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2014 | Buch

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Excitation Energies and Properties of Open-Shell Singlet Molecules

Applications to a New Class of Molecules for Nonlinear Optics and Singlet Fission

verfasst von: Masayoshi Nakano

Verlag: Springer International Publishing

Buchreihe : SpringerBriefs in Molecular Science

Enthalten in: Springer Professional "Wirtschaft+Technik" , Springer Professional "Technik"

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Über dieses Buch

This brief investigates the diradical character, which is one of the ground-state chemical indices for "bond weakness" or "electron correlation" and which allows researchers to explore the origins of the electron-correlation-driven physico-chemical phenomena concerned with electronic, optical and magnetic properties as well as to control them in the broad fields of physics and chemistry. It then provides the theoretical fundamentals of ground and excited electronic structures of symmetric and asymmetric open-shell molecular systems by using model molecular systems. Moreover, it presents the theoretical design guidelines for a new class of open-shell singlet molecular systems for nonlinear optics (NLO) and singlet fission.

Inhaltsverzeichnis

Frontmatter

Chapter 1. Introduction

Abstract

The concept of “diradical character based design” for efficient functional substances is introduced using the dissociation process of a homodinuclear system. The diradical character, which is one of the quantum-chemically well-defined chemical indices and indicates the singlet open-shell nature, is employed for classification of arbitrary electronic structures into three categories, i.e., weak, intermediate and strong electron correlation regions. In this book, we present a simple relationship between diradical character and the ground/excited electronic structures, and illuminate that the systems in the intermediate diradical character region have the advantage of exhibiting highly efficient optoelectronic functionality. As examples, we show the diradical character based molecular design principles for highly efficient nonlinear optical (NLO) and singlet fission (SF) properties.

Masayoshi Nakano

Chapter 2. Electronic Structures of Symmetric Diradical Systems

Abstract

In general, the electronic structures of a molecular system is characterized by using the “diradical character”, which is well defined in quantum chemistry and implies a chemical index of a bond nature. In this chapter, we present analytical expressions for electronic energies and wavefunctions of the ground- and excited states as well as for the excitation energies and transition properties based on symmetric two-site diradical models with different diradical characters using the valence configuration interaction method.

Masayoshi Nakano

Chapter 3. Electronic Structures of Asymmetric Diradical Systems

Abstract

In this chapter, we present analytical expressions for electronic energies and wavefunctions of the ground and excited states as well as for the excitation energies and transition properties of asymmetric two-site diradical models as the functions of diradical character using the valence configuration interaction method. Such asymmetric diradical systems are realized by symmetric diradical molecules under static electric fields and/or by diradical molecules with asymmetric structures, e.g., donor-acceptor substituted diradicals. Several nondimensional physical factors concerned with “asymmetricity” are introduced in order to describe the electronic structures of these systems.

Masayoshi Nakano

Chapter 4. Diradical Character View of (Non)Linear Optical Properties

Abstract

In this chapter, we clarify the diradical character dependences of (hyper)polarizabilities, which are molecular origins of (non)linear optical responses, in static and resonant cases based on the diradical character dependences of excitation energies and properties of two-site symmetric and asymmetric diradical models with two electrons in two active orbitals. The analysis results highlight the differences of optical response properties between open-shell and closed-shell molecular systems, and contribute to the construction of novel molecular design guidelines for highly efficient nonlinear optical systems.

Masayoshi Nakano

Chapter 5. Diradical Character View of Singlet Fission

Abstract

Singlet fission is one of the internal conversion process in which a singlet exciton splits into two triplet excitons having long lifetimes. This phenomenon is expected to be useful for significantly improving the photoelectric conversion efficiency in organic photovoltaic cells. In this chapter, we present diradical character based molecular design guidelines for efficient singlet fission molecules based on the energy level matching conditions between the lowest singlet and triplet excited states, which are found to be described by the multiple diradical characters. A simple model, i.e., tetraradical hydrogen cluster, is investigated in order to reveal the multiple diradical character dependences of relative excitation energies and to build a diradical character based design guideline. On the basis of this guideline, several candidate molecules are proposed.

Masayoshi Nakano

Chapter 6. Summary and Future Prospects

Abstract

The diradical character based design principles for efficient functional substances—highly efficient open-shell singlet nonlinear optical (NLO) systems and singlet fission (SF) molecules—are summarized. The remaining problems to be solved for designing open-shell singlet NLO and SF materials are presented together with future possible extension of the present concept.

Masayoshi Nakano

Backmatter

Titel: Excitation Energies and Properties of Open-Shell Singlet Molecules
verfasst von: Masayoshi Nakano
Verlag: Springer International Publishing
Electronic ISBN: 978-3-319-08120-5
Print ISBN: 978-3-319-08119-9
DOI: https://doi.org/10.1007/978-3-319-08120-5

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