Intermolecular Vibrations Research Articles

Temperature Dependence of Intermolecular Dynamics and Liquid Properties of Deep Eutectic Solvent, Reline.

We investigated the temperature dependence of the intermolecular dynamics, including intermolecular vibrations and collective orientational relaxation, of one of the most typical deep eutectic solvents, reline, using femtosecond Raman-induced Kerr effect spectroscopy (fs-RIKES), subpicosecond optical Kerr effect spectroscopy (ps-OKES), and molecular dynamics (MD) simulations. According to fs-RIKES results, the temperature-dependent intermolecular vibrational band peak at ∼90 cm-1 exhibited a redshift with increasing temperature. The density-of-state (DOS) spectrum of reline by MD simulations reproduced this fs-RIKES spectral feature. The decomposition analysis of the DOS spectra showed that all constituent components, including urea, cholinium cation, and chloride anion, also exhibited similar magnitudes of redshifts upon heating, indicating that the three species intermolecularly interact one another. The temperature sensitivity of the intermolecular vibrational frequency was high compared to that of ionic liquids. According to ps-OKES results, the slow orientational relaxation rate increased with increasing temperature; however, this phenomenon was not well explained by the Stokes-Einstein-Debye hydrodynamic model. Analysis of the orientational relaxation time based on the Stokes-Einstein-Debye model indicates that the decoupling between the orientational relaxation time and viscosity occurs at temperatures below ∼330 K. Quantum chemistry calculations of urea and the cholinium cation based on the MP2/6-311++G(d,p) level of theory confirmed that the contribution of intramolecular vibrational bands to low-frequency bands below 200 cm-1 was minimal. The densities, viscosities, electrical conductivities, and surface tensions of reline at various temperatures were also estimated and compared with the dynamics data.

Solvation Structure and Dynamics of the Thiocyanate Anion in mixed N,N-Dimethylformamide-Water Solvents: A Molecular Dynamics Approach.

The solvation structure and dynamics of the thiocyanate anion at infinite dilution in mixed N, N-Dimethylformamide (DMF)-water liquid solvents was studied using classical molecular dynamics simulation techniques. The results obtained have indicated a preferential solvation of the thiocyanate anions by the water molecules, due to strong hydrogen bonding interactions between the anion and water molecules. A first hydration shell at short intermolecular distances is formed around the SCN- anion consisting mainly by water molecules, followed by a second shell consisting by both DMF and water molecules. The strong interactions between the thiocyanate anion and water molecules are further reflected upon the calculated intermittent residence lifetimes of water and DMF in the first and second solvation shells. The dependence of the reorientational relaxation times of the thiocyanate anion upon the mole fraction of DMF in the mixtures has been found to be in good agreement with experiment, revealing strong concentration effects upon these relaxation phenomena. An appreciable solvent composition effect upon the low frequency intermolecular vibrations, due to the anion-water interactions, has also been revealed by calculating the atomic velocity correlation functions and corresponding spectral densities of the anion.

The V30 benchmark set for anharmonic vibrational frequencies of molecular dimers.

Intermolecular vibrations are extremely challenging to describe but are the most crucial part for determining entropy and hence free energies and enable, for instance, the distinction between different crystal-packing arrangements of the same molecule via THz spectroscopy. Herein, we introduce a benchmark dataset-V30-containing 30 small molecular dimers with intermolecular interactions ranging from exclusively van der Waals dispersion to systems with hydrogen bonds. All the calculations are performed with the gold standard of quantum chemistry CCSD(T). We discuss vibrational frequencies obtained via different models starting with the harmonic approximation over independent Morse oscillators up to second-order vibrational perturbation theory (VPT2), which allows a proper anharmonic treatment including coupling of vibrational modes. However, large amplitude motions present in many low-frequency intermolecular modes are problematic for VPT2. In analogy to the often used treatment for internal rotations, we replace such problematic modes by a simple one-dimensional hindered rotor model. We compare selected dimers to the available experimental data or high-level calculations of potential energy surfaces and show that VPT2 in combination with hindered rotors can yield a very good description of fundamental frequencies for the discussed subset of dimers involving small and semi-rigid molecules.

Bandlike charge transport and electron-phonon coupling in organic molecular crystals.

Charge transport is important in organic molecular crystals (OMCs), where high carrier mobilities are desirable for a range of applications. However, modeling and predicting the mobility is chal- lenging in OMCs due to their complex crystal and electronic structures and electron-phonon (e-ph) interactions. Here we show accurate first-principles calculations of electron and hole carrier mobility in several OMCs: benzene, anthracene, tetracene, pentacene, and biphenyl. Our calculations use the Boltzmann transport equation (BTE) formalism with e-ph interactions computed from first principles. These calculations describe transport in the bandlike, weak e-ph coupling regime, and include all phonon modes and electronic bands on equal footing. In all systems studied, we predict the mobility and its temperature dependence in very good agreement with experiments between 100-400 K, where transport is phonon-limited. We show that e-ph scattering from low-frequency (LF) phonons with energy below 150 cm-1 primarily limits the mobility, even though these modes are not the ones with the strongest e-ph coupling. These LF modes are shown to consist mainly of intermolecular vibrations, with admixed long-range intramolecular character in OMCs with larger molecules. Furthermore, we find that the LF-mode scattering rates vary significantly with strain, suggesting that strain engineering can effectively modulate e-ph coupling and enhance the mobility. This work sheds light on bandlike transport mechanisms in OMCs and advances the rational design of high-mobility organic semiconductors.

Low-frequency Raman spectroscopy as a new tool for understanding the behaviour of ionisable compounds in dispersed mesophases.

Low-frequency Raman (LFR) spectroscopy is proposed as a novel non-destructive methodology to probe pH-related phase transitions in self-assembled lipid particles. In this case, dispersed lipid mesophases were composed of ionisable oleic acid (OA) or nicergoline (NG) in monoolein (MO). The sensitivity of LFR spectroscopy to low-energy intermolecular vibrations was hypothesised to be due to structural transformation in ionisable dispersed mesophases upon changes in pH. Phase transitions of dispersed mesophases of MO mixed with OA or NG were induced by varying the pH of the aqueous buffer. The structural transformations were studied using LFR spectroscopy, recording the corresponding changes in the vibrational density of states (VDOS) upon changes in pH and analysed using principal component analysis (PCA). The results were correlated with structural transitions observed in simultaneous small-angle X-ray scattering (SAXS) measurements. The intensity of the VDOS signal of MO+OA mesophases scaled with phase-specific transformations, such as from the bi-continuous cubic Im3¯m phase (V2) or lamellar-based vesicles to the reversed hexagonal p6m phase (H2). For NG subtle changes in the lattice parameter of the V2 phase of NG+MO mesophases coincided with the apparent dissociation constant (pKaapp) of NG, however, slight variations between the pKaapp of NG determined by equilibrated samples analysed using SAXS and non-equilibrated samples analysed using LFR suggest structural hysteresis upon changes in the protonation state of NG. This approach offers an efficient method for studying the phase behaviour of lipid systems under varying pH and potentially other conditions such as temperature.

Real-Time CASSCF (Ehrenfest) Modeling of Electron Dynamics in Organic Semiconductors. Dynamics Reaction Paths Driven by Quantum Coherences. Application to a Radical Organic Semiconductor.

We present a strategy for the modeling of charge carrier dynamics in organic semiconductors using conventional quantum chemistry methods, including the analytic gradient for nuclear motion. The theoretical approach uses real-time CASSCF (Ehrenfest) all-electron dynamics coupled to classical nuclear dynamics for the special case of a small number (4-8) of molecular units. The objective is to obtain mechanistic/atomistic insight at the electronic structure level, relating to spin density dynamics, to the effect of crystal structure (e.g., slippage between spin/charge carriers), and to ferromagnetic and antiferromagnetic effects. The initial conditions for our simulations use the equilibrium structures of all the molecular units. At this geometry, a localized hole on one of the units corresponds to a coherent superposition of adiabatic states. We thus generate a dynamics reaction path driven by quantum coherences. Our aim is to inform experiment and to compare with parametrized theoretical models. The methodology is demonstrated for a perfectly π-stacked ethylene model (up to 8 eclipsed molecular units) for both hole transfer and localized exciton transfer. An application for hole transfer is presented for bisdithiazolyl (S,S) and bisdiselenazolyl (Se,Se) radicals for the special case of ferromagnetic coupling. For these examples, the embedded pyridine radical model organic chromophore (up to 6 eclipsed π-stacked molecular units) has been studied on its own as well as the target bisdithiazolyl (S,S) and bisdiselenazolyl (Se,Se) systems. A significant difference between these systems and the ethylene and pyridine stacks is that the (S,S) and (Se,Se) systems exhibit molecular slippage rather than being perfectly eclipsed. This slippage may result from crystal defects or intermolecular vibrations. For the model systems, the electron dynamics is dominated by the initial and final molecular units, irrespective of the length of the chain. The intervening units act as a "superexchange bridge". Our simulations reveal that, in the presence of slippage, charge migration cannot propagate across the entire system; instead, the coherence length is limited to 3 molecular units. The results also suggest that the mechanism of charge transport is different for bisdiselenazolyl (Se,Se) (superexchange-like A -[B]→ C) and bisdithiazolyl (S,S) (direct A → C). An analysis of the spin density suggests that, in the charge carrier dynamics, the additional charge carried by the Se versus S in the "scaffold" is small. Since we use a small number of molecular units, the coupled nuclear dynamics is seen to be complementary to the electron dynamics (i.e., creating a hole causes bond length contraction while filling a hole with an electron lengthens the bond). In all the cases studied, the mechanism of charge mobility is wave-like, rather than hopping, because we use the time dependent Schrödinger equation to propagate the electronic wave function.

Femtosecond Raman-induced Kerr effect spectroscopic study of the intermolecular dynamics in aqueous solutions of imidazolium hydrochloride, imidazole, sodium triazolide, and triazole: concentration dependence.

In this study, we employed femtosecond Raman-induced Kerr effect spectroscopy to analyze the concentration-dependent intermolecular dynamics in positively or negatively charged aromatics and their neutral analogous aromatics (imidazolium hydrochloride (ImHCl), imidazole (Im), sodium triazolide (NaTr), and triazole (Tr)) in aqueous solutions at 293 K. We also measured their liquid properties, such as density, viscosity, and surface tension, at 293 K, and compared them with their dynamic properties. Furthermore, we performed the quantum chemistry calculations of the target aromatics and some clusters to elucidate their optimized structures, interaction energies, charge populations, and Raman-active normal modes. We characterized the Kerr transients over 2ps using a triexponential function. The results revealed that the aqueous solutions' intermediate and slow relaxation time constants were linearly proportional to the viscosities. The slopes of the time constants to the viscosity of the aqueous ImHCl solutions were steeper than those of the aqueous Im solutions, whereas the slopes of the aqueous NaTr solutions were milder than those of the aqueous Tr solutions. These findings indicated that the charge of the aromatics in the aqueous solutions affected the coupling parameter between the solute and solvent in the orientational dynamics with different ways. The first moment (M1) of the low-frequency band (< 200 cm-1), coming from the intermolecular vibrations, in the difference spectra between the aqueous aromatic solutions and neat water shifted to the high-frequency region as the concentration increased. The M1 slope to the concentration for the aqueous ImHCl solutions was steeper than that for the aqueous Im solutions. Conversely, the concentration dependence of M1 for the aqueous NaTr solutions was similar to that for the aqueous Tr solutions. We used the local structures of the target aromatics based on the quantum chemistry calculations to rationally clarify their concentration-dependent intermolecular dynamics in the aqueous solutions.

HF Trimer: A New Full-Dimensional Potential Energy Surface and Rigorous 12D Quantum Calculations of Vibrational States.

HF trimer, as the smallest and the lightest cyclic hydrogen-bonded (HB) cluster, has long been a favorite prototype system for spectroscopic and theoretical investigations of the structure, energetics, spectroscopy, and dynamics of hydrogen-bond networks. Recently, rigorous quantum 12D calculations of the coupled intra- and intermolecular vibrations of this fundamental HB trimer (J. Chem. Phys. 2023, 158, 234109) were performed, employing an older ab initio-based many-body potential energy surface (PES). While the theoretical results were found to be in reasonably good agreement with the available spectroscopic data, it was also evident that it is highly desirable to develop a more accurate 12D PES of HF trimer. Motivated by this, here we report a new, and the first fully ab initio 12D PES of this paradigmatic system. Approximately 42,540 geometries were sampled and calculated at the level of CCSD(T)-F12a/AVTZ. The permutationally invariant polynomial-neural network based Δ-machine learning approach (J. Phys. Chem. Lett. 2022, 13, 4729) was employed to perform cost-efficient calculations of the basis-set-superposition error (BSSE) correction. By strategically selecting data points, this approach facilitated the construction of a high-precision PES with BSSE correction, while requiring only a minimal number of BSSE value computations. The fitting error of the final PES is only 0.035 kcal/mol. To assess its performance, the 12D fully coupled quantum calculations of excited intra- and intermolecular vibrational states of HF trimer are carried out using the rigorous methodology developed by us earlier. The results are found to be in a significantly better agreement with the available spectroscopic data than those obtained with the previously existing semiempirical 12D PES.

Intermolecular Bending States and Tunneling Splittings of Water Trimer from Rigorous 9D Quantum Calculations: I. Methodology, Energy Levels, and Low-Frequency Spectrum.

We present the computational methodology that enables the first rigorous nine-dimensional (9D) quantum calculations of the intermolecular bending states of the water trimer, as well as its low-frequency spectrum for direct comparison with experiment. The water monomers, treated as rigid, have their centers of mass (cm's) at the corners of an equilateral triangle, and the intermonomer cm-to-cm distance is set to a value slightly larger than that in the equilibrium geometry of the trimer. The remaining nine strongly coupled large-amplitude bending (angular) degrees of freedom (DOFs) enter the 9D bend Hamiltonian of the three coupled 3D rigid-water hindered rotors. Its 9D eigenstates encompass excited librational vibrations of the trimer, as well as their torsional and bifurcation tunneling splittings, which have been the subject of much interest. The calculations of these eigenstates are extremely demanding, and a sophisticated computational scheme is developed that exploits the molecular symmetry group of the water trimer, G48, in order to make them feasible in a reasonable amount of time. The spectrum of the low-frequency vibrations of the water trimer simulated using the eigenstates of the 9D bend Hamiltonian agrees remarkably well with the experimentally observed far-infrared (FIR) spectrum of the trimer in helium nanodroplets over the entire frequency range of the measurements from 70 to 620 cm-1. This shows that most peaks in the experimental FIR spectrum are associated with the intermolecular bending vibrations of the trimer. Moreover, the ground-state torsional tunneling splittings from the present 9D calculations are in excellent agreement with the spectroscopic data. These results demonstrate the high quality of the ab initio 2 + 3-body PES employed for the DOFs included in the bound-state calculations.

Integrated identification and detection of hydration state and its evolution using terahertz technology

The accurate detection of dehydration processes in hydrated drugs can reveal various intermolecular vibration modes mediated by hydrogen bonds between water molecules and other components, which underpin the further development of pharmaceutical science, food safety and biophysics. Herein, terahertz (THz) technology is utilized to investigate the dehydration state of d(+)-Raffinose pentahydrate (Rf·5H2O), in conjunction with imaging-based point by point scanning data acquisition and barcodes methods, to establish an innovative platform integrated identification, trace detection, and application capabilities. Our study demonstrates that the dehydration process of Rf·5H2O can be dynamically monitored through the evolution of its THz absorption peaks, offering more precise results compared to XRD and Raman spectroscopies. Moreover, the absorbance spectra data collected at each individual pixel is utilized to build visualized THz images, achieving an ultralow minimum content required for detection of 0.032 μg/(50 μm)2. Additionally, we introduce a THz spectra-barcode conversion system that not only ensures efficient electronic recordkeeping but also enhances user readability, thereby facilitating the practical applications of THz technology.

Advances in Metasurface‐Based Terahertz Sensing

AbstractTerahertz (THz) technology has attracted significant attention because of its unique applications in biological/chemical sensing, medical imaging, non‐invasive detection, and high‐speed communication. Metasurfaces provide a dynamic platform for THz sensing applications, showcasing greater flexibility in design and the ability to optimize light‐matter interactions for specific target enhancements, which includes enhancing the intramolecular and intermolecular vibration modes of the target biological/chemical molecules, setting them apart from conventional approaches. This review focuses on recent THz metasurface sensing methods, including metasurfaces based on toroidal dipole and quasi‐bound states in the continuum to improve sensing sensitivity, nanomaterial‐assisted metasurfaces for specific recognition, and metasurfaces combined with microfluidic with reduce water absorption loss. Furthermore, the applications of THz metasurface sensing is reviewed, including detecting the concentration of biomolecules, cells, tissues, and microbes, THz biomolecular fingerprint absorption spectra recognition, and identifying chiral compounds using chiral and achiral metasurfaces. Finally, the prospects for the next generation of THz sensors are examined.

Imaging-based terahertz pixelated metamaterials for molecular fingerprint sensing.

With the rapid development of terahertz-enabled devices, the study of miniaturized and integrated systems has attracted significant attention. We experimentally demonstrate an imaging-based pixelated metamaterial for detecting terahertz molecular fingerprints related to intermolecular vibrations and large-amplitude intramolecular modes, including chemical identification and compositional analysis. The compact THz sensor consists of a 4 × 4 pixelated filter-detector array with transmission resonances tuned to discrete frequencies. The absorption spectra of analytes are computationally reconstructed from different spectral responses of meta-pixels, and the resulting information is characterized via near-field imaging. Due to the spectrometer-less operation principle, such imaging-based approaches provide an alternative method for developing sensitive, versatile, and miniaturized THz biosensors, especially for practical field deployment applications.

Discovery and Manipulation of van der Waals Polarons in Sb2O3 Ultrathin Molecular Crystal.

Manipulating single electrons at the atomic scale is vital for mastering complex surface processes governed by the transfer of individual electrons. Polarons, composed of electrons stabilized by electron-phonon coupling, offer a pivotal medium for such manipulation. Here, using scanning tunneling microscopy and spectroscopy (STM/STS) and density functional theory (DFT) calculations, we report the identification and manipulation of a new type of polaron, dubbed van der Waals (vdW) polaron, within mono- to trilayer ultrathin films composed of Sb2O3 molecules that are bonded via vdW attractions. The Sb2O3 films were grown on a graphene-covered SiC(0001) substrate via molecular beam epitaxy. Unlike prior molecular polarons, STM imaging observed polarons at the interstitial sites of the molecular film, presenting unique electronic states and localized band bending. DFT calculations revealed the lowest conduction band as an intermolecular bonding state, capable of ensnaring an extra electron through locally diminished intermolecular distances, thereby forming an intermolecular vdW polaron. We also demonstrated the ability to generate, move, and erase such vdW polarons using an STM tip. Our work uncovers a new type of polaron stabilized by coupling with intermolecular vibrations where vdW interactions dominate, paving the way for designing atomic-scale electron transfer processes and enabling precise tailoring of electron-related properties and functionalities.

Impact of Local and Nonlocal Vibronic Coupling on the Absorption and Emission Spectra of J- and H-Dimers.

The impact of exciton-vibrational (EV) coupling involving low-energy ("slow") intermolecular vibrations and higher-energy ("fast") intramolecular vibrations on the absorption and emission spectra of H- and J-dimers is studied theoretically for a pair of chromophores with excitonic coupling dominated by transition dipole-dipole coupling, JC. Exact quantum-mechanical solutions based on a Frenkel-Holstein-Peierls Hamiltonian reveal a fascinating interplay between the two coupling sources in determining the spectral line widths, Stoke shifts and radiative decay rates. It is shown that the ratio rules derived from the vibronic progression of the fast mode in molecular dimers remain valid under the influence of slow-mode EV coupling under most conditions. However, a highly unusual aggregate behavior occurs when the product of local and nonlocal couplings, |gLgNL|, exceeds 2ℏωs|JC|, where ℏωs is the energy of the slow mode. In this regime and when gL and gNL are in-phase, an H-dimer (JC > 0) becomes strongly emissive and can even be super-radiant, while a J-dimer (JC < 0) with out-of-phase gL and gNL values becomes subradiant. Such behaviors are in marked contrast to the predictions of Kasha theory and demonstrate the richness of the photophysical behavior resulting from EV coupling involving inter- and intramolecular vibrations.

Interplay of intermolecular and intramolecular vibrations mediates ultrafast singlet fission

Singlet fission (SF) is an exciton multiplication process that splits a singlet exciton in organic semiconductors into two triplet excitons and thus, can overcome the Shockley–Queisser limit to improve the solar energy conversion efficiency in photovoltaics. In this paper, we construct a unified model for the ultrafast primary step of the SF process. To achieve this, we investigate the dynamics of vibrational modes and their interactions with the relevant electronic excited states in prototypical SF materials, pentacene (exothermic SF) and tetracene (endothermic SF) single crystals. Additionally, the functional role of the charge transfer (CT) state is also examined. Using the refined parameters obtained from the reported experimental results, we deduce that the intermolecular vibrations mediate the SF in pentacene with the assistance from strong vibronic couplings to intramolecular modes, which drives the SF process to occur within 100 fs. In this timescale, the CT state has a limiting role towards the SF process in pentacene. However, the CT state plays an important role in a relatively slower SF process in tetracene. Our results disentangle the role of underlying vibrational coherences and clarify the importance of the CT state in tetracene crystal. Hence, with our unified model, we can study the coherent dynamics of the SF process, which can principally be extended to other SF materials as well.

Low-Frequency Spectra of Hydrated Ionic Liquids with Kosmotropic and Chaotropic Anions.

In this study, we investigated the water concentration dependence of the intermolecular vibrations of two hydrated ionic liquids (ILs), cholinium dihydrogen phosphate ([ch][dhp]) and cholinium bromide ([ch]Br), using femtosecond Raman-induced Kerr effect spectroscopy (fs-RIKES). The anions of the former and latter hydrated ILs are kosmotropic and chaotropic, respectively. We found that the spectral peak of ∼50 cm-1 shifted to the low-frequency side in hydrated [ch][dhp], indicating the weakening of its intermolecular interactions. In contrast, no change in the peak frequency of the low-frequency band at ∼50 cm-1 was observed with increasing water concentration in hydrated [ch]Br. The vibrational density of states (VDOS) spectra generated from molecular dynamics (MD) simulations were in qualitative agreement with the experimental results. Decomposition analysis of the VDOS spectra for each component revealed that the red shift of the low-frequency band in the hydrated [ch][dhp] upon water addition was essentially due to the contributions of anions and water rather than that of the cholinium cation. We also found from the low-frequency spectra of the two hydrated ILs that they differed in the concentration dependence of the 180 cm-1 band, which is assigned as a hindered translational motion of water molecules combined to form O···O stretching motions. From the relationship between the peak frequency of the low-frequency band and the bulk parameter, which is the square root of the surface tension divided by the density, we found that the peak frequency in the hydrated IL with kosmotropic [dhp]- depends on the bulk parameter, similar to the case for an aqueous solution of the typical deep eutectic solvent reline. However, the peak frequency of the hydrated IL with chaotropic Br- is constant with the bulk parameter.

Terahertz time-domain spectroscopy as a novel tool for crystallographic analysis in cellulose: tracking lattice changes following physical treatments

The authors’ series of studies aimed to explore the potential of terahertz time-domain spectroscopy (THz-TDS) in cellulose crystallographic studies, since THz radiation can detect most intermolecular vibrations and respond to lattice phonons. In this study, we tracked changes in four types of cellulose after ball milling. As the planetary ball milling time increases, it is observed through electron microscopy that the four types of cellulose particles are gradually destroyed into finer particles, while gel permeation chromatography can prove that the molecular weight gradually decreases after ball milling and the dispersity gradually approaches one, which indicates that the dispersion of the material was reduced. The most fascinating observation was made by THz-TDS, that is we have confirmed that after ball milling, the absorption characteristics of cellulose I and II in cellulose I treated with 10% NaOH (crystalline partial transition from cellulose I to II) exhibited an opposite trend. Specifically, the absorption of cellulose II at 2.40THz and 2.77THz increased, while the absorption of cellulose I at 2.11THz and 3.04THz decreased after ball milling, which suggests an increased conversion rate of cellulose I to cellulose II post-milling. Cellulose with different crystalline allomorphs shows different characteristic absorption in the THz region, and the peak position will not change even after the ball milling, only the absorption intensity changes. Although it can be observed through the most traditional X-ray diffraction method that the crystallinity index of all cellulose samples gradually decreases after ball milling. However, different from the THz results, the change after ball milling of cellulose I treated with 10% NaOH is only reflected in very subtle pattern changes, that is, the peak close to the 200 crystalline plane position is slightly shifted after ball milling.

Enhanced charge transport in 2D inorganic molecular crystals constructed with charge‐delocalized molecules

AbstractOutstanding charge transport in molecular crystals is of great importance in modern electronics and optoelectronics. The widely adopted strategies to enhance charge transport, such as restraining intermolecular vibration, are mostly limited to organic molecules, which are nearly inoperative in 2D inorganic molecular crystals currently. In this contribution, charge transport in 2D inorganic molecular crystals is improved by integrating charge‐delocalized Se8 rings as building blocks, where the delocalized electrons on Se8 rings lift the intermolecular orbitals overlap, offering efficient charge transfer channels. Besides, α‐Se flakes composed of charge‐delocalized Se8 rings possess small exciton binding energy. Benefitting from these, α‐Se flake exhibits excellent photodetection performance with an ultrafast response rate (~5 μs) and a high detectivity of 1.08 × 1011 Jones. These findings contribute to a deeper understanding of the charge transport of 2D inorganic molecular crystals composed of electron‐delocalized inorganic molecules and pave the way for their potential application in optoelectronics.

Spectra of the D2O dimer in the O-D fundamental stretch region: The acceptor symmetric stretch fundamental and new combination bands.

The O-D stretch fundamental region of the deuterated water dimer, (D2O)2, is further studied using a pulsed supersonic slit jet and a tunable optical parametric oscillator infrared source. The previously unobserved acceptor symmetric O-D stretch fundamental vibration is detected, with Ka = 0 ← 0 and 1 ← 0 sub-bands at about 2669 and 2674cm-1, respectively. The analysis indicates that the various water dimer tunneling splittings generally decrease in the excited vibrational state, similar to the three other previously observed O-D stretch fundamentals. Two new (D2O)2 combination bands are observed, giving information on intermolecular vibrations in the excited O-D stretch states. The likely vibrational assignments for these and a previously observed combination band are discussed.

Noncovalent interactions and electron transfer between 1,3,5-trinitro-1,3,5-triazinane and Al3O3−

As the first step in energy transfer from oxide passivated metal nanoparticles/surface defects to an energetic molecule for the controlled dissociation of the latter, the nature of the weak interactions between 1,3,5-trinitro-1,3,5-triazinane (RDX) and Al3O3− isomers are studied as a model system by DFT method with PBE0 functional and different basis sets (TZVP, Def2-TZVPP, TZ2P). Different electron density (NCI, IGMH, QTAIM, IQA, EDA-NOCV) and charge analysis methods (Hirshfeld, Hirshfeld-I, NPA) reveal that partial charge-transfer from Al3O3− to RDX via the CH···O (1.851–2.481 Å, O(2p)-to-C-H(σ*) type) and the CH···Al (2.836–2.871 Å, Al(3p)-to-C-H(σ*) type) interactions are possible. Hirshfeld analysis predicts 6–25% transfer of the -1 charge to RDX while Hirshfeld-I and NPA predict 7–22% and 2–7%, transfer, respectively. Al3O3− (HOMO)-RDX (LUMO+n, n = 0–3) type interactions including the charge transfer via the (ON)O···Al (2.846–3.511 Å) interactions are found to excite the Al3O3− (kite) anion. The binding energies are in the -10 to -31 kcal/mol range. Vertical detachment energies of the complexes are within 2.5–3.9 eV, higher than the bare Al3O3− isomers by 0.3–1.3 eV. Complexation weakens the RDX structure and reduces the CH stretching frequencies by 10–350 cm−1. Modulations in the bond lengths in the Al3O3− isomers shift the frequencies in the 0–1300 cm−1 region. New intermolecular vibrations enrich the terahertz region of the IR spectra.