Quantum solvent states and rovibrational spectra of small doped (3)He clusters through the full-configuration-interaction nuclear orbital approach: The ((3)He)(N)-Cl(2)(X) case (N <= 4) - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Journal of Chemical Physics Année : 2010

Quantum solvent states and rovibrational spectra of small doped (3)He clusters through the full-configuration-interaction nuclear orbital approach: The ((3)He)(N)-Cl(2)(X) case (N <= 4)

M. P. de Lara Castells
  • Fonction : Auteur correspondant
  • PersonId : 934704

Connectez-vous pour contacter l'auteur
N. F. Aguirre
  • Fonction : Auteur
P. Villarreal
  • Fonction : Auteur
G. Delgado Barrio
  • Fonction : Auteur

Résumé

A full-configuration-interaction nuclear orbital treatment has been recently developed as a benchmark quantum-chemistry-like method to study small doped (3)He clusters [M. P. de Lara-Castells , J. Chem. Phys. 125, 221101 (2006)]. Our objective in this paper is to extend our previous study on ((3)He)(N)-Cl(2)(B) clusters, using an enhanced implementation that allows employing very large one-particle basis sets [M. P. de Lara-Castells , J. Chem. Phys. 131, 194101 (2009)], and apply the method to the ((3)He)(N)-Cl(2)(X) case, using both a semiempirical T-shaped and an ab initio He-dopant potential with minima at both T-shaped and linear conformations. Calculations of the ground and low-lying excited solvent states stress the key role played by the anisotropy of the He-dopant interaction in determining the global energies and the structuring of the (3)He atoms around the dopant. Whereas (3)He atoms are localized in a broad belt around the molecular axis in ground-state N-sized complexes with N=1-3, irrespective of using the T-shaped or the ab initio He-dopant potential function, the dopant species becomes fully coated by just four (3)He atoms when the He-dopant potential also has a minimum at linear configurations. However, excited solvent states with a central ring-type clustering of the host molecule are found to be very close in energy with the ground state by using the ab initio potential function. A microscopic analysis of this behavior is provided. Additional simulations of the molecular rovibrational Raman spectra, also including excited solvent states, provide further insights into the importance of proper modeling the anisotropy of the He-dopant interaction in these weakly bound systems and of taking into account the low-lying excitations. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3425997]

Dates et versions

hal-00692887 , version 1 (01-05-2012)

Identifiants

Citer

M. P. de Lara Castells, N. F. Aguirre, P. Villarreal, G. Delgado Barrio, Alexander Mitrushchenkov. Quantum solvent states and rovibrational spectra of small doped (3)He clusters through the full-configuration-interaction nuclear orbital approach: The ((3)He)(N)-Cl(2)(X) case (N <= 4). Journal of Chemical Physics, 2010, 132 (19), pp.194313. ⟨10.1063/1.3425997⟩. ⟨hal-00692887⟩
61 Consultations
0 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More