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Modeling properties of the HF dimer in argon clusters
Author(s) -
Nemukhin A. V.,
Grigorenko B. L.
Publication year - 1997
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/(sici)1097-461x(1997)62:1<55::aid-qua6>3.0.co;2-2
Subject(s) - antibonding molecular orbital , chemistry , lone pair , argon , intermolecular force , ab initio , atom (system on chip) , atomic physics , dimer , ab initio quantum chemistry methods , population , bond length , molecular physics , computational chemistry , atomic orbital , crystallography , electron , molecule , physics , crystal structure , demography , organic chemistry , quantum mechanics , sociology , computer science , embedded system
We compare geometry configurations, vibrational properties, and electronic structures of (HF) 2 in a free state and inside argon atom shells Ar n . For the first stage, molecular dynamics calculations for the (HF) 2 · Ar 62 heterocluster are performed with the help of model potentials HF(SINGLE BOND)HF, Ar(SINGLE BOND)Ar, and Ar(SINGLE BOND)HF. Then, ab initio quantum chemistry analysis is carried out for the smaller systems (HF) 2 · Ar 15 and (HF) 2 · Ar 6 when keeping the argon atoms closest to the trapped dimer. We conclude that the hydrogen‐bonded complex (HF) 2 gains some extra stability inside the argon shells, originating primarily from a decrease of intermolecular distance R FF . Electronic structure calculations are in accord with the changes in dynamical properties, namely, a noticeable increase in the vibrational frequency assigned to the F(SINGLE BOND)F stretching mode (+25 cm −1 ) and decrease in rms deviations for the corresponding coordinate δ FF . In addition to these changes, the argon atoms of the nearest solvent shell donate a small fraction of electron charge which is spent for an increase of population of the antibonding orbital σ * H f (SINGLE BOND)F fof the free monomer unit and shift orbital energies primarily of the lone‐pair fluorine species. These shifts are greater than the changes due to geometry alterations and the possible inaccuracies of the calculation scheme. © 1997 John Wiley & Sons, Inc.