Stretch Mode Research Articles

Infrared spectra of neutral dimethylamine clusters: An infrared-vacuum ultraviolet spectroscopic and anharmonic vibrational calculation study.

Infrared-vacuum ultraviolet (IR-VUV) spectra of neutral dimethylamine clusters, (DMA)n (n = 2-5), were measured in the spectral range of 2600-3700 cm-1. The experimental IR-VUV spectra show NH stretch modes gradually redshift to 3200-3250 cm-1 with the increase in the cluster size and complex Fermi Resonance (FR) pattern of the CH3 group in the 2800-3000 cm-1 region. Ab initio anharmonic vibrational calculations were performed on low-energy conformers of (DMA)2 and (DMA)3 to examine vibrational coupling among CH/NH and to understand the Fermi resonance pattern in the observed spectra features. We found that the redshift of NH stretching mode with the size of DMA cluster is moderate, and the overtone of NH bending modes is expected to overlap in frequency with the CH stretching fundamental modes. The FR in CH3 groups is originated from the strong coupling between CH stretching fundamental and bending overtone within a CH3 group. Well-resolved experimental spectra also enable us to compare the performance of ab initio anharmonic algorithms at different levels.

Ultrafast Vibrational Dynamics of CO Ligands on RuTPP/Cu(110) under Photodesorption Conditions

We have studied CO coordinated to ruthenium tetraphenylporphyrin (RuTPP)/Cu(110) and directly adsorbed to Cu(110), using femtosecond pump-sum frequency probe spectroscopy, to alter the degree of electron-vibration coupling between the metal substrate and CO. We observe the facile femtosecond laser-induced desorption of CO from RuTPP/Cu(110), but not from Cu(110). A change in the vibrational transients, in the first few picoseconds, from a red- to blue-shift of the C–O stretching vibration under photodesorption conditions, was also observed. This drastic change can be explained, if the cause of the C–O frequency redshift of Cu(110) is not the usually-assumed anharmonic coupling to low frequency vibrational modes, but a charge transfer from hot electrons to the CO 2π* state. This antibonding state shifts to higher energies on RuTPP, removing the C–O redshift and, instead, reveals a blueshift, predicted to arise from electron-mediated coupling between the coherently excited internal stretch and low frequency modes in the system.

Mid-infrared dual-comb spectroscopy of volatile organic compounds across long open-air paths

Open-path measurements of atmospheric gas species in the air, including volatile organic compounds, are essential to quantify emissions from sources like oil and gas, forest fires, and industry. Here, we extend open-path dual-comb spectroscopy to probe the fundamental mid-infrared C-H stretch modes of volatile organic compounds over up to 1 km long open-air paths. The spectrometer’s high resolution and accuracy facilitates suppression of strong spectral clutter from atmospheric water and methane, allowing quantitative measurements of released acetone and isopropanol with a 1−σ sensitivity of 5.7 ppm·m and 2.4 ppm·m, respectively, and of ambient atmospheric ethane with a 1−σ sensitivity of 0.4 ppb, measured with 1 min time resolution over hours. These results underline the potential of dual-comb spectroscopy for quantifying emissions.

Ab initio molecular dynamics simulation of supercritical aqueous ionic solutions: Spectral diffusion of water in the vicinity of Br− and I− ions

Supercritical aqueous ionic solutions containing bromide (Br−) and iodide (I−) ions have been studied using Car-Parrinello molecular dynamics simulation at two different concentrations and at two different densities. The time dependent trajectory has been used for calculating vibrational spectral diffusion, structural properties and, for other dynamical properties such as hydrogen bond dynamics, orientational relaxation and residence dynamics. The vibrational spectral diffusion of fluctuating OD stretch mode inside the solvation shell of the ions and in the bulk has been studied using frequency-frequency time correlation function. Hydrogen bond dynamics, orientational relaxation and residence dynamics of Sc-water have been investigated using population correlation function approach. The water molecules inside the solvation shell of Br− and I− ions are found to show complex molecular dynamics in comparison to the water-water dynamics. The concentration dependent spectral diffusion has been observed and it occurs in multiple time scales in the solvation shell of Br− and I− ions. At supercritical condition, the ion-water hydrogen bond shows faster dynamics with respect to the same at ambient condition and slower dynamics with respect to the water-water hydrogen bond dynamics at supercritical condition.

Sintering behavior, microwave dielectric properties of Ca0.66Ti0.66Nd0.34Al0.34O3 ceramics revealed by microstructure and Raman scattering

Ca0.66Ti0.66Nd0.34Al0.34O3(CTNA) ceramics were prepared by solid-state reaction method and their sintering behavior, microwave dielectric properties, and microstructure were investigated. CTNA ceramics were examined by Raman scattering to reveal the correlation of perovskite structure with the microwave properties. It found that the area of peak A1g(O) stretch mode reflects the quality factor Q × f value in the perovskite materials. This concludes that the oxygen octahedron plays an important role of the material's microwave performance. Sintering temperature affected the unit cell volume and the lattice parameters of the CTNA ceramics, the grain size distribution, the Gibbs free energy, the thermal expansion coefficient (CTE), and the dielectric properties (εr, Q×f, τf). The samples sintered at 1500 °C displayed the best dielectric constant and Q×f, as 44.94 and 41922.22 GHz, respectively.

Ultrafast Transient Dynamics of Adsorbates on Surfaces Deciphered: The Case of CO on Cu(100)

Time-resolved vibrational spectroscopy constitutes an invaluable experimental tool for monitoring hot-carrier-induced surface reactions. However, the absence of a full understanding of the precise microscopic mechanisms causing the transient spectral changes has limited its applicability. Here we introduce a robust first-principles theoretical framework that successfully explains both the nonthermal frequency and linewidth changes of the CO internal stretch mode on Cu(100) induced by femtosecond laser pulses. Two distinct processes engender the changes: electron-hole pair excitations underlie the nonthermal frequency shifts, while electron-mediated vibrational mode coupling gives rise to linewidth changes. Furthermore, the origin and precise sequence of coupling events are finally identified.

Simultaneous enhancement of transition dipole strength and vibrational lifetime of an alkyne IR probe viaπ-d backbonding and vibrational decoupling.

Alkyne infrared (IR) probes 1-6 with Si and S (or Se) atoms incorporated into the C[triple bond, length as m-dash]C bond were synthesized, and the vibrational properties of their C[triple bond, length as m-dash]C stretch mode were studied using Fourier transform infrared (FTIR) and femtosecond IR pump-probe (IR PP) spectroscopies in combination with quantum chemical calculations. From FTIR studies, the transition dipole strengths (in units of 10-2 D2) of 1-3 having the Si atom were measured to be 1.85, 3.32, and 2.52, whereas those of 4-6 having no Si atom were measured to be 0.13, 0.20, and 0.17, respectively, in CHCl3. Thus, the increase in the transition dipole strength of the C[triple bond, length as m-dash]C stretch mode upon incorporation of the Si atom into the C[triple bond, length as m-dash]C bond is by a factor of about 14 or higher. The large increase in the transition dipole strength of the C[triple bond, length as m-dash]C stretch mode upon such Si incorporation is attributed to π-d backbonding between the C[triple bond, length as m-dash]C group's π and Si atom's d orbitals. From IR PP experiments, the vibrational lifetimes of the C[triple bond, length as m-dash]C stretch mode in 1-3 having none, S, and Se atoms were determined to be 5.7 ± 0.7, 13.0 ± 1.1, and 94.2 ± 5.8 ps, respectively, in CHCl3. Thus, the increase in the vibrational lifetime of the C[triple bond, length as m-dash]C stretch mode upon incorporation of the S (or Se) atom between the phenyl ring and the C[triple bond, length as m-dash]C bond is by a factor of about 2 (or 16) or higher. The large increase in the vibrational lifetime of the C[triple bond, length as m-dash]C stretch mode upon such S (or Se) incorporation is attributed to its heavy atom effect impeding vibrational couplings between the C[triple bond, length as m-dash]C stretch and phenyl ring vibrations. From two-dimensional infrared (2DIR) experiments, the large transition dipole strength and long vibrational lifetime of 3 containing the Si and S (or Se) atoms were shown to enable the measurement of its 2DIR spectra up to 500 ps. The strongly absorbing alkynes with long vibrational lifetimes will be a promising probe of molecular dynamics in nonlinear vibrational spectroscopy and imaging on an extended time scale.

Temperature dependence of the ultrafast vibrational echo spectroscopy of OD modes in liquid water from first principles simulations.

The rate of vibrational spectral diffusion of OD/OH stretch modes of water is known to be interconnected with the hydrogen bond rearrangement dynamics in aqueous media as found in several recent experiments and molecular simulations. In the present study, the temperature dependence of vibrational spectral diffusion of OD stretch modes in liquid water is investigated from first principles by using the method of ab initio molecular dynamics. Kinetic rates obtained from the frequency time correlation function (FTCF), the slope of the 3-pulse photon echo (S3PE) and local structure correlation functions are used in the Arrhenius equation to determine the energy barrier for hydrogen bond rearrangement in liquid water. The slope of the 3-pulse photon echo is determined within the cumulant and Condon approximations. Although the trend found at the low temperature is slightly non-Arrhenius, the barrier for hydrogen bond rearrangement is found to be around 4.2 kcal mol-1 from all the metrics considered here. It is in good agreement with the hydrogen bond energy determined from different experiments and theoretical studies. Based on the findings, a strong correlation between the vibrational spectral diffusion timescale and hydrogen bond dynamics is identified, which gets even more pronounced at low temperatures. Spatio-temporal correlations between frequency fluctuations and the local hydrogen bond network are also explored.

Low energy (1-19 eV) electron scattering from condensed thymidine (dT) II: comparison of vibrational excitation cross sections with those of tetrahydrofuran and the recalibrated values of thymine.

Recent measurements of absolute vibrational cross sections (CSs) for low-energy electron (LEE) scattering from condensed thymidine (dT) allows comparison with CSs of its constituents; thymine and tetrahydrofuran (THF). To facilitate this comparison, the vibrational CSs of condensed thymine were remeasured at six electron incident energies and a correction was applied to the earlier thymine CS values measured by Lévesque et al. [Nucl. Instrum. Methods Phys. Res., Sect. B, 2003, 208, 225]. The incident energy dependence of the CS of each vibrational mode of dT is compared with the corresponding modes in thymine and/or THF. It is found that the magnitude of the CSs of the thymine breathing mode and the C-C stretch mode of THF are greatly attenuated in dT. Finally, the magnitudes of the total vibrational CSs of each molecule are compared. Below 4 eV, the total vibrational CSs of dT is greater than each of its two constituents. Interestingly, at higher energy (>6 eV), the magnitude of the total vibrational CS of dT is roughly equal to that of THF and is greater than thymine by only 15% at 10 eV, showing that the CSs of dT cannot be approximated by the addition of the CSs of its constituents over the entire energy range. These comparisons are discussed in terms of the basic principles involved in the formation and decay of shape resonances, which are known to be responsible for major enhancements of LEE-induced vibrational excitation at low electron energies.

Correction: Sub-Doppler infrared spectroscopy of resonance-stabilized hydrocarbon intermediates: ν3/ν4 CH stretch modes and CH2 internal rotor dynamics of benzyl radical.

Correction for 'Sub-Doppler infrared spectroscopy of resonance-stabilized hydrocarbon intermediates: ν3/ν4 CH stretch modes and CH2 internal rotor dynamics of benzyl radical' by A. Kortyna et al., Phys. Chem. Chem. Phys., 2017, 19, 29812-29821.

Time-resolved imaging of bound and dissociating nuclear wave packets in strong-field ionized iodomethane.

We report the results of a time-resolved coincident ion momentum imaging experiment probing nuclear wave packet dynamics in the strong-field ionization and dissociation of iodomethane (CH3I), a prototypical polyatomic system for photochemistry and ultrafast laser science. By measuring yields, kinetic energies, and angular distributions of CH3+ + I+ and CH3+ + I++ ion pairs as a function of the delay between two 25 fs, 790 nm pump and probe pulses, we map both, bound and dissociating nuclear wave packets in intermediate cationic states, thereby tracking different ionization and dissociation pathways. In both channels, we find oscillatory features with a 130 fs periodicity resulting from vibrational motion (C-I symmetric stretch mode) in the first electronically excited state of CH3I+. This vibrational wave packet dephases within 1 ps, in good agreement with a simple wave packet propagation model. Our results indicate that the first excited cationic state plays a key role in the dissociative ionization of CH3I and that it represents an important intermediate in the sequential double and multiple ionization at moderate intensities.

Rational design of plasma-enhanced catalysis at microscale dimensions for the dissociation of CO2

In this work, we consider the rational design of a plasma catalysis system for the splitting of carbon dioxide (CO2) via one-dimensional PIC/MCC simulations. We show that field emission-driven microdischarges (also called microplasmas) can selectively excite the asymmetric stretch mode, which is known to be more favorable to the dissociation of CO2, relative to the symmetric stretch mode. These results suggest that field emission-driven microdischarges could form the basis for intentionally coupling the plasma state with a catalyst for improving the performance of CO2 reforming.

Aromatic Charge Resonance Interaction Probed by Infrared Spectroscopy

AbstractCharge resonance is a strong attractive intermolecular force in aromatic dimer radical ions. Despite its importance, this fundamental interaction has not been characterized at high resolution by spectroscopy of isolated dimers. We employ vibrational infrared spectroscopy of cold aromatic pyrrole dimer cations to precisely probe the charge distribution by measuring the frequency of the isolated N−H stretch mode (νNH). We observe a linear correlation between νNH and the partial charge q on the pyrrole molecule in different environments. Subtle effects of symmetry reduction, such as substitution of functional groups (here pyrrole replaced by N‐methylpyrrole) or asymmetric solvation (here by an inert N2 ligand), shift the charge distribution toward the moiety with lower ionization energy. This general approach provides a precise experimental probe of the asymmetry of the charge distribution in such aromatic homo‐ and heterodimer cations.

Aromatic Charge Resonance Interaction Probed by Infrared Spectroscopy.

Charge resonance is a strong attractive intermolecular force in aromatic dimer radical ions. Despite its importance, this fundamental interaction has not been characterized at high resolution by spectroscopy of isolated dimers. We employ vibrational infrared spectroscopy of cold aromatic pyrrole dimer cations to precisely probe the charge distribution by measuring the frequency of the isolated N-H stretch mode (νNH ). We observe a linear correlation between νNH and the partial charge q on the pyrrole molecule in different environments. Subtle effects of symmetry reduction, such as substitution of functional groups (here pyrrole replaced by N-methylpyrrole) or asymmetric solvation (here by an inert N2 ligand), shift the charge distribution toward the moiety with lower ionization energy. This general approach provides a precise experimental probe of the asymmetry of the charge distribution in such aromatic homo- and heterodimer cations.

Dinitrogen Coupling to a Terpyridine-Molybdenum Chromophore Is Switched on by Fermi Resonance

Summary The traditional view of a chemical change is inherently local and classical, and such a change relies on a mix of thermodynamic and kinetic parameters to control reactivity. Often, the thermodynamic stability of chemical bonds necessitates significant energy input for activation. One fundamental question is potentially transformative: can quantum mechanics enable selective bond activation? A possible approach involves strategic input of energy to reaction-specific vibrational levels. Toward this goal, our work describes the coupling of vibrational motions in a terpyridine-molybdenum complex hosting a nonreactive substrate—dinitrogen. Ultrafast coherence spectroscopies revealed a Fermi-resonance coupling mechanism connecting in-plane breathing motion of the light-harvesting terpyridines with the stretching motion of the spatially disparate dinitrogen bridge. Notably, the coupling is significantly enhanced in the photoexcited state. This Fermi resonance indicates an energy conduit that drives the two motions in sync and thereby amplifies vibrational energy exchange. Achieving selective bond activation by bridging vibrations could present a quantum-inspired design principle in synthetic chemistry.

Structure and vibrational spectroscopy of methanesulfonic acid.

In this work, we have used a combination of vibrational spectroscopy (infrared, Raman and inelastic neutron scattering) and periodic density functional theory to investigate the structure of methanesulfonic acid (MSA) in the liquid and solid states. The spectra clearly show that the hydrogen bonding is much stronger in the solid than the liquid state. The structure of MSA is not known; however, mineral acids typically adopt a chain structure in condensed phases. A periodic density functional theory (CASTEP) calculation based on the linear chain structure found in the closely related molecule trifluoromethanesulfonic acid gave good agreement between the observed and calculated spectra, particularly with regard to the methyl and sulfonate groups. The model accounts for the large widths of the asymmetric S-O stretch modes; however, the external mode region is not well described. Together, these observations suggest that the basic model of four molecules in the primitive unit cell, linked by hydrogen bonding into chains, is correct, but that MSA crystallizes in a different space group than that of trifluoromethanesulfonic acid.

Ice Nucleation at the Water-Sapphire Interface: Transient Sum-Frequency Response without Evidence for Transient Ice Phase.

Heterogeneous ice nucleation at the water–sapphire interface is studied using sum-frequency generation spectroscopy. We follow the response of the O–H stretch mode of interfacial water during ice nucleation as a function of time and temperature. The ice and liquid states each exhibit very distinct, largely temperature-independent responses. However, at the moment of freezing, a transient response with a significantly different intensity is observed, with a lifetime between several seconds and several minutes. The presence of this transient signal has previously been attributed to a transient phase of ice. Here, we demonstrate that the transient signal can be explained without invoking a transient ice phase, as the transient signal can simply be accounted for by a linear combination of time-dependent liquid and ice responses.

Methods for Nonlinearities Reduction in Micromechanical Beams Resonators

In this paper, two methods for reducing the nonlinearities in microelectromechanical systems flexural beams resonators have been demonstrated with established theoretical models and validated experimental results. The first method improves the conventional method of mutual cancellation between nonlinearities, in which the electrical nonlinearity has been decoupled utilizing the tuning capacitors inside a comb-drive DETF resonator to be used to controllably cancel the mechanical nonlinearity, which makes the nonlinearity reduction tunable and, meanwhile, alleviates the discontinuity of frequency spectrum, thus improving the frequency stability. The second method based on a fundamental view to redesign the DETF resonator into a doublefree semicircular beam resonator that can be operated at an elastic mode to eliminate the axial extension existing in the stretch mode of DETF and minimize the A-f effect. The proposed methods can effectively reduce the nonlinearity to achieve resonators with a wide linear regime, high signal-to-noise ratio, and good capability of power handling. [2017-0313]

Vibrational Coupling between Organic and Inorganic Sublattices of Hybrid Perovskites.

The interplay of electronic and nuclear degrees of freedom in semiconductor hybrid organic-inorganic perovskites determines many of their fundamental photophysical properties. For instance, charge carriers are dressed with phonons, that is, form polarons, and combination modes composed of strongly mixed localized vibrations and delocalized phonons can provide pathways for electronic energy relaxation and dissipation. Mixing of the different types of nuclear motion in vibrational combination modes requires their strong coupling. The direct measurement of coupling between the high-frequency N-H stretch modes of the organic methylammonium and formamidinium ions and low-frequency Pb-I phonon modes of the inorganic sub-lattice in hybrid organic-inorganic perovskites is presented. The results reveal direct and substantial coupling between the non-covalently interacting organic and inorganic sub-lattices.

Role of precursors in controlling the size, shape and morphology in the synthesis of copper sulfide nanoparticles and their application for fluorescence detection

Synthesis of well controlled pure phase of CuS with defined shapes and sizes remains a challenge for effective applications. We studied the role of copper and sulfur source precursors in controlling the size, shape and morphology of CuS nanostructures using synthesized refluxing method. CuS nanoparticles are synthesized by varying Cu(CH3COO)2·H2O, Cu(NO3)2·3H2O, CuSO4·5H2O as copper precursors and CH4N2S, Na2S2O3·5H2O, Na2S as sulfur precursors. As synthesized copper sulfide nanoparticles were characterized by X-ray diffraction (XRD), Field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), energy dispersive X-ray (EDX), Ultra Violet - visible spectrophotometer (UV–Vis), Fourier transform infrared spectroscopy (FT-IR), and micro Raman spectroscopy. All precursors result into nano-size single phase covellite copper sulfide, except sodium sulfide as a sulfur source which resulted into mixed phases. Morphology of nano-systems varies (hexagonal plate like, tube like, cluster of nanoparticles, plate like and ball like nanostructures) with varying precursors. TEM images show particle size variation (particle size 20–25 nm). Elemental analysis using EDX confirm that stoichiometric ratio of Cu/S is approximately 1:1 which is in good agreement with the starting molar ratio. FT-IR and Raman spectra confirm the absence of Cu2S and the band width of S-S stretch mode is correlated with particle size. Optical energy band gap varies in the range 1.80–2.31 eV and is also correlated with crystalline size. The release rate of S2− ions in sulfur source and polarization of counter anion in copper source are found to be the deciding factors in controlling the size, shape and morphology.