioketenyl radical in its X2Π electronic ground state.

We present an ab initio study of the thioketenyl (HCCS) radical in its degenerate X(2)Π electronic ground state. All rotational and vibrational degrees of freedom are taken into account including the electronic orbital and spin angular momenta. The structure of the rovibronic levels and the nature of the corresponding wave functions show resonances even at very low energies due to strong couplings between the bending, rotation, and spin terms in the Hamiltonian. Assignments from the dominant contributions of the eigenvectors are discussed in parallel with previously published data. The rotational structures for the first excited vibronic states are computed as well as transition intensities for the fundamental one.

A new basis set for molecular bending degrees of freedom.

We present a new basis set as an alternative to Legendre polynomials for the variational treatment of bending vibrational degrees of freedom in order to highly reduce the number of basis functions. This basis set is inspired from the harmonic oscillator eigenfunctions but is defined for a bending angle in the range theta in [0:pi]. The aim is to bring the basis functions closer to the final (ro)vibronic wave functions nature. Our methodology is extended to complicated potential energy surfaces, such as quasilinearity or multiequilibrium geometries, by using several free parameters in the basis functions. These parameters allow several density maxima, linear or not, around which the basis functions will be mainly located. Divergences at linearity in integral computations are resolved as generalized Legendre polynomials. All integral computations required for the evaluation of molecular Hamiltonian matrix elements are given for both discrete variable representation and finite basis representation. Convergence tests for the low energy vibronic states of HCCH(++), HCCH(+), and HCCS are presented.

New Variational Method for the Ab Initio Study in Valence Coordinates of the Renner-Teller Effect in Tetra-Atomic Systems.

A new variational methodology for the treatment of the Renner-Teller effect in tetra-atomic 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 Schrödinger 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.