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Removal of dependencies from nearly complete basis sets. Calculations on the helium dimer
Author(s) -
van Mourik Tanja,
Jan Vos Robert,
van Lenthe Joop H.,
van Duijneveldt Frans B.
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)63:4<805::aid-qua1>3.0.co;2-#
Subject(s) - dimer , helium , basis (linear algebra) , computational chemistry , chemistry , chemical physics , atomic physics , materials science , physics , mathematics , organic chemistry , geometry
Abstract A method is devised for dealing with almost linearly dependent basis sets that contain large sets of bond functions. Using the largest of such basis sets, LARSAT, the second‐order Møller‐Plesset polarization dispersion energy of the helium dimer is calculated to be ‐ 17.08 K at R = 5.6 bohrs. MR‐SDCI calculations, employing a set of 37 reference configurations, were performed for the helium dimer with several basis sets at 4.0 and 5.6 bohrs. Size‐extensivity corrections were included to take into account the R dependency of the size‐extensivity error in MR‐SDCI calculations. The He 2 interaction energies computed with basis LARSAT are ‐ 10.92 K at 5.6 bohrs and 295.1 K at 4.0 bohrs. The 37‐MR‐SDCI calculations with basis LARSAT almost reproduce the He 2 full configuration interaction (CI) interaction energies computed with the same basis, at notably smaller cost. © 1997 John Wiley & Sons, Inc. Int J Quant Chem 63: 805–815, 1997