Theoretical Modeling of Interface Specific Vibrational Spectroscopy:  Methods and Applications to Aqueous Interfaces

Perry, Angela; Neipert, Christine; Space, Brian; Moore, Preston B.

doi:10.1021/cr040379y

Cited by 161 publications

(225 citation statements)

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“…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 separating liquid water and its vapor (13)(14)(15)(16)(17)(18)(19)(20)(21)(22)(23)(24)(25)(26)(27)(28). In a vibrational SFG experiment, infrared (IR) and visible laser pulses are incident on the interface, and the signal is detected at the sum of the frequencies of these incoming beams.…”

mentioning

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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mentioning

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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“…In particular, theory has been able to demonstrate the degree to which the spectrum is surface-specific and to attribute specific features in the spectra to specific molecular structures. 178,203 The computational approaches up to 2006 were reviewed by Perry et al 204 Briefly, these methods are based on representing the SFG spectrum by the Fourier transform of a polarizability-dipole quantum time correlation function (QTCF). A fully classical approach to computing the SFG spectrum is then obtained by replacing the QTCF by a classical expression including a harmonic correction factor:…”

Section: The Vibrational Spectrum Of Water At Interfacesmentioning

confidence: 99%

Reactivity and Dynamics at Liquid Interfaces

Benjamin¹

2015

Reviews in Computational Chemistry

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“…This gives rise to a nonlinear optical response which generates a third beam at a frequency that is the sum of the frequencies of the two incident beams (Figure 11) [52,[160][161][162][163][164][165]. The intensity of the output light (SFG signal) is proportional to the second-order non-linear susceptibility which equals zero when a material has inversion symmetry under the electric dipole approximation.…”

Section: Sfg: a Tool For The Biological Surface And Interfacementioning

confidence: 99%

“…This resonance frequency enhancement is unique to each chemical group and can therefore provide the information of surface chemical composition. Alignment, orientation, and orientation distribution (or ordering) of surface functional groups can be deduced by examining SFG spectra collected using different polarization combinations of input and output beams [52,[160][161][162][163][164][165].…”

Section: Sfg: a Tool For The Biological Surface And Interfacementioning

confidence: 99%

Nano-bio interfaces probed by advanced optical spectroscopy: From model system studies to optical biosensors

Zhang

Han

et al. 2013

Chin. Sci. Bull.

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Research in biology and medicine is a rapidly expanding field incorporating some of the most fundamental questions concerning structure, function, and purpose. The forefront of new research demands access to advanced techniques and instrumentation capable of probing these unanswered questions. Over the past several decades, nano-scale materials and devices ranging from quasione dimensional quantum dots to two dimensional graphene sheets have been engineered and have found applications in nano-bio imaging and spectroscopy. In this review, the incorporation of nanomaterials into three influential spectroscopic and microscopic techniques including fluorescence microscopy, surface plasmon resonance, and sum frequency generation will be introduced. Fluorescence imaging has visualized nanomaterials as compliments or replacements to comparable organic fluorphores, act as a quencher for FRET-based sensing, and serve as a nanoscaffold for molecular beacons. Their versatility in coating materials makes nanomaterials an excellent targeting molecule for any cellular macromolecule or structure. In addition to the targeting capabilities of nanomaterials in fluorescence imaging, surface plasmon resonance has incorporated nanomaterials for applications in signal enhancement, selectivity of target molecules, and the development of more refined and accurate detection. Functionalized nanoparticles enhance the capabilities of sum frequency generation vibrational spectroscopy by providing unique surface chemistry which alters target molecule interactions and orientations. In summary, the incorporation of nanomaterials has greatly enhanced the field of biology and medicine and has allowed for the continual advancement of not only research but instrument development. nano-bio interfaces, optical spectroscopy, fluoroscence, SERS, SFG Citation:Zhang X X, Han X F, Wu F G, et al. Nano-bio interfaces probed by advanced optical spectroscopy: From model system studies to optical biosensors. Chin Sci Bull, 2013, 58: 25372556, doi: 10.1007/s11434-013-5700-y Nanomaterials, which size ranges (1-100 nm) coincide with fundamentally important length scales in physics, are considered to be promising building blocks for future electrical, optical and optoelectronic applications [1][2][3][4][5][6][7][8]. For example, in metals, the mean free path of an electron at room temperature is ~10-100 nm [9]; the Bohr radius of photo-excited electron-hole pairs in semiconductors is ~1-10 nm [10]; and the 1-100 nm dimension is the range over which molecules assemble into nucleic acids and proteins [11]. Nanostructures on this size scale provide a unique technology to determine many critical structure/function relationships of biological molecules at the cellular level without introducing substantial interference. Advances in nanotechnology have developed at several stages: materials, devices, and systems. A decade ago, extensive research has focused on the development of various methods to precisely control the synthesis of nanomaterials. Therefore, many differ...

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Theoretical Modeling of Interface Specific Vibrational Spectroscopy: Methods and Applications to Aqueous Interfaces

Cited by 161 publications

References 158 publications

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

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

Reactivity and Dynamics at Liquid Interfaces

Nano-bio interfaces probed by advanced optical spectroscopy: From model system studies to optical biosensors

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