Relativistic effects on linear and non-linear polarizabilities of the furan homologues
2003 (English)In: Journal of Molecular Structure: THEOCHEM, ISSN 0166-1280, Vol. 633, no 2-3, 237-246 p.Article in journal (Refereed) Published
First principles calculations including relativistic effects are carried out for dipole moments, polarizabilities, first- and second-order hyperpolarizabilities for the series of furan homologues XC4H 4, X = O, S, Se, Te, at three different levels of theory, time-dependent Dirac-Hartree-Fock (DHF), time-dependent Hartree-Fock with a Douglas-Kroll transformed one-component Hamiltonian, and time-dependent Hartree-Fock using effective-core potentials. By comparison with the corresponding non-relativistic results, the influence of relativistic effects on the properties as well as the accuracy of previously reported calculations on these molecules using effective-core potentials for selenium and tellurium can be addressed. The obtained results indicate that relativistic effects can be described with comparable accuracy at all three employed levels, and that non-scalar effects, which are explicitly treated only at the time-dependent DHF level, are of minor importance. Frequency dispersion and relativity are found to be additive at the single-determinant level. We find that relativistic effects cannot make up for the earlier identified mismatch between theory and experiment for the non-linear polarizabilities of the heavier homologues. A Bishop-Kirtman analysis of vibrational effects indicates that the same can be said about these. © 2003 Elsevier B.V. All rights reserved.
Place, publisher, year, edition, pages
2003. Vol. 633, no 2-3, 237-246 p.
National CategoryEngineering and Technology
IdentifiersURN: urn:nbn:se:liu:diva-46514DOI: 10.1016/S0166-1280(03)00278-1OAI: oai:DiVA.org:liu-46514DiVA: diva2:267410