TY - JOUR

T1 - Ambiguities in Decomposing Molecular Polarizability into Atomic Charge Flow and Induced Dipole Contributions

AU - Mikkelsen, Jonas E.S.

AU - Jensen, Frank

N1 - Publisher Copyright:
© 2024 American Chemical Society

PY - 2024/5

Y1 - 2024/5

N2 - The molecular dipole polarizability can be decomposed into components corresponding to the charge flow between atoms and changes in atomic dipole moments. Such decompositions are recognized to depend on how atoms are defined within a molecule, as, for example, by Hirshfeld, iterative Stockholder, or quantum topology partitioning of the electron density. For some of these, however, there are significant differences between the numerical results obtained by analytical response methods and finite field calculations. We show that this difference is due to analytical response methods accounting for (only) the change in electron density by a perturbation, while finite field methods may also include a component corresponding to a perturbation-dependent change in the definition of an atom within a molecule. For some atom-in-molecule definitions, such as the iterative Hirshfeld, iterative Stockholder, and quantum topology methods, the latter effect significantly increases the charge flow component. The decomposition of molecular polarizability into atomic charge flow and induced dipole components thus depends on whether the atom-in-molecule definition is taken to be perturbation-dependent.

AB - The molecular dipole polarizability can be decomposed into components corresponding to the charge flow between atoms and changes in atomic dipole moments. Such decompositions are recognized to depend on how atoms are defined within a molecule, as, for example, by Hirshfeld, iterative Stockholder, or quantum topology partitioning of the electron density. For some of these, however, there are significant differences between the numerical results obtained by analytical response methods and finite field calculations. We show that this difference is due to analytical response methods accounting for (only) the change in electron density by a perturbation, while finite field methods may also include a component corresponding to a perturbation-dependent change in the definition of an atom within a molecule. For some atom-in-molecule definitions, such as the iterative Hirshfeld, iterative Stockholder, and quantum topology methods, the latter effect significantly increases the charge flow component. The decomposition of molecular polarizability into atomic charge flow and induced dipole components thus depends on whether the atom-in-molecule definition is taken to be perturbation-dependent.

UR - http://www.scopus.com/inward/record.url?scp=85193477866&partnerID=8YFLogxK

U2 - 10.1021/acs.jpca.4c01890

DO - 10.1021/acs.jpca.4c01890

M3 - Journal article

C2 - 38743593

AN - SCOPUS:85193477866

SN - 1089-5639

VL - 128

SP - 4168

EP - 4175

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 20

ER -