TY - JOUR

T1 - Ar n HF van der Waals clusters revisited

T2 - II. Energetics and HF vibrational frequency shifts from diffusion Monte Carlo calculations on additive and nonadditive potential-energy surfaces for n=1-12

AU - Jiang, Hao

AU - Xu, Minzhong

AU - Hutson, Jeremy M.

AU - Bačić, Zlatko

N1 - Funding Information:
Three of the authors (Z.B., H.J., and M.X.) have been supported in part by the National Science Foundation Grant No. CHE-0315508. They also acknowledge the donors of the Petroleum Research Fund, administered by the ACS, for partial support of this research.

PY - 2005

Y1 - 2005

N2 - The ground-state energies and HF vibrational frequency shifts of Arn HF clusters have been calculated on the nonadditive potential-energy surfaces (PESs) for n=2-7 and on the pairwise-additive PESs for the clusters with n=1-12, using the diffusion Monte Carlo (DMC) method. For n>3, the calculations have been performed for the lowest-energy isomer and several higher-lying isomers which are the closest in energy. They provide information about the isomer dependence of the HF redshift, and enable direct comparison with the experimental data recently obtained in helium nanodroplets. The agreement between theory and experiment is excellent, in particular, for the nonadditive DMC redshifts. The relative, incremental redshifts are reproduced accurately even at the lower level of theory, i.e., the DMC and quantum five-dimensional (rigid Arn) calculations on the pairwise-additive PESs. The nonadditive interactions make a significant contribution to the frequency shift, on the order of 10%-12%, and have to be included in the PESs in order for the theory to yield accurate magnitude of the HF redshift. The energy gaps between the DMC ground states of the cluster isomers are very different from the energy separation of their respective minima on the PES, due to the considerable variations in the intermolecular zero-point energy of different Arn HF isomers.

AB - The ground-state energies and HF vibrational frequency shifts of Arn HF clusters have been calculated on the nonadditive potential-energy surfaces (PESs) for n=2-7 and on the pairwise-additive PESs for the clusters with n=1-12, using the diffusion Monte Carlo (DMC) method. For n>3, the calculations have been performed for the lowest-energy isomer and several higher-lying isomers which are the closest in energy. They provide information about the isomer dependence of the HF redshift, and enable direct comparison with the experimental data recently obtained in helium nanodroplets. The agreement between theory and experiment is excellent, in particular, for the nonadditive DMC redshifts. The relative, incremental redshifts are reproduced accurately even at the lower level of theory, i.e., the DMC and quantum five-dimensional (rigid Arn) calculations on the pairwise-additive PESs. The nonadditive interactions make a significant contribution to the frequency shift, on the order of 10%-12%, and have to be included in the PESs in order for the theory to yield accurate magnitude of the HF redshift. The energy gaps between the DMC ground states of the cluster isomers are very different from the energy separation of their respective minima on the PES, due to the considerable variations in the intermolecular zero-point energy of different Arn HF isomers.

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U2 - 10.1063/1.1991856

DO - 10.1063/1.1991856

M3 - Article

AN - SCOPUS:23944432235

VL - 123

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 5

M1 - 054305

ER -