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Computation of spectroscopic properties of van der Waals systems from post-SCF ab initio potentials including the EICP alternative counterpoise technique

✍ Scribed by S. Tolosa; J. Espinosa; F. J. Olivares del Valle


Publisher
John Wiley and Sons
Year
1991
Tongue
English
Weight
749 KB
Volume
12
Category
Article
ISSN
0192-8651

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✦ Synopsis


The basis set superposition error (BSSE) is studied using the Counterpoise (CP) technique at SCF and post-SCF level in weakly bonded systems, with the aim of making manifest the overestimate introduced by the Boys and Bernardi method which does not facilitate a valid ab initio construction of potentials in van der Waals systems. The results show that the excess correction introduced by the CP method is to a large extent corrected using the version called the Indirect Counterpoise (ICP) method. The extension of this method to the exchange-polarization and exchange-charge transfer coupling terms provides good ab initio potentials from which quite satisfactory spectroscopic properties can be extracted.