Optical Spectra of Oligofurans. A Theoretical Approach to the Transition Energies, Reorganization Energies, and the Vibronic Activity

There is experimental evidence of high vibronic activity that accompanies the strongly allowed transition between the ground state and the lowest electronic singlet excited state of oligofurans that contain 2,3, and 4 furan rings. The absorption and emission spectra of the three lowest oligofurans measured in liquid nitrogen temperature show distinct fine structures that are reproduced using the projection-based model of vibronic coupling (with Dushinsky rotation included) parameterized utilizing either DFT (with several different exchange-correlation functionals) or ab initio (CC2) quantum chemistry calculations. Using as reference the experimental data concerning the electronic absorption and fluorescence for the 8 lowest oligofurans we first analyze the performance of the exchange-correlation functionals for the electronic transition energies and the reorganization energies. Subsequently, we use the best functionals alongside the CC2 method to explore how the reorganization energies are distributed among the totally symmetric vibrations, identify the normal modes that dominate in the fine structures present in the absorption and emission bands, and trace their evolution with the increasing number of rings in the oligofuran series. Confrontation of the simulated spectra with the experiment allows for verification of the performance of the selected DFT functionals and the CC2 method.

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Optical Spectra of Oligofurans: A Theoretical Approach to the Transition Energies, Reorganization Energies, and the Vibronic Activity

Molecules ◽

10.3390/molecules26237163 ◽

2021 ◽

Vol 26 (23) ◽

pp. 7163

Author(s):

Karolina Filipowska ◽

Marek T. Pawlikowski ◽

Marcin Andrzejak

Keyword(s):

Density Functional ◽

Normal Modes ◽

Emission Spectra ◽

Liquid Nitrogen Temperature ◽

Transition Energies ◽

Absorption And Emission ◽

Exchange Correlation ◽

Quantum Chemistry Calculations ◽

Fine Structures ◽

Reorganization Energies

There is experimental evidence of high vibronic activity that accompanies the allowed transition between the ground state and the lowest electronic singlet excited state of oligofurans that contain two, three, and four furan rings. The absorption and emission spectra of the three lowest oligofurans measured at liquid nitrogen temperature show distinct fine structures that are reproduced using the projection-based model of vibronic coupling (with Dushinsky rotation included) parameterized utilizing either Density Functional Theory (DFT, with several different exchange-correlation functionals) or ab initio (CC2) quantum chemistry calculations. Using as a reference the experimental data concerning the electronic absorption and fluorescence for the eight lowest oligofurans, we first analyzed the performance of the exchange-correlation functionals for the electronic transition energies and the reorganization energies. Subsequently, we used the best functionals alongside with the CC2 method to explore how the reorganization energies are distributed among the totally symmetric vibrations, identify the normal modes that dominate in the fine structures present in the absorption and emission bands, and trace their evolution with the increasing number of rings in the oligofuran series. Confrontation of the simulated spectra with the experiment allows for the verification of the performance of the selected DFT functionals and the CC2 method.

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Analysis of Charge-Transfer Absorption and Emission Spectra on an Absolute Scale: Evaluation of Free Energies, Matrix Elements, and Reorganization Energies

The Journal of Physical Chemistry A ◽

10.1021/jp052532d ◽

2005 ◽

Vol 109 (38) ◽

pp. 8572-8578 ◽

Cited By ~ 5

Author(s):

Dustin Levy ◽

Bradley R. Arnold

Keyword(s):

Charge Transfer ◽

Emission Spectra ◽

Matrix Elements ◽

Free Energies ◽

Absorption And Emission ◽

Scale Evaluation ◽

Absorption And Emission Spectra ◽

Absolute Scale ◽

Reorganization Energies

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Studies on the Effectes of XC Functionals and Basis Sets on the Geometrical Structures, Absorption and Emission Spectra of a 1,8-naphthalimide Derivative

Advanced Materials Research ◽

10.4028/www.scientific.net/amr.904.195 ◽

2014 ◽

Vol 904 ◽

pp. 195-199

Author(s):

Yuan Fang Hu ◽

Guang Hua Nie

Keyword(s):

Density Functional ◽

Emission Spectra ◽

Electron Transition ◽

Basis Set ◽

Basis Sets ◽

Property A ◽

Geometrical Structures ◽

Transition Energies ◽

Absorption And Emission ◽

Polarizable Continuum

N-Hexyl-4-(thiophen-2-yl)-1,8-naphthalimide (HTNI) is one of the 1,8-naphthalimide derivatives with excellent fluorescence property. A scheme of time-dependent density functional theory (TDDFT) and configuration interaction singles (CIS) approach in conjunction with polarizable continuum models (PCMs) are employed to make a detailed investigation of the emitting energy. The transition energies of absorption and emission are computed using five exchange-correlation (XC) functionals, B3LYP, PBE0, M06, CAM-B3LYP, and wB97XD as well as 6-31G* and 6-31+G* basis sets. The results show that the predicted emitting energies as well as the absorption ones are dominated mainly by XC functional to be used. By comparing the calculated electron transition energies to experimental observations, it is found that PBE0 functional in combination with 6-31G* basis set is the best method to reproduce the experimental spectra of HTNI.

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Push-pull effect on the geometrical, optical and charge transfer properties of disubstituted derivatives of mer-tris(4-hydroxy-1,5-naphthyridinato) aluminum (mer-AlND3)

Open Chemistry ◽

10.1515/chem-2016-0001 ◽

2016 ◽

Vol 14 (1) ◽

pp. 20-32 ◽

Cited By ~ 2

Author(s):

Joshi Laxmikanth Rao ◽

Kotamarthi Bhanuprakash

Keyword(s):

Molecular Orbital ◽

High Mobility ◽

Emission Spectra ◽

Blue Shift ◽

Pyridyl Ring ◽

Type I ◽

Type Ii ◽

Absorption And Emission ◽

Absorption And Emission Spectra ◽

Reorganization Energies

AbstractTo design innovative and novel optical materials with high mobility, two kinds of disubstituted derivatives for mer-tris(4-hydroxy-1,5-naphthyridinato) aluminum (mer-AlND3) with push (EDG)–pull (EWG) substituents have been designed. The structures of mer-tris(8-EDG-2-EWG-4-hydroxy-1,5-naphthyridinato) aluminum (type I) and mer-tris(8-EWG-2-EDG-4-hydroxy-1,5-naphthyridinato) aluminum (type II) in the ground and first excited states have been optimized at the B3LYP/6-31G(D) and CIS/6-31G(D) level of theory, respectively. It can be seen from frontier molecular orbitals analysis, in all these complexes, the highest occupied molecular orbital (HOMO) is localized on the pyridine-4-ol ring of A-ligand while lowest unoccupied molecular orbital (LUMO) is on the pyridyl ring of B-ligand in ground state irrespective of electron donor/acceptor substitution present on the ligands similar to that of mer-tris(8-hydroxyquinoline) aluminum (mer-Alq3) and parent mer-AlND3.The absorption and emission wavelengths have been evaluated at the TD-PBE0/6-31G(D) level and it can be see that all the type I derivatives show blue shift while most of the type II derivatives show red shift compared to mer-AlND3. All the disubstituted complexes have showed hypsochromic shifts in both the absorption and emission spectra when compared with the calculated absorption and emission spectra respectively of mer-Alq3. It can be seen that the reorganization energies of some of the disubstituted derivatives are comparable with mer-Alq3 and these derivatives might be good candidates for emitting materials in OLED.

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Theoretical Study of Optical and Electronic Properties of Unsymmetrical Dendritic Molecules with Different Bridge Moieties

Australian Journal of Chemistry ◽

10.1071/ch11114 ◽

2011 ◽

Vol 64 (11) ◽

pp. 1475 ◽

Cited By ~ 3

Author(s):

Yanling Wang ◽

Qiang Peng ◽

Ying Liang ◽

Benlin Li ◽

Weiguo Zhu

Keyword(s):

Electronic Properties ◽

Emission Spectra ◽

Polarizable Continuum Model ◽

Excitation Energies ◽

Light Emitting ◽

Absorption And Emission ◽

Optical And Electronic Properties ◽

Structural And Electronic Properties ◽

Reorganization Energies ◽

Polarizable Continuum

Molecules bearing polyphenylphenyl dendrons show great potential for applications in organic light-emitting diodes. In this paper, quantum-chemical calculations have been applied to investigate the structural and electronic properties of typical molecules bearing polyphenylphenyl dendrons, 2-(2′,3′,4′,5′-tetraphenyl)phenyl-5-(p-N,N-dimethyl)phenyl pyridine (A), 1-(2′,3′,4′,5′-tetraphenyl)phenyl-4-(p-N,N-dimethyl)phenyl benzene (B), 2-(2′,3′,4′,5′-tetraphenyl)phenyl-5-(p-N,N-dimethyl)phenyl thiophene (C), 1-(2′,3′,4′,5′-tetraphenyl)phenyl-2,5-dimethoxy-4-(p-N,N-dimethyl)phenyl benzene (D), and 2-(2′,3′,4′,5′-tetraphenyl)phenyl-5-(p-N,N-dimethyl)phenyl furan (E). The geometrical and electronic structures in the ground state and lowest singlet excited states have been optimized by B3LYP/6-31G(d) and TD-B3LYP/6-31G(d) methods, respectively. The important parameters, including ionization potential (IP), electron affinity, the reorganization energies (λ), hole extraction potential, and electron extraction potential, first lowest singlet excitation energies, maximum absorption and emission wavelengths are also systematically investigated. The result implied that the HOMO, energy gaps, and IP are affected by the central aromatic ring in the order of phenylene>pyrryl> 2,5-dimethoxyphenylene>thienyl>furyl. The solvent effects on absorption and emission spectra were further examined using the polarizable continuum model.

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THEORY OF COHERENT RESONANT ABSORPTION AND EMISSION AT INFRARED AND OPTICAL FREQUENCIES

Canadian Journal of Physics ◽

10.1139/p67-142 ◽

1967 ◽

Vol 45 (5) ◽

pp. 1833-1859 ◽

Cited By ~ 30

Author(s):

Helen Freedhoff ◽

J. Van Kranendonk

Keyword(s):

Three Dimensional ◽

Normal Modes ◽

Emission Spectra ◽

Dipole Interaction ◽

Resonant Absorption ◽

Spin Model ◽

Absorption And Emission ◽

Lorentz Oscillator ◽

Optical Region ◽

A Chain

The theory of the line shape in coherent resonant absorption and emission in the infrared and optical region is developed. The Dicke spin model and the Lorentz oscillator model of a radiating molecule are discussed in detail, and the complications arising for degenerate levels are analyzed. The absorption and emission spectra are expressed in terms of the damped normal modes of the system of equivalent oscillators interacting via the retarded dipole–dipole interaction, and the results are shown to be identical with those derived using Heitler's quantum theory of radiation damping. The theory is applied to small clusters and linear chains of molecules. For a chain that is small compared with the wavelength, the natural line width is proportional to the total number of molecules, whereas for a long chain the width approaches a constant value. The discussion of three-dimensional systems, and the application to the zero-phonon lines in the infrared spectrum of solid hydrogen will be given in a separate paper.

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Electronic transition energies for a contact ion pair (CCl+3·Cl- of C2v-symmetry: An ab initio CI study

International Journal of Radiation Applications and Instrumentation Part C Radiation Physics and Chemistry ◽

10.1016/1359-0197(88)90024-0 ◽

1988 ◽

Vol 32 (1) ◽

pp. 117-119

Author(s):

Tae-Kyu Ha ◽

Rolf E. Bühler

Keyword(s):

Ab Initio ◽

Electronic Transition ◽

Ion Pair ◽

Transition Energies ◽

Contact Ion Pair ◽

Electronic Transition Energies

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Aromaticity and photophysics of tetrasila- and tetragerma-annelated tetrathienylenes as new representatives of the hetero[8]circulene family

Physical Chemistry Chemical Physics ◽

10.1039/c9cp01608b ◽

2019 ◽

Vol 21 (18) ◽

pp. 9246-9254 ◽

Cited By ~ 11

Author(s):

G. V. Baryshnikov ◽

R. R. Valiev ◽

V. N. Cherepanov ◽

N. N. Karaush-Karmazin ◽

V. A. Minaeva ◽

...

Keyword(s):

Electronic Structure ◽

Emission Spectra ◽

Absorption And Emission ◽

Absorption And Emission Spectra ◽

Photophysical Behavior

The electronic structure, absorption and emission spectra, aromaticity and photophysical behavior of the recently synthesized tetrasilatetrathia[8]circulene and tetragermatetrathia[8]circulene compounds have been studied computationally.

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