Application of the energy gap law to excited-state decay of osmium(II)-polypyridine complexes: calculation of relative nonradiative decay rates from emission spectral profiles

1986 ◽  
Vol 90 (16) ◽  
pp. 3722-3734 ◽  
Author(s):  
Edward M. Kober ◽  
Jonathan V. Caspar ◽  
Richard S. Lumpkin ◽  
Thomas J. Meyer
Keyword(s):  
Excited State ◽  
Energy Gap ◽  
Decay Rates ◽  
Nonradiative Decay ◽  
State Decay ◽  
Energy Gap Law ◽  
Spectral Profiles ◽  
Polypyridine Complexes

Application of the energy gap law to nonradiative, excited-state decay

1983 ◽  
Vol 87 (6) ◽  
pp. 952-957 ◽  
Author(s):  
Jonathan V. Caspar ◽  
Thomas J. Meyer
Keyword(s):  
Excited State ◽  
Energy Gap ◽  
State Decay ◽  
Energy Gap Law

Photoinduced ligand dissociation follows reverse energy gap law: nitrile photodissociation from low energy 3MLCT excited states

2020 ◽  
Vol 56 (29) ◽  
pp. 4070-4073
Author(s):  
Lauren M. Loftus ◽  
Jeffrey J. Rack ◽  
Claudia Turro
Keyword(s):  
Excited State ◽  
Excited States ◽  
Absorption Spectroscopy ◽  
Transient Absorption ◽  
Energy Gap ◽  
Low Energy ◽  
Transient Absorption Spectroscopy ◽  
Ligand Dissociation ◽  
Energy Gap Law

Transient absorption spectroscopy is used to show that stabilization of the 3MLCT excited state in a series of Ru(ii) complexes leads to decreased population of the 3LF state, but does not reduce the efficiency of photoinduced nitrile dissociation.

scholarly journals Inverted energy gap law for the nonradiative decay in fluorescent floppy molecules: larger fluorescence quantum yields for smaller energy gaps

2019 ◽  
Vol 6 (12) ◽  
pp. 1948-1954 ◽  
Author(s):  
Junqing Shi ◽  
Maria A. Izquierdo ◽  
Sangyoon Oh ◽  
Soo Young Park ◽  
Begoña Milián-Medina ◽  
...  
Keyword(s):  
Radiative Decay ◽  
Energy Gap ◽  
Quantum Yields ◽  
Nonradiative Decay ◽  
Fluorescence Quantum Yields ◽  
Energy Gaps ◽  
Energy Gap Law ◽  
Solution Increase ◽  
Floppy Molecules ◽  
Franck Condon

The non-radiative decay of substituted dicyano-distyrylbenzenes in solution increase with the Franck–Condon energy, being opposite to the conventional energy gap law.

[Ru(bpy)3]2+* and other remarkable metal-to-ligand charge transfer (MLCT) excited states

2013 ◽  
Vol 85 (7) ◽  
pp. 1257-1305 ◽  
Author(s):  
David W. Thompson ◽  
Akitaka Ito ◽  
Thomas J. Meyer
Keyword(s):  
Excited State ◽  
Charge Transfer ◽  
Energy Gap ◽  
Hybrid Approach ◽  
Medium Effects ◽  
New Approach ◽  
Dye Sensitized ◽  
Ligand Charge Transfer ◽  
Energy Gap Law

In 1974, the metal-to-ligand charge transfer (MLCT) excited state, [Ru(bpy)3]2+*, was shown to undergo electron transfer quenching by methylviologen dication (MV2+), inspiring a new approach to artificial photosynthesis based on molecules, molecular-level phenomena, and a “modular approach”. In the intervening years, application of synthesis, excited-state measurements, and theory to [Ru(bpy)3]2+* and its relatives has had an outsized impact on photochemistry and photophysics. They have provided a basis for exploring the energy gap law for nonradiative decay and the role of molecular vibrations and solvent and medium effects on excited-state properties. Much has been learned about light absorption, excited-state electronic and molecular structure, and excited-state dynamics on timescales from femtoseconds to milliseconds. Excited-state properties and reactivity have been exploited in the investigation of electron and energy transfer in solution, in molecular assemblies, and in derivatized polymers and oligoprolines. An integrated, hybrid approach to solar fuels, based on dye-sensitized photoelectrosynthesis cells (DSPECs), has emerged and is being actively investigated.

scholarly journals Multiple Resonance Deep-red Emitters with Hybridized π-bonding/ non-bonding Orbitals to Surpass the Energy Gap Law

2021 ◽  
Author(s):  
Yuewei Zhang ◽  
Dongdong Zhang ◽  
Tianyu Huang ◽  
Alexander Gillett ◽  
Yang Liu ◽  
...  
Keyword(s):  
Radiative Decay ◽  
Near Infrared ◽  
Energy Gap ◽  
Light Emitting Diode ◽  
Resonance Effect ◽  
Infrared Region ◽  
Decay Rates ◽  
Quantum Yields ◽  
Multiple Resonance ◽  
Energy Gap Law

Abstract Efficient organic emitters in the deep-red to near infrared region are rare due to the ‘energy gap law’. Here, multiple boron (B)- and nitrogen (N)-atoms embedded polycyclic heteroaromatics featuring hybridized π-bonding/ non-bonding molecular orbitals are constructed, providing a way to overcome the above luminescent boundary. The introduction of B-phenyl-B and N-phenyl-N structures enhances the electronic coupling of those para-positioned atoms, forming restricted π-bonds on the phenyl-core for delocalized excited states and thus a narrow energy gap. The mutually ortho-positioned B- and N-atoms also induce a multiple resonance effect on the peripheral skeleton for the non-bonding orbitals, creating shallow potential energy surfaces to eliminate the high-frequency vibrational quenching. The corresponding deep-red emitters with peaks at 662 nm and 692 nm exhibit narrow full-width at half-maximums of 38 nm, high radiative decay rates of ~108 s-1, ~100% photo-luminance quantum yields and record-high maximum external quantum efficiencies of >28% in a normal planar organic light-emitting diode structure, simultaneously.

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