Dipolar group polarizability as a multipurpose tool for predicting molecular and bulk properties

Anna Krawczuk

Institute of Inorganic Chemistry, Georg-August University, Göttingen, Tammanstrasse 4, 37077 Göttingen, Germany

anna.krawczuk@uni-goettingen.de

The extraction of functional-group properties in condensed matter is very useful for predicting material’s behaviors, including those of biomaterials. For example, when one extracts information on functional-group dipole moments and distributed polarizabilities it is possible to predict electrostatic and electronic properties with reasonably high accuracy. Some time ago, together with my international colleagues, we proposed a build-up of a group polarizability database towards efficient fast screening of materials with potential linear optical properties such as high refractive index materials.[^1] The idea of having a database for building blocks, extracted from small molecules, is particularly useful, due to well-known transferability of the mentioned properties. The building blocks can be easily recombined, allowing the estimation of properties of much bigger systems, such as proteins. In order to harvest functional-groups properties from molecules, hence enabling the creation of the database, a partitioning scheme must be used to cut the electron density into smaller fragments. Despite many available methods special attention is given to the QTAIM hard-space partitioning introduced by Bader. It provides unique atomic boundaries and a possibility to determine origin-independent dipole moments, being very useful when exportable properties are desired. Details on the procedure are given in our earlier works and have been implemented into PolaBer software. ^{[2], [3]}

Here I will present a general overview on the distributed polarizabilities concept, including definition bond polarizability and its application towards reactivity of molecules. I will also discuss application of atomic polarizability towards prediction of electrical and optical properties of crystalline materials such as susceptibility or refractive index. Finally, I will focus on the polarizability database, GruPol and its utilization in prediction of molecular dipole moment and electrostatic potential.^[4]

[1] M. Ernst, L. H.R. Dos Santos, A. Krawczuk, P. Macchi. “Towards a Generalized Database of Atomic Polarizabilities”. In: Understanding Intermolecular Interactions in the Solid State: Approaches and Techniques. Ed. by D. Chopra. London: RSC, 2019, 7, 211.

[2] A. Krawczuk, D. Perez, P. Macchi J. Appl. Cryst. 2014, 57, 1452

[3] L.H.R. Dos Santos, A. Krawczuk, P. Macchi. J. Phys. Chem. 2015, 119, 3285; P. Macchi, A. Krawczuk Comput. Theor. Chem. 2015, 1053, 165; A. Jabłuszewska, A. Krawczuk, L.H.R. Dos Santos, P. Macchi ChemPhysChem 2020, 21, 2155; R.F. Ligorio, A. Krawczuk, L.H.R. Dos Santos J. Phys. Chem. A 2020, 124. 10008

[4] R.F. Ligorio, J.L. Rodrigues, A. Zuev, L.H.R. Dos Santos, A. Krawczuk, Phys. Chem. Chem. Phys. 2022, 24, 29495