Formic acid-methanol complexation vs. esterification: elusive pre-reactive species identified by vibrational spectroscopy.

Vibrational spectra of the mixed dimer and the two mixed trimers of methanol and formic acid as well as some of their isotopologues are presented. Out of the eight expected OH stretching fundamentals of these three pre-reactive hydrogen-bonded complexes, the three modes mainly involving an acid OH group bound to the alcohol appear to be missing in the jet-cooled spectra despite a combination of infrared and Raman probing. A possibility of spectral overlap is discussed in the mixed dimer case, but largely discarded. The missing modes correspond to (fractional) concerted elongation of all engaged OH bonds, promoting synchronous degenerate proton transfer between the molecules. One other trimer mode is very tentatively attributed to a broad spectral feature, whereas all OH bonds contacting carbonyl groups can be unambiguously identified by four relatively narrow infrared absorptions. The spectral features are confirmed by vibrational perturbation theory and deviate in a subtle but systematic way from scaled harmonic predictions which were previously validated for the formic acid complex with a more acidic alcohol. Despite being exothermic and exergonic, ester formation can only be detected in the rarefied gas expansions after extended pre-mixture of the gases, which somewhat contrasts the recent microwave spectroscopic evidence of in situ ester formation and in particular the lack of pre-reactive complex signals.

Mid-infrared Laser Spectroscopy of Jet-Cooled Formic Acid Trimer: Mode-Dependent Line Broadening in the C-O Stretching Region.

Building on recent progress in the vibrational spectroscopy of the formic acid trimer, we present the first high-resolution measurements of the jet-cooled laser absorption spectrum of (HCOOH)3. The spectra of the lowest- and highest-frequency C-O stretching fundamentals are analyzed whereas the third band is not observed, complicated by monomer and dimer absorptions at 1219 cm-1 (8.2 µm). Vibration-rotation parameters are obtained for the band at 1172.31512(68) cm-1 whereas the C-O stretch at 1246.33(5) cm-1 exhibits a significantly larger breadth, allowing only resolution of the coarse PQR structure. Vibrational predissociation can be ruled out, and intramolecular vibrational redistribution mechanisms are discussed, particularly coupling to the concerted proton exchange within the cyclic dimer subunit. Ultimately, the question remains open. The prospects of high-resolution measurements of other trimer bands or isotope substitution experiments, which might assist in revealing the mode-specificity of the underlying broadening mechanisms, are discussed.

Subtle hydrogen bond preference and dual Franck-Condon activity - the interesting pairing of 2-naphthol with anisole.

The hydrogen-bonded complexes between 2-naphthol (or ß-naphthol) and anisole are explored by detecting their IR absorption in the OH stretching range as well as their UV absorption by means of laser-induced fluorescence and resonance-enhanced two-photon UV ionisation. For the more stable cis and the metastable trans conformations of the OH group in 2-naphthol, hydrogen bonding to the oxygen atom of anisole is consistently detected in different supersonic jet expansions. Alternative hydrogen bonding to the aromatic ring of anisole remains elusive, although the majority of state-of-the-art hybrid DFT functionals with London dispersion correction and - less surprisingly - MP2 wavefunction theory predict it to be slightly more stable at zero-point level, unless three-body dispersion correction is added to the B3LYP-D3(BJ) approach. This changes at the CCSD(T) level, which forecasts an energy advantage of 1-3 kJ mol-1 for the classical hydrogen bond arrangement even after including (DFT) zero-point energy contributions. The UV and IR spectra of the cis complex exhibit clear evidence for intensity redistribution of the primary OH stretch oscillator to combination states with the same low-frequency intermolecular bending mode by Franck-Condon-type vertical excitation mechanisms. This rare case of dual (vibronic and vibrational) Franck-Condon activity of a low-frequency mode invites future studies of homologues where aromatic ring docking of the OH group may be further stabilised, e.g. through anisole ring methylation.

Coupled proton vibrations between two weak acids: the hinge complex between formic acid and trifluoroethanol.

When formic acid and 2,2,2-trifluoroethanol are co-expanded through a slit nozzle into vacuum, a single dominant, hinge-like 1 : 1 complex is formed in significant amounts and its two OH stretching fundamentals separated by 100 cm-1 can be unambiguously assigned by a combination of infrared absorption and Raman scattering. Quantum chemical calculations at different levels reproduce this finding in a satisfactory way and suggest that in-phase (Raman-sensitive and lower wavenumber) OH stretch excitation more or less along the concerted degenerate proton transfer coordinate in the hydrogen-bonded ring stays below the barrier for this concerted exchange. Anharmonic calculations indicate only weak intensity sharing with dark states coming into reach due to the hydrogen bond downshift of the OH stretching vibration. This well-behaved system sets the stage for acid combinations with more basic alcohols, where the in-phase OH stretching vibration is more difficult to detect, possibly due to fast intra-complex vibrational dynamics. It thus provides a benchmark point from which one can explore the evolution of vibrational resonances when the acidic proton meets a more electron-rich alcoholic oxygen.

Slow monomer vibrations in formic acid dimer: Stepping up the ladder with FTIR and Raman jet spectroscopy.

In an effort to extend the cold gas phase spectroscopic database of the cyclic formic acid dimer (FAD), we present and analyze the jet-cooled vibrational infrared and Raman spectrum of (HCOOH)2 in the monomer fingerprint region between 600 and 1500 cm-1. The present study bridges the gap between the intermolecular dimerization-induced and the carbonyl stretching fundamentals that have already been reexamined using jet-cooled or high-resolution spectroscopy. This completes the characterization of the jet-cooled vibrational (HCOOH)2 spectrum below the complex OH (CH) stretching fundamentals, and we report resonance-induced FAD combination/overtone transitions that will serve as a valuable reference for a theoretical modeling of its vibrational dynamics. As a by-product, several new formic acid trimer fundamentals are identified in the jet spectra and assigned with the help of second-order vibrational perturbation theory (VPT2). The polar formic acid dimer still eludes detection in a supersonic jet, but we are able to estimate an experimental upper-bound of the polar dimer-to-trimer-to-cyclic dimer intensity ratio to about 1:10:100 under typical expansion conditions. Using VPT2 with resonance treatment (VPT2+K), we reinvestigate the notorious ν22 resonance triad. Generally, we find that VPT2, which is, of course, inadequate for modeling the resonance-rich OH stretching spectrum of FAD, is performing very satisfactorily in predicting fundamental and two-quantum state term values for the slower modes below 1500 cm-1. As these modes are the building blocks for the ultrafast energy dissipation in the OH stretching region, the present work opens the door for its quantitative understanding.

CC-stretched formic acid: isomerisation, dimerisation, and carboxylic acid complexation.

The cis-trans-isomerism of the propiolic acid monomer (HC[triple bond, length as m-dash]C-COOH) is examined with linear Raman jet spectroscopy, yielding the first environment-free vibrational band centres of a higher-energy cis-rotamer beyond formic acid (HCOOH) in addition to all fundamentals and a large number of hot and combination/overtone bands of the trans-conformer. Two near-isoenergetic trans-fundamentals of different symmetry (CC[double bond, length as m-dash]O bend and OH torsion) prove to be a sensitive benchmarking target, as their energetic order is susceptible to the choice of electronic structure method, basis set size, and inclusion of vibrational anharmonicity. For the infrared- and Raman-active C[double bond, length as m-dash]O stretching fundamentals of the cyclic (C2h) trans-propiolic acid dimer, resonance couplings are found that in part extend to the Cs-symmetric heterodimer of trans-propiolic and trans-formic acid. Exploratory vibrational perturbation theory (VPT2) calculations show that all perturbing states involve displacements of the OH moieties located on the doubly hydrogen bonded ring. The comparison of the infrared spectra of the propiolic acid dimer and its heterodimer with formic acid to that of several other carboxylic acid dimers from the literature reveals a notable similarity regarding a non-fundamental dimer band around 1800 cm-1, which in most cases is so far unassigned. VPT2 calculations and a simple harmonic model suggest an assignment to a combination vibration of the symmetric and antisymmetric OH torsion.

The Raman jet spectrum of trans-formic acid and its deuterated isotopologs: Combining theory and experiment to extend the vibrational database.

Revisiting recently published Raman jet spectra of monomeric formic acid with accurate high order perturbative calculations based on two explicitly correlated coupled-cluster quality potential energy surfaces from the literature, we assign and add 11 new vibrational band centers to the trans-HCOOH database and 53 for its three deuterated isotopologs. Profiting from the synergy between accurate calculations and symmetry information from depolarized Raman spectra, we reassign eight literature IR bands up to 4000 cm-1. Experimental detection of highly excited torsional states (ν9) of trans-HCOOH, such as 4ν9 and ν6 + 2ν9, reveals substantial involvement of the C-O stretch ν6 into the O-H bend/torsion resonance ν5/2ν9, which is part of a larger resonance polyad. Depolarization and isotopic C-D substitution experiments further elucidate the nature of Raman peaks in the vicinity of the O-H stretching fundamental (ν1), which seem to be members of a large set of interacting states that can be identified and described with a polyad quantum number and that gain intensity via resonance mixing with ν1.

A Rather Universal Vibrational Resonance in 1:1 Hydrates of Carbonyl Compounds.

When the lower frequency OH stretching fundamental of a water molecule is shifted to the 3500 cm-1 spectral range by the solvation of a carbonyl compound, in this case a ketone, its infrared intensity is shared with a dark state. It is shown by chemical and isotope substitution for more than a dozen systems that the location of this resonance is remarkably substitution-independent. Harmonic and anharmonic model calculations support its assignment to a combination of the water bending overtone and in-plane water libration. This previously unrecognized intramolecular-intermolecular coupling in single solvent water has a strength of 7-10 cm-1. It may have been sporadically observed before in a few other carbonyl compounds such as amides, without any previous exploration of its potential universality. The resulting generic picosecond energy redistribution channel for aqueous solutions may represent a slow counterpart and doorway model of what happens on a subpicosecond time scale when the hydrogen bonds become stronger, such as in carboxylic acid dimers or protonated water clusters.

Increasing the weights in the molecular work-out of cis- and trans-formic acid: extension of the vibrational database via deuteration.

The higher-energy cis- as well as the global minimum trans-rotamers of the four H/D isotopologues of the formic acid monomer have been examined with Raman jet spectroscopy extending the vibrational gas phase reference database by eleven new cis-band positions for HCOOD, DCOOH, and DCOOD. With these new additions, all O-H/D, C-H/D, and C[double bond, length as m-dash]O stretching as well as the O-D in-plane bending vibrations of these higher-energy rotamers are known in addition to the previously determined C-O stretch and OH torsion of cis-HCOOH. Further, a comparison of the vibrational spectra of all four H/D isotopologues of the globally stable trans-rotamer of formic acid is shown to be very helpful in revealing similarities and differences in these systems, particularly with regard to Fermi resonances. Amongst the most prominent ones is the ν5/2ν9 resonance doublet of trans-HCOOH, for which we provide more insight into a recently suggested label switch of the resonance partners via the comparison of infrared and Raman jet spectra.

On the separability of large-amplitude motions in anharmonic frequency calculations.

Nuclear vibrational theories based upon the Watson Hamiltonian are ubiquitous in quantum chemistry, but are generally unable to model systems in which the wavefunction can delocalise over multiple energy minima, i.e. molecules that have low-energy torsion and inversion barriers. In a 2019 Chemical Reviews article, Puzzarini et al. note that a common workaround is to simply decouple these problematic modes from all other vibrations in the system during anharmonic frequency calculations. They also point out that this approximation can be "ill-suited", but do not quantify the errors introduced. In this work, we present the first systematic investigation into how separating out or constraining torsion and inversion vibrations within potential energy surface (PES) expansions affects the accuracy of computed fundamental wavenumbers for the remaining vibrational modes, using a test set of 19 tetratomic molecules for which high quality analytic potential energy surfaces and fully-coupled anharmonic reference fundamental frequencies are available. We find that the most effective and efficient strategy is to remove the mode in question from the PES expansion entirely. This introduces errors of up to +10 cm-1 in stretching fundamentals that would otherwise couple to the dropped mode, and ±5 cm-1 in all other fundamentals. These errors are approximately commensurate with, but not necessarily additional to, errors due to the choice of electronic structure model used in constructing spectroscopically accurate PES.

Glycolic Acid as a Vibrational Anharmonicity Benchmark.

Three energetically close pairs of vibrational states in glycolic acid are investigated by Raman spectroscopy in a supersonic jet to provide challenging benchmarks for vibrational and electronic structure theory and to solve some open issues in this prototypical hydroxy acid. The alcoholic OH stretching fundamental is located only 8 cm-1 below the acidic OH stretch at 3586 cm-1, much less shifted than predicted by previous anharmonic calculations and by experimental analogy to a fluorene derivative. This and further near-degeneracies in the CH and C=O stretching region are used to assess the predictive power of an exploratory set of quantum chemical calculations including anharmonic VPT2 corrections.