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.

[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.

Effect of complexation on the excited state of uranyl β-diketonato complexes: applications of the energy gap law

1994 ◽  
Vol 90 (21) ◽  
pp. 3253-3259 ◽  
Author(s):  
Tomoo Yayamura ◽  
Sugio Iwata ◽  
Shun-ichi Iwamaru ◽  
Hiroshi Tomiyasu
Keyword(s):  
Excited State ◽  
Energy Gap ◽  
Energy Gap Law

Diffusional distortion of the free‐energy gap law

1995 ◽  
Vol 103 (18) ◽  
pp. 7927-7933 ◽  
Author(s):  
A. I. Burshtein
Keyword(s):  
Free Energy ◽  
Energy Gap ◽  
Energy Gap Law

scholarly journals Breakdown of energy transfer gap laws revealed by full-dimensional quantum scattering between HF molecules

2019 ◽  
Vol 10 (1) ◽  
Author(s):  
Dongzheng Yang ◽  
Jing Huang ◽  
Xixi Hu ◽  
Hua Guo ◽  
Daiqian Xie
Keyword(s):  
Energy Transfer ◽  
Angular Momentum ◽  
Vibrational Energy ◽  
Energy Gap ◽  
Inelastic Collisions ◽  
Rate Coefficients ◽  
Quantum Scattering ◽  
Final States ◽  
Energy Gap Law ◽  
Quantitative Basis

Abstract Inelastic collisions involving molecular species are key to energy transfer in gaseous environments. They are commonly governed by an energy gap law, which dictates that transitions are dominated by those between initial and final states with roughly the same ro-vibrational energy. Transitions involving rotational inelasticity are often further constrained by the rotational angular momentum. Here, we demonstrate using full-dimensional quantum scattering on an ab initio based global potential energy surface (PES) that HF–HF inelastic collisions do not obey the energy and angular momentum gap laws. Detailed analyses attribute the failure of gap laws to the exceedingly strong intermolecular interaction. On the other hand, vibrational state-resolved rate coefficients are in good agreement with existing experimental results, validating the accuracy of the PES. These new and surprising results are expected to extend our understanding of energy transfer and provide a quantitative basis for numerical simulations of hydrogen fluoride chemical lasers.

Sign in / Sign up

Export Citation Format

Share Document