Abstract
Static polarizability and second hyperpolarizability have been calculated for a number of small moleculesCO2, OCS, CS2, C2H2, C2H6, C3H8, cyclo‐C3H6, C3H4, C3H6, SiH4, Si2H6in the framework of the coupled‐perturbed Hartree‐Fock (CPHF) theory. The linear and nonlinear coefficients have been calculated with standard Gaussian basis sets and 3‐21G bases moderately enlarged with diffuse functions. It is shown that the parallel component of the polarizability saturates rapidly, which suggests that a 3‐21G basis containing s and p diffuse functions is sufficient to reproduce αzz. For the αxx and αyy components, a 3‐21G basis with s, p, and d diffuse functions is required. In general, the concordance between α computed with this basis set and the experimental static polarizability is at least of the order of 80%. On the contrary, the computation of the second hyperpolarizability with the same basis set for CO2, CS2, and C2H2 gives values that are 30% too low, compared to the experimental value. Better results are observed for ethane, propane, and cyclopropane for which the error is lower than 50%. The better agreement observed for the saturated compounds can probably be explained by their saturated character.
| Original language | English |
|---|---|
| Pages (from-to) | 1577-1594 |
| Number of pages | 18 |
| Journal | International Journal of Quantum Chemistry |
| Volume | 42 |
| Issue number | 5 |
| DOIs | |
| Publication status | Published - 1992 |
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ASJC Scopus subject areas
- Atomic and Molecular Physics, and Optics
- Condensed Matter Physics
- Physical and Theoretical Chemistry
Cite this
Ab initio CPHF calculations of the static polarizability and second hyperpolarizability of small molecules : Comparisons between standard and moderately large basis sets augmented with diffuse functions. / Dory, M.; Beudels, L.; Fripiat, J. G.; Delhalle, J.; André, J. M.; Dupuis, Michel.
In: International Journal of Quantum Chemistry, Vol. 42, No. 5, 1992, p. 1577-1594.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Ab initio CPHF calculations of the static polarizability and second hyperpolarizability of small molecules
T2 - Comparisons between standard and moderately large basis sets augmented with diffuse functions
AU - Dory, M.
AU - Beudels, L.
AU - Fripiat, J. G.
AU - Delhalle, J.
AU - André, J. M.
AU - Dupuis, Michel
PY - 1992
Y1 - 1992
N2 - Static polarizability and second hyperpolarizability have been calculated for a number of small moleculesCO2, OCS, CS2, C2H2, C2H6, C3H8, cyclo‐C3H6, C3H4, C3H6, SiH4, Si2H6in the framework of the coupled‐perturbed Hartree‐Fock (CPHF) theory. The linear and nonlinear coefficients have been calculated with standard Gaussian basis sets and 3‐21G bases moderately enlarged with diffuse functions. It is shown that the parallel component of the polarizability saturates rapidly, which suggests that a 3‐21G basis containing s and p diffuse functions is sufficient to reproduce αzz. For the αxx and αyy components, a 3‐21G basis with s, p, and d diffuse functions is required. In general, the concordance between α computed with this basis set and the experimental static polarizability is at least of the order of 80%. On the contrary, the computation of the second hyperpolarizability with the same basis set for CO2, CS2, and C2H2 gives values that are 30% too low, compared to the experimental value. Better results are observed for ethane, propane, and cyclopropane for which the error is lower than 50%. The better agreement observed for the saturated compounds can probably be explained by their saturated character.
AB - Static polarizability and second hyperpolarizability have been calculated for a number of small moleculesCO2, OCS, CS2, C2H2, C2H6, C3H8, cyclo‐C3H6, C3H4, C3H6, SiH4, Si2H6in the framework of the coupled‐perturbed Hartree‐Fock (CPHF) theory. The linear and nonlinear coefficients have been calculated with standard Gaussian basis sets and 3‐21G bases moderately enlarged with diffuse functions. It is shown that the parallel component of the polarizability saturates rapidly, which suggests that a 3‐21G basis containing s and p diffuse functions is sufficient to reproduce αzz. For the αxx and αyy components, a 3‐21G basis with s, p, and d diffuse functions is required. In general, the concordance between α computed with this basis set and the experimental static polarizability is at least of the order of 80%. On the contrary, the computation of the second hyperpolarizability with the same basis set for CO2, CS2, and C2H2 gives values that are 30% too low, compared to the experimental value. Better results are observed for ethane, propane, and cyclopropane for which the error is lower than 50%. The better agreement observed for the saturated compounds can probably be explained by their saturated character.
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U2 - 10.1002/qua.560420530
DO - 10.1002/qua.560420530
M3 - Article
VL - 42
SP - 1577
EP - 1594
JO - International Journal of Quantum Chemistry
JF - International Journal of Quantum Chemistry
SN - 0020-7608
IS - 5
ER -