Abstract
This article proposes a gauge-origin independent formalism of the nuclear magnetic shielding constant in the two-component relativistic framework based on the unitary transformation. The proposed scheme introduces the gauge factor and the unitary transformation into the atomic orbitals. The two-component relativistic equation is formulated by block-diagonalizing the Dirac Hamiltonian together with gauge factors. This formulation is available for arbitrary relativistic unitary transformations. Then, the infinite-order Douglas-Kroll-Hess (IODKH) transformation is applied to the present formulation. Next, the analytical derivatives of the IODKH Hamiltonian for the evaluation of the nuclear magnetic shielding constant are derived. Results obtained from the numerical assessments demonstrate that the present formulation removes the gauge-origin dependence completely. Furthermore, the formulation with the IODKH transformation gives results that are close to those in four-component and other two-component relativistic schemes.
| Original language | English |
|---|---|
| Article number | 114109 |
| Journal | Journal of Chemical Physics |
| Volume | 148 |
| Issue number | 11 |
| DOIs | |
| Publication status | Published - 2018 Mar 21 |
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ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry
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Gauge-origin independent formalism of two-component relativistic framework based on unitary transformation in nuclear magnetic shielding constant. / Hayami, Masao; Seino, Junji; Nakai, Hiromi.
In: Journal of Chemical Physics, Vol. 148, No. 11, 114109, 21.03.2018.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Gauge-origin independent formalism of two-component relativistic framework based on unitary transformation in nuclear magnetic shielding constant
AU - Hayami, Masao
AU - Seino, Junji
AU - Nakai, Hiromi
PY - 2018/3/21
Y1 - 2018/3/21
N2 - This article proposes a gauge-origin independent formalism of the nuclear magnetic shielding constant in the two-component relativistic framework based on the unitary transformation. The proposed scheme introduces the gauge factor and the unitary transformation into the atomic orbitals. The two-component relativistic equation is formulated by block-diagonalizing the Dirac Hamiltonian together with gauge factors. This formulation is available for arbitrary relativistic unitary transformations. Then, the infinite-order Douglas-Kroll-Hess (IODKH) transformation is applied to the present formulation. Next, the analytical derivatives of the IODKH Hamiltonian for the evaluation of the nuclear magnetic shielding constant are derived. Results obtained from the numerical assessments demonstrate that the present formulation removes the gauge-origin dependence completely. Furthermore, the formulation with the IODKH transformation gives results that are close to those in four-component and other two-component relativistic schemes.
AB - This article proposes a gauge-origin independent formalism of the nuclear magnetic shielding constant in the two-component relativistic framework based on the unitary transformation. The proposed scheme introduces the gauge factor and the unitary transformation into the atomic orbitals. The two-component relativistic equation is formulated by block-diagonalizing the Dirac Hamiltonian together with gauge factors. This formulation is available for arbitrary relativistic unitary transformations. Then, the infinite-order Douglas-Kroll-Hess (IODKH) transformation is applied to the present formulation. Next, the analytical derivatives of the IODKH Hamiltonian for the evaluation of the nuclear magnetic shielding constant are derived. Results obtained from the numerical assessments demonstrate that the present formulation removes the gauge-origin dependence completely. Furthermore, the formulation with the IODKH transformation gives results that are close to those in four-component and other two-component relativistic schemes.
UR - http://www.scopus.com/inward/record.url?scp=85044202633&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85044202633&partnerID=8YFLogxK
U2 - 10.1063/1.5016581
DO - 10.1063/1.5016581
M3 - Article
AN - SCOPUS:85044202633
VL - 148
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
SN - 0021-9606
IS - 11
M1 - 114109
ER -