Universität zu Köln

Brueckner, Charlotte, Walter, Christof, Stolte, Matthias, Braida, Benoit, Meerholz, Klaus ORCID: 0000-0001-7450-4672, Wuerthner, Frank and Engels, Bernd (2015). Structure-Property Relationships for Exciton and Charge Reorganization Energies of Dipolar Organic Semiconductors: A Combined Valence Bond Self-Consistent Field and Time-Dependent Hartree-Fock and DFT Study of Merocyanine Dyes. J. Phys. Chem. C, 119 (31). S. 17602 - 17612. WASHINGTON: AMER CHEMICAL SOC. ISSN 1932-7447

Full text not available from this repository.

Abstract

We present an analysis of the optoelectronic properties of merocyanine dyes by means of valence bond self-consistent field (VBSCF), time-dependent Hartree-Fock (TD-HF), density functional theory (DFT), and high-level ab initio calculations. The electronic structure of merocyanines can be described as a superposition of two resonance structures, a neutral one and a zwitterionic one. Calculated valence bond (VB) weights for these resonance structures demonstrate the importance of strong accepting groups when increasing the weight of the zwitterionic structures of different merocyanines. The dependence of exciton and charge reorganization energies on VB weights composition is analyzed, demonstrating that the special case of equal contributions of both structures, the so-called cyanine limit, goes along with minimal exciton and charge reorganization energies. For the latter, it is shown that the external (outer-sphere) reorganization energy plays a crucial role. Furthermore, a careful investigation of the excited-state behavior of merocyanines indicates that a possible excited-state torsion might be another important parameter for merocyanine-based optoelectronic devices, whereas internal (inner-sphere) charge reorganization energies of a variety of merocyanines are in a typical range for molecular semiconductors.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Brueckner, Charlotte UNSPECIFIED UNSPECIFIED UNSPECIFIED Walter, Christof UNSPECIFIED UNSPECIFIED UNSPECIFIED Stolte, Matthias UNSPECIFIED UNSPECIFIED UNSPECIFIED Braida, Benoit UNSPECIFIED UNSPECIFIED UNSPECIFIED Meerholz, Klaus UNSPECIFIED orcid.org/0000-0001-7450-4672 UNSPECIFIED Wuerthner, Frank UNSPECIFIED UNSPECIFIED UNSPECIFIED Engels, Bernd UNSPECIFIED UNSPECIFIED UNSPECIFIED
URN:	urn:nbn:de:hbz:38-396609
DOI:	10.1021/acs.jpcc.5b06206
Journal or Publication Title:	J. Phys. Chem. C
Volume:	119
Number:	31
Page Range:	S. 17602 - 17612
Date:	2015
Publisher:	AMER CHEMICAL SOC
Place of Publication:	WASHINGTON
ISSN:	1932-7447
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Physical Chemistry
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language DENSITY-FUNCTIONAL-THEORY; MOLECULAR-ORBITAL METHODS; BASIS-SETS; ELECTRIC-FIELD; STATE DYNAMICS; SPECTRA; DESIGN; PHTHALOCYANINE; FLUOROPHORES; SPECTROSCOPY Multiple languages Chemistry, Physical; Nanoscience & Nanotechnology; Materials Science, Multidisciplinary Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/39660