TY  - JOUR
A1  - Röhr, Merle I. S.
A1  - Lisinetskaya, Polina G.
A1  - Mitric, Roland
T1  - Excitonic Properties of Ordered Metal Nanocluster Arrays: 2D Silver Clusters at Multiporphyrin Templates
JF  - Journal of Physical Chemistry A
N2  - The design of ordered arrays of metal nanoclusters such as for example 2D cluster organic frameworks might open a new route towards the development of materials with tailored optical properties. Such systems could serve as plasmonically enhanced light-harvesting materials, sensors or catalysts. We present here a theoretical approach for the simulation of the optical properties of ordered arrays of metal clusters that is based on the ab initio parametrized Frenkel exciton model. We demonstrate that small atomically precise silver clusters can be assembled in one- and two-dimensional arrays on suitably designed porphyrin templates exhibiting remarkable optical properties. By employing explicit TDDFT calculations on smaller homologs, we show that the intrinsic optical properties of metal clusters are largely preserved but undergo J- and H-type excitonic coupling that results in controllable splitting of their excited states.
Furthermore, ab initio parameterized Frenkel exciton model calculations allow us to predict an energetic splitting of up to 0.77 eV in extended two-dimensional square arrays and 0.79 eV in tilted square aggregates containing up to 25 cluster-porphyrin subunits.
KW  - Excitons
KW  - Porphyrin arrays
Y1  - 2016
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-159464
UR  - https://pubs.acs.org/doi/10.1021/acs.jpca.6b04243
N1  - Accepted version
VL  - 120
IS  - 26
ER  -