Recent advances in multidimensional ultrafast spectroscopy

Oliver, Thomas A. A.

doi:10.1098/rsos.171425

Cited by 67 publications

(70 citation statements)

References 233 publications

(323 reference statements)

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“…From an experimental perspective, we envisage one route to address this issue is via extension of two-dimensional electronic-vibrational spectroscopy into the ultraviolet, enabling time-dependent correlations between broadband (delocalised) UV electronic excitation and (localised) vibrational emission. [49][50][51]…”

Section: Discussionmentioning

confidence: 99%

Exploring ultraviolet photoinduced charge-transfer dynamics in a model dinucleotide of guanine and thymine

Duchi

O’Hagan

Kumar

et al. 2019

Phys. Chem. Chem. Phys.

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An understanding of the initial photoexcited states of DNA is essential to unravelling deleterious photoinduced chemical reactions and the intrinsic ultrafast photoprotection of the genetic code for all life.In our combined experimental and theoretical study, we have elucidated the primary non-radiative relaxation dynamics of a model nucleotide of guanine and thymine (2 0 -deoxyguanosine 3 0 -monophosphate 5 0 -thymidine, d(GpT)) in buffered aqueous solution. Experimentally, we unequivocally demonstrate that the Franck-Condon excited states of d(GpT) are significantly delocalised across both nucleobases, and mediate d(G + pT À ) exciplex product formation on an ultrafast (o350 fs) timescale. Theoretical studies show that the nature of the vertical excited states is very dependent on the specific geometry of the dinucleotide, and dictate the degree of delocalised, charge-transfer or localised character. Our mechanism for prompt exciplex formation involves a rapid change in electronic structure and includes a diabatic surface crossing very close to the Franck-Condon region mediating fast d(G + pT À ) formation. Exciplexes are quickly converted back to neutral ground state molecules on a B10 ps timescale with a high quantum yield, ensuring the photostability of the nucleotide sequence.

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Section: Discussionmentioning

confidence: 99%

Exploring ultraviolet photoinduced charge-transfer dynamics in a model dinucleotide of guanine and thymine

Duchi

O’Hagan

Kumar

et al. 2019

Phys. Chem. Chem. Phys.

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“…[9] Broadband mid-infrared ultrafast pump and probe laser pulses (central frequency = 1720 cm -1 ) were used for the mixed timefrequency domain measurements. [10] 2DIR correlation spectra for many values of the waiting time, t 2 . Measurements were performed with pump and probe pulses aligned parallel (I para ) and perpendicular (I perp ).…”

Section: Methodsmentioning

confidence: 99%

Investigating Electron-Phonon Coupling in Formamidinium Lead Iodide Perovskite Using Ultrafast Laser Spectroscopy

Taylor

Duchi

Donaldson

et al. 2018

2018 IEEE 18th International Conference on Nanotechnology (IEEE-NANO)

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The high charge carrier mobilities of hybrid inorganic-organic lead halide perovskites has previously been linked to ferroelectric domain formation due to alignment of organic cations within films.[1], [2] Our two-dimensional infrared ultrafast spectroscopy studies reveal that organic cations re-orient within several picoseconds, and therefore ferroelectric domain formation is very unlikely and unable to account for the observed long carrier lifetimes.[3] Complimentary time-resolved infrared measurements examined the electron-phonon coupling in the conduction band. Analysis of the spectral line shapes indicates that carriers form polarons within the instrument response.

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“…Multidimensional optical spectroscopies have shown to be effective tools to understand the photophysics of a large set of extremely challenging phenomena such as quantum coherence in natural light harvesting, [42], structural dynamics [44], non-radiative relaxation, chemical reaction or solvation dynamics [45,46]. Advances in multidimensional ultrafast spectroscopies have been realized thanks to advances in femtosecond pulse generation, amplitude and phase control of laser light with pulse shapers such as Acousto-Optic Modulators (AOMs) or Spatial Light Modulators (SLMs) [47][48][49].…”

Section: Recent Advances In Multidimensional Ultrafast Spectroscopy Amentioning

confidence: 99%

“…Changes in the 2D line shapes give information on the Frequency-Frequency Correlation Function (FFCF) [51]. FFCF dynamics contain information about amplitudes and timescales associated with changes in the optical frequencies investigated which are related to molecular structure rearrangements and to solvation dynamics [47].…”

Section: Recent Advances In Multidimensional Ultrafast Spectroscopy Amentioning

confidence: 99%

Synergistic Approach of Ultrafast Spectroscopy and Molecular Simulations in the Characterization of Intramolecular Charge Transfer in Push-Pull Molecules

et al. 2020

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The comprehensive characterization of Intramolecular Charge Transfer (ICT) stemming in push-pull molecules with a delocalized π-system of electrons is noteworthy for a bespoke design of organic materials, spanning widespread applications from photovoltaics to nanomedicine imaging devices. Photo-induced ICT is characterized by structural reorganizations, which allows the molecule to adapt to the new electronic density distribution. Herein, we discuss recent photophysical advances combined with recent progresses in the computational chemistry of photoactive molecular ensembles. We focus the discussion on femtosecond Transient Absorption Spectroscopy (TAS) enabling us to follow the transition from a Locally Excited (LE) state to the ICT and to understand how the environment polarity influences radiative and non-radiative decay mechanisms. In many cases, the charge transfer transition is accompanied by structural rearrangements, such as the twisting or molecule planarization. The possibility of an accurate prediction of the charge-transfer occurring in complex molecules and molecular materials represents an enormous advantage in guiding new molecular and materials design. We briefly report on recent advances in ultrafast multidimensional spectroscopy, in particular, Two-Dimensional Electronic Spectroscopy (2DES), in unraveling the ICT nature of push-pull molecular systems. A theoretical description at the atomistic level of photo-induced molecular transitions can predict with reasonable accuracy the properties of photoactive molecules. In this framework, the review includes a discussion on the advances from simulation and modeling, which have provided, over the years, significant information on photoexcitation, emission, charge-transport, and decay pathways. Density Functional Theory (DFT) coupled with the Time-Dependent (TD) framework can describe electronic properties and dynamics for a limited system size. More recently, Machine Learning (ML) or deep learning approaches, as well as free-energy simulations containing excited state potentials, can speed up the calculations with transferable accuracy to more complex molecules with extended system size. A perspective on combining ultrafast spectroscopy with molecular simulations is foreseen for optimizing the design of photoactive compounds with tunable properties.

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Recent advances in multidimensional ultrafast spectroscopy

Cited by 67 publications

References 233 publications

Exploring ultraviolet photoinduced charge-transfer dynamics in a model dinucleotide of guanine and thymine

Exploring ultraviolet photoinduced charge-transfer dynamics in a model dinucleotide of guanine and thymine

Investigating Electron-Phonon Coupling in Formamidinium Lead Iodide Perovskite Using Ultrafast Laser Spectroscopy

Synergistic Approach of Ultrafast Spectroscopy and Molecular Simulations in the Characterization of Intramolecular Charge Transfer in Push-Pull Molecules

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