An ab initio investigation of the molecular properties rationalizing the electric-field-gradient induced birefringence (Buckingham effect) for Cl2 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 Cl2 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.
The molecular electric quadrupole moment and electric-field-gradient induced birefringence (Buckingham effect) of Cl2
CAPPELLI, Chiara;
2004
Abstract
An ab initio investigation of the molecular properties rationalizing the electric-field-gradient induced birefringence (Buckingham effect) for Cl2 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 Cl2 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.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
