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Intermolecular bond lengths: extrapolation to the basis set limit on uncorrected and BSSE‐corrected potential energy hypersurfaces
Author(s) -
Paizs Béla,
Salvador Pedro,
Császár Attila G.,
Duran Miquel,
Suhai Sándor
Publication year - 2000
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/1096-987x(20010130)22:2<196::aid-jcc7>3.0.co;2-y
Subject(s) - extrapolation , counterpoise , intermolecular force , intramolecular force , limit (mathematics) , basis set , computational chemistry , bond length , chemistry , physics , statistical physics , quantum mechanics , mathematics , molecule , density functional theory , mathematical analysis
Geometry optimizations were carried out for the (HF) 2 , (H 2 O) 2 , and HF–H 2 O intermolecular complexes using the MP2/aug‐cc‐pV X Z { X =2, 3, 4, and 5} theoretical models on both the uncorrected and counterpoise (CP) corrected potential energy hypersurfaces (PES). Our results and the available literature data clearly show that extrapolation of intermolecular distances to the complete basis set (CBS) limit is satisfactory on PESs corrected for BSSE. On the other hand, one should avoid such extrapolations using data obtained from uncorrected PESs. Also, fixing intramolecular parameters at their experimental values could cause difficulties during the extrapolation. As the available literature data and our results clearly show, the MP2/aug‐cc‐pV X Z { X =2, 3, 4} data series of intermolecular distances obtained from the CP‐corrected surfaces can be safely used for the purpose of CBS extrapolations. © 2000 John Wiley & Sons, Inc. J Comput Chem 22: 196–207, 2001