Publication

Relevance of effective bond orders in heterodiatomic molecules and role of the spin-orbit coupling in the AtX (X = At - F) series

Pech, C. G., Haase, P. A. B., Galland, N., Borschevsky, A. & Maurice, R., 30-Sep-2019, In : Physical Review A. 100, 3, 8 p., 032518.

Research output: Contribution to journalArticleAcademicpeer-review

APA

Pech, C. G., Haase, P. A. B., Galland, N., Borschevsky, A., & Maurice, R. (2019). Relevance of effective bond orders in heterodiatomic molecules and role of the spin-orbit coupling in the AtX (X = At - F) series. Physical Review A, 100(3), [032518]. https://doi.org/10.1103/PhysRevA.100.032518

Author

Pech, Cecilia Gomez ; Haase, Pi A. B. ; Galland, Nicolas ; Borschevsky, Anastasia ; Maurice, Remi. / Relevance of effective bond orders in heterodiatomic molecules and role of the spin-orbit coupling in the AtX (X = At - F) series. In: Physical Review A. 2019 ; Vol. 100, No. 3.

Harvard

Pech, CG, Haase, PAB, Galland, N, Borschevsky, A & Maurice, R 2019, 'Relevance of effective bond orders in heterodiatomic molecules and role of the spin-orbit coupling in the AtX (X = At - F) series', Physical Review A, vol. 100, no. 3, 032518. https://doi.org/10.1103/PhysRevA.100.032518

Standard

Relevance of effective bond orders in heterodiatomic molecules and role of the spin-orbit coupling in the AtX (X = At - F) series. / Pech, Cecilia Gomez; Haase, Pi A. B.; Galland, Nicolas; Borschevsky, Anastasia; Maurice, Remi.

In: Physical Review A, Vol. 100, No. 3, 032518, 30.09.2019.

Research output: Contribution to journalArticleAcademicpeer-review

Vancouver

Pech CG, Haase PAB, Galland N, Borschevsky A, Maurice R. Relevance of effective bond orders in heterodiatomic molecules and role of the spin-orbit coupling in the AtX (X = At - F) series. Physical Review A. 2019 Sep 30;100(3). 032518. https://doi.org/10.1103/PhysRevA.100.032518


BibTeX

@article{f9f809289c33431d8f436cb9cb7ce07d,
title = "Relevance of effective bond orders in heterodiatomic molecules and role of the spin-orbit coupling in the AtX (X = At - F) series",
abstract = "Scalar and spin-dependent relativistic effects can influence the geometries and wave functions of the ground and excited states of molecular systems in a way that is not always trivial. However, it is still common for researchers, in particular within the quantum chemistry community, to neglect the spin-dependent effects while discussing the binding between atoms in heavy-element systems. Within multiconfigurational self-consistent field frameworks, the binding in diatomic molecules can be derived from the occupation of the natural orbitals, which by definition form a basis that diagonalizes the one-body density matrix. This does not fully prevent arbitrariness, and the first objective of the present paper will be to review the concept of effective bond order, in particular with respect to the rounding up rule. Then, the respective roles of the scalar and the spin-dependent relativistic effects on the bond lengths are investigated by means of state-of-the-art nonrelativistic, scalarrelativistic, and exact two-component coupled-cluster calculations, providing reference molecular geometries for the whole AtX (X = At - F) series. A diagnostic of relevance for defining effective bond orders in heterodiatomic molecules is introduced and applied to this series, showing that the more dissymmetric the system, the less defined the effective bond order is. Finally, the role of the spin-orbit coupling on the effective bond orders is discussed. AtI appears as a key intermediate in the series in terms of the ground-state pi bonding or antibonding character. Although emphasis will be put on ground states, the present methodology is readily applicable to the description of excited states.",
keywords = "STATE PERTURBATION-THEORY, BASIS-SETS, ELECTRONIC-STRUCTURE, MAGNETIC-PROPERTIES, NATURAL ORBITALS, QUANTUM-THEORY, COMPLEXES, IMPLEMENTATION, ASTATINE, METAL",
author = "Pech, {Cecilia Gomez} and Haase, {Pi A. B.} and Nicolas Galland and Anastasia Borschevsky and Remi Maurice",
year = "2019",
month = "9",
day = "30",
doi = "10.1103/PhysRevA.100.032518",
language = "English",
volume = "100",
journal = "Physical Review A",
issn = "1050-2947",
publisher = "AMER PHYSICAL SOC",
number = "3",

}

RIS

TY - JOUR

T1 - Relevance of effective bond orders in heterodiatomic molecules and role of the spin-orbit coupling in the AtX (X = At - F) series

AU - Pech, Cecilia Gomez

AU - Haase, Pi A. B.

AU - Galland, Nicolas

AU - Borschevsky, Anastasia

AU - Maurice, Remi

PY - 2019/9/30

Y1 - 2019/9/30

N2 - Scalar and spin-dependent relativistic effects can influence the geometries and wave functions of the ground and excited states of molecular systems in a way that is not always trivial. However, it is still common for researchers, in particular within the quantum chemistry community, to neglect the spin-dependent effects while discussing the binding between atoms in heavy-element systems. Within multiconfigurational self-consistent field frameworks, the binding in diatomic molecules can be derived from the occupation of the natural orbitals, which by definition form a basis that diagonalizes the one-body density matrix. This does not fully prevent arbitrariness, and the first objective of the present paper will be to review the concept of effective bond order, in particular with respect to the rounding up rule. Then, the respective roles of the scalar and the spin-dependent relativistic effects on the bond lengths are investigated by means of state-of-the-art nonrelativistic, scalarrelativistic, and exact two-component coupled-cluster calculations, providing reference molecular geometries for the whole AtX (X = At - F) series. A diagnostic of relevance for defining effective bond orders in heterodiatomic molecules is introduced and applied to this series, showing that the more dissymmetric the system, the less defined the effective bond order is. Finally, the role of the spin-orbit coupling on the effective bond orders is discussed. AtI appears as a key intermediate in the series in terms of the ground-state pi bonding or antibonding character. Although emphasis will be put on ground states, the present methodology is readily applicable to the description of excited states.

AB - Scalar and spin-dependent relativistic effects can influence the geometries and wave functions of the ground and excited states of molecular systems in a way that is not always trivial. However, it is still common for researchers, in particular within the quantum chemistry community, to neglect the spin-dependent effects while discussing the binding between atoms in heavy-element systems. Within multiconfigurational self-consistent field frameworks, the binding in diatomic molecules can be derived from the occupation of the natural orbitals, which by definition form a basis that diagonalizes the one-body density matrix. This does not fully prevent arbitrariness, and the first objective of the present paper will be to review the concept of effective bond order, in particular with respect to the rounding up rule. Then, the respective roles of the scalar and the spin-dependent relativistic effects on the bond lengths are investigated by means of state-of-the-art nonrelativistic, scalarrelativistic, and exact two-component coupled-cluster calculations, providing reference molecular geometries for the whole AtX (X = At - F) series. A diagnostic of relevance for defining effective bond orders in heterodiatomic molecules is introduced and applied to this series, showing that the more dissymmetric the system, the less defined the effective bond order is. Finally, the role of the spin-orbit coupling on the effective bond orders is discussed. AtI appears as a key intermediate in the series in terms of the ground-state pi bonding or antibonding character. Although emphasis will be put on ground states, the present methodology is readily applicable to the description of excited states.

KW - STATE PERTURBATION-THEORY

KW - BASIS-SETS

KW - ELECTRONIC-STRUCTURE

KW - MAGNETIC-PROPERTIES

KW - NATURAL ORBITALS

KW - QUANTUM-THEORY

KW - COMPLEXES

KW - IMPLEMENTATION

KW - ASTATINE

KW - METAL

U2 - 10.1103/PhysRevA.100.032518

DO - 10.1103/PhysRevA.100.032518

M3 - Article

VL - 100

JO - Physical Review A

JF - Physical Review A

SN - 1050-2947

IS - 3

M1 - 032518

ER -

ID: 118184055