Hydrogen Bonding and OH-Stretch Spectroscopy in Water: Hexamer (Cage), Liquid Surface, Liquid, and Ice

Tainter, Craig J.; Ni, Yicun; Shi, Liang; Skinner, James

doi:10.1021/jz301780k

Cited by 95 publications

(113 citation statements)

References 28 publications

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“…This is related to the non-coincidence effect, 55 which can be spectrally resolved in the case of cold clusters. 23 Table 6 summarizes the robust OH and OD oscillator coupling constants for the water trimer (W3), the tetramer (W4) and the pentamer (W5). The deuteration and methylation 19 effects are systematic and expected.…”

Section: Discussionmentioning

confidence: 99%

The Raman spectrum of isolated water clusters

Otto

Xue

Zielke

et al. 2014

Phys. Chem. Chem. Phys.

111

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Cold water oligomers (H 2 O) n and (D 2 O) n with n = 2-5 are assigned in spontaneous Raman scattering spectra of seeded rare gas expansions for the first time. Comparison with infrared spectra provides direct experimental insights into the hydrogen bond-mediated excitonic OH oscillator coupling, which is responsible for ultrafast energy transfer between water molecules, usually suppressed by isotopic dilution in femtosecond experiments for the condensed phase. The experimental coupling constants are compared to those in state-of-the-art full-dimensional water potential energy hypersurfaces, leaving room for improvement in the description of the coupled dynamics in water. Evidence for intensified Fermi resonance between OH stretching and OH bending motion beyond water trimers is collected.

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Section: Discussionmentioning

confidence: 99%

The Raman spectrum of isolated water clusters

Otto

Xue

Zielke

et al. 2014

Phys. Chem. Chem. Phys.

111

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“…Still, one would like to know the timescale that a free OD converts into molecules that produce the negative feature [in the (1D)SFG spectrum] at 2,575 cm , etc. To this end, we have very recently tried again (97) to identify those molecules that produce the various spectral features, and we find that the largest contribution to the free-OD peak comes from 2 S molecules [those with one acceptor and one donor hydrogen bond (60)], the largest contribution to the negative peak comes from hydrogen bonds between a 2 S donor and a 4 D acceptor (a 4 D molecule has two donor and two acceptor hydrogen bonds), and the largest contribution to the positive peak at low frequency comes from hydrogen bonds between a 4 D donor and a 2 S acceptor.…”

Section: Dsfg Spectroscopymentioning

confidence: 99%

Slow hydrogen-bond switching dynamics at the water surface revealed by theoretical two-dimensional sum-frequency spectroscopy

Gruenbaum

Skinner

2013

Proc. Natl. Acad. Sci. U.S.A.

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Using our newly developed explicit three-body (E3B) water model, we simulate the surface of liquid water. We find that the timescale for hydrogen-bond switching dynamics at the surface is about three times slower than that in the bulk. In contrast, with this model rotational dynamics are slightly faster at the surface than in the bulk. We consider vibrational two-dimensional (2D) sum-frequency generation (2DSFG) spectroscopy as a technique for observing hydrogen-bond rearrangement dynamics at the water surface. We calculate the nonlinear susceptibility for this spectroscopy for two different polarization conditions, and in each case we see the appearance of cross-peaks on the timescale of a few picoseconds, signaling hydrogen-bond rearrangement on this timescale. We thus conclude that this 2D spectroscopy will be an excellent experimental technique for observing slow hydrogen-bond switching dynamics at the water surface. Interfaces play important roles in many disciplines of science. The water liquid/vapor interface, for example, is of great interest in chemistry, biology, and earth science and is an important model system for water in a heterogeneous environment. Of particular interest is understanding the extent to which the structure and dynamics, and ultimately reactivity, of water at the interface differ from those in the bulk. For example, how does the distribution of hydrogen bonds differ between interfacial and bulk water? How anisotropic is the orientation of the water molecules at the interface? In terms of dynamics, how do the diffusion constant, rotational relaxation time, and hydrogen-bond rearrangement time vary as the interface is approached? One can also consider vibrational dynamics processes such as energy relaxation and transfer.One important technique for addressing these questions is computer simulation. Models used in these calculations for the water surface range from rigid, fixed-point-charge two-body models (1-3), to fluctuating charge or polarizable models (4, 5), to ab initio molecular dynamics calculations (6-10). Regarding static properties, for example, some effort has been expended toward understanding what fraction of H atoms in the surface layer are hydrogen bonded, and what fraction of molecules do not donate any hydrogen bonds (nondonors or "acceptor-only" molecules) (6, 9). In terms of dynamics, it is generally found that diffusion is faster at the interface than in the bulk (1, 4, 10), and rotational relaxation is also faster (3,6,7,10). On the other hand, two studies with fixed-charge two-body models show that hydrogenbond rearrangement is slower at the interface (2, 3), whereas one study with a fluctuating-charge model shows that hydrogen-bond rearrangement is faster (5). In this latter study the authors conclude that this is generally true for polarizable models.Because of its surface sensitivity, vibrational sum-frequency generation (SFG) spectroscopy (11, 12) has become one of the most powerful experimental techniques for the study of interfaces, including the one separa...

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“…Nonetheless, we determined that the low-frequency positive feature was due primarily to 4 D -2 S pairs, the intermediate-frequency negative feature was due primarily to 2 S -4 D pairs, and the free-OH was due primarily to 2 S molecules. 17 In 2015, two new heterodyne-detected experiments with a more careful consideration of the reference used to determine the phase were performed by Yamaguchi, and Tahara and co-workers, which showed, in fact, that for neat H 2 O the low-frequency positive feature was absent 19,20 21 which does essentially confirm the result that there is no positive feature at low frequencies. We note that Nagata and co-workers have recently calculated sum-frequency spectra with ab initio MD simulations, 22 and Medders and Paesani have done the same 23 using their MB-pol model, 24 and the results of both groups are in good agreement with these new experiments.…”

mentioning

confidence: 94%

“…15,16 We interpreted the spectrum in terms of pairs of hydrogen-bond donor and acceptor molecules in different hydrogen-bond classes. 17 Thus, a water molecule is classified according to the total number of hydrogen bonds it participates in, and how many of those hydrogen bonds are H-atom donors (none, N; single, S; double, D). For example, a 3 S molecule makes one donor and two acceptor hydrogen bonds.…”

mentioning

confidence: 99%

“…To this end we will closely follow the notation and discussion from Tainter et al 17 and focus on the additive contributions to the "spectral density" from different donoracceptor pairs. We find that the four largest donor-acceptor pair contributions to the spectral density (and the four most prevalent pairs in the interface region as well 17 ) are shown in Fig. 2 17), that explains why the theoretical HOD spectrum in Fig.…”

mentioning

confidence: 99%

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