A b i n i t i o calculation of near-equilibrium potential and multipole moment surfaces and vibrational frequencies of H+3 and its isotopomers

Abstract

H+3 potential energies and multipole moments are calculated from a full CI with a 10s, 4p, 2d GTO hydrogen basis. 69 calculated energy points with energies of up to 25 000 cm−1 above the minimum are fitted by a power series expansion in terms of a Morse-type coordinate with a mean square error of less than 1 cm−1. Rotationless vibrational states with energies of up to 12 000 cm−1 above equilibrium are calculated variationally for ten isotopomers. The resulting band origins for the seven analyzed fundamental transitions show a mean deviation of less than 2 cm−1. For the other predicted frequencies, the errors are expected to be below 0.1% also. The equilibrium bond length of H+3 is predicted to be 0.8732(2) Å.

Potential energy surface and wave packet calculations on the Li+HF→LiF+H reaction

“…If we add to all of these conformations the 69 proposed by Meyer et al 9 and used by Cencek et al 7 in their very accurate H 3 ϩ ground-state calculations, we obtain a total number of 8469 conformations and 36 FCI energy values for each one ͑304 884 energy values that we do not quote here for obvious reasons͒. A file containing the 8469 ground-state H 3 ϩ data points used to obtain the GPES reported in this paper has been placed in the electronic depository EPAPS.…”

“…6 Local potential energy surfaces ͑LPES͒ on the highest level of sophistication have appeared recently, 7,8 but covering only 69 points on the minimum region of the ground-state potential energy surface, based on previous full configuration interaction ͑FCI͒ calculations due to Meyer et al ͑the so-called MBB LPES͒. 9 Dinelli et al, 10 using high-resolution spectroscopic data for H 3 ϩ , H 2 D ϩ , D 2 H ϩ , and D 3 ϩ , have determined effective mass-dependent LPES for each isotopomer. These potential surfaces are expressed as a sum of the massindependent Born-Oppenheimer potential and a massdependent adiabatic correction.…”

Simulation of à 1B1→X̃ 1A1 CF2 single vibronic level emissions: Including anharmonic and Duschinsky effects

“…Harmonic basis functions up to h (10,30) with the restriction of v 1 ϩv 2 Ͻ30 were employed for the ground state calculation. For the à 1 B 1 state, harmonic basis functions of up to h (10,15) with the restriction v 1 ϩv 2 Ͻ15 were used. The total numbers of basis functions used in the variational calculations were 286 and 121 for the X 1 A 1 and à 1 B 1 states of CF 2 , respectively.…”

Chemical probing spectroscopy of H3+ above the barrier to linearity

“…Owing to its fundamental relevance, triatomic hydrogen is a much-studied system -experimentally as well as theoretically. Since the publication of the Meyer-Botschwina-Burton (MBB) potential energy surface [6] the low-energy regime of the H + 3 potential is known with high precision. Today, the most sophisticated theoretical studies include adiabatic and relativistic corrections and reach an accuracy of 0.02 cm −1 near the equilibrium geometry [7].…”