The Li···HF van der Waals minimum and the barrier to the deep HF–Li potential well

^†Special Issue of Molecular Physics: Seventh Molecular Quantum Mechanics Conference, Lugano, Switzerland, 2–7 June 2013.

Abstract

Molecular beam experiments (lithium atom plus hydrogen fluoride) by both Becker and co-workers (C.H. Becker, P. Casavecchia, P.W. Tiedemann, J.J.Valentini, and Y.T. Lee, J. Chem. Phys. 73, 2833 (1980)) and Loesch and Stienkemeier (H.J. Loesch and F. Stienkemeier, J. Chem. Phys. 98, 9570 (1993)) deduced a van der Waals complex of type Li···HF. In this research, molecular electronic structure theory [aug-cc-pCVQZ CCSD(T)] has been used to predict a well depth of 0.86 kcal mol⁻¹ relative to separated Li + HF. However, the barrier from this vdW well to the more strongly bound (∼6.2 kcal mol⁻¹) HFLi complex lies 0.43 kcal mol⁻¹ below separated Li + HF.

Keywords:

• van der Waals systems
• fluorine
• lithium
• hydrogen fluoride
• lithium fluoride
• chemical reactions
• potential energy surfaces
• quantum tunnelling
• computational chemistry
• quantum chemistry
• electronic structure theory

Notes

^† Special Issue of Molecular Physics: Seventh Molecular Quantum Mechanics Conference, Lugano, Switzerland, 2–7 June 2013.

Additional information

Funding

This study was supported in part by the National Natural Science Foundation of China [grant no. 11204244]; the Program for New Century Excellent Talents [grant no. NCET-10-0949]; the Youth Foundation [grant no. 2012JQ0055] of the Department of Science and Technology, and the Fund for the Key Laboratory of Advanced Scientific Computation, Xihua University, China. Research in Georgia was supported by the US Department of Energy, Offices of Basis Energy Sciences, Division of Chemistry [grant no. DE-FG02-97ER1474].