Pressure-induced hydrogen bonding modulating Fermi resonance between fundamental modes in xylitol molecule.

Xylitol, as a typical polyol, has a broad range of application prospects. However, the molecular states of xylitol under different environments are rarely reported until now. In this work, the state changes of xylitol molecules under high pressure were analyzed by Raman spectra. A Fermi resonance phenomenon in the fundamental mode of xylitol at 2945 (±0.06) cm-1 and 2955 (±0.41) cm-1 was observed at 0.99 GPa. The Fermi doublets possess the same symmetry and close energy levels, which had not been changed by pressures. However, the high pressure shortened the atomic distances and applied the extra disturbance, providing the necessary conditions for energy transfer. Besides, the Fermi doublets decoupling happened at 4 GPa due to the breaking of hydrogen bonding. This work provides an important reference for studying molecular states and weak interactions of polyols under high pressures.

DMSO synergized with sugars: optical clearing agent modulation of optical coherence tomography of skin tissues.

The stratum corneum of the outermost skin is an important barrier impeding transdermal permeation, and permeation enhancers can reduce the barrier resistance of the stratum corneum and enhance the permeation of drugs in tissues. The optical imaging depth, signal intensity, and scattering coefficient variation rules of skin tissues in time dimension are obtained by using optical coherence tomography (OCT). The effect of optical clearing agents (OCAs) on OCT imaging is obtained by quantitatively analyzing the changes in the optical properties of tissues. D-fructose, one of the monosaccharides, and sucrose, one of the disaccharides, were selected for the ex vivo optical clearing experiments on pig skin tissues utilizing the dimethyl sulfoxide (DMSO) carrier effect. We find that DMSO synergized with sugars applied to skin tissue has a more significant increase in the optical imaging depth and signal intensity, and a reduction in the scattering coefficient with an increasing concentration of DMSO. DMSO with a high concentration and D-fructose with saturated concentration (10:1; v/v) effectively reduce light attenuation in OCT imaging and improve the image quality. This operation will also shorten the application time to minimize skin damage from hyperosmotic agents.

Investigating local field tuning Fermi resonance of CS2 by Raman spectroscopy and DFT calculations.

In the spectroscopic study of polyatomic molecules, Fermi resonance (FR) is a vibrational coupling and energy transfer phenomenon that widely exists intra- and intermolecular. In particular, the FR coupling between the fundamental mode ν1 and the doubling mode 2ν2 of the CS2 molecule has attracted extensive research. In this work, we investigate the effect of local field on tuning the FR of CS2. By analyzing the Raman spectra of CS2 mixed with methanol and ethanol with different mole fractions, the results indicated that weak HBs interactions in binary solutions can be reflected by the linear frequency shift of the C-H bond vibrations (in methanol and ethanol) with different molar concentrations. Furthermore, the geometrical structure was optimized using DFT simulation, and the vibration analysis and interaction energy were carried out. The simulated Raman spectra are in good agreement with the experiments. In addition, high-pressure Raman spectra of CS2 were obtained by diamond anvil cell technique (up to 9.19 GPa) and a pressure-induced phase transition was observed at 1.71 GPa. The results demonstrated that the pressure-induced polymerization phase transition of CS2 molecules causes the close packing and more orderly arrangement of molecules, resulting in the enhancement of FR coupling. HB and high pressure tune the FR of the CS2 molecule differently.

Enhancement of stimulated Raman scattering of a weak vibration mode in tetrahydrofuran through the energy-transfer resonance of lycopene.

A method of energy-transfer resonance of lycopene used to enhance stimulated Raman scattering (SRS) of a weak vibration C-O mode in tetrahydrofuran (THF) was developed in this study. Only C-H SRS was observed in pure THF at high energies. When lycopene was added, the C-O SRS located at 915 cm-1 of the weak vibration mode in THF was observed. The maximum SRS enhancement of the C-O mode was achieved when the concentration was 3.72 × 10-6 mol/L because of the resonance enhancement of the solute, which transferred the excess vibrational energy to the solvent. Moreover, the pulse width compression phenomenon of the C-H vibration in the presence of C-O SRS was obtained.

Cationic complex-enhanced C-H stimulated Raman scattering in naphthalene-benzene solution.

Ring skeleton vibrations of aromatic series are dominant in Raman spectroscopy compared with the C-H stretching vibrations. When a laser-induced plasma (LIP) was generated in a mixed solution of naphthalene and benzene, an anomalous enhancement was observed in stimulated Raman scattering (SRS) of aromatic C-H stretching vibrations of naphthalene (3055 cm-1). However, SRS of C-H stretching vibrations of benzene at 3060 cm-1 disappeared. The LIP produced electrons and cations, and the transient production of ionized material contributed to the enhancement of SRS of C-H vibrations of naphthalene. Density functional theory calculations showed that the C-H Raman activity of the naphthalene molecules in (naphthalene-benzene)+ heterodimer was significantly enhanced compared with neutral naphthalene. In addition, SRS pulse durations were better compressed in pure benzene and naphthalene due to the self-focusing effect.

Temperature dependence of stimulated Raman scattering from a VYO4 crystal.

The microstructural, electrical, and optical properties of crystals are critical to laser device performance, and the temperature-dependence effect of crystals has gained a great deal of attention in research. The linewidth, stimulated Raman scattering (SRS) shift, and intensity of the characteristic peak at 890 cm-1 of YVO4 crystal have been investigated between 148 and 448 K. As the crystal temperature increases, the bond length increases and the crystal force constant decreases, and the phonon softening process arises in the crystal at high temperature. The temperature effect on Raman shift and full width at half maximum is explained in detail in terms of the phonon anharmonic effect. The temperature dependence of SRS can be well demonstrated by an empirical equation. This work can provide new insights into the further understanding of lattice anharmonicity and contribute to the discovery of new optoelectronic materials.

Pressure-induced Fermi resonance between fundamental modes in α-Hydroquinone.

Fermi resonance (FR), a prevalent phenomenon in molecules, has an important effect in spectrum analysis. As an effective way to change the molecular structure and tune symmetry, high-pressure techniques can often induce FR. Hydroquinone (HQ) is a hydrogen-bonded crystal that tends to form a solid inclusion compound with a suitable guest and has wide applications. Inthiswork, a high-pressure technique was used to investigate α-HQ using high pressure to tune the symmetry to produce FR. Raman and infrared spectra of α-HQ were investigated at ambient pressure, and then Raman spectra under high pressure of α-HQ were investigated up to 19.64 GPa. Results indicated that there were two phase transitions found at about 3.61 and 12.46 GPa. Fundamental FR was not present in α-HQ molecules at ambient pressure. At 3.61 GPa, the first-order phase transition occurred due to the pressure-induced symmetry change, resulting in two Raman modes at 831 cm-1 and 854 cm-1 with the same symmetry, thereby providing evidence that the fundamental FR phenomenon occurred. Furthermore, the pressure-induced changes of the FR parameters were elucidated. Thus pressure provided an effective way to study FR between two asymmetric species.

Exploring electronic energy level structure and excited electronic states of ß-carotene using DFT.

Carotenoids are a class of natural pigments that play a fundamental role in photosynthesis and optoelectronics. However, the complexity of their energy level structure and electronic states has prevented a clear interpretation of their photophysics and photochemistry. The mediating nonradiative decay of the bright S2 state to the dark S1 state of carotenoids involves a population of bridging intermediate state. Herein, time-dependent DFT was used to study the energy level and electronic excitation process of ß-carotene. A π-π* transition and π electron delocalization of electron excitation could be inferred based on the difference in the electron cloud distribution of the HOMO and LUMO orbitals. Through the electronic transition contribution in the UV-vis spectra and the electron density difference between the ground state and the excited state, the electronic energy level structure and possible dark state were analyzed. On this basis, the electronic excitation process of ß-carotene was theoretically studied by combining electron-hole analysis and transition density matrix (TDM). There was a charge transfer from the ß-ionone ring to the long-chain in the (S0) → (S2), (S0) → (S4) and (S0) → (S5).

Intermolecular energy transfer-enhanced super-broadband stimulated Raman scattering in cyclohexane-benzene mixtures.

Supercontinuum radiation has found numerous applications in diverse fields encompassing spectroscopy, pulse compression, and tunable laser sources. Anomalous enhanced stimulated Raman scattering (SRS) of cyclohexane-benzene mixtures was obtained in this study. SRS of the pure solvent, the multi-order Stokes of the strongest fundamental vibration modes, and energy transfer in intra-molecular modes were observed. SRS of the mixture revealed that the cross-pumping effect was generated between the C-H stretching (v2) mode of cyclohexane and the C=C ring skeleton (v1) mode of benzene, thereby producing the intermolecular secondary stimulated Raman emission and the appearance of two super-broadband radiations at 664.36-673.9 nm and 704.62-729.22 nm. The results suggest that the energy transfer of intermolecular vibrational modes, where the strongest vibrational mode excites other vibrational modes, is a simple approach for generating supercontinuum coherent radiation.

Hydrogen bond network dynamics of heavy water resolved by alcohol hydration under an intense laser.

Despite a great deal of effort spanning for decades, it remains yet puzzling concerning how alcohol molecules functionalize the hydrogen bond (H-bond) networks of water. We employed an isotopic substitution method (using alcohol-heavy water system) to avoid spectral overlap between the alcohol hydroxyl groups and water hydrogen bonds. We showed spectrometrically that under the strong pulse laser, the low mixing ratio (VA < 20%) of alcohol can strengthen the H-bond network structure of D2O through :ÖC2H6↔ D2Ö: compression. But when VA > 20%, H-bond network of D2O will deform via the self-association between alcohol molecules. Our experiments not only reveal the H-bond kinetics of heavy water-alcohol interactions but also provide important reference for understanding the distinctive properties of H-bond in water-organic system.

Hydrogen-Bond Dynamics and Water Structure in Aqueous Ethylene Glycol Solution via Two-Dimensional Raman Correlation Spectroscopy.

The hydrogen-bond (H-bond) dynamics and water structural transitions in aqueous ethylene glycol (EG) solution were investigated on the basis of concentration- and temperature-dependent two-dimensional Raman correlation spectroscopy (2D Raman-COS). At room temperature, EG-induced enhancement of the water structure when the EG/water molar ratio is less than 1:28 resulted from the hydrophobic effect around the methylene groups of EG. The decrease in the temperature caused an enhancement of the Raman peak at about 3200 cm-1, representing an increase in the orderliness of water molecules. Further analysis of the water-specific structures by 2D Raman-COS reveals that the strong H-bond structure preferentially responds to external perturbations and induces a weak H-bond structural transition in water. Finally, EG-induced water structural transitions were calculated by the density functional theory (DFT). Hopefully, 2D Raman-COS combined with DFT calculations would advance the study of solute-induced water structural transitions in water-organic chemistry.

Tuning the Fermi resonance of pyridine using ethanol molecules.

The Fermi resonance (FR) phenomenon is prevalent in infrared and Raman spectroscopy, and it can be observed in a variety of molecules. In particular, pyridine is a compound that has two Fermi doublets: ν1 âˆ¼ ν12 and ν1 + ν6 âˆ¼ ν8. To analyze the effect of environmental changes on the FR, this study first investigated the Raman spectra of pyridine mixed with ethanol at different concentrations. Results indicated that the FR parameters exhibited a nonlinear dependence on the pyridine concentration fractions, and changing the concentration fraction of pyridine led to different hydrogen bond strengths. Second, the interaction mechanism of pyridine-ethanol binary solutions was analyzed by two-dimensional correlation Raman spectroscopy (2DCRS). In addition, high-pressure Raman spectra of a 50% pyridine-ethanol binary solution were measured up to a pressure of 19.65 GPa by a diamond anvil cell technique, and the phase transition of the binary solution occurred at 6.35 GPa. Finally, the impact of ethanol on the FR of pyridine was determined by deducing the FR parameters at different pressures. The turning point at 6.35 GPa was consistent with the Raman frequency-pressure relationships. The results demonstrated that changes in the intensity of ν1 did not affect the FR of ν1 + ν6 âˆ¼ ν8, whereas the undisturbed frequency ν1 still played a role in the FR. When the pressure was compressed to 13.36 GPa, the disappearance of the Raman peaks (ν1 and ν1') was attributed to the tuning of the molecular symmetry by pressure during the phase transition.

Hydrogen bonding network dynamics of 1,2-propanediol-water binary solutions by Raman spectroscopy and stimulated Raman scattering.

Raman spectroscopy and stimulated Raman scattering (SRS) were used to investigate the hydrogen bonding (HB) network in 1,2-propanediol (1,2-PD)-water binary solutions. Abnormal changes in hydrogen bonds (HBs) were detected when V1,2-PD (volume fraction of the1,2-PD) was 0.4. In the case of Raman spectroscopy, the HB strength of water is weakened and then strengthened with the increase of 1,2-PD volume fraction. In the case of SRS, two new peaks at 3283 cm-1 and 3319 cm-1 were appeared, which demonstrated the appearance of ice-like structures near the methyl group and the weakening of HBs. Based on these phenomena, the HB structure of this binary system underwent a transition from H2O-H2O to H2O-1,2-PD when the V1,2-PD was 0.4 as V1,2-PD increased. This work serves as a reference value for the study of HB networks in alcohol-water binary solutions.

Efficient frequency conversion and the crossing-pump effect of stimulated Raman scattering in an aqueous sodium sulfate solution.

The cascaded stimulated Raman scattering (SRS) of an aqueous sodium sulfate solution was investigated as well as the generation of the crossing-pump effect. With the introduction of dual sample cells, the first-order Stokes of the O-H stretching vibrational mode was able to act as the pump light to excite the Stokes of the S-O stretching vibrational mode, and a new Raman peak was obtained at 4423 cm-1. The dual sample cell device not only lowered the SRS threshold, but also enhanced the four-wave mixing (FWM) process. Compared to the input laser of 7 ns/pulse, the first-order Stokes of O-H was compressed to a pulse width of 413 ps after passing through the dual sample cells. The SRS of aqueous sodium sulfate solution covered an ultrabroad wavelength ranging from 441 nm to 720 nm (a Raman shift ranging from -3859 cm-1 to 4923 cm-1). The cone-shaped launch ring of the FWM process was also recorded. This work provides a reference for the establishment of laser frequency conversion devices using an aqueous sodium sulfate solution as the Raman medium.

Investigated hydrogen-bond network kinetics of acetone-water solutions by spontaneous and stimulated Raman spectroscopy.

The hydrogen bond (HB) network structure and kinetics of the acetone-water mixed solutions were investigated by the spontaneous Raman and stimulated Raman scattering (SRS) spectra. The HB network of water molecules was enhanced when the volume fraction of acetone ranged from 0 to 0.25. Two new SRS peaks of water at 3272 and 3380 cm-1 were obtained, resulting from the cooperation of the polar carbonyl (C = O)-enhanced HB and the ice-like structure formed around the methyl groups. However, when the volume fraction went beyond 0.25, the spontaneous Raman main peak at 3445 cm-1 showed a significant blue-shift, and the corresponding SRS signal disappeared, indicating that the HB of water was weakened, which originated from the self-association of acetone. In the meantime, the fully tetrahedral HB structure among water molecules was destroyed at the higher volume fraction (≥ 0.8). Hopefully, our study here would advance the study of HB network structures and kinetics in other aqueous solutions.

Generation of dual-supercontinuum coherent radiation in acetone mixed with carbon disulfide by stimulated Raman scattering.

Stimulated Raman scattering (SRS) in a liquid has been a major focus of nonlinear optics. Traditional SRS generates single or cascaded Stokes components arising from spontaneous Raman noise. Herein, we report the formation mechanism of a specific spectrum-continuous spectroscopy technique based on SRS of mixed liquids. SRS of a mixed acetone and carbon disulfide solution is investigated by a pulsed Nd:YAG laser with a wavelength of 532 nm. Two remarkably asymmetric broadened SRS lines are obtained. When the volume ratio is 7:3, the broadened spectral bands are optimized. The supercontinuum spectroscopy phenomenon is explained by hydrogen bond formation, adjacent vibrational modes coupling, and laser-induced plasma generation. This technique has the potential to contribute to the development of a supercontinuum Raman laser.

Coherent Raman comb generation in H2O2aqueous solutions by crossing-pump stimulated Raman scattering.

The cascaded stimulated Raman scattering (SRS) of 30% H2O2 aqueous solutions was investigated using a pulsed Nd: YAG laser with a wavelength of 532 nm. The transfer of excess electrons between H2O2 and H2O molecules enhanced the SRS. Together, the decomposition of H2O2 and the intense SRS Stokes led to the generation of the crossing-pump effect of H2O2 aqueous solutions and the appearance of a new peak at 4229 cm-1 that is excited by Stokes as the pump source. Crossing-pump not only reduced the threshold but also generated the broadband-coherent Raman comb, defined as a coherent radiation wavelength ranging from 434 to 831 nm (i.e., a Raman shift ranging from -4225 to 6756 cm-1). The anti-Stokes SRS was attributed to the four-wave mixing (FWM) process.

Modulated excited state geometry and Electron-Phonon coupling of lutein by temperature and solvent polarizability.

Resonance Raman spectroscopy is one of the spectroscopic methods often chosen for studying linear polyene molecules because the Raman intensities of their υ1 (C = C) and υ2 (C-C) stretching vibrations are sensitive to electron-phonon coupling and the π-electron energy gap. Here, the resonance Raman and absorption spectra of lutein were studied as a function of solvent polarizabilities and of temperature in the CS2 solvent. For lutein in CS2, as the temperature decreased and CS solidified, the Raman scattering cross-section (RSCS) and the electron-phonon coupling constant had opposite dependence trends on temperature. The wavenumber of the lutein 0-0 electronic transition showed a marked shift to lower wavenumbers when the polarizability of the solvents decreased, and the Huang-Rhys (HR) factors and electron-phonon coupling also decreased. This work helps explore the influence of the external environment (e.g., temperature and solvent) on the excited state geometry of linear polyene molecules.

Determination of temperature-dependent Fermi resonance in acetonitrile-water binary solution by two-dimensional correlation Raman spectroscopy.

Acetonitrile (AN), as an organic solvent, has a wide range of applications. The C≡N stretching vibration mode (ν2) and the combination mode (ν3 + ν4) are coupled by Fermi resonance (FR). In this work, the phase transition and the interaction mechanism of the 60% AN-water binary solution (AN-Water) were analyzed by calculating FR parameters and two-dimensional correlation Raman spectroscopy (2DCRS). The change in the ν2 band and the base bands ν3 and ν4 caused energy transfer by anharmonic interaction, which led to a change in FR parameters. With a reduced temperature, the energy transfer was caused by microheterogeneity and the energy transfer effect (293-273 K), the phase separation (263-233 K), and the phase transition of AN (223-173 K). The 2DCRS and Gaussian deconvolution provided more information on FR, which revealed the interaction mechanism of the Fermi doublet. The polarity and binding modes of molecules provided a new perspective for analyzing the transmission of electrons and ions in the electrolyte at different temperatures.

Short-pulse broadband stimulated Raman scattering in carbon disulfide via resonance cascading.

Cascaded stimulated Raman scattering (SRS) of carbon disulfide (CS2) was investigated by a pulsed Nd:YAG laser with a wavelength of 532 nm. The fourth-order Stokes and second-order anti-Stokes lines were generated when the pump laser energy was about 1.909 mJ in one sample cell (C1) only. However, the same result was obtained in the second sample cell (C2) with a pump energy of 0.883 mJ. At the same time, the fifth-order Stokes line was produced in C2 when the pump energy increased to 1.208 mJ, and the coherent radiation wavelength ranged from 498 to 644 nm. The result was attributed to the resonance enhancement effect, where the frequency difference between the pump laser and the Stokes light emitted from the working medium (CS2) self-matched with the vibrational energy level of C=S, which resulted in the generation of the cascaded broadband SRS. The anti-Stokes SRS was attributed to four-wave mixing. Simultaneously, the pulse durations of the Stokes and anti-Stokes were compressed to about 380 ps by SRS and laser-induced breakdown. The resonance effect not only reduced the threshold, but it also generated broadband and short-pulse SRS.