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 03-feb, 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 XC4H4, 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.
Place, publisher, year, edition, pages
2003. Vol. 633, no 03-feb, 237-246 p.
level-correlated calculations, molecular electric properties, polarized basis-sets, dynamic dipole polarizabilities, x = o, c4h4x x, 2nd hyperpolarizability, douglas-kroll, atoms, integrals
IdentifiersURN: urn:nbn:se:kth:diva-22756DOI: 10.1016/s0166-1280(03)00278-1ISI: 000184850000015OAI: oai:DiVA.org:kth-22756DiVA: diva2:341454
QC 201005252010-08-102010-08-10Bibliographically approved