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We recorded the hyper-Raman spectra resulting from the interaction of a near-infrared (near-IR) picosecond pulse and a terahertz (THz) ultrashort pulse at the surface of a (111) silicon sample. A simple model is proposed to analyze the evolution of the hyper-Raman spectra vs the time delay between the near-IR and THz pulses. It links the hyper-Raman spectra to the multi-phonon absorption in silicon. This approach makes it possible to demonstrate that, during carrier generation by the near-IR pulse, the two-phonon and three-phonon absorption bands are enhanced in modes involving optical phonons. This process results from the very rapid and strong population of the optical phonons induced by the photo-generated hot carriers. It occurs over a few hundreds of femtoseconds and lasts throughout the duration of the near-IR pulse. [ABSTRACT FROM AUTHOR]

The strong tendency for self-aggregation together with an intriguing mechanism for the microhydration of monoethanolamine (MEA) have been explored by low-temperature far-infrared cluster spectroscopy in doped neon "quantum" matrices at 4 K complemented by high-level quantum chemical modeling. In addition to the assignment of new mid-infrared perturbed intramolecular transitions, a distinct far-infrared transition is unambiguously assigned to the concerted large-amplitude hydrogen bond librational motion of the MEA homodimer. This observation confirms a global "head-to-head" intermolecular potential energy minimum associated with the formation of a compact doubly intermolecular OH⋯N hydrogen-bonded cyclic structure, where both monomeric intramolecular OH⋯N hydrogen bonds are broken upon complexation. By means of relative mixing ratio dependencies, dedicated annealing procedures, and selective complexation between MEA and isotopic H 2 16 O and H 2 18 O samples, distinct far-infrared transitions associated with large-amplitude intra-molecular hindered OH torsional motion and inter-molecular H2O librational (hindered c-type overall rotational) motion of the MEA monohydrate are furthermore assigned unambiguously for the first time. These spectroscopic observations reveal an intriguing metastable conformation, where H2O acts as a OH⋯O hydrogen bond donor to the hydroxy group instead of the amino group of MEA upon microhydration in the cryogenic neon environment, where the microhydration strengthens the intramolecular OH⋯N hydrogen bond of MEA due to hydrogen bond cooperativity. [ABSTRACT FROM AUTHOR]

Through comprehensive data analysis, we demonstrate that a χ(2)-induced artifact, arising from imperfect balancing in the conventional electro-optic sampling detection scheme, contributes significantly to the measured signal in 2D Raman–THz spectroscopy of non-centrosymmetric materials. The artifact is a product of two 1D responses, overwhelming the desired 2D response. We confirm that by analyzing the 2D Raman–THz response of an x-cut beta barium borate crystal. We furthermore show that this artifact can be effectively suppressed by implementing a special detection scheme. We successfully isolate the desired third-order 2D Raman–THz response, revealing a distinct cross-peak feature, whose frequency position suggests the coupling between two crystal phonons. [ABSTRACT FROM AUTHOR]

We use optical–optical double-resonance spectroscopy with a continuous wave (CW) pump and a cavity-enhanced frequency comb probe to measure the energy levels of methane in the upper part of the triacontad polyad (P6) with higher rotational quantum numbers than previously assigned. A high-power CW optical parametric oscillator, tunable around 3000 cm−1, is consecutively locked to the P(7, A2), Q(7, A2), R(7, A2), and Q(6, F2) transitions in the ν3 band, and a comb covering the 5800–6100 cm−1 range probes sub-Doppler ladder-type transitions from the pumped levels with J′ = 6 to 8, respectively. We report 118 probe transitions in the 3ν3 ← ν3 spectral range with uncertainties down to 300 kHz (1 × 10−5 cm−1), reaching 84 unique final states in the 9070–9370 cm−1 range with rotational quantum numbers J between 5 and 9. We assign these states using combination differences and by comparison with theoretical predictions from a new ab initio-based effective Hamiltonian and dipole moment operator. This is the first line-by-line experimental verification of theoretical predictions for these hot-band transitions, and we find a better agreement of transition wavenumbers with the new calculations compared to the TheoReTS/HITEMP and ExoMol databases. We also compare the relative intensities and find an overall good agreement with all three sets of predictions. Finally, we report the wavenumbers of 27 transitions in the 2ν3 spectral range, observed as V-type transitions from the ground state, and compare them to the new Hamiltonian, HITRAN2020, ExoMol, and the WKMLC line lists. [ABSTRACT FROM AUTHOR]

Two-dimensional electronic spectroscopy (2DES) is a powerful spectroscopic tool that allows us to study the dynamics of excited states. Exciton–exciton annihilation is at least a fifth order process, which corresponds to intrachromophoric internal conversion from the double-excited high-energy chromophoric state into the single-excited state of the same chromophore. At high excitation intensities, this effect becomes apparent in standard 2DES and can be inspected via high order n K 1 ⃗ − n K 2 ⃗ + K 3 ⃗ nonlinear processes. We calculate 2DES based on K 1 ⃗ − K 2 ⃗ + K 3 ⃗ and 2 K 1 ⃗ − 2 K 2 ⃗ + K 3 ⃗ wave mixing processes to reveal exciton–exciton annihilation (EEA) induced exciton symmetry breaking, which occurs at high excitation intensities. We present the general theory that captures all these processes for bosonic and paulionic quasiparticles in a unified way and demonstrate that the NEEs can be easily utilized for highly nonlinear two-dimensional spectra calculations by employing phase cycling for separating various phase matching conditions. The approach predicts various excitonic third- to fifth-order features; however, due to high excitation intensities, contributions of different order processes become comparable and overlap, i.e., the signals no longer can be associated with well-defined order-to-the-field contributions. In addition, EEA leads to breaking of the exciton symmetries, thus enabling population of dark excitons. Such effects are due to the local nature of the EEA process. [ABSTRACT FROM AUTHOR]

The dynamics of spin and charge-ordered phases in La1.67Sr0.33NiO4 single crystal have been investigated using high-frequency dielectric spectroscopy. The measurements were carried out in frequencies between 0.156 and 316 MHz and temperatures from 50 to 320 K. The intrinsic part of the response by excluding the Maxwell–Wagner relaxation region is obtained below TSDW ∼ 120 K. The intrinsic frequency-dependent real dielectric constant ɛ′ and conductivity σ′ can be well described in terms of the constant phase element revealing a complex charge-hopping process. Our results are in agreement with the spin-density-wave puddles' picture observed by the scanning micro-x-ray diffraction technique. These demonstrate that high-frequency dielectric spectroscopy can be utilized for investigating the various order phases in other transition metal oxides by considering their intrinsic responses. [ABSTRACT FROM AUTHOR]

This second paper in a series of two describes the chirped-pulse ice apparatus that permits the detection of buffer gas cooled molecules desorbed from an energetically processed ice using broadband mm-wave rotational spectroscopy. Here, we detail the lower ice stage developed to generate ices at 4 K, which can then undergo energetic processing via UV/VUV photons or high-energy electrons and which ultimately enter the gas phase via temperature-programmed desorption (TPD). Over the course of TPD, the lower ice stage is interfaced with a buffer gas cooling cell that allows for sensitive detection via chirped-pulse rotational spectroscopy in the 60–90 GHz regime. In addition to a detailed description of the ice component of this apparatus, we show proof-of-principle experiments demonstrating the detection of H2CO products formed through irradiation of neat methanol ices or 1:1 CO + CH4 mixed ices. [ABSTRACT FROM AUTHOR]

Fluorescent lipid probes such as 1-palmitoyl-2-(6-[7-nitro-2-1,3-benzoxadiazol-4-yl]amino-hexanoyl)-sn-glycero-3-phosphocholine (C6 NBD-PC) have been used extensively to study the kinetics of lipid flip-flop. However, the efficacy of these probes as reliable reporters of native lipid translocation has never been tested. In this study, sum-frequency vibrational spectroscopy (SFVS) was used to measure the kinetics of C6 NBD-PC lipid flip-flop and the flip-flop of native lipids in planar supported lipid bilayers. C6 NBD-PC was investigated at concentrations of 1 and 3 mol. % in both chain-matched 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and chain-mismatched 1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC) to assess the ability of C6 NBD-PC to mimic the behavior of the surrounding matrix lipids. It was observed that C6 NBD-PC exhibited faster flip-flop kinetics compared to the native lipids in both DPPC and DSPC matrices, with notably accelerated rates in the chain-mismatched DSPC system. SFVS was also used to measure the acyl chain orientation and gauche content of C6 NBD-PC in both DPPC and DSPC membranes. In the DSPC matrix (chain mismatched), C6 NBD-PC was more disordered in terms of both gauche content and acyl tilt, whereas it maintained an orientation similar to that of the native lipids in the DPPC matrix (chain matched). In addition, the flip-flop kinetics of C6 NBD-PC were also measured using second-harmonic generation (SHG) spectroscopy, by probing the motion of the NBD chromophore directly. The flip-flop kinetics measured by SHG were consistent with those obtained from SFVS. This study also marks the first instance of phospholipid flip-flop kinetics being measured via SHG. The results of this study clearly demonstrate that C6 NBD-PC does not adequately mimic the behavior of native lipids within a membrane. These findings also highlight the significant impact of the lipid matrix on the flip-flop behavior of the fluorescently labeled lipid, C6 NBD-PC. [ABSTRACT FROM AUTHOR]

Vibrational sum frequency generation can provide valuable structural information at surfaces and buried interfaces. Relating the measured spectra to the complex-valued second-order susceptibility χ(2) is at the heart of the technique and a requisite step in nearly all subsequent analyses. The magnitude and phase of χ(2) as a function of frequency reveal important information about molecules and materials in regions where centrosymmetry is broken. In this tutorial-style perspective, the origins of the χ(2) phase are first described, followed by the utility of phase determination. Finally, some practical methods of phase extraction are discussed. [ABSTRACT FROM AUTHOR]

8-oxo-7,8-dihydro-2′-dexyoguanine (8-oxo-dG) can be tautomerized to a 6-enolate,8-keto tautomer through nearby-NH deprotonation at elevated pH. In this work, the N3-protonated 8-oxo-dG tautomers in deuterated pH-buffer solutions were studied using steady-state UV/Vis, FTIR, and ultrafast two-dimensional IR spectroscopies. The presence of 6,8-diketo and C6-anionic tautomers at neutral to basic conditions (pD = 7.4–12.0) was revealed by UV/Vis and FTIR results and was further confirmed by 2D IR signals in both diagonal and off-diagonal regions. However, the C6-enol tautomer, which may be an intermediate during the transition from 6,8-diketo to C6-enolate,C8-keto, was not observed appreciably due to its extreme low population. Furthermore, the neutral-to-anionic tautomeric transition of N3H-8-oxo-dG studied in this work occurs under more basic conditions than the N1H-8-oxo-dG reported previously, showing a higher pKa value for N3H than N1H. Finally, vibrational relaxation of the carbonyl stretching mode was found to be both molecular site dependent and pD dependent for 8oxo-dG. Taken together, this work shows that the ultrafast infrared spectroscopic method is effective for examining tautomers and their dynamics in nucleic acids. [ABSTRACT FROM AUTHOR]

In the continuity of a previous jet-cooled rovibrational study of trans and cis conformers of 2-furfural in the mid-infrared region (700–1750 cm−1) [Chawananon et al., Molecules 28 (10), 4165 (2023)], the present work investigates the far-infrared spectroscopy of 2-furfural using a long path absorption cell coupled to a high-resolution Fourier transform spectrometer and synchrotron radiation at the AILES beamline of the SOLEIL synchrotron. Guided by anharmonic calculations, vibrational energy levels and excited-state rotational constants are sufficiently predictive for a complete assignment of all fundamental and combination bands up to 700 cm−1, as well as the rovibrational analysis of 4 (1) low-frequency modes of trans-(cis-)2-furfural. A global rovibrational simulation, including far-infrared rovibrational lines and microwave and millimeter-wave rotational lines assigned in a previous study [Motiyenko et al., J. Mol. Spectrosc., 244, 9 (2007)] provides a reliable set of ground- and excited-state rotational parameters involving ring torsion, bending, and ring puckering modes of 2-furfural. In a second step, a rovibrational analysis of several hot band sequences, mainly involving the lowest frequency ring CHO torsion mode, is carried out. Reliable values of some anharmonic coefficients are obtained experimentally and could serve as a benchmark for validating advanced anharmonic calculations related to these large amplitude motions of flexible molecules. [ABSTRACT FROM AUTHOR]

Photocurrent measurements are widely used to study the intrinsic optoelectronic properties of semiconductors, such as photocarrier generation efficiency and carrier mobility, as well as evaluate the performance of optoelectronic devices, such as solar cells and photodetectors. Interferometric spectroscopy precisely measures optical properties and gathers optical spectra information on semiconductors. Consequently, photocurrent-based interferometric measurements, with high signal-to-noise ratios, high resolution, and broad frequency bandwidths, can probe the energy distributions of low-density defects and impurities and investigate charge transport in materials and devices. Here, we demonstrate that photocurrent interference spectroscopy reveals the intrinsic properties of solar-cell materials: bulk crystals of GaAs and halide perovskite, and thin films of halide perovskite and quantum dot. We show that homodyne interference spectroscopy of photocurrent can monitor low-density localized states in semiconductors and that it can be used in combination with other spectroscopy techniques, such as photoluminescence measurements, to provide a deep understanding of photocurrent generation processes. Furthermore, we show that heterodyne interference spectroscopy of photocurrent can be used to investigate the frequency dependence of material parameters, such as the dielectric constant, absorption coefficient, and reflectance. As an application, we used interference spectroscopy of photocurrent to show the impact of multiexcitons on the photoabsorption and photocarrier generation processes in quantum dot solar cells. Finally, we used it to reveal the distinctive spectral characteristics at the band edge of a halide perovskite, which is considered to be an exceptional solar-cell material with high energy conversion efficiency. [ABSTRACT FROM AUTHOR]

Vibrational coherences in ultrafast pump–probe (PP) and 2D electronic spectroscopy (2DES) provide insights into the excited state dynamics of molecules. Femtosecond coherence spectra and 2D beat maps yield information about displacements of excited state surfaces for key vibrational modes. Half-broadband 2DES uses a PP configuration with a white light continuum probe to extend the detection range and resolve vibrational coherences in the excited state absorption (ESA). However, the interpretation of these spectra is difficult as they are strongly dependent on the spectrum of the pump laser and the relative displacement of the excited states along the vibrational coordinates. We demonstrate the impact of these convoluting factors for a model based upon cresyl violet. A careful consideration of the position of the pump spectrum can be a powerful tool in resolving the ESA coherences to gain insights into excited state displacements. This paper also highlights the need for caution in considering the spectral window of the pulse when interpreting these spectra. [ABSTRACT FROM AUTHOR]

Azidoiron complexes serve as valuable photochemical precursors for catalytically active species containing high-valent iron. In bioinorganic chemistry, azido(tetraphenylporphinato)iron(III), i.e., [FeIII(tpp)(N3)] with tpp = 5, 10, 15, 20-tetraphenylporphyrin-21, 23-diido, constitutes the archetypal model system that was used to access for the first time the terminal nitridoiron core, FeV ≡ N, in the biomimetic redox-non-innocent ligand environment. So far, the light-induced dynamics leading to the oxidation of the metal and the release of dinitrogen from the N3-ligand have only been studied for precursors featuring redox-innocent auxiliary ligands that simplify the electronic structure change accompanying the photo-transformation. Here, we monitored the primary events of the above paradigmatic complex, following its optical excitation in the ultraviolet-to-visible spectral range using femtosecond spectroscopy with probing in both the UV–vis and mid-infrared regions. Following ultrafast Soret-excitation at 400 nm, the complex relaxes to the lowest excited sextet state by a first internal conversion in less than 200 fs. The excited state then undergoes vibrational relaxation on a time scale of roughly 2 ps before internally converting yet again to recover the sextet electronic ground state within 19.5 ps. Spectroscopic evidence is obtained neither for a transient occupation of the energetically lowest metal-centered state, 41A1, nor for vibrational relaxation in the ground-state. The primary processes seen here are thus in contrast to those previously derived from ultrafast UV-pump/vis-probe and UV-pump/XANES-probe spectroscopies for the halide congener [FeIII(tpp)(Cl)]. Any photochemical transformation of the complex arises from two-photon-induced dynamics. [ABSTRACT FROM AUTHOR]

We propose a new semiclassical approach to the calculation of molecular IR spectra. The method employs the time averaging technique of Kaledin and Miller upon symmetrization of the quantum dipole–dipole autocorrelation function. Spectra at high and low temperatures are investigated. In the first case, we are able to point out the possible presence of hot bands in the molecular absorption line shape. In the second case, we are able to reproduce accurate IR spectra as demonstrated by a calculation of the IR spectrum of the water molecule, which is within 4% of the exact intensity. Our time averaged IR spectra can be directly compared to time averaged semiclassical power spectra as shown in an application to the CO2 molecule, which points out the differences between IR and power spectra and demonstrates that our new approach can identify active IR transitions correctly. Overall, the method features excellent accuracy in calculating absorption intensities and provides estimates for the frequencies of vibrations in agreement with the corresponding power spectra. In perspective, this work opens up the possibility to interface the new method with the semiclassical techniques developed for power spectra, such as the divide-and-conquer one, to get accurate IR spectra of complex and high-dimensional molecular systems. [ABSTRACT FROM AUTHOR]

Time-domain spectroscopy encompasses a wide range of techniques, such as Fourier-transform infrared, pump–probe, Fourier-transform Raman, and two-dimensional electronic spectroscopies. These methods enable various applications, such as molecule characterization, excited state dynamics studies, or spectral classification. Typically, these techniques rarely use sampling schemes that exploit the prior knowledge scientists typically have before the actual experiment. Indeed, not all sampling coordinates carry the same amount of information, and a careful selection of the sampling points may notably affect the resulting performance. In this work, we rationalize, with examples, the various advantages of using an optimal sampling scheme tailored to the specific experimental characteristics and/or expected results. We show that using a sampling scheme optimizing the Fisher information minimizes the variance of the desired parameters. This can greatly improve, for example, spectral classifications and multidimensional spectroscopy. We demonstrate how smart sampling may reduce the acquisition time of an experiment by one to two orders of magnitude, while still providing a similar level of information. [ABSTRACT FROM AUTHOR]

The ultra-wide bandgap of gallium oxide provides a rich plethora of electrically active defects. Understanding and controlling such defects is of crucial importance in mature device processing. Deep-level transient spectroscopy is one of the most sensitive techniques for measuring electrically active defects in semiconductors and, hence, a key technique for progress toward gallium oxide-based components, including Schottky barrier diodes and field-effect transistors. However, deep-level transient spectroscopy does not provide chemical or configurational information about the defect signature and must, therefore, be combined with other experimental techniques or theoretical modeling to gain a deeper understanding of the defect physics. Here, we discuss the current status regarding the identification of electrically active defects in beta-phase gallium oxide, as observed by deep-level transient spectroscopy and supported by first-principles defect calculations based on the density functional theory. We also discuss the coordinated use of the experiment and theory as a powerful approach for studying electrically active defects and highlight some of the interesting but challenging issues related to the characterization and control of defects in this fascinating material. [ABSTRACT FROM AUTHOR]

We investigate how electronic excitations and subsequent dissipative dynamics in the water soluble chlorophyll-binding protein (WSCP) are connected to features in two-dimensional (2D) electronic spectra, thereby comparing results from our theoretical approach with experimental data from the literature. Our calculations rely on third-order response functions, which we derived from a second-order cumulant expansion of the dissipative dynamics involving the partial ordering prescription, assuming a fast vibrational relaxation in the potential energy surfaces of excitons. Depending on whether the WSCP complex containing a tetrameric arrangement of pigments composed of two dimers with weak excitonic coupling between them binds the chlorophyll variant Chl a or Chl b, the resulting linear absorption and circular dichroism spectra and particularly the 2D spectra exhibit substantial differences in line shapes. These differences between Chl a WSCP and Chl b WSCP cannot be explained by the slightly modified excitonic couplings within the two variants. In the case of Chl a WSCP, the assumption of equivalent dimer subunits facilitates a reproduction of substantial features from the experiment by the calculations. In contrast, for Chl b WSCP, we have to assume that the sample, in addition to Chl b dimers, contains a small but distinct fraction of chemically modified Chl b pigments. The existence of such Chl b derivates has been proposed by Pieper et al. [J. Phys. Chem. B 115, 4042 (2011)] based on low-temperature absorption and hole-burning spectroscopy. Here, we provide independent evidence. [ABSTRACT FROM AUTHOR]

Chromones are a class of naturally occurring compounds, renowned for their diverse biological activities with significant relevance in medicine and biochemistry. This study marks the first analysis of rotational spectra of both the chromone monomer and its monohydrate through Fourier transform microwave spectroscopy. The observation of nine mono-substituted 13C isotopologues facilitated a semi-experimental determination of the equilibrium structure of the chromone monomer. In the case of chromone monohydrate, two distinct isomers were identified, each characterized by a combination of O–H⋯O and C–H⋯O hydrogen bonds involving the chromone's carbonyl group. This study further delved into intermolecular non-covalent interactions, employing different theoretical approaches. The relative population ratio of the two identified isomers was estimated to be about 2:1 within the supersonic jet. [ABSTRACT FROM AUTHOR]

The dissociative double ionization of CH3I and CH2I2 irradiated with extreme ultraviolet light at hv = 100 eV is investigated by multi-electron–ion coincidence spectroscopy using a magnetic bottle type electron spectrometer. The spin–orbit state-resolved Auger electron spectra for the I 4d core-hole states, (I 4d3/2)−1 and (I 4d5/2)−1, provide clear identifications of electronic states of CH3I2+ and CH2I22+. The dominant ion species produced after the double ionization correlate with the Auger electron energy, showing that different fragmentation pathways are open depending on the electronic states populated by the Auger decay. Theoretical calculations are performed to understand the fragmentation from the doubly charged states and the observed spin–orbit specificity in the Auger decay. [ABSTRACT FROM AUTHOR]

When used as pump pulses in transient absorption spectroscopy measurements, femtosecond laser pulses can produce oscillatory signals known as quantum beats. The quantum beats arise from coherent superpositions of the states of the sample and are best studied in the Fourier domain using Femtosecond Coherence Spectroscopy (FCS), which consists of one-dimensional amplitude and phase plots of a specified oscillation frequency as a function of the detection frequency. Prior works have shown ubiquitous amplitude nodes and π phase shifts in FCS from excited-state vibrational wavepackets in monomer samples. However, the FCS arising from vibronic-exciton states in molecular aggregates have not been studied theoretically. Here, we use a model of vibronic-exciton states in molecular dimers based on displaced harmonic oscillators to simulate FCS for dimers in two important cases. Simulations reveal distinct spectral signatures of excited-state vibronic-exciton coherences in molecular dimers that may be used to distinguish them from monomer vibrational coherences. A salient result is that, for certain relative orientations of the transition dipoles, the key resonance condition between the electronic coupling and the frequency of the vibrational mode may yield strong enhancement of the quantum-beat amplitude and, perhaps, also cause a significant decrease of the oscillation frequency to a value far lower than the vibrational frequency. Future studies using these results will lead to new insights into the excited-state coherences generated in photosynthetic pigment–protein complexes. [ABSTRACT FROM AUTHOR]

The conformational space of cis-1,2-cyclohexanediol, a model molecule for cyclic vicinal diols, was investigated using rotational spectroscopy and density functional theory calculations. Four low energy conformers within an energy window of 5 kJ mol−1 were identified computationally. A rotational spectrum of jet-cooled cis-1,2-cyclohexanediol was recorded with a chirped pulse Fourier transform microwave spectrometer. Two sets of rotational transitions were observed and could be assigned to conformers of cis-1,2-cyclohexanediol. The non-observation of other low energy conformers was explained by conformational conversion barrier height calculations and results from experimental spectra recorded with different carrier gases. Eight isotopologues, including those with 13C and 18O, of the lowest energy conformer were observed, allowing the determination of the semi-experimental equilibrium structure, reSE. Interestingly, the structural analysis revealed that the C–O bond length of the intramolecular hydrogen-bond donor is shorter than that of the acceptor. This appears to be a general characteristic of vicinal diols and can be used as a novel hydrogen-bond marker in such compounds. [ABSTRACT FROM AUTHOR]

The C–H⋯S–S interactions are fundamentally important to understand the stability of biomacromolecules and their binding with small molecules, but they are still underappreciated. Herein, we characterized the C–H⋯S–S interactions in model molecular complexes. The rotational spectra of the complexes of diethyl disulfide with CH2CH2 and CH2CHF were measured and analyzed. All the detected structures are mainly stabilized by a C–H⋯S–S hydrogen bond, providing stabilization energies of 2.3–7.2 kJ mol−1. Incidental C–H⋯π or C–H⋯F interactions enhance the stabilization of the complexes. London dispersion, which accounts for 54%–68% of the total attractions, is the main driving force of stabilization. The provided bonding features of C–H⋯S–S are crucial for understanding the stabilizing role of this type of interaction in diverse processes such as supramolecular recognition, protein stability, and enzyme activity. [ABSTRACT FROM AUTHOR]

High-resolution spectroscopy of lead monoxide was performed in a range of 22 400–25 300 cm−1. A new Ω = 1 state located between the a1 and A0+ states was observed, and it is labeled c1. Spectroscopic constants, including the hyperfine interaction coefficient, were determined for the a1 and c1 states. The vibrational levels of these two electronic states are located closely to each other, and the interaction between them causes gradual exchange of electronic state properties in our observation wave number range. Our observation poses a question for the band assignment for the b0− state, which has some resemblance with this c1 state. [ABSTRACT FROM AUTHOR]

Proflavine (PF), an acridine DNA intercalating agent, has been widespread applied as an anti-microbial and topical antiseptic agent due to its ability to suppress DNA replication. On the other hand, various studies show that PF intercalation to DNA can increase photogenotoxicity and has potential chances to induce carcinomas of skin appendages. However, the effects of PF intercalation on the photophysical and photochemical properties of DNA have not been sufficiently explored. In this study, the excited state dynamics of the PF intercalated d(GC)9 • d(GC)9 and d(AT)9 • d(AT)9 DNA duplex are investigated in an aqueous buffer solution. Under 267 nm excitation, we observed ultrafast charge transfer (CT) between PF and d(GC)9 • d(GC)9 duplex, generating a CT state with an order of magnitude longer lifetime compared to that of the intrinsic excited state reported for the d(GC)9 • d(GC)9 duplex. In contrast, no excited state interaction was detected between PF and d(AT)9 • d(AT)9. Nevertheless, a localized triplet state with a lifetime over 5 µs was identified in the PF–d(AT)9 • d(AT)9 duplex. [ABSTRACT FROM AUTHOR]

In view of the current situation in which the OD-stretch vibrational spectra have been scarcely computed with non-polarizable rigid D2O models, we investigate the IR and Raman spectra of D2O by using a newly-reported model TIP4P/2005-HW. From the comparison between the calculations and experimental data, we find the excellent performance of TIP4P/2005-HW for vibrational spectroscopy of D2O in the same manner as TIP4P/2005 for H2O, although one may still conveniently employ an alternative method that regards OH as putative OD to calculate the OD-stretch spectra with similar quality from TIP4P/2005 trajectories. We also demonstrate that the appropriate setting for the spectral simulation of D2O under the time-averaging approximation reflects the slower dynamics (i.e., slower motion of translation and rotation due to the heavier mass and stronger hydrogen bond) of D2O than H2O. Moreover, we show from the theoretical calculations that the established interpretation of the OH-stretch spectra of H2O is finely applicable to the OD-stretch of D2O. [ABSTRACT FROM AUTHOR]

This article is a response to criticisms raised by Hirano et al. regarding research on sum frequency vibrational spectroscopy (SFVS) of benzene at interfaces. The authors address five points raised in the comment, including the local field effect, symmetry breaking of benzene, and field variations at interfaces. They argue that Hirano et al. underestimated the interfacial EQ SFVS and did not calculate the absolute amplitude of SFVS, which undermines the credibility of their research. The authors' computational SFVS aligns well with experimental results in terms of vibrational frequencies, amplitude, and line shapes, but there are discrepancies in vibrational frequencies and spectral line shapes between their results and the experimental data. [Extracted from the article]

We demonstrate massively parallel spectroscopic measurements of 12C2H2 using an optical frequency comb. This allows for the rapid and simultaneous estimation of self-broadening and self-shifting of more than 50 optical transitions between 1512 and 1538 nm. The use of a temperature-controlled sealed gas cell allows us to measure both pressure- and temperature-mediated broadening and shifting. We present the results for the pressure-mediated self-broadening and self-shifting coefficients for 59 optical lines that make up the v1 + v3 combination band and a selection of hot bands. Our ability to measure the broadening of numerous transitions allows for the confirmation of prior work that shows that there is no measurable vibrational dependence across all acetylene bands, despite the strong dependence of the broadening coefficient on the rotational number. We also present an extensive measurement of the temperature dependence of the self-broadening for each of these 59 lines. This work shows the revolutionary power afforded by the frequency combs for rapid generation of large datasets related to thermodynamic variations of the key spectroscopic parameters of important gases. [ABSTRACT FROM AUTHOR]

Hard ticks (Acari: Ixodidae) have been historically identified by morphological methods which require highly specialized expertise and more recently by DNA-based molecular assays that involve high costs. Although both approaches provide complementary data for tick identification, each method has limitations which restrict their use on large-scale settings such as regional or national tick surveillance programs. To overcome those obstacles, the matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) has been introduced as a cost-efficient method for the identification of various organisms, as it balances performance, speed, and high data output. Here we describe the use of this technology to validate the distinction of two closely related Dermacentor tick species based on the development of the first nationwide MALDI-TOF MS reference database described to date. The dataset obtained from this protein-based approach confirms that tick specimens collected from United States regions west of the Rocky Mountains and identified previously as Dermacentor variabilis are the recently described species, Dermacentor similis. Therefore, we propose that this integrative taxonomic tool can facilitate vector and vector-borne pathogen surveillance programs in the United States and elsewhere.

The dispersion properties of the absorption coefficients [α(ν)] of different multi-component silicate oxide glasses have been studied in the frequency region below the boson peak by using THz-time-domain spectroscopy. The value of α(ν)/ν2 has been shown to exhibit a minimum level (R) at low frequency and subsequently a linear increase in the form of r(ν/νBP + E) with increasing frequency, where νBP is the boson peak frequency and R, r, and E are material-specific constants. It has also been found that R ∝ r and E is a constant common to most glasses. This α(ν)/ν2 behavior is ascribed to the dispersion property of the light-vibration coupling coefficient under the reasonable vibrational density of state function. The minimum (constant) and linear terms of the α(ν)/ν2 spectrum are originated from the physical/chemical disorder-induced charge fluctuations in the long-range scale (constant term) and short-range scale (linear term), respectively. The fluctuating charge (σ1) caused by uncorrelated, long-range disorders has primary significance for determining the sub-THz absorption dispersion properties, and its value has been determined for each glass material. [ABSTRACT FROM AUTHOR]

Rotationally resolved Fourier-transform spectra of laser-induced fluorescence A 1 Σ u + ∼ b 3 Π u → X 1 Σ g + of K2 molecules were recorded and analyzed, yielding 4053 term values of the spin–orbit (SO) coupled A ∼ b complex of the 39K2 isotopologue with ∼0.01 cm−1 accuracy. Their compilation with 1739 term values from previously published sources allowed them to cover the energy range [9955, 17 436] cm−1 from the bottom of the lower-lying b3Πu state up to the vicinity of the atomic asymptote 4 s 2 S 1 2 + 4 p 2 P 1 2 , with a rotational quantum number J ∈ [0, 149]. The experimental data were processed by a direct 6 × 6 coupled-channel (CC) deperturbation treatment, which accounted explicitly for both SO and electronic-rotational interactions between all six e-symmetry states: A 1 Σ u + ( 0 u + ), b3Πu( 0 u + , 1 u , 2 u ), c3Σu(1u), and B1Πu(1u). The initial parameters of the global deperturbation model have been estimated in the framework of ab initio electronic structure calculations applying multi-reference configuration-interaction and coupled-clusters methods. The interatomic potentials analytically defined for A and b states, as well as SO-splitting of the triplet b state and A ∼ b SO-coupling functions, have been particularly refined to fit the 5792 term values of the 39K2 isotopologue, whereas the rest parameters were fixed on their ab initio values. The resulting mass-invariant parameters of the 6 × 6 CC model reproduced the overall rovibronic term energies of the A ∼ b complex of 39K2 with accuracy, which is well within the experimental errors. The quality of the deperturbation analysis was independently confirmed by comparison with the present obtained 705 and 14 term values of respective 39K41K and 41K2 isotopologues, as well as by agreement between measured and predicted relative intensity distributions in long A ∼ b → X(vX) band progressions. This deperturbation analysis provided the refined dissociation energy Tdis = 17 474.569(5) cm−1 and the long-range coefficient C 3 Σ = 5.501(4) × 105 cm−1 Å3 relevant to the non-relativistic atomic limit 4s + 4p. The derived Tdis yielded the accurate well depth De = 4450.910(5) cm−1 for the ground X 1 Σ g + state, whereas the new C 3 Σ value yielded the improved estimates for atomic K(4 p 2 P 1 2 ; 3 2 ) radiative lifetimes, τ 1 2 = 26.67(3) and τ 3 2 = 26.32(3) ns. [ABSTRACT FROM AUTHOR]

Partially fluorinated dimyristoylphosphatidylcholines (DMPCs) involving double alkyl chains are employed to control the phonon generation in thin films, which is examined by infrared (IR) spectroscopy coupled with multiple-angle incidence resolution spectrometry (MAIRS). technique. Compounds having perfluoroalkyl (Rf) chains are known to exhibit phonon bands in IR spectra because of the strong dipole–dipole interactions. Since the phonon bands of an organic matter have a similar shape to the normal absorption bands, however, recognition of the phonon modes is difficult and confusing for IR spectroscopists. Here, we show that MAIRS works out for finding phonon modes in monolayers: the Berreman shift is readily captured by the MAIRS in-plane and out-of-plane (OP) spectra. By measuring the longitudinal-optic (LO) energy-loss function spectrum of a bulk sample, the degree of molecular aggregation in the monolayer is also revealed by comparing the OP spectrum of the monolayer to the LO one. In addition, partially fluorinated DMPC compounds having both hydrocarbon and Rf chains are prepared, and they are used to obstruct the self-aggregation of the Rf groups in the film. As a result, the phonon characteristics are mostly lost in the MAIRS spectra as expected. [ABSTRACT FROM AUTHOR]

This study examines the structures, energies, and IR vibrational spectra of the sulfur dioxide–water SO2(H2O) complexes by employing coupled cluster theory CCSD(T) with Dunning style correlation consistent type basis sets aug-cc-pV(n+d)Z (n = D, T, Q, 5). Complete basis set (CBS) extrapolations have been carried out to predict binding energies for two isomers of the SO2(H2O) complex: a stacked global minimum (1A) structure and a hydrogen-bonded local minimum (1B) structure. The CCSD(T)/CBS extrapolation predicts an intermolecular S–O distance rS⋯O = 2.827 Å for the stacked isomer, which is in excellent agreement with an experimental measurement of 2.824 Å [K. Matsumura et al., J. Chem. Phys., 91, 5887 (1989)]. The CCSD(T)/CBS binding energy for the stacked dimer 1A and hydrogen-bonded form 1B is De = −4.37 kcal/mol and De = −2.40 kcal/mol, respectively. This study also employs anharmonic VPT2 MP2/aug-cc-pV(n+d)Z level corrections to CCSD(T)/aug-cc-pV(n+d)Z vibrational frequencies in both forms of SO2(H2O). The anharmonic CCSD(T)/aug-cc-pV(Q+d)Z OH stretching frequencies in the stacked structure 1A are 3743 cm−1 (ν3) and 3647 cm−1 (ν1), and these align well with the recorded IR spectroscopic values of 3745 and 3643 cm−1, respectively [C. Wang et al., J. Phys. Chem. Lett., 13, 5654 (2022)]. If we combine CCSD(T)/aug-cc-pV(n+d)Z De values with VPT2 vibrational frequencies, we obtain a new CCSD(T)/aug-cc-pV(Q+d)Z anharmonic dissociation energy D0 = −3.48 kcal/mol for 1A and D0 = −1.74 kcal/mol for 1B. In summary, the results presented here demonstrate that the application of CCSD(T) calculations with aug-cc-pV(n+d)Z basis sets and CBS extrapolations is critical in probing the structure and IR spectroscopic properties of the sulfur dioxide–water complex. [ABSTRACT FROM AUTHOR]

This Perspective focuses on experimental and theoretical aspects of positron annihilation spectroscopy. This set of methods is highly suitable for identifying and quantifying vacancy-type defects in semiconductors and also allows for analyzing their physics characteristics. We present selected examples from the past decade, where the methods have been used for obtaining timely and useful insights into the defect-controlled phenomenon in narrow-gap (Ge, GaSb) and wide-gap (III-nitride, oxide) semiconductors. We also discuss possible future developments that may allow more detailed studies in novel semiconductor materials and devices with ever more complex lattice structures. [ABSTRACT FROM AUTHOR]

Two-dimensional terahertz–infrared–visible (2D TIRV) spectroscopy directly measures the coupling between quantum high-frequency vibrations and classical low-frequency modes of molecular motion. In addition to coupling strength, the signal intensity in 2D TIRV spectroscopy can also depend on the selection rules of the excited transitions. Here, we explore the selection rules in 2D TIRV spectroscopy by studying the coupling between the high-frequency CH3 stretching and low-frequency vibrations of liquid dimethyl sulfoxide (DMSO). Different excitation pathways are addressed using variations in laser pulse timing and different polarizations of exciting pulses and detected signals. The DMSO signals generated via different excitation pathways can be readily distinguished in the spectrum. The intensities of different excitation pathways vary unequally with changes in polarization. We explain how this difference stems from the intensities of polarized and depolarized Raman and hyper-Raman spectra of high-frequency modes. These results apply to various systems and will help design and interpret new 2D TIRV spectroscopy experiments. [ABSTRACT FROM AUTHOR]

We demonstrate an approach to two-dimensional electronic spectroscopy (2DES) that combines the benefits of shot-to-shot detection at high-repetition rates with the simplicity of a broadband white light continuum input and conventional optical elements to generate phase-locked pump pulse pairs. We demonstrate this through mutual synchronization between the laser repetition rate, the acousto-optical deflector, the pump delay stage, and the CCD line camera, which allows for rapid scanning of pump optical delay synchronously with the laser repetition rate, while the delay stage is moved at a constant velocity. The resulting shot-to-shot detection scheme is repetition rate scalable and only limited by the CCD line rate and the maximum stage velocity. Using this approach, we demonstrate the measurement of an averaged 2DES absorptive spectrum in as much as 1.2 s of continuous sample exposure per 2D spectrum. We achieve a signal-to-noise ratio of 6.8 for optical densities down to 0.05 with 11.6 s of averaging at 100 kHz laser repetition rate. Combining rapid scanning of mechanical delay lines with shot-to-shot detection as demonstrated here provides a viable alternative to acousto-optic pulse shaping approaches that is repetition-rate scalable, has comparable throughput and sensitivity, and minimizes sample exposure per 2D spectrum with promising micro-spectroscopy applications. [ABSTRACT FROM AUTHOR]

Sum frequency generation (SFG) spectroscopy is an interface-selective spectroscopic technique that enables us to selectively observe the vibrational or electronic resonances of molecules within a very thin interface layer. The interfacial properties probed by SFG are contained in a complex quantity called the second-order nonlinear susceptibility ( χ 2 ). It is usually believed that the imaginary part of χ 2 (Im χ 2 ) exhibits the resonant responses of the system, whereas the nonresonant responses appear solely in the real part of χ 2 (Re χ 2 ). However, it was recently theoretically pointed out that a portion of the nonresonant responses actually contributes to the observed Im χ 2 spectra when the finite thickness of the interface layer is taken into account. In this study, by considering a simple air/liquid interface without any solutes as a model system, we theoretically evaluate the nonresonant contribution to experimentally accessible Im χ 2 as well as to Re χ 2 , from which the complex phase of the nonresonant background is estimated. It is shown that the deviation of the complex phase from 0° or 180° is less than 1° even if the thickness of the interface layer is taken into account. This means that the nonresonant contribution to Im χ 2 is practically negligible, and it is a very good approximation to think that the nonresonant background appears solely in Re χ 2 in the case of air/liquid interfaces. This result implies that Im χ 2 practically contains only the resonant responses of the system, and molecular resonances at the interface can be conveniently studied using Im χ 2 spectra at such interfaces. [ABSTRACT FROM AUTHOR]

In this paper, we explore the molecular basis of combining photodynamic therapy (PDT), a light-triggered targeted anticancer therapy, with the traditional chemotherapeutic properties of the well-known cytotoxic agent gemcitabine. A photosensitizer prerequisite is significant absorption of biocompatible light in the visible/near IR range, ideally between 600 and 1000 nm. We use highly accurate multiconfigurational CASSCF/MS-CASPT2/MM and TD-DFT methodologies to determine the absorption properties of a series of gemcitabine derivatives with the goal of red-shifting the UV absorption band toward the visible region and facilitating triplet state population. The choice of the substitutions and, thus, the rational design is based on important biochemical criteria and on derivatives whose synthesis is reported in the literature. The modifications tackled in this paper consist of: (i) substitution of the oxygen atom at O2 position with heavier atoms (O → S and O → Se) to red shift the absorption band and increase the spin–orbit coupling, (ii) addition of a lipophilic chain at the N7 position to enhance transport into cancer cells and slow down gemcitabine metabolism, and (iii) attachment of aromatic systems at C5 position to enhance red shift further. Results indicate that the combination of these three chemical modifications markedly shifts the absorption spectrum toward the 500 nm region and beyond and drastically increases spin–orbit coupling values, two key PDT requirements. The obtained theoretical predictions encourage biological studies to further develop this anticancer approach. [ABSTRACT FROM AUTHOR]

Microbial biofilms represent an important lifestyle for bacteria and are dynamic three-dimensional structures. Cyclic dimeric guanosine monophosphate (c-di-GMP) is a ubiquitous signaling molecule that is known to be tightly regulated with biofilm processes. While measurements of global levels of c-di-GMP have proven valuable toward understanding the genetic control of c-di-GMP production, there is a need for tools to observe the local changes of c-di-GMP production in biofilm processes. We have developed a label-free method for the direct detection of c-di-GMP in microbial colony biofilms using matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI-MSI). We applied this method to the enteric pathogen Vibrio cholerae, the marine symbiont V. fischeri, and the opportunistic pathogen Pseudomonas aeruginosa PA14 and detected spatial and temporal changes in c-di-GMP signal that accompanied genetic alterations in factors that synthesize and degrade the compound. We further demonstrated how this method can be simultaneously applied to detect additional metabolites of interest from a single sample.

Fluorescent proteins (FPs) are ubiquitous tools in research, yet their endogenous functions in nature are poorly understood. In this work, we describe a combination of functions for FPs in a clade of intertidal sea anemones whose FPs control a genetic color polymorphism together with the ability to combat oxidative stress. Focusing on the underlying genetics of a fluorescent green "Neon" color morph, we show that allelic differences in a single FP gene generate its strong and vibrant color, by increasing both molecular brightness and FP gene expression level. Natural variation in FP sequences also produces differences in antioxidant capacity. We demonstrate that these FPs are strong antioxidants that can protect live cells against oxidative stress. Finally, based on structural modeling of the responsible amino acids, we propose a model for FP antioxidant function that is driven by molecular surface charge. Together, our findings shed light on the multifaceted functions that can co-occur within a single FP and provide a framework for studying the evolution of fluorescence as it balances spectral and physiological functions in nature.

Infrared spectra of C60+ and C120+, obtained via helium messenger spectroscopy, are reported. For C60+, new absorption features have been found just above the discrete vibrational spectrum of the ion. The absorption profile, which is broad and contains little structure, is assigned to one or more electronic absorption transitions and is in good agreement with predictions from time-dependent density functional theory. It seems likely that the transitions observed correspond to excitation from the 2A1u electronic ground state to one or both of the low-lying 2E1u and 2E2u electronic states previously identified as dark states of C60+. These states presumably become optically bright through vibronic coupling and specifically the Jahn–Teller effect. In the case of C120+, the simplest positively charged oligomer of C60, we present the first vibrational spectrum of this ion. Through a comparison with theory, vibrational features are best explained by a peanut-shaped structure for C120+, maintained by covalent bonding between the two C60 units. We have also discovered electronic transitions for C120+, which, similar to C60+, lie just above the vibrational spectrum. [ABSTRACT FROM AUTHOR]

Developing fluorescence-encoded infrared (FEIR) vibrational spectroscopy for single-molecule applications requires a detailed understanding of how the molecular response and external experimental parameters manifest in the detected signals. In Paper I [L. Whaley-Mayda, A. Guha, and A. Tokmakoff, J. Chem. Phys. 159, 194201 (2023)] we introduced a nonlinear response function theory to describe vibrational dynamics, vibronic coupling, and transition dipole orientation in FEIR experiments with ultrashort pulses. In this second paper, we apply the theory to investigate the role of intermode vibrational coherence, the orientation of vibrational and electronic transition dipoles, and the effects of finite pulse durations in experimental measurements. We focus on measurements at early encoding delays—where signal sizes are largest and therefore of most value for single-molecule experiments, but where many of these phenomena are most pronounced and can complicate the appearance of data. We compare experiments on coumarin dyes with finite-pulse response function simulations to explain the time-dependent behavior of FEIR spectra. The role of the orientational response is explored by analyzing polarization-dependent experiments and their ability to resolve relative dipole angles in the molecular frame. This work serves to demonstrate the molecular information content of FEIR experiments, and develop insight and guidelines for their interpretation. [ABSTRACT FROM AUTHOR]

Metal halide perovskite nanocrystals have been under intense investigation for their promise in optoelectronic devices due to their remarkable physics, such as liquid/solid duality. This liquid/solid duality may give rise to their defect tolerance and other such useful properties. This duality means that the electronic states are fluctuating in time, on a distribution of timescales from femtoseconds to picoseconds. Hence, these lattice induced energy fluctuations that are connected to polaron formation are also connected to exciton formation and dynamics. We observe these correlations and dynamics in metal halide perovskite nanocrystals of CsPbI3 and CsPbBr3 using two-dimensional electronic (2DE) spectroscopy, with its unique ability to resolve dynamics in heterogeneously broadened systems. The 2DE spectra immediately reveal a previously unobserved excitonic splitting in these 15 nm NCs that may have a coarse excitonic structure. 2D lineshape dynamics reveal a glassy response on the 300 fs timescale due to polaron formation. The lighter Br system shows larger amplitude and faster timescale fluctuations that give rise to dynamic line broadening. The 2DE signals enable 1D transient absorption analysis of exciton cooling dynamics. Exciton cooling within this doublet is shown to take place on a slower timescale than within the excitonic continuum. The energy dissipation rates are the same for the I and Br systems for incoherent exciton cooling but are very different for the coherent dynamics that give rise to line broadening. Exciton cooling is shown to take place on the same timescale as polaron formation, revealing both as coupled many-body excitation. [ABSTRACT FROM AUTHOR]