Systematic study of the static electrical properties of the CO molecule: influence of the basis set size and correlation energy
dc.contributor.author
dc.date.accessioned
2011-02-08T13:20:18Z
dc.date.available
2010-12-14T12:53:28Z
2011-02-08T13:20:18Z
dc.date.issued
1995
dc.identifier.issn
0021-9606
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dc.description.abstract
The influence of the basis set size and the correlation energy in the static electrical properties of the CO molecule is assessed. In particular, we have studied both the nuclear relaxation and the vibrational contributions to the static molecular electrical properties, the vibrational Stark effect (VSE) and the vibrational intensity effect (VIE). From a mathematical point of view, when a static and uniform electric field is applied to a molecule, the energy of this system can be expressed in terms of a double power series with respect to the bond length and to the field strength. From the power series expansion of the potential energy, field-dependent expressions for the equilibrium geometry, for the potential energy and for the force constant are obtained. The nuclear relaxation and vibrational contributions to the molecular electrical properties are analyzed in terms of the derivatives of the electronic molecular properties. In general, the results presented show that accurate inclusion of the correlation energy and large basis sets are needed to calculate the molecular electrical properties and their derivatives with respect to either nuclear displacements or/and field strength. With respect to experimental data, the calculated power series coefficients are overestimated by the SCF, CISD, and QCISD methods. On the contrary, perturbation methods (MP2 and MP4) tend to underestimate them. In average and using the 6-311 + G(3df) basis set and for the CO molecule, the nuclear relaxation and the vibrational contributions to the molecular electrical properties amount to 11.7%, 3.3%, and 69.7% of the purely electronic μ, α, and β values, respectively
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application/pdf
dc.language.iso
eng
dc.publisher
American Institute of Physics
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Reproducció digital del document publicat a: http://dx.doi.org/10.1063/1.469089
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© Journal of Chemical Physics, 1995, vol. 102, núm. 19, p. 7573-7583
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Articles publicats (D-Q)
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Tots els drets reservats
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dc.title
Systematic study of the static electrical properties of the CO molecule: influence of the basis set size and correlation energy
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info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.identifier.doi
dc.identifier.eissn
1089-7690