Computation of Electromagnetic Properties of Molecular Ensembles

Ivan Fernandez-Corbaton, Dominik Beutel, Carsten Rockstuhl, Ansgar Pausch, Wim Klopper

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

We outline a methodology for efficiently computing the electromagnetic response of molecular ensembles. The methodology is based on the link that we establish between quantum-chemical simulations and the transfer matrix (T-matrix) approach, a common tool in physics and engineering. We exemplify and analyze the accuracy of the methodology by using the time-dependent Hartree-Fock theory simulation data of a single chiral molecule to compute the T-matrix of a cross-like arrangement of four copies of the molecule, and then computing the circular dichroism of the cross. The results are in very good agreement with full quantum-mechanical calculations on the cross. Importantly, the choice of computing circular dichroism is arbitrary: Any kind of electromagnetic response of an object can be computed from its T-matrix. We also show, by means of another example, how the methodology can be used to predict experimental measurements on a molecular material of macroscopic dimensions. This is possible because, once the T-matrices of the individual components of an ensemble are known, the electromagnetic response of the ensemble can be efficiently computed. This holds for arbitrary arrangements of a large number of molecules, as well as for periodic or aperiodic molecular arrays. We identify areas of research for further improving the accuracy of the method, as well as new fundamental and technological research avenues based on the use of the T-matrices of molecules and molecular ensembles for quantifying their degrees of symmetry breaking. We provide T-matrix-based formulas for computing traditional chiro-optical properties like (oriented) circular dichroism, and also for quantifying electromagnetic duality and electromagnetic chirality. The formulas are valid for light-matter interactions of arbitrarily-high multipolar orders.
Original languageEnglish
Pages (from-to)878-887
JournalChemPhysChem
Volume21
Issue number9
DOIs
Publication statusPublished - 5 May 2020
Externally publishedYes

Funding

I.F.‐C. and C.R. gratefully acknowledge support by the VIRTMAT project at KIT. D.B. and C.R. gratefully acknowledge support by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany's Excellence Strategy via the Excellence Cluster 3D Matter Made to Order (EXC‐2082/1 – 390761711). A.P. is grateful to Fonds der chemischen Industrie and Studienstiftung des deutschen Volkes for funding. W.K. acknowledges support by the DFG Research Training Group 2450. I.F.-C. and C.R. gratefully acknowledge support by the VIRTMAT project at KIT. D.B. and C.R. gratefully acknowledge support by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany's Excellence Strategy via the Excellence Cluster 3D Matter Made to Order (EXC-2082/1 ? 390761711). A.P. is grateful to Fonds der chemischen Industrie and Studienstiftung des deutschen Volkes for funding. W.K. acknowledges support by the DFG Research Training Group 2450.

FundersFunder number
Fonds der chemischen Industrie and Studienstiftung des deutschen Volkes
Karlsruhe Institute of Technology
Deutsche ForschungsgemeinschaftEXC‐2082/1 – 390761711
Korea Institute of Toxicology
Studienstiftung des Deutschen Volkes

    Fingerprint

    Dive into the research topics of 'Computation of Electromagnetic Properties of Molecular Ensembles'. Together they form a unique fingerprint.

    Cite this