Theoretical study of the relativistic molecular rotational g-tensor
An original formulation of the relativistic molecular rotational g-tensor valid for heavy atom containing compounds is presented. In such formulation, the relevant terms of a molecular Hamiltonian for non-relativistic nuclei and relativistic electrons in the laboratory system are considered. Terms l...
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2014
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| Acceso en línea: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00219606_v141_n19_p_Aucar http://hdl.handle.net/20.500.12110/paper_00219606_v141_n19_p_Aucar |
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paper:paper_00219606_v141_n19_p_Aucar2023-06-08T14:44:26Z Theoretical study of the relativistic molecular rotational g-tensor Density functional theory Hamiltonians Perturbation techniques Relativity Tensors Molecular Hamiltonian Molecular parameters Molecular properties Perturbation theory Relativistic effects Relativistic electron Susceptibility tensors Uniform magnetic fields Atoms An original formulation of the relativistic molecular rotational g-tensor valid for heavy atom containing compounds is presented. In such formulation, the relevant terms of a molecular Hamiltonian for non-relativistic nuclei and relativistic electrons in the laboratory system are considered. Terms linear and bilinear in the nuclear rotation angular momentum and an external uniform magnetic field are considered within first and second order (relativistic) perturbation theory to obtain the rotational g-tensor. Relativistic effects are further analyzed by carrying out the linear response within the elimination of the small component expansion. Quantitative results for model systems HX (X=F, Cl, Br, I), XF (X=Cl, Br, I), and YH+ (Y=Ne, Ar, Kr, Xe, Rn) are obtained both at the RPA and density functional theory levels of approximation. Relativistic effects are shown to be small for this molecular property. The relation between the rotational g-tensor and susceptibility tensor which is valid in the non-relativistic theory does not hold within the relativistic framework, and differences between both molecular parameters are analyzed for the model systems under study. It is found that the non-relativistic relation remains valid within 2% even for the heavy HI, IF, and XeH+ systems. Only for the sixth-row Rn atom a significant deviation of this relation is found. © 2014 AIP Publishing LLC. 2014 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00219606_v141_n19_p_Aucar http://hdl.handle.net/20.500.12110/paper_00219606_v141_n19_p_Aucar |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Density functional theory Hamiltonians Perturbation techniques Relativity Tensors Molecular Hamiltonian Molecular parameters Molecular properties Perturbation theory Relativistic effects Relativistic electron Susceptibility tensors Uniform magnetic fields Atoms |
| spellingShingle |
Density functional theory Hamiltonians Perturbation techniques Relativity Tensors Molecular Hamiltonian Molecular parameters Molecular properties Perturbation theory Relativistic effects Relativistic electron Susceptibility tensors Uniform magnetic fields Atoms Theoretical study of the relativistic molecular rotational g-tensor |
| topic_facet |
Density functional theory Hamiltonians Perturbation techniques Relativity Tensors Molecular Hamiltonian Molecular parameters Molecular properties Perturbation theory Relativistic effects Relativistic electron Susceptibility tensors Uniform magnetic fields Atoms |
| description |
An original formulation of the relativistic molecular rotational g-tensor valid for heavy atom containing compounds is presented. In such formulation, the relevant terms of a molecular Hamiltonian for non-relativistic nuclei and relativistic electrons in the laboratory system are considered. Terms linear and bilinear in the nuclear rotation angular momentum and an external uniform magnetic field are considered within first and second order (relativistic) perturbation theory to obtain the rotational g-tensor. Relativistic effects are further analyzed by carrying out the linear response within the elimination of the small component expansion. Quantitative results for model systems HX (X=F, Cl, Br, I), XF (X=Cl, Br, I), and YH+ (Y=Ne, Ar, Kr, Xe, Rn) are obtained both at the RPA and density functional theory levels of approximation. Relativistic effects are shown to be small for this molecular property. The relation between the rotational g-tensor and susceptibility tensor which is valid in the non-relativistic theory does not hold within the relativistic framework, and differences between both molecular parameters are analyzed for the model systems under study. It is found that the non-relativistic relation remains valid within 2% even for the heavy HI, IF, and XeH+ systems. Only for the sixth-row Rn atom a significant deviation of this relation is found. © 2014 AIP Publishing LLC. |
| title |
Theoretical study of the relativistic molecular rotational g-tensor |
| title_short |
Theoretical study of the relativistic molecular rotational g-tensor |
| title_full |
Theoretical study of the relativistic molecular rotational g-tensor |
| title_fullStr |
Theoretical study of the relativistic molecular rotational g-tensor |
| title_full_unstemmed |
Theoretical study of the relativistic molecular rotational g-tensor |
| title_sort |
theoretical study of the relativistic molecular rotational g-tensor |
| publishDate |
2014 |
| url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00219606_v141_n19_p_Aucar http://hdl.handle.net/20.500.12110/paper_00219606_v141_n19_p_Aucar |
| _version_ |
1768542112572243968 |