OH Stretch Research Articles

Microhydration of ionized building blocks of DNA/RNA: infrared spectra of pyrimidine^{+}-(hbox {H}_{2}hbox {O})_{text {1-3}} clusters

Hydration of biomolecules is an important physiological process that governs their structure, stability, and function. Herein, we probe the microhydration structure of cationic pyrimidine (Pym), a common building block of DNA/RNA bases, by infrared photodissociation spectroscopy (IRPD) of mass-selected microhydrated clusters, hbox {Pym}^{+}-hbox {W}_{n} (W=hbox {H}_{2}hbox {O}), in the size range n=1–3. The IRPD spectra recorded in the OH and CH stretch range are sensitive to the evolution of the hydration network. Analysis with density functional theory calculations at the dispersion-corrected B3LYP-D3/aug-cc-pVTZ level provides a consistent picture of the most stable structures and their energetic and vibrational properties. The global minima of hbox {Pym}^{+}-hbox {W}_{n} predicted by the calculations are characterized by H-bonded structures, in which the H-bonded hbox {W}_{n} solvent cluster is attached to the most acidic C4–H proton of hbox {Pym}^{+} via a single CH...O ionic H-bond. These isomers are identified as predominant carrier of the IRPD spectra, although less stable local minima provide minor contributions. In general, the formation of the H-bonded solvent network (exterior ion solvation) is energetically preferred to less stable structures with interior ion solvation because of cooperative nonadditive three-body polarization effects. Progressive hydration activates the C4–H bond, along with increasing charge transfer from hbox {Pym}^{+} to hbox {W}_{n}, although no proton transfer is observed in the size range nleqslant 3. The solvation with protic, dipolar, and hydrophilic W ligands is qualitative different from solvation with aprotic, quadrupolar, and hydrophobic hbox {N}_{2} ligands, which strongly prefer interior ion solvation by uppi stacking interactions. Comparison of hbox {Pym}^{+}-W with Pym-W and hbox {H}^{+}Pym-W reveals the drastic effect of ionization and protonation on the Pym...W interaction.Graphic

Vibrational Signature of Dynamic Coupling of a Strong Hydrogen Bond.

Elucidating the dynamic couplings of hydrogen bonds remains an important and challenging goal for spectroscopic studies of bulk systems, because their vibrational signatures are masked by the collective effects of the fluctuation of many hydrogen bonds. Here we utilize size-selected infrared spectroscopy based on a tunable vacuum ultraviolet free electron laser to unmask the vibrational signatures for the dynamic couplings in neutral trimethylamine-water and trimethylamine-methanol complexes, as microscopic models with only one single hydrogen bond holding two molecules. Surprisingly broad progression of OH stretching peaks with distinct intensity modulation over ∼700 cm-1 is observed for trimethylamine-water, while the dramatic reduction of this progression in the trimethylamine-methanol spectrum offers direct experimental evidence for the dynamic couplings. State-of-the-art quantum mechanical calculations reveal that such dynamic couplings are originated from strong Fermi resonance between the stretches of hydrogen-bonded OH and several motions of the solvent water/methanol, such as translation, rocking, and bending, which are significant in various solvated complexes commonly found in atmospheric and biological systems.

Role of Intermolecular Charge Fluxes in the Hydrogen-Bond-Induced Frequency Shifts of the OH Stretching Mode of Water.

The relation between the vibrational properties and the electrostatic situations of the vibrating functional group is useful to predict vibrational spectroscopic features based on, for example, classical molecular dynamics of liquids or biomolecular systems, but to pursue its generality or the extent of applicability, it is required to understand the mechanisms giving rise to it. Here such an analysis is carried out for the OH stretching mode of water. By examining the correlations among various (structural, vibrational, and electrostatic) properties and by analyzing the spatial characteristics of the behavior of electrons occurring upon the vibration, it is shown that the dependence of the vibrational frequency and the dipole derivative of the OH stretching mode on the electric field is not of purely electrostatic origin, and the delocalized electronic motions occurring with this mode, called intermolecular charge fluxes, related to both the dipole first and second derivatives play important roles.

Vibrational Energy Flow in the Uracil-H2O Complexes.

In the uracil-H2O complex, the vibrational energy initially stored in the OH(v = 1) stretch efficiently transfers to the first overtone-bending mode under a near-resonant condition. The relaxation of the overtone vibration redistributes its energy to uracil and the two hydrogen bonds in the intermolecular zone, which consists of the OH bond and the bonds between nearby C, N, O, and H atoms of uracil. The uracil NH bond and the hydrogen bond it formed with the H2O molecule, N-H···O, store the major portion of the energy released by the relaxing bending mode, thus forming a localized hot band in the intermolecular zone. Energy transfer to the bonds beyond the zone is found to be not significant. The excited uracil NH is found to transfer its energy to the bending mode, thus indicating that the hydrogen bond of N-H···O is the principal energy pathway in both directions. In the presence of efficient near-resonant energy transfer pathways, the time evolution of the centers of mass distance shows the phenomenon of beats. One global and two different local minima energy structures are considered. The results of energy transfer do not differ significantly, suggesting that the two hydrogen bonds in all three structures have similar contributions to the energy transfer.

Hyper‐Raman spectroscopy of alcohols excited at 532 nm: Methanol, ethanol, 1‐propanol, and 2‐propanol

AbstractHyper‐Raman (HR) measurements of four simple alcohols have been demonstrated. High‐quality HR spectra with high signal to noise ratios allow us to discuss spectral features in detail. Measured HR spectra are compared with IR and Raman spectra. High similarities between HR and IR spectra are found both in the fingerprint and the CH stretching regions. Meanwhile, HR and IR spectra show differences in spectral features including relative intensities of the OH stretch to the CH stretches. Besides, the frequencies of the hydrogen‐bonded OH stretching mode in HR spectra locate around 3,360 cm−1, higher than those observed in IR spectra. These differences reflect the difference in the selection rules of spectroscopic methods.

Comparative Analysis of Alkaline-Extracted Hemicelluloses from Beech, African Rose and Agba Woods using FTIR and HPLC

The vast application of hemicellulose in industry is greatly influenced by its chemical components. The hydroxyl spectra vibrations (3919-3671 cm -1 ) from the FTIR spectra indicates the presence of non-hydrogen bonded OH stretch and normal polymeric OH stretch (3454-3211 cm -1 ) in the three samples. The samples contained residual lignin indicated by IR absorption bands at 1592 and 1525 cm -1 . The presence of C=O stretching vibrations of acetyl groups at 1734 cm -1 indicated that African rosewood was generally an acetylated molecule. Each heteropolysaccharide also contained reducing monosaccharides at their ends suggested by the C-H stretching vibrations. Infrared absorptions characteristic of asymmetric β-1,6-glycosidic stretching was present in Beechwood and Agbawood, respectively, and African rosewood gave three absorption bands β-1,3-glycosidic stretch, β-1,4-glycosidic stretch and an asymmetric β 1,6-glycosidic stretch, respectively. Agbawood gave a major absorption band at 923.75 cm -1 corresponding to the absorption band at β-1,4-glycosidic stretching. African rosewood contained 96% mannose and 4% of an unidentified sugar. Beechwood contained primarily glucose, but Agbawood contained 20, 14, 8 and 57% glucose, mannose, galactose, and an unidentified sugar, respectively.

Signature of the surface hydrated proton and associated restructuring of water at model membrane interfaces: a vibrational sum frequency generation study.

Hydrated proton at membrane interfaces plays an important role in the bioenergetic process of almost all organisms. Herein, the signature of the hydrated proton at membrane interfaces has been investigated by measuring the vibrational sum frequency generated (VSFG) spectra of negatively charged and zwitterionic lipids in the presence of different concentrations of acids. The addition of acids decreases the intensity of the OH stretch of the VSFG signal of water present at the negatively charged and zwitterionic lipids along with the enhanced intensity of the broad VSFG signal in the range of 2500-2800 cm-1. The enhanced intensity of the broad continuum observed in the range of 2500-2800 cm-1 has been assigned to the signature of the hydrated proton at the lipid interfaces. The decrease in the VSFG signal of the OH stretch of water along with the appearance of the broad signal suggests that the hydrated proton exists in the vicinity of the lipid interfaces and restructures the interaction between the interfacial water molecules.

Optimization and Study of the Response Surface of Properties for the Synthesis of ZSM-5 Zeolites with Hierarchical Pore Structure Obtained by Desilication

Hierarchical ZSM-5 zeolites were prepared by alkali treatment (desilication) at two temperatures, two reaction times, and two NaOH concentrations. A 23 factorial design was used to study the effect of these variables on the crystallinity, microporosity, and mesoporosity of the zeolite due to the desilication treatment. The factorial design analysis showed that the temperature, reaction time and NaOH concentration and the second order interaction between temperature and time have statistically significant effect on the micropore volume. On mesopore volumes (Vmeso) and areas (Smeso), the reaction time and NaOH concentration factors have statistically significant effects. In the case of mesopore volumes, the second order reaction time and NaOH concentration interaction factor are also significant. On the other hand, only the alkali concentration affected, negatively, the relative crystallinity. Two hierarchical ZSM-5 zeolites with the highest relative crystallinity and mesoporosity were selected and further characterized by inductively coupled plasma (ICP) analysis, 29Si nuclear magnetic resonance (NMR), 27Al NMR, Fourier transform infrared (FTIR) spectroscopy in the OH stretch region and pyridine adsorbed FTIR spectroscopy. NMR and FTIR results showed that the alkali treatment selectively removed silica from the zeolite framework, decreasing the SAR (silica-to-alumina ratio) values, while decreasing Brønsted acid site concentrations and increasing Lewis acid sites concentrations.

Representing molecular ground and excited vibrational eigenstates with nuclear densities obtained from semiclassical initial value representation molecular dynamics.

We present in detail and validate an effective Monte Carlo approach for the calculation of the nuclear vibrational densities via integration of molecular eigenfunctions that we have preliminary employed to calculate the densities of the ground and the excited OH stretch vibrational states in the protonated glycine molecule [Aieta et al., Nat Commun 11, 4348 (2020)]. Here, we first validate and discuss in detail the features of the method on a benchmark water molecule. Then, we apply it to calculate on-the-fly the ab initio anharmonic nuclear densities in the correspondence of the fundamental transitions of NH and CH stretches in protonated glycine. We show how we can gain both qualitative and quantitative physical insight by inspection of different one-nucleus densities and assign a character to spectroscopic absorption peaks using the expansion of vibrational states in terms of harmonic basis functions. The visualization of the nuclear vibrations in a purely quantum picture allows us to observe and quantify the effects of anharmonicity on the molecular structure, also to exploit the effect of IR excitations on specific bonds or functional groups, beyond the harmonic approximation. We also calculate the quantum probability distribution of bond lengths, angles, and dihedrals of the molecule. Notably, we observe how in the case of one type of fundamental NH stretching, the typical harmonic nodal pattern is absent in the anharmonic distribution.

Wettability of Graphene and Interfacial Water Structure

Understanding the graphene-water interaction, referred to as ‘wettability,’ is important for various applications, such as water desalination, filtration, energy storage, and catalysis. However, most studies on graphene's wettability have been performed with either macroscopic water contact angle measurements or molecular dynamics simulations. The detailed hydrogen-bonding network structure of water molecules at the graphene-water interface has not been fully understood at the molecular level. Here, using vibrational sum frequency generation (VSFG) spectroscopy, we elucidate the interfacial water structure and graphene hydrophobicity at a multilayer graphene-water interface. As the number of graphene layers increases, water molecules with dangling OH group become more populated. We compare the contact angles of water on the multilayer graphene surfaces with VSFG results. An excellent correlation between water adhesion energy of graphene and fraction of dangling OH groups estimated from the water OH stretch VSFG spectrum is established. This observation suggests that the VSFG could be an incisive technique for measuring water's adhesion energy on any spatially confined or blocked surface where the water contact angle cannot be measured. We further anticipate that the VSFG result on the transition from wetting transparency to translucency upon increasing the number of graphene layers will be used to understand the wettability of low-dimensional materials and the role of water structure on electric double layers of graphene-based electrodes.

Vibrational Coupling in Solvated H3O+: Interplay between Fermi Resonance and Combination Band.

Complex vibrational features of solvated hydronium ion, H3O+, in 3 μm enable us to look into the vibrational coupling among O-H stretching modes and other degrees of freedom. Two anharmonic coupling schemes have often been engaged to explain observed spectra: coupling with the OH bending overtone, known as Fermi resonance (FR), has been proposed to account for the splitting of the OH stretch band at ∼3300 cm-1 in H3O+···Ar3, but an additional peak in H3O+···(N2)3 at the similar frequency region has been assigned to a combination band (CB) with the low-frequency intermolecular stretches. While even stronger vibrational coupling is expected in H3O+···(H2O)3, such pronounced peaks are absent. In the present study, vibrational spectra of H3O+···Kr3 and H3O+···(CO)3 are measured to complement the existing spectra. Using ab initio anharmonic algorithms, we are able to assign the observed complex spectral features, to resolve seemingly contradictory notions in the interpretations, and to reveal simple pictures of the interplay between FR and CB.

Guided Diffusion Monte Carlo: A Method for Studying Molecules and Ions That Display Large Amplitude Vibrational Motions.

Diffusion Monte Carlo provides an effective and efficient approach for calculating ground state properties of molecular systems based on potential energy surfaces. The approach has been shown to require increasingly large ensembles when intra- and intermolecular vibrations are weakly coupled. We recently proposed a guided variant of diffusion Monte Carlo to address these challenges for water clusters [Lee, V. G. M.; McCoy, A. B. J. Phys. Chem. A 2019, 123, 8063-8070]. In the present study, we extend this approach and apply it to more strongly bound molecular ions, specifically CH5+ and H+(H2O)n=1-4. For the protonated water systems, we show that the guided DMC approach that was developed for studies of (H2O)n can be used to describe the OH stretches and HOH bends in the solvating water molecules, as well as the free OH stretches in the hydronium core. For the hydrogen bonded OH stretches in the H3O+ core of H+(H2O)n and the CH stretches in CH5+, we develop adaptive guiding functions based on the instantaneous structure of the ion of interest. Using these guiding functions, we demonstrate that we are able to obtain converged zero-point energies and ground state wave functions using ensemble sizes that are as small as 10% the size that is needed to obtain similar accuracy from unguided calculations.

Nanoinsecticidal Efficacy of Ag/Ni Bimetallic Nanoparticles (BMNPs) on Lymphatic Filariasis Vector

Aims: Nanoparticles are gradually gaining wide scientific interest due to their various applications in catalysis, magnetism, medicine, optics, as antibacterial and nanolarvicidal agents. This research aimed at evaluating the larvicidal activity of green synthesized Ag/Ni BMNPs from the aqueous root extract of Borassus aethiopum as the stabilizing agent as well as their spectroscopic investigation using UV-Visible and FT-IR spectroscopy.
 Place and Duration of Study: The study was conducted in Gombe State University between August and December, 2019.
 Methodology: In this study, Ag/Ni hybrid bimetallic nanoparticles was synthesized using an eco-friendly method from the secondary metabolites of Borassus aethiopum acting as the reducing agent.
 Results: Optical measurements using UV-Vis showed the maximum absorption wavelength at 410nm while the FT-IR result for the root extract showed peaks at 3443.26cm-1, 2929.48 cm-1, 1651.28 cm-1, and 1080.12 cm-1 corresponding to OH stretch, sp3 C-H stretch, C=C stretch and C-O-C stretching respectively. These were replaced in the spectra of the BMNPs with the absence and appearance of some others indicating that they were involved in the capping process. The lethal concentration (LC50) was found to be 5.730, 13.585 and 15.735 mg/L for 1st, 2nd and 3rd/4th instars respectively. Also, the lethal concentration (LC90) was found to be 88.444, 195.689 and 236.889 mg/L for 1st, 2nd and 3rd/4th instars respectively.
 Conclusion: The larvicidal bioassay result showed a dose-dependent mortality rates against Culex quinquefasciatus larvae which suggest they can be developed to control the insect population.

Intrinsic physicochemical interactions of calcium hydroxide-based medications.

To investigate intrinsic physicochemical properties and interactions of three different calcium hydroxide-based medications via means of different analytical methods. Two-commercial premixed medications: TempCanal(TCmx) and ProCalR(PCmx) and powder-form ProCal(PCpw) with glycerin were used. Vibrational modes were analyzed using Raman spectroscopy. Spectral mapping of samples was carried out using characteristic vibrational modes of calcium hydroxide and barium sulfate. Crystalline and amorphous phases were studied with X-rays powder diffraction analysis. Topographic features were examined by scanning electron microscope examination and quantitative analysis was determined using energy-dispersive X-ray spectroscopy analysis. Strong OH stretch of in Raman spectra were observed at 3,697 and 3,615 cm-1 for TCmx and reference, respectively. However, OH mode was not observed for PCmx and PCpw. Moreover, some peaks in the fingerprint areas of TCmx and PCpw overlapped with each other. The characteristic vibration bands of barium sulfate and calcium hydroxide were observed in all samples, and no new peak was observed in the Raman spectra of samples. Calcium hydroxide-based medications were seen as differed in their chemical composition. No new crystalline or amorphous phase peak was observed. Only calcium hydroxide and barium sulfate were matched in X-rays powder-diffraction analysis. Energy-dispersive X-ray spectroscopy analysis showed that amount of Ba and S elements in the PCpw were lower than TCmx and PCmx whereas, for Ca in the PCpw was higher than TCmx and PCmx. The present study revealed the structural difference among different forms of calcium hydroxide-based medications. The vehicle and substrates of the tested medications altered the physicochemical properties of the compound via electrostatic interactions.

A comprehensive infrared spectroscopic and theoretical study on phenol-ethyldimethylsilane dihydrogen-bonded clusters in the S0 and S1 states.

To investigate microscopic characters of Si-H⋯H-O type dihydrogen bonds, we observed OH and SiH stretch bands in both the S0 and S1 states of phenol-ethyldimethylsilane (PhOH-EDMS) clusters by infrared (IR)-ultraviolet (UV) and UV-IR double resonance spectroscopies. Density functional theory (DFT) calculations and energy decomposition analysis were also performed. Structures of two isomers identified were unambiguously determined through the analysis of IR spectra and DFT calculations. To discuss the strength of dihydrogen bond in various systems, we performed theoretical calculations on clusters of EDMS with several acidic molecules in addition to PhOH. It was revealed that charge-transfer interaction energies from a bonding σ orbital of SiH bond to an anti-bonding σ* orbital of OH bond well reflect strengths of dihydrogen bonds. Additionally, it was found that the red shift of SiH stretch frequencies can be used as a crude measure of the strength of dihydrogen bonds. Relationship between the red shifts of OH/SiH stretch frequencies and various electrostatic components of the interaction energy was examined. In the S1 state, large increases in red shifts were observed for both the OH and SiH stretch frequencies. Since the EDMS moiety is not associated with the electronic excitation in a cluster, the strength of dihydrogen bonds in the S1 and S0 states was able to be directly compared based on the red shifts of the SiH stretch bands. A significant increase in the red shift of SiH stretch frequency indicates a strengthening of the dihydrogen bonds during the electronic excitation of the PhOH moiety.

Vibrational spectroscopy of the cryogenically cooled O- and N-protomers of 4-aminobenzoic acid: Tag effects, isotopic labels, and identification of the E,Z isomer of the O-protomer

4-Aminobenzoic acid (4ABA) is a biologically relevant, small organic molecule with two protonation sites: the amino group (N-protomer) and the carboxyl group (O-protomer). The O-protomer is energetically preferred in the gas-phase, while the higher energy N-protomer can be trapped using aprotic solvents such as acetonitrile during electrospray ionization. Here, we focus on the structure of the O-protomer, which can occur in three low-lying isomeric forms that result from different orientations of the OH groups relative to the benzene ring. We report the vibrational spectra of both N- and O-protomers of the cryogenically cooled ions in the gas phase over the spectral range 800–4000 cm−1. The bands arising from the OH stretches are isolated from the nearby NH stretching fundamentals using isotopic labeling as well as by analysis of the shifts in these fundamentals upon attachment of D2 and N2 molecules to the OH groups of the O-protomer. The spectra of isomers derived from the different locations of the adducts were isolated using two-color, IR-IR photofragmentation spectroscopy. The docking motifs by which the O-protomer binds to another 4ABA molecule is also explored and found to feature a bifurcated arrangement involving attachment of both OH groups of the protonated head group to the carbonyl group of the neutral partner.

Temperature and Nuclear Quantum Effects on the Stretching Modes of the Water Hexamer.

The water hexamer has many low-lying isomers, e.g., ring, book, cage, and prism, shifting from two- to three-dimensional structures. We show that this dimensionality change is accompanied by a drop in the quantum nature of the cluster, as manifested in the red shift of the quantal OH stretching modes as compared with their classical counterparts. We obtain this “nuclear quantum effect” (NQE) as the mean deviation between the OH stretch frequencies from velocity autocorrelation Fourier transforms from classical trajectories on a high-level water potential (MB-pol) as compared with scaled harmonic frequencies from high-level quantum chemistry calculations. With a universal scaling factor, the predicted OH frequencies agree with experiment to a mean absolute deviation ≤10 cm–1, which allows unequivocal isomer assignments. By assuming temperature-independent NQEs, we produce the temperature dependence of the cage isomer OH stretch spectrum below 70 K, where it is the dominant structure. All bands widen and blue-shift with increasing temperature, most conspicuously the reddest mode, which thus constitutes a “vibrational thermometer”.

Adsorption of Iodine Species (I3-, I-, and IO3-) at the Nuclear Paint Monolayer-Water Interface and Its Relevance to a Nuclear Accident Scenario.

Following a nuclear accident, radioactive iodine causes great concern to public health and safety. Organic iodide, because of its ability to escape reactor containment building and high environmental mobility, constitutes a predominant fraction of airborne radioiodine at places far away from the accident site. As the iodine released from a reactor core is inorganic iodine, it is vital to understand the mechanism of organic iodide formation inside reactor containment. In this context, we investigated the surface prevalence and adsorption of various inorganic iodines, I-, I3-, and IO3-, at a nuclear paint (used in nuclear installations) monolayer-water interface, mimicking the painted inner walls of an accident-affected containment building that are exposed to the iodine-containing condensed water layer. Vibrational sum frequency generation (VSFG) measurements in the OH and CH stretch regions reveal that the paint-water interface changes its charge characteristics with the pH of the water that affects the degree of interaction with the iodine species. At the acidic condition (bulk pH < 7), the paint becomes positively charged and strongly adsorbs the negatively charged iodine species dissolved in the aqueous phase, whereas at the alkaline condition (bulk pH > 9.5), the paint becomes net neutral and weakly interacts with the iodine species. These interactions change the conformation of the paint such that its hydrophobic alkyl groups orient increasingly away from the aqueous phase. The order of adsorption increases as IO3- < I- < I3- for the different iodine species studied.

Switching a HO···π Interaction to a Nonconventional OH···π Hydrogen Bond: A Completed Crystallographic Puzzle.

In this article, we present crystallographic and spectroscopic evidence of a tunable system wherein a HO···π interaction switches incrementally to a nonconventional OH···π hydrogen bonding (HB) interaction. More specifically, we report the synthesis of substituted forms of model system 1 to study the effects of aryl ring electronic density on the qualitative characteristics of OH···π hydrogen bonds therein. The OH stretch in experimental infrared data, in agreement with density-functional theory (DFT) calculations, shows continuous red-shifts as the adjacent ring becomes more electron rich. For example, the OH stretch of an amino-substituted analogue is red-shifted by roughly 50 cm-1 compared to the same stretch in the CF3 analogue, indicating a significantly stronger HB interaction in the former. Moreover, DFT calculations (ωB97XD/6-311+G**) predict that increasing electronic density on the adjacent top ring reduces the aryl π-OH σ* energy gap with a concomitant enhancement of the OH n-π* energy gap. Consequently, a dominant π-σ* interaction in the amino substituted analogue locks the system in the in-form while a favorable n-π* interaction reverses the orientation of the oxygen-bound hydrogen in its protonated form. Additionally, the 1H NMR data of various analogues reveal that stronger OH···π interactions in systems with electron-rich aromatic rings slow exchange of the alcoholic proton, thereby revealing coupling with the geminal proton. Finally, X-ray crystallographic analyses of a spectrum of analogues clearly visualize the three distinct stages of "switch"-starting with exclusive HO···π, to partitioned HO···π/OH···π, and finally to achieving exclusive OH···π forms. Furthermore, the crystal structure of the amino analogue reveals an interesting feature in which an extended HB network, involving two conventional (NH···O) and two nonconventional (OH···π) HBs, dimerizes and anchors the molecule in the unit cell.

Vibrational Spectroscopy of a Potential Interstellar Ion: Protonated Methyl Formate

Abstract The abundance of methyl formate (MF, HCOOCH3) in star-forming regions of the interstellar medium (ISM) suggests the presence of protonated MF (H+MF). However, no spectroscopic data exist for isolated H+MF. Here, we address the vibrational properties of H+MF and its H+MF-L n≤2 clusters (L = Ar/N2) by infrared photodissociation (IRPD) spectroscopy and density functional theory calculations. Protonation of MF occurs at the CO oxygen, resulting in four different isomers arising from the syn/anti (s/a) and cis/trans (c/t) orientation between OCH3 and the excess proton. H+MF photofragments into protonated methanol by CO elimination. The IRPD spectrum exhibits redshifted OH stretch bands of the most stable H+MF(t/s) and H+MF(c/a) conformers because of the high internal energy required for dissociation. Tagging of H+MF with inert ligands drastically reduces both the internal energy and the dissociation threshold. The resulting higher-resolution IRPD spectra allow determination of the most stable H+MF rotamers as (t/s) and (c/a). In the cold H+MF-L dimers, the ligand forms an OH...L hydrogen bond, while bonding to the positively charged 2pz orbital of the carbonyl C atom is less favorable. The latter allows estimation of the free OH stretch fundamental of the most stable H+MF(t/s) rotamer as 3545 ± 5 cm−1. While for neutral MF the more stable syn rotamer MF(s) dominates the population in both the laboratory and the ISM (&gt;99%), the anti conformer is substantially populated for H+MF (∼30%), which is rationalized by protonation-induced isomerization. This mechanism may lead to an enhanced abundance of MF(a) in certain regions of the ISM.