Doubly resonant SFG and DFG spectroscopies: An analytic model for data analysis including distorted and rotated vibronic levels. I. Theory

Busson, Bertrand

doi:10.1063/5.0022760

Cited by 10 publications

(17 citation statements)

References 94 publications

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“…This validates this methodology for the first time on DR-SFG. This also shows that the assumptions made in this study are indeed fulfilled: separability in DR-SFG between molecular amplitudes and energy lineshapes; Franck-Condon nature of the 1655 cm −1 mode; neglect of the higher order contributions to the excitation profile 47 and of the interference effects with neighbouring vibration modes. The experimental shape in Fig.…”

Section: Modeling Of the Excitation Spectrasupporting

confidence: 66%

“…As discussed in Ref. 47, expressing the doubly resonant hyperpolarizability into Lorentzian sum-over-states or in integral form requires an explicit decomposition over the vibronic structure. The required parameters (vibronic energies, Huang-Rhys factors, coupling constants) start becoming accessible through quantum chemistry calculations.…”

Section: A Advantages and Limitations Of The Methodsmentioning

confidence: 99%

“…the whole molecular vibronic structure (see Ref. 47 for a review). The vibronic structure is considered as a first approximation identical to the vibrational one, which is equivalent to considering only linear electron-vibration couplings; extension to quadratic coupling leading to mode distortion and Duschinsky rotation may be found in the literature 47,73,74 but will not be considered here.…”

Section: A Double Resonance Sfg Spectroscopymentioning

confidence: 99%

“…32 Finally, SFG gives access to ultrafast vibrational dynamics in molecules 46 and, as we will explain below, the DR-SFG spectroscopic response in the visible is strongly related to the excited state vibrational wavepacket dynamics through the overlap spectral function. 47,48 For all these reasons, DR-SFG appears suitable to complement the panel of optical spectroscopic techniques applied to study charge transfer processes in situ, from static absorption and resonance Raman to ultrafast pump-probe and two-dimensional electronic 40 and infrared spectroscopies. Historically, DR-SFG with tunable visible lasers has been applied to investigate the model chiral response of coupled oscillators 49 like binapthol in the liquid phase [50][51][52] or in monolayers [53][54][55] both theroretically and experimentally; the vibrational and electronic structures of chromophores [56][57][58][59][60] and conjugated polymers; 61,62 and the charge transfer states induced by molecular adsorption on metals.…”

Section: Introductionmentioning

confidence: 99%

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All-experimental analysis of doubly resonant sum-frequency generation spectra: Application to aggregated rhodamine films

Busson

Farhat

Teunda

et al. 2021

The Journal of Chemical Physics

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A new method is proposed to analyze doubly-resonant infrared-visible sum-frequency (DR-SFG) spectra. Based on the transform technique, this approach is free from assumptions about vibronic modes, energies, or line widths, and accurately captures through the overlap spectral function all required aspects of the vibronic structure from simple experimental linear absorption spectra. Details and implementation of the method are provided, along with three examples treating rhodamine thin films about one monolayer thick. The technique leads to a perfect agreement between experiment and simulations of the visible DR-SFG lineshapes, even in the case of complex intermolecular interactions resulting from J-aggregated chromophores in heterogeneous films. For films with mixed H-and J-aggregates, separation of their responses shows that the J-aggregate DR-SFG response is dominant. Our analysis also accounts for the unexplained results published in the early times of DR-SFG experiments.

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Section: Modeling Of the Excitation Spectrasupporting

confidence: 66%

Section: A Advantages and Limitations Of The Methodsmentioning

confidence: 99%

Section: A Double Resonance Sfg Spectroscopymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

All-experimental analysis of doubly resonant sum-frequency generation spectra: Application to aggregated rhodamine films

Busson

Farhat

Teunda

et al. 2021

The Journal of Chemical Physics

Self Cite

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“…The above-mentioned description of the SFG response of an interface is phenomenological and easy to use for data fitting. In addition, it is worth noting that recent theoretical and analytical models developed for doubly resonant SFG and DFG spectroscopies give a quantified description of complex phenomena related to vibronic couplings inside molecules [75,76].…”

Section: Ir Absorptionmentioning

confidence: 99%

A Unified Mathematical Formalism for First to Third Order Dielectric Response of Matter: Application to Surface-Specific Two-Colour Vibrational Optical Spectroscopy

Humbert

Noblet

2021

Symmetry

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To take advantage of the singular properties of matter, as well as to characterize it, we need to interact with it. The role of optical spectroscopies is to enable us to demonstrate the existence of physical objects by observing their response to light excitation. The ability of spectroscopy to reveal the structure and properties of matter then relies on mathematical functions called optical (or dielectric) response functions. Technically, these are tensor Green’s functions, and not scalar functions. The complexity of this tensor formalism sometimes leads to confusion within some articles and books. Here, we do clarify this formalism by introducing the physical foundations of linear and non-linear spectroscopies as simple and rigorous as possible. We dwell on both the mathematical and experimental aspects, examining extinction, infrared, Raman and sum-frequency generation spectroscopies. In this review, we thus give a personal presentation with the aim of offering the reader a coherent vision of linear and non-linear optics, and to remove the ambiguities that we have encountered in reference books and articles.

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Development of Two-Dimensional Electronic-Vibrational Sum Frequency Generation (2D-EVSFG) for Vibronic and Solvent Couplings of Molecules at Interfaces and Surfaces

et al. 2023

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Many photoinduced excited states’ relaxation processes and chemical reactions occur at interfaces and surfaces, including charge transfer, energy transfer, proton transfer, proton-coupled electron transfer, configurational dynamics, conical intersections, etc. Of them, interactions of electronic and vibrational motions, namely, vibronic couplings, are the main determining factors for the relaxation processes or reaction pathways. However, time-resolved electronic-vibrational spectroscopy for interfaces and surfaces is lacking. Here we develop interface/surface-specific two-dimensional electronic-vibrational sum frequency generation spectroscopy (2D-EVSFG) for time-dependent vibronic coupling of excited states at interfaces and surfaces. We further demonstrate the fourth-order technique by investigating vibronic coupling, solvent correlation, and time evolution of the coupling for photoexcited interface-active molecules, crystal violet (CV), at the air/water interface as an example. The two vibronic absorption peaks for CV molecules at the interface from the 2D-EVSFG experiments were found to be more prominent than their counterparts in bulk from 2D-EV. Quantitative analysis of the vibronic peaks in 2D-EVSFG suggested that a non-Condon process participates in the photoexcitation of CV at the interface. We further reveal vibrational solvent coupling for the zeroth level on the electronic state with respect to that on the ground state, which is directly related to the magnitude of its change in solvent reorganization energy. The change in the solvent reorganization energy at the interface is much smaller than that in bulk methanol. Time-dependent center line slopes (CLSs) of 2D-EVSFG also showed that kinetic behaviors of CV at the air/water interface are significantly different from those in bulk methanol. Our ultrafast 2D-EVSFG experiments not only offer vibrational information on both excited states and the ground state as compared with the traditional doubly resonant sum frequency generation and electronic-vibrational coupling but also provide vibronic coupling, dynamical solvent effects, and time evolution of vibronic coupling at interfaces.

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Doubly resonant SFG and DFG spectroscopies: An analytic model for data analysis including distorted and rotated vibronic levels. I. Theory

Cited by 10 publications

References 94 publications

All-experimental analysis of doubly resonant sum-frequency generation spectra: Application to aggregated rhodamine films

All-experimental analysis of doubly resonant sum-frequency generation spectra: Application to aggregated rhodamine films

A Unified Mathematical Formalism for First to Third Order Dielectric Response of Matter: Application to Surface-Specific Two-Colour Vibrational Optical Spectroscopy

Development of Two-Dimensional Electronic-Vibrational Sum Frequency Generation (2D-EVSFG) for Vibronic and Solvent Couplings of Molecules at Interfaces and Surfaces

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