The Second-Order-Polarization-Propagator Approximation SOPPA in a Four Component Spinor Basis
Research output: Contribution to journal › Journal article › Research › peer-review
Standard
The Second-Order-Polarization-Propagator Approximation SOPPA in a Four Component Spinor Basis. / Schnack-Petersen, Anna Kristina; Simmermacher, Mats; Fasshauer, Elke; Jensen, Hans Jørgen Aagaard; Sauer, Stephan P. A.
In: The Journal of Chemical Physics, Vol. 152, 134113, 2020.Research output: Contribution to journal › Journal article › Research › peer-review
Harvard
APA
Vancouver
Author
Bibtex
}
RIS
TY - JOUR
T1 - The Second-Order-Polarization-Propagator Approximation SOPPA in a Four Component Spinor Basis
AU - Schnack-Petersen, Anna Kristina
AU - Simmermacher, Mats
AU - Fasshauer, Elke
AU - Jensen, Hans Jørgen Aagaard
AU - Sauer, Stephan P. A.
PY - 2020
Y1 - 2020
N2 - A theoretical framework for understanding molecular structures is crucial for the development of new technologies such as catalysts or solar cells. Apart from electronic excitations energies however, only spectroscopic properties of molecules consisting of lighter elements can be computationally described at high level of theory today, since heavy elements require a relativistic framework and most methods have only been derived in a non-relativistic one so far. Important new technologies like the above mentioned require molecules that contain heavier elements and hence there is a great need for the development of relativistic computational methods at higher level of accuracy. Here, the Second-Order-Polarization-Propagator-Approximation (SOPPA), which has proven very successful in the non-relativistic case, is adapted to a relativistic framework. The equations for SOPPA are presented in their most general form, i.e., in a non-canonical spin-orbital basis, which can be reduced to the canonical case, and the expressions needed for a relativistic four-component SOPPA are obtained. The equations are one-index transformed, giving more compact expressions that correspond to those already available for the four-component RPA. The equations are ready for implementation in a four-component quantum chemistry program, which will allow both linear response properties and excitation energies to be calculated relativistically at the SOPPA level.
AB - A theoretical framework for understanding molecular structures is crucial for the development of new technologies such as catalysts or solar cells. Apart from electronic excitations energies however, only spectroscopic properties of molecules consisting of lighter elements can be computationally described at high level of theory today, since heavy elements require a relativistic framework and most methods have only been derived in a non-relativistic one so far. Important new technologies like the above mentioned require molecules that contain heavier elements and hence there is a great need for the development of relativistic computational methods at higher level of accuracy. Here, the Second-Order-Polarization-Propagator-Approximation (SOPPA), which has proven very successful in the non-relativistic case, is adapted to a relativistic framework. The equations for SOPPA are presented in their most general form, i.e., in a non-canonical spin-orbital basis, which can be reduced to the canonical case, and the expressions needed for a relativistic four-component SOPPA are obtained. The equations are one-index transformed, giving more compact expressions that correspond to those already available for the four-component RPA. The equations are ready for implementation in a four-component quantum chemistry program, which will allow both linear response properties and excitation energies to be calculated relativistically at the SOPPA level.
KW - Faculty of Science
KW - second order polarization propagator approximation
KW - SOPPA
KW - Relativistic Effects
KW - linear response function
KW - Dirac equation
U2 - 10.1063/5.0002389
DO - 10.1063/5.0002389
M3 - Journal article
C2 - 32268739
VL - 152
JO - The Journal of Chemical Physics
JF - The Journal of Chemical Physics
SN - 0021-9606
M1 - 134113
ER -
ID: 237716025