Hydrogen bond network structures of protonated short-chain alcohol clusters.

Because of the hydrogen bond coordination properties of alcohols, their possible hydrogen bond network structures are categorized into only a few types. Therefore, gas phase clusters of alcohols can be a very simple model system to examine the properties of hydrogen bond networks, such as structural development with cluster size and temperature dependence. In this perspective, we focus on the structural study of protonated short-chain alcohol clusters, whose excess protons (charge) enable size-selective spectroscopy in combination with mass spectrometric techniques. Size-selective infrared spectroscopy and a theoretical multi-scale isomer search were applied to protonated clusters of methanol, which is a prototype of short-chain alcohols, and their hydrogen bond network development is elucidated in detail. Complete isomer population switching with increasing temperature was predicted by the quantum harmonic superposition approximation and this isomer switching was evidenced by the remarkable temperature (internal vibrational energy) dependence of the observed infrared spectra. The characteristics of the temperature dependence of protonated methanol were compared with those of water and neutral methanol. In addition, possible hydrogen bond networks of methanolated ions were discussed on the basis of the results for protonated methanol. Stepwise changes in the internal energy of clusters with inert gas tagging are demonstrated. Convergence of the hydrogen bond network to the bulk-like network in large clusters is also discussed. The hydrogen bond structures of the protonated clusters of longer normal alkyl chain alcohols (ethanol, 1-propanol, 1-butanol, and 1-pentanol) are determined by comparison of their infrared spectra with those of the protonated methanol clusters. It is demonstrated that the normal alkyl chain interferes only slightly with the most stable hydrogen bond structure, although a few exceptional cases were also found. These exception cases serve as good model systems for further theoretical and computational studies.

Hydrogen-bonded ring closing and opening of protonated methanol clusters H(+)(CH3OH)(n) (n = 4-8) with the inert gas tagging.

The preferential hydrogen bond (H-bond) structures of protonated methanol clusters, H(+)(MeOH)n, in the size range of n = 4-8, were studied by size-selective infrared (IR) spectroscopy in conjunction with density functional theory calculations. The IR spectra of bare clusters were compared with those with the inert gas tagging by Ar, Ne, and N2, and remarkable changes in the isomer distribution with the tagging were found for clusters with n≥ 5. The temperature dependence of the isomer distribution of the clusters was calculated by the quantum harmonic superposition approach. The observed spectral changes with the tagging were well interpreted by the fall of the cluster temperature with the tagging, which causes the transfer of the isomer distribution from the open and flexible H-bond network types to the closed and rigid ones. Anomalous isomer distribution with the tagging, which has been recently found for protonated water clusters, was also found for H(+)(MeOH)5. The origin of the anomaly was examined by the experiments on its carrier gas dependence.

Folding of the hydrogen bond network of H(+)(CH3OH)7 with rare gas tagging.

A number of isomer structures can be formed in hydrogen-bonded clusters, reflecting the essential variety of structural motifs of hydrogen bond networks. Control of isomer distribution of a cluster is important not only in practical use for isomer-specific spectroscopy but also in understanding of isomerization processes of hydrogen bond networks. Protonated methanol clusters have relatively simple networks and they are model systems suitable to investigate isomer distribution changes. In this paper, isomer distribution of H(+)(CH(3)OH)(7) is studied by size-selective infrared spectroscopy in the OH and CH stretching vibrational region and density functional theory calculations. While the clusters produced by a supersonic jet expansion combined with electron ionization were predominantly isomers having open hydrogen bond networks such as a linear chain, the Ar or Ne attachment (so-called rare gas tagging) entirely switches the isomer structures to compactly folded ones, which are composed only of closed multiple rings. The origin of the isomer switching is discussed in terms of thermal effects and specific isomer preference.

Spectral signatures of four-coordinated sites in water clusters: infrared spectroscopy of phenol-(H2O)n (∼20 ≤ n ≤ ∼50).

We report infrared spectra of phenol-(H(2)O)(n) (∼20 ≤ n ≤ ∼50) in the OH stretching vibrational region. Phenol-(H(2)O)(n) forms essentially the same hydrogen bond (H-bond) network as that of the neat water cluster, (H(2)O)(n+1). The phenyl group enables us to apply the scheme of infrared-ultraviolet double resonance spectroscopy combined with mass spectrometry, achieving the moderate size selectivity (0 ≤ Δn ≤ ∼6). The observed spectra show clear decrease of the free OH stretch band intensity relative to that of the H-bonded OH band with increasing cluster size n. This indicates increase of the relative weight of four-coordinated water sites, which have no free OH. Corresponding to the suppression of the free OH band, the absorption peak of the H-bonded OH stretch band rises at ∼3350 cm(-1). This spectral change is interpreted in terms of a signature of four-coordinated water sites in the clusters.

Anticooperative effect induced by mixed solvation in H+ (CH3OH)m(H2O)n (m + n = 5 and 6): a theoretical and infrared spectroscopic study.

When a solvent molecule is replaced by another molecule with larger proton affinity, the strength of all other hydrogen bonds decreases. This is the concept of anticooperativity by successive substitution in a mixed solvation system. In the present study, this concept is demonstrated in H(+)(CH(3)OH)(m)(H(2)O)(n) (m + n = 5 and 6) mixed clusters by a joint theoretical and infrared (IR) spectroscopic approach. The observed IR spectra of the mixed clusters exhibit two high-frequency shifts of hydrogen-bonded OH stretch bands with increasing methanol content. These trends are well reproduced by first-principle IR spectra simulated by thermal averaging over a set of configurational isomers under the quantum harmonic superposition approach. Theoretical analysis on the magnitude of charge transfer from the protonated site to the solvent molecules is found to be in agreement with the spectroscopic measurement that the individual hydrogen bond in the mixed clusters is weakened with an increase of the mixing ratio of methanol to water.

Comprehensive analysis on the structure and proton switch in H+ (CH3OH)m(H2O)n (m + n = 5 and 6).

Theoretical and experimental methods were integrated to investigate the structures of H(+)(CH(3)OH)(m)(H(2)O)(n) clusters for m + n = 5 and 6. An effective theoretical approach is presented to search for extensive sets of structural isomers using an empirical model and substitution schemes. Stable isomers were then reoptimized by the B3LYP level of computations with the 6-31+G* basis set. Canonical averages of these structural isomers were analyzed by harmonic superposition approximation (HSA) to study their finite temperature behavior and enable quantitative comparisons with experimental results. Thermal energy is found to have a significant effect on the structure of these clusters. Our calculations show that cyclic isomers are preferred at low temperature, while linear and tree forms become more favorable at high temperature (>200 K). Furthermore, we found that proton can reside on both water and methanol ion cores and the proton switch is associated with morphology change. Experimental IR spectra in the free OH stretching region were also obtained and compared with calculated spectra.

Infrared spectroscopy of phenol-(H2O)(n>10): structural strains in hydrogen bond networks of neutral water clusters.

To investigate hydrogen bond network structures of tens of water molecules, we report infrared spectra of moderately size (n)-selected phenol-(H2O)n (approximately 10 < or = n < or = approximately 50), which have essentially the same network structures as (H2O)(n+1). The phenyl group in phenol-(H2O)(n) allows us to apply photoionization-based size selection and infrared-ultraviolet double resonance spectroscopy. The spectra show a clear low-frequency shift of the free OH stretching band with increasing n. Detailed analyses with density functional theory calculations indicate that this shift is accounted for by the hydrogen bond network development from highly strained ones in the small (n < approximately 10) clusters to more relaxed ones in the larger clusters, in addition to the cooperativity of hydrogen bonds.

Comprehensive analysis of the hydrogen bond network morphology and OH stretching vibrations in protonated methanol-water mixed clusters, H(+)(MeOH)1(H2O)n (n = 1-8).

Density functional theory (DFT) calculations of protonated methanol-water mixed clusters, H (+)(MeOH) 1(H 2O) n ( n = 1-8), were extensively carried out to analyze the hydrogen bond structures of the clusters. Various structural isomers were energy optimized, and their relative energies with zero point energy corrections and temperature dependence of the free energies were examined. Coexistence of different morphological isomers was suggested. Infrared spectra were simulated on the basis of the optimized structures. The infrared spectra were also experimentally measured for n = 3-9 in the OH stretching vibrational region. The observed broad bands in the hydrogen-bonded OH stretch region were assigned in comparison with the simulations. From the DFT calculations, the preferential proton location was also investigated. Clear correlations between the excess proton location and the cluster morphology were found.