Influence of intramolecular vibrations in third-order, time-domain resonant spectroscopies. II. Numerical calculations

Abstract

Articles you may be interested inAnalysis of cross peaks in two-dimensional electronic photon-echo spectroscopy for simple models with vibrations and dissipation J. Chem. Phys. 126, 074314 (2007); 10.1063/1.2435353Photoelectron spectroscopy of S 1 toluene: II. Intramolecular dynamics of selected vibrational levels in S 1 toluene studied by nanosecond and picosecond time-resolved photoelectron spectroscopies Site-specific vibrational dynamics of the CD3ζ membrane peptide using heterodyned two-dimensional infrared photon echo spectroscopyWe model recent experimental wavelength dependent Three Pulse Photon Echo Peak Shift ͑WD-3PEPS͒ and Transient Grating ͑WD-TG͒ signals considering both solvation dynamics and vibrational contributions. We present numerical simulations of WD-3PEPS and WD-TG signals of two probe molecules: Nile Blue and N,N-bisdimethylphenyl-2,4,6,8-perylenetetracarbonyl diamide to investigate the influence of intramolecular vibrations in the signals. By varying the excitation wavelength, we show that the different initial conditions for the vibrational wave packets significantly affect the signals, especially through the contributions associated with high frequency modes, often neglected in experimental analyses. We show that the temporal properties of both WD-TG and WD-3PEPS signals display sensitivities to both the excitation wavelength and the vibronic structure of the specific probe molecule used. Several mechanisms for generating vibronic modulations in the signals are discussed and their effects on the signals are described. Quantitative agreement between experiment and simulated signals requires accurate characterization of the laser pulses, specifically the magnitude and sign of chirp has a significant effect on the initial temporal properties of the signals. We provide a description of the experimental considerations required for accurate determination of molecular dynamics from 3PEPS and TG experiments and conclude with a brief discussion of the implications of our results for previous analyses of such experiments.

Excitons in a photosynthetic light-harvesting system: A combined molecular dynamics, quantum chemistry, and polaron model study

“…Eqs. (56,57)], and the corresponding experimental result I exp (ω) [42]. The peak of I B850 is located at 1.46 eV (≈ 849 nm), and coincides with the position of the other two spectra.…”

“…We note that the autocorrelation function in Fig. 11a, resembles the transition frequency autocorrelation function for Nile Blue [57], obtained through a model that combines in both the intramolecular vibrations and solvent dependent contributions.…”

Coherent coupling of vibrational states in the MEH-PPV film investigated through Multi-Color Photon Echo

“…For τ 12 =0 fs in particular, this process known as transient grating (TG) is a special case of the PE process and the weak quantum beats are not pronounced as shown in Figures 4(b) and 4(e). When two vibrational states are excited and they are closely spaced in energy, the coherent superposition is created, and the quantum beats in signal are observed in the time domain [12,13]. In our system the PE and FID can obtain the dynamics of vibrational states both on the excited and ground states.…”

Vibrational phase relaxation of O–H stretch in bulk water: Role of large amplitude angular jumps and negative cross-correlations among the forces on the O–H bond

“…The timescale of the initial decay of FFTCF is $60 fs [3]. It has been observed in vibrational peak shift measurements (PS) that the amplitude and the phase characteristics of the pulse strongly influence the initial value and early decay timescale [41]. In Fig.…”