A new molecular theory of field gradient induced birefringence used for measuring electric quadrupole moments

Imrie, D. A.; Raab, R. E.

doi:10.1080/00268979100102611

Cited by 46 publications

(11 citation statements)

References 17 publications

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“…[23], the Buckingham birefringence of solvated molecules was investigated, thereby assessing the ability of our approach to simulate the effect of the environment. Our studies of carbon monoxide, nitrous oxide and carbonyl sulfide [14,15] have resolved a controversy regarding the semiclassical theory of Buckingham birefringence [4,24], supporting [25][26][27] the original derivation by Buckingham and Longuet-Higgins [4]. The dependence of Buckingham birefringence on the density for helium, neon and argon was analyzed in Ref.…”

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confidence: 61%

Relativistic four-component calculations of Buckingham birefringence using London atomic orbitals

et al. 2011

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We present the first relativistic study of the electric-field-gradient induced birefringence (Buckingham birefringence), with application to the series of molecules CX 2 (X = O, S, Se, Te). A recently developed atomicorbital-driven scheme for the calculation of time-dependent molecular properties using one-, two-and four-component relativistic wave functions (Bast et al. in Chem Phys 356:177, 2009) is extended to first-order frequencydependent magnetic-field perturbations, using London atomic orbitals to ensure gauge-origin independent results and to improve basis-set convergence. Calculations are presented at the Hartree-Fock and Kohn-Sham levels of theory and results for CO 2 and CS 2 are compared with previous high-level coupled-cluster calculations. Except for the heaviest member of the series, relativistic effects are small-in particular for the temperature-independent contribution to the birefringence. By contrast, the effects of electron correlation are significant. However, the reliability of standard exchange-correlation functionals in describing Buckingham birefringence remains unclear based on the comparison with high-level coupled-cluster singles-anddoubles calculations.

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confidence: 61%

Relativistic four-component calculations of Buckingham birefringence using London atomic orbitals

et al. 2011

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“…To understand the theory of the Buckingham effect requires some background knowledge of the relevant molecular properties [2,11,14]. To assist the reader we first provide a brief account of them.…”

Section: Introductionmentioning

confidence: 99%

“…Quantum-mechanical expressions have been derived for the seven tensors in (1) and (5), from which multipole orders and intrinsic symmetries may be deduced [2,11,14] electric dipole : ð¼ Þ, ð¼ Þ ð11Þ…”

Section: Introductionmentioning

confidence: 99%

On the theory of the Buckingham effect

Lange

Raab

2006

Molecular Physics

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We apply general arguments (based on spatial transformation properties, intrinsic symmetry and dimensional analysis) to the theory of the Buckingham effect (electric-field-gradientinduced birefringence in a gas). These yield, in a simple manner, the temperature-dependent and temperature-independent terms in the birefringence (each to within a numerical factor), and also the expression, derived by Buckingham and Longuet-Higgins, for the effective quadrupole centre of a molecule. We show in addition how the calculation of the two numerical factors can be simplified in our approach.

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“…The "Buckingham constant" m Q͑ , T͒ connects the anisotropy of the refractive index to the strength of the EFG and to the microscopic properties of the gas. [45][46][47] For an axial molecule,…”

Section: 25mentioning

confidence: 99%

A computational study of some electric and magnetic properties of gaseous BF3 and BCl3

Rizzo

Cappelli

Junquera‐Hernández

et al. 2005

The Journal of Chemical Physics

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We present the results of an extended computational study of the electric and magnetic properties connected to Cotton-Mouton birefringences, on the trifluoro-and trichloroborides in the gas phase. The electric dipole polarizabilities, magnetizabilities, quadrupole moments, and higher-order hypersusceptibilities-expressed as quadratic and cubic frequency-dependent response functionsare computed within Hartree-Fock, density-functional, and coupled-cluster response theories employing singly and doubly augmented correlation-consistent basis sets and London orbitals in the magnetic property calculations. The results, which illustrate the capability of time-dependent density-functional theory for electron-rich systems, are compared with available experimental data. Revised values of both experimentally derived quadrupole moment of BF 3 , 2.72± 0.15 a . u., and magnetizability anisotropy of BCl 3 , −0.45± 0.09 a . u., both obtained in birefringence experiments that neglect the effects of higher-order hypersusceptibilities, are presented. In the theoretical limit the traceless quadrupole moments of BF 3 and BCl 3 are determined to be 3.00± 0.01 and 0.71± 0.01 a . u., respectively.

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A new molecular theory of field gradient induced birefringence used for measuring electric quadrupole moments

Cited by 46 publications

References 17 publications

Relativistic four-component calculations of Buckingham birefringence using London atomic orbitals

Relativistic four-component calculations of Buckingham birefringence using London atomic orbitals

On the theory of the Buckingham effect

A computational study of some electric and magnetic properties of gaseous BF3 and BCl3

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