Femtosecond vibrational spectroscopy as a tool for dynamical studies of site-specific excited-state solute-solvent interactions

2005 ◽  
Author(s):  
C. Chudoba ◽  
E.T.J. Nibbering ◽  
T. Elaesser
Keyword(s):  
Excited State ◽  
Vibrational Spectroscopy ◽  
Site Specific ◽  
Solvent Interactions

scholarly journals Mapping the ultrafast vibrational dynamics of all-trans and 13-Cis retinal isomerization in Anabaena Sensory Rhodopsin

2019 ◽  
Vol 205 ◽  
pp. 10001
Author(s):  
Partha Pratim Roy ◽  
Rei Youshizumi ◽  
Hideki Kandori ◽  
Tiago Buckup
Keyword(s):  
Excited State ◽  
Frequency Shift ◽  
Vibrational Spectroscopy ◽  
Vibrational Modes ◽  
Sensory Rhodopsin ◽  
Vibrational Dynamics ◽  
State Evolution ◽  
Shift Dynamics

The ground and excited state evolution of fingerprint vibrational modes of all-trans-and 13-cis-retinal are mapped by impulsive vibrational spectroscopy. All-trans-retinal shows slower frequency shift dynamics in the excited state in comparison to 13-cis-retinal.

scholarly journals Vibronic coherence evolution in multidimensional ultrafast photochemical processes

2019 ◽  
Vol 10 (1) ◽  
Author(s):  
James D. Gaynor ◽  
Jason Sandwisch ◽  
Munira Khalil
Keyword(s):  
Excited State ◽  
Charge Transfer ◽  
Vibrational Spectroscopy ◽  
Low Frequency ◽  
Coherence Transfer ◽  
Transfer Energy ◽  
Electronic Delocalization ◽  
Vibronic States ◽  
High Frequency Vibrations ◽  
Vibronic Couplings

AbstractThe complex choreography of electronic, vibrational, and vibronic couplings used by photoexcited molecules to transfer energy efficiently is remarkable, but an unambiguous description of the temporally evolving vibronic states governing these processes has proven experimentally elusive. We use multidimensional electronic-vibrational spectroscopy to identify specific time-dependent excited state vibronic couplings involving multiple electronic states, high-frequency vibrations, and low-frequency vibrations which participate in ultrafast intersystem crossing and subsequent relaxation of a photoexcited transition metal complex. We discover an excited state vibronic mechanism driving long-lived charge separation consisting of an initial electronically-localized vibrational wavepacket which triggers delocalization onto two charge transfer states after propagating for ~600 femtoseconds. Electronic delocalization consequently occurs through nonadiabatic internal conversion driven by a 50 cm−1 coupling resulting in vibronic coherence transfer lasting for ~1 picosecond. This study showcases the power of multidimensional electronic-vibrational spectroscopy to elucidate complex, non-equilibrium energy and charge transfer mechanisms involving multiple molecular coordinates.

Isomerization and intermolecular solute–solvent interactions of ethyl isocyanate: Ultrafast infrared vibrational echoes and linear vibrational spectroscopy

2003 ◽  
Vol 118 (3) ◽  
pp. 1312-1326 ◽  
Author(s):  
Nancy E. Levinger ◽  
Paul H. Davis ◽  
Pradipta Kumar Behera ◽  
D. J. Myers ◽  
Christopher Stromberg ◽  
...  
Keyword(s):  
Vibrational Spectroscopy ◽  
Solvent Interactions ◽  
Ethyl Isocyanate ◽  
Ultrafast Infrared

Photophysics of some substituted 3H-indole probe molecules and their charged species

1994 ◽  
Vol 72 (11) ◽  
pp. 2239-2248 ◽  
Author(s):  
Michel Belletête ◽  
Ranjit S. Sarpal ◽  
Gilles Durocher
Keyword(s):  
Excited State ◽  
Radiative Decay ◽  
Mirror Image ◽  
Good Tool ◽  
Decay Rate Constant ◽  
Solvent Interactions ◽  
Cationic Species ◽  
Photophysical Parameters ◽  
Ring Nitrogen ◽  
Ring Nitrogen Atom

The spectroscopic and photophysical parameters of neutral and cationic species of the following molecules have been discussed: 2-phenyl-3,3-dimethyl-3H-indole (1), 2-[(p-amino)phenyl]-3,3-dimethyl-3H-indole (2), 2-[(p-dimethylamino)phenyl]-3,3-dimethyl-3H-indole (3), 2-[(p-amino)phenyl]-3,3-dimethyl-5-carboethoxy-3H-indole (4), 2-[(p-methylamino)phenyl]-3,3-dimethyl-5-carboethoxy-3H-indole (5), 2-[(p-dimethylamino)phenyl]-3,3-dimethyl-5-carboethoxy-3H-indole (6). Solvatochromic shifts have been interpreted in terms of the nature of the substituent groups and the state of solute–solvent interactions and complexation. The theoretical radiative decay rate constant [Formula: see text] along with the bandwidth of the absorption profile of the different species involved have been used to discuss the geometrical changes from one species to the other in the ground state. The mirror-image relationship between absorption and fluorescence spectra has proven to be a good tool to discuss any geometrical changes occurring in the excited state. A radiationless torsional mechanism takes place in the excited state relaxation of the various species. The protonation of the ring nitrogen atom generates a highly planar cationic species which retains its conformation in the relaxed excited state. The very effective quenching of the monocation fluorescence is interpreted by the formation of a non-emissive TICT state.

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