The molecular electric quadrupole moment and electric field gradient induced birefringence (Buckingham effect) of Cl2
2004 (English)In: Journal of Computational Methods in Sciences and Engineering, ISSN 1472-7978 (Print) 1875-8983 (Online), Vol. 4, no 3, 365-380 p.Article in journal (Refereed) Published
An ab initio investigation of the molecular properties rationalizing the electric-field-gradient induced birefringence (Buckingham effect) for Cl_2 is presented. The quadrupole moment is determined using hierarchies of basis sets and wavefunction models. The electric dipole polarizability, the dipole - dipole - quadrupole and dipole - dipole - magnetic dipole hyperpolarizabilities are determined exploiting a Coupled Cluster Singles and Doubles (CCSD) response approach. The properties are zero-point vibrationally averaged, and the contribution of excited ro-vibrational states accounted for. To this end, the interatomic ^1Σ_g^+ ground state potential has been computed at CCSD plus perturbative triples - CCSD(T) - level employing a large augmented correlation consistent basis set. The effect of relativity is estimated at the Dirac-Hartree-Fock level. Our best value for the quadrupole moment of Cl_2 is (2.327 ± 0.010) au and it is in excellent agreement with experiment which, after revision and dependent on the procedure employed for correcting the original estimate of (2.24 ± 0.04) au of Graham et al., [Mol. Phys., 93, 49, (1998)], ranges from (2.31 ± 0.04) au to (2.36 ± 0.04) au.
Place, publisher, year, edition, pages
2004. Vol. 4, no 3, 365-380 p.
molecular quadrupole moment, birefringence, electric field gradient, electric dipole (hyper)polarizabilities, coupled cluster theory, relativistic effects, molecular vibrations
IdentifiersURN: urn:nbn:se:liu:diva-12696OAI: oai:DiVA.org:liu-12696DiVA: diva2:16870