On the excitation wavelength dependence and Arrhenius behavior of stilbene isomerization rates in solution

Kovalenko, Sergey A.; Dobryakov, A. L.

doi:10.1016/j.cplett.2013.03.073

Cited by 24 publications

(42 citation statements)

References 34 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Figure 2A shows the evolution of the transient absorption spectrum of trans-stilbene following excitation with one-photon at 310 nm (total energy of 4.0 eV). Consistent with earlier studies, 8,12,15,18,[60][61][62] the TA spectrum is dominated by an excited-state absorption (ESA) band centered near 585 nm and a weaker stimulated emission (SE) band near 365 nm. The asymmetry of the ESA band, including a weak shoulder near 550 nm, was previously assigned as a vibronic progression in the S n ←S 1 transition.…”

Section: Excited-state Dynamics Following One-and Two-photon Excitationsupporting

confidence: 88%

Two-Photon Excitation of trans-Stilbene: Spectroscopy and Dynamics of Electronically Excited States above S₁

et al. 2014

View full text Add to dashboard Cite

The photoisomerization dynamics of trans-stilbene have been well studied in the lowest excited state, but much less is known about the behavior following excitation to higher-lying electronically excited states. This contribution reports a combined study of the spectroscopy and dynamics of two-photon accessible states above S1. Two-photon absorption (2PA) measurements using a broadband pump-probe technique reveal distinct bands near 5.1 and 6.4 eV. The 2PA bands have absolute cross sections of 40 ± 16 and 270 ± 110 GM, respectively, and a pump-probe polarization dependence that suggests both of the transitions access Ag-symmetry excited states. Separate transient absorption measurements probe the excited-state dynamics following two-photon excitation into each of the bands using intense pulses of 475 and 380 nm light, respectively. The initially excited states rapidly relax via internal conversion, leading to the formation of an S1 excited-state absorption band that is centered near 585 nm and evolves on a time scale of 1-2 ps due to intramolecular vibrational relaxation. The subsequent evolution of the S1 excited-state absorption is identical to the behavior following direct one-photon excitation of the lowest excited state at 4.0 eV. The complementary spectroscopy and dynamics measurements provide new benchmarks for computational studies of the electronic structure and dynamics of this model system on excited states above S1. Probing the dynamics of molecules in their higher-lying excited states is an important frontier in chemical reaction dynamics.

show abstract

Section: Excited-state Dynamics Following One-and Two-photon Excitationsupporting

confidence: 88%

Two-Photon Excitation of trans-Stilbene: Spectroscopy and Dynamics of Electronically Excited States above S₁

et al. 2014

View full text Add to dashboard Cite

show abstract

“…The amplitude ratios of the two components Aa A b % 0:1 , which are approximately determined by k 1 k À1 , indicate that the equilibrium is strongly favored for the 1 t* state and that t À1 % t a and t 1 %10 t a . The much slower forward barrier crossing times in both solvents ($700 ps in CHX and $1300 ps in HXD) than those found for bare trans-stilbene in non-viscous solvents ($100 ps) [34,47] suggests a higher barrier for the ethylenic bond twisting in the trans form of the DMANS S 1 state. The slower barrier crossing rate in HXD than that in CHX is consistent with the fact that the former has a much higher viscosity.…”

Section: Excited-state Deactivation Mechanism In Nonpolar Solventsmentioning

confidence: 70%

Excited-state vibrational relaxation and deactivation dynamics of trans-4-(N,N-dimethylamino)-4′-nitrostilbene in nonpolar solvents studied by ultrafast time-resolved broadband fluorescence spectroscopy

Chiu

Chen

Cheng

2015

Journal of Photochemistry and Photobiology A: Chemistry

View full text Add to dashboard Cite

“…Photoexcitation launches a wave packet on this potential energy surface based on the amount of vibrational energy deposited by excitation (above the 0−1 transition energy). The excitationwavelength dependence of stilbene photoisomerization is heavily influenced by vibrational motion along the isomerization coordinate 94 increasing the rate and quantum yield in solution compared to those in the gas phase. The barrierless isomerization in rhodopsin is also dependent on wavelength because of excited-state vibrational wave packets, 95 with a significant drop in yields above 500 nm.…”

Section: ■ Discussionmentioning

confidence: 99%

Excitation-Wavelength-Dependent Photocycle Initiation Dynamics Resolve Heterogeneity in the Photoactive Yellow Protein from Halorhodospira halophila

et al. 2018

View full text Add to dashboard Cite

Photoactive yellow proteins (PYPs) make up a diverse class of blue-light-absorbing bacterial photoreceptors. Electronic excitation of the p-coumaric acid chromophore covalently bound within PYP results in triphasic quenching kinetics; however, the molecular basis of this behavior remains unresolved. Here we explore this question by examining the excitation-wavelength dependence of the photodynamics of the PYP from Halorhodospira halophila via a combined experimental and computational approach. The fluorescence quantum yield, steady-state fluorescence emission maximum, and cryotrapping spectra are demonstrated to depend on excitation wavelength. We also compare the femtosecond photodynamics in PYP at two excitation wavelengths (435 and 475 nm) with a dual-excitation-wavelength-interleaved pump-probe technique. Multicompartment global analysis of these data demonstrates that the excited-state photochemistry of PYP depends subtly, but convincingly, on excitation wavelength with similar kinetics with distinctly different spectral features, including a shifted ground-state beach and altered stimulated emission oscillator strengths and peak positions. Three models involving multiple excited states, vibrationally enhanced barrier crossing, and inhomogeneity are proposed to interpret the observed excitation-wavelength dependence of the data. Conformational heterogeneity was identified as the most probable model, which was supported with molecular mechanics simulations that identified two levels of inhomogeneity involving the orientation of the R52 residue and different hydrogen bonding networks with the p-coumaric acid chromophore. Quantum calculations were used to confirm that these inhomogeneities track to altered spectral properties consistent with the experimental results.

show abstract

On the excitation wavelength dependence and Arrhenius behavior of stilbene isomerization rates in solution

Cited by 24 publications

References 34 publications

Two-Photon Excitation of trans-Stilbene: Spectroscopy and Dynamics of Electronically Excited States above S₁

Two-Photon Excitation of trans-Stilbene: Spectroscopy and Dynamics of Electronically Excited States above S₁

Excited-state vibrational relaxation and deactivation dynamics of trans-4-(N,N-dimethylamino)-4′-nitrostilbene in nonpolar solvents studied by ultrafast time-resolved broadband fluorescence spectroscopy

Excitation-Wavelength-Dependent Photocycle Initiation Dynamics Resolve Heterogeneity in the Photoactive Yellow Protein from Halorhodospira halophila

Contact Info

Product

Resources

About

On the excitation wavelength dependence and Arrhenius behavior of stilbene isomerization rates in solution

Cited by 24 publications

References 34 publications

Two-Photon Excitation of trans-Stilbene: Spectroscopy and Dynamics of Electronically Excited States above S1

Two-Photon Excitation of trans-Stilbene: Spectroscopy and Dynamics of Electronically Excited States above S1

Excited-state vibrational relaxation and deactivation dynamics of trans-4-(N,N-dimethylamino)-4′-nitrostilbene in nonpolar solvents studied by ultrafast time-resolved broadband fluorescence spectroscopy

Excitation-Wavelength-Dependent Photocycle Initiation Dynamics Resolve Heterogeneity in the Photoactive Yellow Protein from Halorhodospira halophila

Contact Info

Product

Resources

About

Two-Photon Excitation of trans-Stilbene: Spectroscopy and Dynamics of Electronically Excited States above S₁

Two-Photon Excitation of trans-Stilbene: Spectroscopy and Dynamics of Electronically Excited States above S₁