ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
In an endeavor to establish a suitable ab initio basis set for the description of the structure and vibrational spectra of phosphorus chlorides, the effect of adding center-of-bond (cb) s and p functions to 3-21G* basis sets was explored. To ensure generality of 3-21G*cb results were compared with various simpler bases for a range of molecules containing second row elements. While geometries and vibrational frequency patterns are well reproduced using the 3-21G* basis, dipole moments are less adequately reproduced. By addition of s and p orbitals at the bond centers there is a marked improvement in the polar properties with the other properties being little affected. Use of only s orbitals in this context is, if anything, detrimental. The results are applied to a study of the simplest of phosphorus chlorides, PCl3. Among the extant literature force fields, field A of Cazzoli is identified as being near correct. As with this field, all the ab initio fields show that the experimentally estimated first order Coriolis constant of ζ4 is too negative by ∼0.2.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.453077
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