Three-pulse photon echoes for model reactive systems

Yang, Mino; Ohta, Kaoru; Fleming, Graham R.

doi:10.1063/1.478957

Cited by 47 publications

(68 citation statements)

References 29 publications

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“…13 When the back-reaction from the product to the original ground state is very slow (τ d is very large), the last term R gg'e will not contribute. The above formula Figure 1.…”

Section: Theoretical Backgroundmentioning

confidence: 98%

Isomerization Dynamics of 1,1’-Diethyl-4,4’-Cyanine (1144C) Studied by Different Third-Order Nonlinear Spectroscopic Measurements

Fleming

2001

J. Phys. Chem. A

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The isomerization of 1,1'-diethyl-4,4'-cyanine (1144C) in two solvents, ethanol and hexanol, was studied by three different third-order four-wave mixing techniques: three-pulse photon echo peak shift (3PEPS), transient grating (TG), and pump-probe (PP) to provide complimentary information on different aspects of the reaction dynamics. A double-sided Feynman diagram analysis was used to assist in the formulation of the kinetic behavior in the TG and PP signals. The ground-state recovery process can be described as a single exponential process which is dominated by the bond-twisting motion on the excited-state surface. The rate is strongly viscosity and temperature dependent. A larger yield of the isomer is obtained in less viscous solvents or with greater excess excitation energy. Apparently, contradictory wavelength-dependent decay behavior was found in the TG and PP signals. This can be understood by considering the different real and imaginary contributions to the signals from hot ground-state absorption and its subsequent recovery to the equilibrated state and from the product state. I. IntroductionThe development of short laser pulses has made it possible to explore molecular motions on the time scale of femtoseconds via the nonlinear optical response. 1-3 Many different nonlinear spectroscopic techniques have been developed to probe different aspects of the molecular dynamics. 2,3 The third-order nonlinearity is the lowest order nonzero term in isotropic media and has been exploited to study the reaction dynamics in various types of four-wave mixing spectroscopies, 3-7 including photon echo, transient grating, and pump-probe measurements.The three-pulse photon echo peak shift (3PEPS) is a novel technique that has been applied by our group and others to study solvation dynamics and energy-transfer processes for several years. 5,[8][9][10][11][12] The insensitivity of 3PEPS to the excited-state lifetime makes it a suitable technique to study solvation dynamics and solvent effects in reactive systems. 7,13 One distinct feature of 3PEPS is its capability of differentiating the rephasing contribution and the free induction decay (FID) contribution, which contribute in a similar way to conventional populationbased techniques, such as fluorescence up-conversion, pumpprobe (PP), and transient grating (TG) spectroscopies. 5,10 This is the basis of the application of 3PEPS in the study of energy transfer. 10 Recently, we extended the 3PEPS technique to the study of reactive systems, such as electron transfer in electrondonating solvents 7 and torsional dynamics of the triphenylmethane (TPM) dye molecules. 14 Since 3PEPS is not sensitive to the excited-state lifetime, it can provide information on processes such as solvation and vibrational relaxation during reactions. Similar information is difficult to obtain from population-based techniques. Therefore, a combination of 3PEPS with population-based techniques such as TG or PP is attractive for the study of solution-phase reactive systems.Photoinduced isomerization rea...

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“…13 When the back-reaction from the product to the original ground state is very slow (τ d is very large), the last term R gg'e will not contribute. The above formula Figure 1.…”

Section: Theoretical Backgroundmentioning

confidence: 98%

Isomerization Dynamics of 1,1’-Diethyl-4,4’-Cyanine (1144C) Studied by Different Third-Order Nonlinear Spectroscopic Measurements

Fleming

2001

J. Phys. Chem. A

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“…The response function formalism for calculating spectroscopic properties of a molecular system from a model of a nuclear dynamics has been extensively discussed. 17,24,[34][35][36][37][38][39] This formalism describes the response of matter to a time-dependent light field and can be used to calculate the third-order nonlinear polarization function. It also allows the ultrafast nonlinear optical responses, such as the three pulse echo peak shift, transient grating, transient absorption signals, and so on, to be calculated ͑see Ref.…”

Section: B Numerical Calculationmentioning

confidence: 99%

Unified explanation for linear and nonlinear optical responses inβ-carotene: A sub-20−fsdegenerate four-wave mixing spectroscopic study

et al. 2007

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The four-wave mixing signal of ␤-carotene measured under the resonant excitation is reported. A clear coherent oscillation with a period of a few tens of femtoseconds was observed. We have estimated the line broadening function required to simulate this oscillation behavior. The parameters, including the solvation effect, which are essential for calculating the optical signals have also been determined. The validity of our simulation has been evaluated by comparing the theoretically calculated linear and nonlinear optical signals with the experimental results. It was found that in addition to the C u C and C v C stretching modes the methyl in-plane rocking mode significantly contributes to the optical responses of ␤-carotene. Calculations based on the Brownian oscillator model were performed under the impulsive excitation limit, and we find that the memory of the vibronic coherence generated in the S 2 state is lost via relaxation processes, which include the S 1 state. Comparison between the simulation and experiment revealed that the two-photon absorption process plays an important role in the very early optical process taking place in ␤-carotene. The vibronic decoherent time of the system is estimated to be 1 ps, which is about five times longer than the population lifetime of the S 2 state determined in the previous studies. The possible relationship between the lifetime of the vibronic coherence and the efficient energy transfer in light-harvesting antenna complexes is discussed.

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“…The dynamics still reflect the correlation between the electronic and vibrational transitions, primarily induced via the fluctuations of the vibrational zero-point energies on the electronic excited state, but interference effects may complicate the precise dynamics. 37,38 A detailed analysis of the information that can be extracted from these slopes is left for future considerations.…”

Section: Simulation Resultsmentioning

confidence: 99%

“…|), which drive energy transfer between the excitons. To account for energy transfer processes, we include the dynamics in an ad hoc manner similar to that used previously in the development of response functions for energy transfer and reactive systems, 37,38 modified so that the dynamics are equivalent to Redfield theory under the secular approximation. 39,40 The details of the method by which we include these dynamics in the response functions are given in Appendix A.…”

Section: A Dimer Hamiltonianmentioning

confidence: 99%

A method for the direct measurement of electronic site populations in a molecular aggregate using two-dimensional electronic-vibrational spectroscopy

Lewis

Dong

Oliver

et al. 2015

The Journal of Chemical Physics

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Two dimensional electronic spectroscopy has proved to be a valuable experimental technique to reveal electronic excitation dynamics in photosynthetic pigment-protein complexes, nanoscale semiconductors, organic photovoltaic materials, and many other types of systems. It does not, however, provide direct information concerning the spatial structure and dynamics of excitons. 2D infrared spectroscopy has become a widely used tool for studying structural dynamics but is incapable of directly providing information concerning electronic excited states. 2D electronic-vibrational (2DEV) spectroscopy provides a link between these domains, directly connecting the electronic excitation with the vibrational structure of the system under study. In this work, we derive response functions for the 2DEV spectrum of a molecular dimer and propose a method by which 2DEV spectra could be used to directly measure the electronic site populations as a function of time following the initial electronic excitation. We present results from the response function simulations which show that our proposed approach is substantially valid. This method provides, to our knowledge, the first direct experimental method for measuring the electronic excited state dynamics in the spatial domain, on the molecular scale.

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Three-pulse photon echoes for model reactive systems

Cited by 47 publications

References 29 publications

Isomerization Dynamics of 1,1’-Diethyl-4,4’-Cyanine (1144C) Studied by Different Third-Order Nonlinear Spectroscopic Measurements

Isomerization Dynamics of 1,1’-Diethyl-4,4’-Cyanine (1144C) Studied by Different Third-Order Nonlinear Spectroscopic Measurements

Unified explanation for linear and nonlinear optical responses inβ-carotene: A sub-20−fsdegenerate four-wave mixing spectroscopic study

A method for the direct measurement of electronic site populations in a molecular aggregate using two-dimensional electronic-vibrational spectroscopy

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