-
[show abstract]
[hide abstract]
ABSTRACT: We present infrared spectra of nominal water cluster radical cations (H2O)n+ (n = 3-8) , or to be precise, ion-radical complexes H+(H2O)n-1(OH), with and without an Ar tag. These clusters are closely related to the ionizing radiation-induced processes in water and are a good model to characterize solvation structures of the ion-radical pair. The spectra of Ar-tagged species show narrower bandwidths relative to those of the bare clusters due to the reduced internal energy via an Ar-attachment. The observed spectra are analyzed by comparing with those of the similar system, H+(H2O)n, and calculated ones. We find the observed spectra are attributable to ion-radical separated motifs in n ≥ 5 as reported in the previous study (Mizuse et al., Chem. Sci. 2011, 2, 868-876). Beyond the structural trends found in the previous study, we characterize isomeric structures and determine the number of water molecules between the charged site and the OH radical in each cluster size. In all the characterized cluster structures (n = 5-8), the most favorable position of OH radical is the next neighbor of the charged site (H3O+ or H5O2+). The positions and cluster structures are governed by the balance among the hydrogen bonding abilities of the charged site, H2O, and OH radical. These findings on the ionized water networks lead to understanding of the detailed processes of ionizing radiation-initiated reactions in liquid water and aqueous solutions.
The Journal of Physical Chemistry A 01/2013; · 2.95 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: 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 letter, isomer distribution of H+(CH3OH)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 discharge 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.
The Journal of Physical Chemistry A 12/2012; · 2.95 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: Infrared spectroscopy of gas-phase hydrated clusters provides us much information on structures and dynamics of water networks. However, interpretation of spectra is often difficult because of high internal energy (vibrational temperature) of clusters and coexistence of many isomers. Here we report an approach to vary these factors by using the inert gas (so-called "messenger")-mediated cooling technique. Protonated water clusters with a messenger (M), H(+)(H(2)O)(4-8)·M (M = Ne, Ar, (H(2))(2)), are formed in a molecular beam and probed with infrared photodissociation spectroscopy in the OH stretch region. Observed spectra are compared with each other and with bare H(+)(H(2)O)(n). They show clear messenger dependence in their bandwidths and relative band intensities, reflecting different internal energy and isomer distribution, respectively. It is shown that the internal energy follows the order H(+)(H(2)O)(n) > H(+)(H(2)O)(n)·(H(2))(2) > H(+)(H(2)O)(n)·Ar > H(+)(H(2)O)(n)·Ne, while the isomer-selectivity, which changes the isomer distribution in the bare system, follows the order H(+)(H(2)O)(n)·Ar > H(+)(H(2)O)(n)·(H(2))(2) > H(+)(H(2)O)(n)·Ne ~ (H(+)(H(2)O)(n)). Although the origin of the isomer-selectivity is unclear, comparison among spectra measured with different messengers is very powerful in spectral analyses and makes it possible to easily assign spectral features of each isomer.
The Journal of Physical Chemistry A 05/2012; 116(20):4868-77. · 2.95 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: Structures of the [C(6)H(6)-(CH(3)OH)(2)](+) cluster cation are investigated with infrared (IR) spectroscopy. While the noncovalent type structure has been confirmed for the n = 1 cluster of [C(6)H(6)-(CH(3)OH)(n)](+), only contradictory interpretations have been given for the spectra of n = 2, in which significant changes have been observed with the Ar tagging. In the present study, we revisit IR spectroscopy of the n = 2 cluster from the viewpoint of the σ-complex structure, which includes a covalent bond formation between the benzene and methanol moieties. The observed spectral range is extended to the lower-frequency region, and the spectrum is measured with and without Ar and N(2) tagging. A strongly hydrogen-bonded OH stretch band, which is characteristic to the σ-complex structure, is newly found with the tagging. The remarkable spectral changes with the tagging are interpreted by the competition between the σ-complex and noncovalent complex structures in the [C(6)H(6)-(CH(3)OH)(2)](+) system. This result shows that the microsolvation only with one methanol molecule can induce the σ-complex structure formation.
The Journal of Physical Chemistry A 06/2011; 115(41):11156-61. · 2.95 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: Although messenger mediated spectroscopy is a widely-used technique to study gas phase ionic species, effects of messengers themselves are not necessarily clear. In this study, we report infrared photodissociation spectroscopy of H(+)(H(2)O)(6)·M(m) (M = Ne, Ar, Kr, Xe, H(2), N(2), and CH(4)) in the OH stretch region to investigate messenger(M)-dependent cluster structures of the H(+)(H(2)O)(6) moiety. The H(+)(H(2)O)(6), the protonated water hexamer, is the smallest system in which both the H(3)O(+) (Eigen) and H(5)O(2)(+) (Zundel) hydrated proton motifs coexist. All the spectra show narrower band widths reflecting reduced internal energy (lower vibrational temperature) in comparison with bare H(+)(H(2)O)(6). The Xe-, CH(4)-, and N(2)-mediated spectra show additional band features due to the relatively strong perturbation of the messenger. The observed band patterns in the Ar-, Kr-, Xe-, N(2)-, and CH(4)-mediated spectra are attributed mainly to the "Zundel" type isomer, which is more stable. On the other hand, the Ne- and H(2)-mediated spectra are accounted for by a mixture of the "Eigen" and "Zundel" types, like that of bare H(+)(H(2)O)(6). These results suggest that a messenger sometimes imposes unexpected isomer-selectivity even though it has been thought to be inert. Plausible origins of the isomer-selectivity are also discussed.
Physical Chemistry Chemical Physics 03/2011; 13(15):7129-35. · 3.57 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: 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.
The Journal of Physical Chemistry A 02/2011; 115(5):620-5. · 2.95 Impact Factor
-
Angewandte Chemie International Edition 12/2010; 49(52):10119-22. · 13.45 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: We report infrared (IR) and electronic spectra of benzene-ammonia cluster radical cations [C(6)H(6)(NH(3))(n)](+) (n = 1 and 2) in the gas phase to explore cluster structures and chemical reactivity of the simplest aromatic radical cation with base (nucleophile) molecules. The electronic spectra in the visible region indicate that these cluster cations no longer have the benzene cation chromophore as a result of an intracluster reaction. Analyses of the IR spectra, on the basis quantum chemical calculations and the vibration-internal rotation analysis, reveal that both [C(6)H(6)(NH(3))(1,2)](+) form σ-complex structures, in which the ammonia moiety is covalently bonded to the benzene moiety due to the intracluster nucleophilic addition. For [C(6)H(6)(NH(3))(2)](+), it is also shown that the second ammonia molecule solvates the σ-complex core via a N-H···N hydrogen bond. Such σ-complex structures are generally supposed to be a key intermediate of aromatic substitution reactions. The observed mass spectra and energetics calculations, however, show that [C(6)H(6)(NH(3))(n)](+) systems are inert for aromatic substitutions. The present experimental observations indicate the inherent stability of these σ-complex structures, even though they do not show the aromatic substitution reactivity.
The Journal of Physical Chemistry A 03/2010; 114(42):11060-9. · 2.95 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: 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.
The Journal of Physical Chemistry A 09/2009; 113(44):12134-41. · 2.95 Impact Factor
-
Angewandte Chemie International Edition 08/2008; 47(32):6008-10. · 13.45 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: Infrared spectra of completely size-selected protonated water clusters H+(H2O)n are reported for clusters ranging from n=15 to 100. The behavior of the dangling OH stretch bands shows that the hydrogen bond structure in H+(H2O)n is uniquely different to that of (H2O)n up to the size of n=100, at least. This finding indicates that the presence of an excess proton creates a characteristic morphology in the hydrogen bond network architecture of more than 100 surrounding water molecules.
The Journal of Chemical Physics 07/2007; 126(23):231101. · 3.33 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: Infrared spectra of large-sized protonated methanol-water mixed clusters, H(+)(MeOH)(m)(H(2)O)(n) (m=1-4, n=4-22), were measured in the OH stretch region. The free OH stretch bands of the water moiety converged to a single peak due to the three-coordinated sites at the sizes of m+n=21, which is the magic number of the protonated water cluster. This is a spectroscopic signature for the formation of the three-dimensional cage structure in the mixed cluster, and it demonstrates the compatibility of a small number of methanol molecules with water in the hydrogen-bonded cage formation. Density functional theory calculations were carried out to examine the relative stability and structures of selected isomers of the mixed clusters. The calculation results supported the microscopic compatibility of methanol and water in the hydrogen-bonded cage development. The authors also found that in the magic number clusters, the surface protonated sites are energetically favored over their internal counterparts and the excess proton prefers to take the form of H(3)O(+) despite the fact that the proton affinity of methanol is greater than that of water.
The Journal of Chemical Physics 06/2007; 126(19):194306. · 3.33 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: Infrared and electronic spectroscopy was applied to the benzene-ammonia cluster cation in the gas phase, and the observed spectra revealed the formation of a new C-N valence bond between the benzene and ammonia moieties, which has been predicted by the quantum chemical calculations (Tachikawa, H. Phys. Chem. Chem.Phys. 2002, 4, 6018). This cluster cation is regarded as a model for the cyclohexadienyl type intermediate in nucleophilic substitution reactions.
The Journal of Physical Chemistry A 06/2006; 110(20):6387-90. · 2.95 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: The nature of water networks exposed to ionizing radiation is important in various radiation-related chemistry and biology. To understand structural evolution of ionized water networks at the molecular level, we report here infrared spectra of water cluster radical cations (H 2 O) n + (n ¼ 3 À 11) in the gas phase. Spectral features of free OH stretch modes are quite similar to those of protonated water clusters H + (H 2 O) n , of which the hydrogen-bond network structures have been revealed. In addition, we observed an extra band attributed to the stretch of an OH radical in (H 2 O) n + . These results indicate that nominal (H 2 O) n + should be regarded as H + (H 2 O) nÀ1 (OH) motifs having similar network shapes to those of H + (H 2 O) n . We also analyzed hydrogen-bonded OH stretch bands and found that hydrogen-bond strength is a key factor to determine the position of the OH radical relative to the protonated site (H 3 O + /H 5 O 2 +). Because an OH radical is a weaker hydrogen bond acceptor than water, the first solvation shell of the protonated site is preferentially filled with water. As a result, the OH radical is separated from the protonated (charged) site by at least one water molecule in n $ 5 clusters. This result shows the instability of the H 3 O + -OH ion-radical contact pair in water networks, and implies the higher mobility of the OH radical due to its release from the charged site. Observed structural preferences are confirmed both in cold and warm cluster ion sources.
