Theoretical characterization of intermolecular vibrational states through the multi-configuration time dependent Hartree approach: The He2,3ICl clusters

Valdés, Álvaro; Prosmiti, Rita; Villarreal, Pablo; Delgado-Barrio, Gerardo

doi:doi:10.1063/1.3671611

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The ab initio ground-state potential energy function of beryllium monohydride, BeH

The accurate ground-state potential energy function of beryllium monohydride, BeH, has been determined from large-scale ab initio calculations using the multi-reference averaged coupled-pair functional (MR-ACPF) method in conjunction with the correlation-consistent core-valence basis sets up to septuple-zeta quality. The effects of electron correlation beyond the MR-ACPF level of approximation were taken into account. The scalar relativistic and adiabatic (the diagonal correction) effects, as we...

Accurate ab initio quartic force fields of cyclic and bent HC₂N isomers

Highly correlated ab initio quartic force fields (QFFs) are used to calculate the equilibrium structures and predict the spectroscopic parameters of three HC2N isomers. Specifically, the ground state quasilinear triplet and the lowest cyclic and bent singlet isomers are included in the present study. Extensive treatment of correlation effects were included using the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations, ...

Benchmark, full-dimensional calculations on the ground and excited vibrational states for the tetra-, and penta-atomic weakly bound He_2,3ICl complexes are reported. The representation of the potential energy surfaces includes three-body HeICl potentials parameterized to coupled-cluster singles, doubles, and perturbative triples ab initio data. These terms are important in accurately describing the interactions of such highly floppy systems. The corresponding 6D/9D computations are performed with the multi-configuration time dependent Hartree method, using natural potential fits, and a mode combination scheme to optimize the computational effort in the improved relaxation calculations. For these complexes several low-lying vibrational states are computed, and their binding energies and radial/angular probability density distributions are obtained. We found various isomers which are assigned to different structural models related with combinations of the triatomic isomers, like linear, T-shaped, and antilinear ones. Comparison of these results with recent experimental data is presented, and the quantitative deviations found with respect to the experiment are discussed.

Article Outline

INTRODUCTION
COMPUTATIONS, RESULTS, AND DISCUSSION
1. Ab initio calculations and potential form
2. MCTDH calculations
3. Vibrational bound states
CONCLUSIONS

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KEYWORDS and PACS

Keywords

atomic clusters, binding energy, coupled cluster calculations, excited states, ground states, helium compounds, HF calculations, isomerism, vibrational states

PACS

36.40.Mr

Spectroscopy and geometrical structure of clusters
31.15.bw

Coupled-cluster theory
31.15.xr

Self-consistent-field methods
33.15.Hp

Barrier heights (internal rotation, inversion, rotational isomerism, conformational dynamics)
33.15.Ry

Ionization potentials, electron affinities, molecular core binding energy
33.20.Tp

Vibrational analysis

ARTICLE DATA

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http://dx.doi.org/10.1063/1.3671611

PUBLICATION DATA

ISSN

0021-9606 (print)

1089-7690 (online)

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$abstract.society.value is a Member of CrossRef

American Institute of Physics

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