Sebald’s dissertation, University of Fribourg

Sebald, Winfried Georg

doi:10.1177/0047244111417050

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“…The Hamiltonian matrix is set up in a basis of Morse oscillator functions for the symmetric stretch, harmonic oscillator functions for the antisymmetric stretch and Legendre polynomials for the bending vibration. The basis set and the size of the final rovibrational Hamiltonian matrix were optimised to ensure convergence of all C8VPRO is a program written by one of us [34], which uses Watson's isomorphic Hamiltonian for linear molecules [35] and a basis set of harmonic oscillator/rigid rotor functions. There is no limit in the program for an upper value of J and it is capable of calculating electric transition dipole moments.…”

Section: Rovibrational Calculationsmentioning

confidence: 99%

Theoretical rovibrational spectroscopy beyond fc-CCSD(T): the cation CNC⁺

2015

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An accurate near-equilibrium potential energy surface (PES) for CNC + is constructed based on a high-level composite ab initio method. By combining explicitly correlated all-electron CCSD(T)-F12b with scalar relativistic effects and higher order correlation up to coupled cluster theory with singles, doubles, triples and quadruples (CCSDTQ) we achieve convergence in the wavenumbers of the fundamentals to ca. 1 cm −1 . Rovibrational energies are calculated in a variational approach and vibrational term energies and rotational constants are in excellent agreement with available experimental data. Accurate values for centrifugal distortion constants of CNC + in different vibrational states are predicted. Especially the centrifugal distortion constants in the vibrational ground state of D 0 = 0.563 · 10 −6 cm −1 and H 0 = 0.188 · 10 −10 cm −1 should be superior to experimentally derived values. Reassignments of some experimentally observed transitions are suggested based on a comparison of experimental and calculated term differences. The bending part of the PES appears to be almost quartic and the band origin of the bending vibration is predicted at 94.2 cm −1 . Absolute line intensities are calculated for various transitions in CNC + . For the bending vibration, an intensity is predicted that is three orders of magnitude smaller than for the antisymmetric stretching vibration.

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Section: Rovibrational Calculationsmentioning

confidence: 99%