TY - JOUR

T1 - Density functional theory investigation of the polarizability and second hyperpolarizability of polydiacetylene and polybutatriene chains

T2 - Treatment of exact exchange and role of correlation

AU - Champagne, Benoit

AU - Bulat, Felipe A.

AU - Yang, Weitao

AU - Bonness, Sean

AU - Kirtman, Bernard

PY - 2006/12/12

Y1 - 2006/12/12

N2 - The static polarizability and second hyperpolarizability of increasingly large polydiacetylene and polybutatriene (PBT) chains have been evaluated using the optimized effective potential for exact exchange (OEP-EXX) method developed by Yang and Wu [Phys. Rev. Lett. 89, 143002 (2002)], where the unknown part of the effective potential is expressed as a linear combination of Gaussian functions. Various conventional atomic orbital basis sets were employed for the exchange potential (X basis) as well as for the Kohn-Sham orbitals [molecular orbital (MO) basis]. Our results were compared to coupled-perturbed Hartree-Fock (CPHF) calculations and to ab initio correlated values obtained at various levels of approximation. It turns out that (a) small conventional basis sets are, in general, unsatisfactory for the X basis; (b) the performance of a given X basis depends on the MO basis and is generally improved when using a larger MO basis; (c) these effects are exaggerated for the second hyperpolarizability compared to the polarizability; (d) except for the second hyperpolarizability of PBT chains, using 6-311++G* for the X basis gives reasonable agreement with the CPHF results for all MO basis sets; (e) our results suggest that in the limit of a complete X basis the OEP-EXX values may approach the CPHF data; and (f) in general, the quality of a given conventional X basis degrades with the length of the oligomer, which correlates with the fact that the number of X basis functions becomes a smaller fraction of the number required to reproduce exactly the finite-basis-set Hartree-Fock energies. Linear and especially nonlinear electric field responses constitute a very stringent test for assessing the quality of functionals and potentials; appropriately tailored basis sets are needed to describe the latter. Finally, this study further highlights the importance of electron correlation effects on linear and nonlinear responses, for which correlated functionals with OEP are required.

AB - The static polarizability and second hyperpolarizability of increasingly large polydiacetylene and polybutatriene (PBT) chains have been evaluated using the optimized effective potential for exact exchange (OEP-EXX) method developed by Yang and Wu [Phys. Rev. Lett. 89, 143002 (2002)], where the unknown part of the effective potential is expressed as a linear combination of Gaussian functions. Various conventional atomic orbital basis sets were employed for the exchange potential (X basis) as well as for the Kohn-Sham orbitals [molecular orbital (MO) basis]. Our results were compared to coupled-perturbed Hartree-Fock (CPHF) calculations and to ab initio correlated values obtained at various levels of approximation. It turns out that (a) small conventional basis sets are, in general, unsatisfactory for the X basis; (b) the performance of a given X basis depends on the MO basis and is generally improved when using a larger MO basis; (c) these effects are exaggerated for the second hyperpolarizability compared to the polarizability; (d) except for the second hyperpolarizability of PBT chains, using 6-311++G* for the X basis gives reasonable agreement with the CPHF results for all MO basis sets; (e) our results suggest that in the limit of a complete X basis the OEP-EXX values may approach the CPHF data; and (f) in general, the quality of a given conventional X basis degrades with the length of the oligomer, which correlates with the fact that the number of X basis functions becomes a smaller fraction of the number required to reproduce exactly the finite-basis-set Hartree-Fock energies. Linear and especially nonlinear electric field responses constitute a very stringent test for assessing the quality of functionals and potentials; appropriately tailored basis sets are needed to describe the latter. Finally, this study further highlights the importance of electron correlation effects on linear and nonlinear responses, for which correlated functionals with OEP are required.

UR - http://www.scopus.com/inward/record.url?scp=33845344728&partnerID=8YFLogxK

U2 - 10.1063/1.2388262

DO - 10.1063/1.2388262

M3 - Article

AN - SCOPUS:33845344728

VL - 125

JO - The journal of chemical physics

JF - The journal of chemical physics

SN - 0021-9606

IS - 19

M1 - 194114

ER -