Intermolecular Modes Research Articles

The High-Pressure Response of 9,9′-Spirobifluorene Studied by Raman Spectroscopy

The pressure response of crystalline 9,9′-spirobifluorene up to 8 GPa was studied by means of Raman spectroscopy using a diamond anvil cell as a pressure chamber. With increasing pressure, the observed Raman peaks shifted to higher frequencies, reflecting the bond hardening upon volume reduction, which was much more pronounced for the initially weaker intermolecular interactions than for the stronger intramolecular covalent bonds. The significant changes in the Raman spectrum and the pressure evolution of the frequencies at ~1.3 GPa for both the intermolecular and the intramolecular Raman peaks signaled a pressure-induced structural and molecular conformation transition with a little hysteretic behavior (~0.5 GPa) upon pressure release. For P > 4 GPa, the reversible decrease of the pressure coefficients of the majority of the intermolecular and some intramolecular peak frequencies indicated another structural modification of the studied molecular crystal. A value of ~9 GPa for the bulk modulus of the system at zero pressure was estimated from the logarithmic pressure coefficients of the frequencies of the intermolecular modes in the low-pressure phase. These coefficients were reduced by ~6 times at 4.2 GPa, indicating that the considerable stiffening of the material in the high-pressure phase emanated from the selective strengthening of the intermolecular interactions.

New Infrared Spectra of the Water-CO2 Complex: Determination of Four Intermolecular Modes and Test of a High-Level Potential Energy Surface.

High resolution infrared spectra of water-CO2 dimers are further studied using tunable infrared sources to probe a pulsed slit jet supersonic expansion. The relatively weak transition of D2O-CO2 in the D2O ν1 fundamental region (≈2760 cm-1) is observed for the first time, as are various spectra of D2O-13CO2. Combination bands involving the intermolecular in plane geared bend (disrotatory) mode are observed for H2O-CO2 (≈1642, 2397 cm-1) in the H2O ν2 and CO2 ν3 regions, for HDO-CO2 (≈2761 cm-1) in the HDO ν3 region, and for D2O-CO2 (≈2386, 2705 and 2821 cm-1) in the CO2 ν3, D2O ν1, and D2O ν3 regions. A combination band involving the intermolecular in plane antigeared bend (conrotatory) mode is observed for D2O-13CO2 (≈2425 cm-1) in the CO2 ν3 region. And finally, a combination band involving the intermolecular twist (internal rotation) mode is observed for D2O-CO2 (≈2874 cm-1) in the D2O ν3 region. But this twist transition actually appears as two bands of similar intensity, separated by 2 cm-1, suggesting an "accidental" near-coincidence of the "real" combination state with a "dark" background state of the same symmetry. Intermolecular mode frequencies determined from the combination bands are in very good agreement with a recent theoretical calculation based on a high-level ab initio potential surface.

Low-frequency (0-450 cm-1) dynamics of n-alkyl cyanide liquids studied by optical Kerr effect spectroscopy and density functional theory.

This article presents a study of the dynamics of n-alkyl cyanides (CnH2n+1CN with n = 1-5) in the 0-450 cm-1 spectral region as a function of alkyl chain length. The spectra were measured using femtosecond optical Kerr effect (OKE) spectroscopy. The OKE spectra are characterized by a broad band in the 0-150 cm-1 region arising mainly from intermolecular modes and by narrow bands in the 150-450 cm-1 region arising from intramolecular modes. The intramolecular bands in the OKE spectra are in good agreement with the bands in simulated spectra obtained from density functional theory calculations. For cyanide molecules with long alkyl chains (n = 3-5), a low frequency intramolecular band associated with a torsional vibrational mode overlaps with the intermolecular band. Applying multicomponent line-shape analysis to the broad low-frequency band allowed us to obtain the intermolecular component of the band. We find the frequency and amplitude of the intermolecular band decrease with increasing chain length. Based on previous theoretical studies of the OKE spectrum of methyl cyanide and OKE reorientational studies of n-alkyl cyanides, we show that the dependence of the frequency of the intermolecular band on alkyl chain length is consistent with the band being primarily due to the hindered rotational motion of the molecules in the extended configuration about an axis perpendicular to the long axis of the molecule. The dependence of the amplitude of the intermolecular band on alkyl chain length is a mass effect associated with suppression of the collision-induced contribution to the intermolecular band.

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.

Dynamic coupling of intra- and intermolecular effective modes in H-bonded water clusters in the long-wavelength infrared range

Dynamic coupling of intra- and intermolecular effective modes in H-bonded water clusters in the long-wavelength infrared range

Chiral Metal Self‐Assemblies of Zirconium‐Tetrahedra and Their Second Harmonic Generation Activity

AbstractThe chirality of metal‐organic cages holds enormous potential for novel applications in diverse fields, while it is relatively rare to employ such asymmetric units for the construction of noncentrosymmetric materials. Herein, by self‐assembling the 4,4′,4′′‐nitrilotribenzoic acid (H3NBA) with bis(cyclopentadienyl)‐zirconium dichloride (Cp2ZrCl2, Cp=η5‐C5H5) in different solvent conditions, we have obtained three hierarchical packing modes of metallo‐tetrahedra with distinct spatial symmetry groups (designated as Zr‐α, Zr‐β, and Zr‐γ). Among them, Zr‐α employs a simple cubic arrangement and is a common centrosymmetric superstructure, which consists of a pair of equimolar metallo‐tetrahedra enantiomers in its unit cell. While Zr‐β results in conglomerates with spontaneous resolution without using any resolving agents, giving rise to two enantiopure entities separately (Zr‐β‐P, Zr‐β‐M). More importantly, Zr‐γ breaks the inversion center of symmetry and crystallizes into a racemic yet non‐centrosymmetric superstructure with face‐centered cubic packing mode. Based on the non‐centrosymmetric nature, the hierarchical superstructure Zr‐γ displayed good second harmonic generation activities. This work presents a successful instance wherein the reaction solvent induces the modulation of intermolecular packing mode to afford non‐centrosymmetric solid materials, which can greatly promote the development of noncentrosymmetric solid (NCS) materials.

Chiral Metal Self-Assemblies of Zirconium-Tetrahedra and Their Second Harmonic Generation Activity.

The chirality of metal-organic cages holds enormous potential for novel applications in diverse fields, while it is relatively rare to employ such asymmetric units for the construction of noncentrosymmetric materials. Herein, by self-assembling the 4,4',4''-nitrilotribenzoic acid (H3NBA) with bis(cyclopentadienyl)-zirconium dichloride (Cp2ZrCl2, Cp=η5-C5H5) in different solvent conditions, we have obtained three hierarchical packing modes of metallo-tetrahedra with distinct spatial symmetry groups (designated as Zr-α, Zr-β, and Zr-γ). Among them, Zr-α employs a simple cubic arrangement and is a common centrosymmetric superstructure, which consists of a pair of equimolar metallo-tetrahedra enantiomers in its unit cell. While Zr-β results in conglomerates with spontaneous resolution without using any resolving agents, giving rise to two enantiopure entities separately (Zr-β-P, Zr-β-M). More importantly, Zr-γ breaks the inversion center of symmetry and crystallizes into a racemic yet non-centrosymmetric superstructure with face-centered cubic packing mode. Based on the non-centrosymmetric nature, the hierarchical superstructure Zr-γ displayed good second harmonic generation activities. This work presents a successful instance wherein the reaction solvent induces the modulation of intermolecular packing mode to afford non-centrosymmetric solid materials, which can greatly promote the development of noncentrosymmetric solid (NCS) materials.

Quinoline Substituted Anthracene Isomers: A Case Study for Simultaneously Optimizing High Mobility and Strong Luminescence in Herringbone-Packed Organic Semiconductors.

The development of high mobility emissive organic semiconductors is significant for advancing optoelectronic devices with simplified architecture and enhanced performance. The herringbone-packed structure is regarded as the ideal arrangement for simultaneously achieving high mobility and strong emission in organic semiconductors. However, it remains a great challenge that the relationship between molecular structure and optoelectronic property is still elusive. Herein, four quinoline-substituted anthracene isomers were designed and synthesized by introducing quinoline groups to anthracene core. Their intermolecular interactions and packing mode in the herringbone-packed structures were regularly tuning by subtle changing the nitrogen position on quinoline group, resulting in the superior integration of optoelectronic properties. Through a comprehensive analysis of aggregation states and optoelectronic properties, we revealed that in herringbone-packed aggregates, a centroid distance of approximately 7-7.5 Å along CH-π direction and 6-6.5 Å along π-π direction is beneficial for simultaneously achieving high mobility and strong emission. These properties are closely related to the molecular twist angles, which are influenced by intramolecular interactions. This structure-property relationship has been further validated in other herringbone-packed high mobility emissive organic semiconductors, demonstrating its broad applicability and universal potential. This work figures out the practical molecular design principle for high mobility emissive organic semiconductors.

On the nature of hydrogen bonding in the H2S dimer

Hydrogen bonding is a central concept in chemistry and biochemistry, and so it continues to attract intense study. Here, we examine hydrogen bonding in the H2S dimer, in comparison with the well-studied water dimer, in unprecedented detail. We record a mass-selected IR spectrum of the H2S dimer in superfluid helium nanodroplets. We are able to resolve a rotational substructure in each of the three distinct bands and, based on it, assign these to vibration-rotation-tunneling transitions of a single intramolecular vibration. With the use of high-level potential and dipole-moment surfaces we compute the vibration-rotation-tunneling dynamics and far-infrared spectrum with rigorous quantum methods. Intramolecular mode Vibrational Self-Consistent-Field and Configuration-Interaction calculations provide the frequencies and intensities of the four SH-stretch modes, with a focus on the most intense, the donor bound SH mode which yields the experimentally observed bands. We show that the intermolecular modes in the H2S dimer are substantially more delocalized and more strongly mixed than in the water dimer. The less directional nature of the hydrogen bonding can be quantified in terms of weaker electrostatic and more important dispersion interactions. The present study reconciles all previous spectroscopic data, and serves as a sensitive test for the potential and dipole-moment surfaces.

Structural Rigidification Strategy Based on Self-Assembly Enabled Reversible Excited-State Conversion of Iridium(III) Complexes for Multiple-Stimulus-Responsive Data Encryption.

Stimulus-responsive chromic materials exhibit color-switching properties under specific external stimuli and have been widely used in various fields. Transition-metal complexes show great potential applications as promising candidates for stimulus-responsive chromic materials, as their excited states not only depend on the chemical composition but are also affected by the intermolecular stacking modes. Owing to the intrinsic difficulty in the ordered stacking of the octahedral configuration, changing the stacking modes of iridium(III) complexes for multiple-stimulus responsiveness remains a significant challenge. In this work, we propose a structural rigidification strategy based on self-assembly to reversibly regulate the excited states of iridium(III) complexes, therefore achieving color switch under different stimulus conditions. We prepare cationic iridium(III) complexes by using tetrakis(perfluorophenyl)-borate ([B(PhF5)4]-) as the counterion, whose matching tetrahedral configuration and electron-deficient aromaticity enables polar-π interaction with the octahedral iridium(III) cations, inducing self-assembly to form structural rigidification. The structural rigidity restricts the large conformational changes of the metal-to-ligand charge transfer (3MLCT) excited state, and facilitates the conversion from the 3MLCT to the ligand-center (3LC) excited state in aggregated states. The excited-state conversion results in a 54 nm blue shift (from yellow to sky blue) in the photoluminescence spectra. As a result, we report a series of cationic iridium(III) complexes with different responses to low temperature, vapor fuming, and mechanical force, therefore achieving multiple-stimulus-responsive data encryption. Our work provides a novel strategy to achieve ordered stacking of octahedral complexes, shows a deeper understanding of the photophysical processes of transition-metal complexes, and offers a new perspective to develop multiple-stimulus-responsive chromic materials.

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.

On the shape of the simulated infrared spectral density of strongly hydrogen-bonded systems: Mapping and identification of Hadži ABC structure in phosphonic acid dimers in gas phase

Herein, we explore the origin of three-peaked structure, referred to as the Hadži ABC structure, illustrated within the absorption bands in infrared (IR) spectra of strongly H-bonded systems. The exploration is particularly elucidated for two phosphinic acid dimers (R2POOH) in gas phase, namely bis-(iodomethyl)-phosphinic acid dimer (i.e., R = CH2I) at 465 K and dibutyl-phosphinic acid dimer (i.e., R = C4H9O) at 425 K. A direct theoretical illustration of this spectral signature, related predominantly to very strongly hydrogen bonded complexes, is proposed. The spectral density, υSO−H,is determined by the aid of an approach describing the high-frequency O − H stretching modes by harmonic potentials. The intermolecular potential modes (O…O) are assumed to be of anharmonic nature. The approach is founded on the strong anharmonic coupling approximation, which prescribes a linear dependency of the O − H frequency on the O…O stretching coordinate as rationalized by the fundamental model of Maréchal and Witkowski. Both direct relaxation of the O − H vibrational mode and its homolog, indirect one, affecting the O…O stretching mode are taken into consideration. The model also considers Davydov coupling, which describes the mutual interaction that takes place in the centrosymmetric dimer between the two existent hydrogen bonds as well as Fermi resonances, which occur between the bending modes arising in- and out-of-plane of the dimer and the fundamental O − H stretching mode. Interestingly, we illustrate how the (A, B, and C) triplet detected in the IR absorption band of phosphonic acids can be generated and discuss how the ABC structure can be numerically simulated. The approach provides a direct explanation of the emergence of this unusual feature and mainly reveals that the A peak is due to the Davydov coupling mechanism, whereas the BC diad is found to be generated by Fermi resonances. This was elucidated in a distinctly different approach, rationalized by Sheppard and Claydon, affirming that the provenance of the BC diad is exclusively due to Fermi resonances mechanism. Altogether, our results highlight the congregated effects of both Fermi resonance mechanism and Davydov coupling for the formation of the ABC structure. The model paves the way for a deeper understanding of the ABC structure, characteristic of very toxic strongly hydrogen-bonded dimers. This is of capital importance as it allows one to develop a solid understanding of nerve agents, such as phosphonic acids, from theory alone, so as to avoid difficult and dangerous experiments since they are extremely toxic.

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.

Low-Frequency Raman Spectroscopy on Amorphous Poly(Ether Ether Ketone) (PEEK).

Low-frequency peaks in the Raman spectra of amorphous poly(ether ether ketone) (PEEK) were investigated. An amorphous sample with zero crystallinity, as confirmed by wide-angle X-ray diffraction, was used in this study. In a previous study, two peaks were observed in the low-frequency Raman spectra of the crystallized samples. Among these, the peaks at 135 cm-1 disappeared for the amorphous sample. Meanwhile, for the first time, the peak at 50 cm-1 was observed in the crystallized sample. Similar to the peak at 135 cm-1, the peak at 50 cm-1 disappeared in the amorphous state, and its intensity increased with increasing crystallinity. The origins of the two peaks were associated with the Ph-CO-Ph-type intermolecular vibrational modes in the simulation. This suggests that the Ph-CO-Ph vibrational mode observed in the low-frequency region of PEEK was strongly influenced by the intermolecular order.

Label-free detection of inclusion body formation in E. coli with application of terahertz

Extensive production of recombinant protein is essential for use in various fields. Bacterial cells, especially the Escherichia coli (E. coli) expression system, are widely used for the production of recombinant proteins due to their advantages in time and cost. However, the formation of inclusion bodies (IBs) caused by the production of recombinant protein is a significant issue. Therefore, a precise tool for the detection of IBs is in high demand. In this study, we demonstrated a label-free and rapid sensing platform for the detection of IBs formation in E. coli using terahertz-time domain spectroscopy (THz-TDS) system and terahertz metamaterials. The detection was based on the local polarity difference between E. coli samples with induced (positive) and non-induced (negative) protein overexpression. The formation of IBs in positive samples resulted in a decrease in local polarity compared to negative samples. This local polarity difference, strongly related to intermolecular interactions, influenced THz absorption as the THz regime involves weak intermolecular vibrational modes. Experimental results showed that the THz transmittance (ΔT) and resonance frequency shift (Δf) were significantly different between positive and negative samples, confirming the effectiveness of our method. Specifically, positive samples exhibited a ΔT value of 26.57% and a Δf value of 0.12 THz, while negative samples showed a ΔT value of 31.83% and a Δf value of 0.14 THz. These results highlight the capability of our platform to detect IBs rapidly and accurately.

UV‐A/B High‐Sensitivity Organic Photodetectors Containing Butterfly‐Shaped Furan‐Fused BN‐Dihydropyrene with Push‐Pull Electron “Wings” toward Image Sensor

AbstractReplacement of C─C unit with its isoelectronic B─N unit in aromatics provides a new class of molecules with appealing properties. Herein, Five novel butterfly‐shaped furan‐fused bis‐BN dihydropyrenes (FBN) derivatives are synthesized with different push‐pull electron “wings”. These compounds exhibit prominent UV‐A/B absorption, high energy levels, and p‐type characteristics. Thanks to the side‐chain engineering and BN dipole manipulation, their intramolecular dipole moments and intermolecular stacking mode are effectively regulated to improve intra‐ and inter‐molecular charge transfer, thus achieving high hole mobilities. Five FBN‐X compounds are doped with PC71BM as heterojunction photosensitive layers to fabricate solution‐processed high performance organic photodetectors (OPDs), which exhibit self‐powered effect and high sensitivity to UV‐A/B. Especially, the FBN‐CN‐based device presents a high detectivity up to 1.72 × 1012 Jones, a peak external quantum efficiency of 19.1%, and an extremely low dark current density of 8.90 × 10−10 A cm−2 under 320 nm at 0 V. To the best of authors knowledge, it is the first report of photodiode‐type UV‐OPDs containing BN‐doped polycyclic aromatic hydrocarbons as active layer to date. And the optimal device shows a significant advantage over the reported 300–380 nm UV‐OPDs. In addition, a 10 × 10 array of organic image sensor is successfully demonstrated, which showcases excellent low‐light imaging capability.

HCl trimer: HCl-stretch excited intramolecular and intermolecular vibrational states from 12D fully coupled quantum calculations employing contracted intra- and inter-molecular bases.

We present fully coupled, full-dimensional quantum calculations of the inter- and intra-molecular vibrational states of HCl trimer, a paradigmatic hydrogen-bonded molecular trimer. They are performed utilizing the recently developed methodology for the rigorous 12D quantum treatment of the vibrations of the noncovalently bound trimers of flexible diatomic molecules [Felker and Bačić, J. Chem. Phys. 158, 234109 (2023)], which was previously applied to the HF trimer by us. In this work, the many-body 12D potential energy surface (PES) of (HCl)3 [Mancini and Bowman, J. Phys. Chem. A 118, 7367 (2014)] is employed. The calculations extend to the intramolecular HCl-stretch excited vibrational states of the trimer with one- and two-quanta, together with the low-energy intermolecular vibrational states in the two excited v = 1 intramolecular vibrational manifolds. They reveal significant coupling between the intra- and inter-molecular vibrational modes. The 12D calculations also show that the frequencies of the v = 1 HCl stretching states of the HCl trimer are significantly redshifted relative to those of the isolated HCl monomer. Detailed comparison is made between the results of the 12D calculations on the two-body PES, obtained by removing the three-body term from the original 2 + 3-body PES, and those computed on the 2 + 3-body PES. It demonstrates that the three-body interactions have a strong effect on the trimer binding energy as well as on its intra- and inter-molecular vibrational energy levels. Comparison with the available spectroscopic data shows that good agreement with the experiment is achieved only if the three-body interactions are included. Some low-energy vibrational states localized in a secondary minimum of the PES are characterized as well.

Balancing Flexible Side Chains on 2D Conjugated Acceptors Enables High-Performance Organic Solar Cell.

Balancing the rigid backbones and flexible side chains of light-harvesting materials is crucially important to reach optimized intermolecular packing, micromorphology, and thus photovoltaic performance of organic solar cells (OSCs). Herein, based on a distinctive CH-series acceptor platform with 2D conjugation extended backbones, a series of nonfullerene acceptors (CH-6F-Cn) are synthesized by delicately tuning the lengths of flexible side chains from n-octyl to n-amyl. A systemic investigation has revealed that the variation of the side chain's length can not only modulate intermolecular packing modes and crystallinity but also dramatically improve the micromorphology of the active layer and eventual photovoltaic parameters of OSCs. Consequently, the highest PCE of 18.73% can be achieved by OSCs employing D18:PM6:CH-6F-C8 as light-harvesting materials.

Zero-point energy effects on the stability of water clusters: Implications on the uptake of hydrogen isotope substituted water on ice and clathrate hydrate phases

To study the effect of hydrogen isotope substitution on the uptake of water during formation of clathrate hydrates, the harmonic intermolecular librational modes of selected water clusters (X2O)n with n = 2–6 and hydrogen isotopes X = H, D, and T are studied. The effects of the quantum mechanical zero-point energy (ZPE) in each cluster on the binding energies of the H2O, D2O, and T2O clusters are determined, with ZPE leading to the smallest binding energies in the H2O clusters and the largest binding energies in the T2O clusters. Corrections for anharmonicity of the librational modes are considered, and these bring the frequency ranges of the calculated intermolecular librational modes in the clusters to the experimental ranges of the librational modes in the infrared spectra of H2O and D2O solid ice and clathrate hydrate phases, and liquid H2O water. These calculations show the expected ranges of the binding energy of tritiated water onto a solid ice and clathrate hydrate surface and can help quantify the isotopic enrichment on a growing clathrate hydrate phase from the solution.

Theory and experiment on the terahertz vibrational spectrum of ferulic acid

Ferulic acid (FA, C10H10O4), a type of hydroxycinnamic acid derivative, has beneficial pharmacological effects and biological activities and is known for its high application value in medicine, health care, and cosmetic products. The vibration spectrum of FA ranging from 0.3 THz to 2.0 THz has been investigated by terahertz time-domain spectroscopy. The characteristic absorption peaks located at 0.937, 1.159, 1.464, 1.694, and 1.910 THz are obtained experimentally. To understand the origin of the characteristic absorption peaks of FA, density functional theory calculations based on isolated molecule and crystalline structure are separately performed to differentiate the intramolecular and intermolecular vibrational modes. Combined analysis of the experimental and theoretical results informs that the characteristic absorption peak at 1.464 THz comes from intramolecular interaction, and the ones at 0.937, 1.159, 1.694, and 1.910 THz originate from intermolecular collective vibrational modes.