Ultrafast intermolecular energy transfer in heavy water

Piątkowski, Łukasz; Eisenthal, Kenneth B.; Bakker, Huib J.

doi:10.1039/b908975f

Cited by 72 publications

(123 citation statements)

References 20 publications

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“…In all cases the anisotropy in small reverse micelles decays much slower than in the large ones where water properties are closer to those of bulk. As in the bulk water the anisotropy decay is dominated by intermolecular interactions between densely packed OH oscillators, 24,26,63,67 we conclude that these interactions are substantially weakened in small reverse micelles as is evident from the 3590 cm À1 excitation/probe data (Fig. 4a).…”

Section: Methodsmentioning

confidence: 67%

Reduced coupling of water molecules near the surface of reverse micelles

Bakulin

Pshenichnikov

2011

Phys. Chem. Chem. Phys.

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Section: Methodsmentioning

confidence: 67%

Reduced coupling of water molecules near the surface of reverse micelles

Bakulin

Pshenichnikov

2011

Phys. Chem. Chem. Phys.

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“…The cleanest test whether such a mechanism contributes to spectral diffusion is an isotope dilution experiment. [51][52][53] This is reasoned by the fact that the Förster-type mechanism is a resonant effect with a strong (r −6 ) distance dependence. Hence, upon isotope dilution, the spectral diffusion rate should decrease significantly as the absorption frequencies are shifted out of resonance.…”

Section: Resultsmentioning

confidence: 99%

“…16,[49][50][51][52][53] In this case, one molecule is initially excited but subsequently transfers its excitation energy to another oscillator that may have a different transition frequency. Such a mechanism may be particularly relevant in ML samples, where the vibrational probes are fairly close to each other.…”

Section: Resultsmentioning

confidence: 99%

2D attenuated total reflectance infrared spectroscopy reveals ultrafast vibrational dynamics of organic monolayers at metal-liquid interfaces

Kraack

Lotti

Hamm

2015

The Journal of Chemical Physics

101

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We present two-dimensional infrared (2D IR) spectra of organic monolayers immobilized on thin metallic films at the solid liquid interface. The experiments are acquired under Attenuated Total Reflectance (ATR) conditions which allow a surface-sensitive measurement of spectral diffusion, sample inhomogeneity, and vibrational relaxation of the monolayers. Terminal azide functional groups are used as local probes of the environment and structural dynamics of the samples. Specifically, we investigate the influence of different alkyl chain-lengths on the ultrafast dynamics of the monolayer, revealing a smaller initial inhomogeneity and faster spectral diffusion with increasing chain-length. Furthermore, by varying the environment (i.e., in different solvents or as bare sample), we conclude that the most significant contribution to spectral diffusion stems from intra-and intermolecular dynamics within the monolayer. The obtained results demonstrate that 2D ATR IR spectroscopy is a versatile tool for measuring interfacial dynamics of adsorbed molecules. We present two-dimensional infrared (2D IR) spectra of organic monolayers immobilized on thin metallic films at the solid liquid interface. The experiments are acquired under Attenuated Total Reflectance (ATR) conditions which allow a surface-sensitive measurement of spectral diffusion, sample inhomogeneity, and vibrational relaxation of the monolayers. Terminal azide functional groups are used as local probes of the environment and structural dynamics of the samples. Specifically, we investigate the influence of different alkyl chain-lengths on the ultrafast dynamics of the monolayer, revealing a smaller initial inhomogeneity and faster spectral diffusion with increasing chain-length. Furthermore, by varying the environment (i.e., in different solvents or as bare sample), we conclude that the most significant contribution to spectral diffusion stems from intra-and intermolecular dynamics within the monolayer. The obtained results demonstrate that 2D ATR IR spectroscopy is a versatile tool for measuring interfacial dynamics of adsorbed molecules. C 2015 AIP Publishing LLC. [http://dx

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“…Thus, the experiment naturally reports on dynamic processes such as spectral diffusion and chemical exchange (53). 2DIR spectroscopy has been widely used to study dynamics in bulk water, including hydrogen-bond dynamics (54)(55)(56)(57)(58)(59)(60), rotations (61)(62)(63), and vibrational energy transfer (64)(65)(66)(67)(68)(69). However, 2DIR, a third-order nonlinear spectroscopy, is not surface sensitive.…”

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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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Ultrafast intermolecular energy transfer in heavy water

Cited by 72 publications

References 20 publications

Reduced coupling of water molecules near the surface of reverse micelles

Reduced coupling of water molecules near the surface of reverse micelles

2D attenuated total reflectance infrared spectroscopy reveals ultrafast vibrational dynamics of organic monolayers at metal-liquid interfaces

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

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