Development of Two-Dimensional Electronic-Vibrational Sum Frequency Generation (2D-EVSFG) for Vibronic and Solvent Couplings of Molecules at Interfaces and Surfaces.

Many photoinduced excited states' relaxation processes and chemical reactions occur at interfaces and surfaces, including charge transfer, energy transfer, proton transfer, proton-coupled electron transfer, configurational dynamics, conical intersections, etc. Of them, interactions of electronic and vibrational motions, namely, vibronic couplings, are the main determining factors for the relaxation processes or reaction pathways. However, time-resolved electronic-vibrational spectroscopy for interfaces and surfaces is lacking. Here we develop interface/surface-specific two-dimensional electronic-vibrational sum frequency generation spectroscopy (2D-EVSFG) for time-dependent vibronic coupling of excited states at interfaces and surfaces. We further demonstrate the fourth-order technique by investigating vibronic coupling, solvent correlation, and time evolution of the coupling for photoexcited interface-active molecules, crystal violet (CV), at the air/water interface as an example. The two vibronic absorption peaks for CV molecules at the interface from the 2D-EVSFG experiments were found to be more prominent than their counterparts in bulk from 2D-EV. Quantitative analysis of the vibronic peaks in 2D-EVSFG suggested that a non-Condon process participates in the photoexcitation of CV at the interface. We further reveal vibrational solvent coupling for the zeroth level on the electronic state with respect to that on the ground state, which is directly related to the magnitude of its change in solvent reorganization energy. The change in the solvent reorganization energy at the interface is much smaller than that in bulk methanol. Time-dependent center line slopes (CLSs) of 2D-EVSFG also showed that kinetic behaviors of CV at the air/water interface are significantly different from those in bulk methanol. Our ultrafast 2D-EVSFG experiments not only offer vibrational information on both excited states and the ground state as compared with the traditional doubly resonant sum frequency generation and electronic-vibrational coupling but also provide vibronic coupling, dynamical solvent effects, and time evolution of vibronic coupling at interfaces.

Orientational Coupling of Molecules at Interfaces Revealed by Two-Dimensional Electronic-Vibrational Sum Frequency Generation (2D-EVSFG).

Photoinduced relaxation processes at interfaces are intimately related to many fields such as solar energy conversion, photocatalysis, and photosynthesis. Vibronic coupling plays a key role in the fundamental steps of the interface-related photoinduced relaxation processes. Vibronic coupling at interfaces is expected to be different from that in bulk due to the unique environment. However, vibronic coupling at interfaces has not been well understood due to the lack of experimental tools. We have recently developed a two-dimensional electronic-vibrational sum frequency generation (2D-EVSFG) for vibronic coupling at interfaces. In this work, we present orientational correlations in vibronic couplings of electronic and vibrational transition dipoles as well as the structural evolution of photoinduced excited states of molecules at interfaces with the 2D-EVSFG technique. We used malachite green molecules at the air/water interface as an example, to be compared with those in bulk revealed by 2D-EV. Together with polarized VSFG and ESHG experiments, polarized 2D-EVSFG spectra were used to extract relative orientations of an electronic transition dipole and vibrational transition dipoles at the interface. Combined with molecular dynamics calculations, time-dependent 2D-EVSFG data have demonstrated that structural evolutions of photoinduced excited states at the interface have different behaviors than those in bulk. Our results showed that photoexcitation leads to intramolecular charge transfer but no conical interactions in 25 ps. Restricted environment and orientational orderings of molecules at the interface are responsible for the unique features of vibronic coupling.

Direct observation of bicarbonate and water reduction on gold: understanding the potential dependent proton source during hydrogen evolution.

The electrochemical conversion of CO2 represents a promising way to simultaneously reduce CO2 emissions and store chemical energy. However, the competition between CO2 reduction (CO2R) and the H2 evolution reaction (HER) hinders the efficient conversion of CO2 in aqueous solution. In water, CO2 is in dynamic equilibrium with H2CO3, HCO3 -, and CO3 2-. While CO2 and its associated carbonate species represent carbon sources for CO2R, recent studies by Koper and co-workers indicate that H2CO3 and HCO3 - also act as proton sources during HER (J. Am. Chem. Soc. 2020, 142, 4154-4161, ACS Catal. 2021, 11, 4936-4945, J. Catal. 2022, 405, 346-354), which can favorably compete with water at certain potentials. However, accurately distinguishing between competing reaction mechanisms as a function of potential requires direct observation of the non-equilibrium product distribution present at the electrode/electrolyte interface. In this study, we employ vibrational sum frequency generation (VSFG) spectroscopy to directly probe the interfacial species produced during competing HER/CO2R on Au electrodes. The vibrational spectra at the Ar-purged Na2SO4 solution/Au interface, where only HER occurs, show a strong peak around 3650 cm-1, which appears at the HER onset potential and is assigned to OH-. Notably, this species is absent for the CO2-purged Na2SO4 solution/gold interface; instead, a peak around 3400 cm-1 appears at catalytic potential, which is assigned to CO3 2- in the electrochemical double layer. These spectral reporters allow us to differentiate between HER mechanisms based on water reduction (OH- product) and HCO3 - reduction (CO3 2- product). Monitoring the relative intensities of these features as a function of potential in NaHCO3 electrolyte reveals that the proton donor switches from HCO3 - at low overpotential to H2O at higher overpotential. This work represents the first direct detection of OH- on a metal electrode produced during HER and provides important insights into the surface reactions that mediate selectivity between HER and CO2R in aqueous solution.

The Solvation-Induced Onsager Reaction Field Rather than the Double-Layer Field Controls CO2 Reduction on Gold.

The selectivity and activity of the carbon dioxide reduction (CO2R) reaction are sensitive functions of the electrolyte cation. By measuring the vibrational Stark shift of in situ-generated CO on Au in the presence of alkali cations, we quantify the total electric field present at catalytic active sites and deconvolute this field into contributions from (1) the electrochemical Stern layer and (2) the Onsager (or solvation-induced) reaction field. Contrary to recent theoretical reports, the CO2R kinetics does not depend on the Stern field but instead is closely correlated with the strength of the Onsager reaction field. These results show that in the presence of adsorbed (bent) CO2, the Onsager field greatly exceeds the Stern field and is primarily responsible for CO2 activation. Additional measurements of the cation-dependent water spectra using vibrational sum frequency generation spectroscopy show that interfacial solvation strongly influences the CO2R activity. These combined results confirm that the cation-dependent interfacial water structure and its associated electric field must be explicitly considered for accurate understanding of CO2R reaction kinetics.

Two-dimensional electronic-vibrational sum frequency spectroscopy for interactions of electronic and nuclear motions at interfaces.

Interactions of electronic and vibrational degrees of freedom are essential for understanding excited-states relaxation pathways of molecular systems at interfaces and surfaces. Here, we present the development of interface-specific two-dimensional electronic-vibrational sum frequency generation (2D-EVSFG) spectroscopy for electronic-vibrational couplings for excited states at interfaces and surfaces. We demonstrate this 2D-EVSFG technique by investigating photoexcited interface-active (E)-4-((4-(dihexylamino) phenyl)diazinyl)-1-methylpyridin-1- lum (AP3) molecules at the air-water interface as an example. Our 2D-EVSFG experiments show strong vibronic couplings of interfacial AP3 molecules upon photoexcitation and subsequent relaxation of a locally excited (LE) state. Time-dependent 2D-EVSFG experiments indicate that the relaxation of the LE state, S2, is strongly coupled with two high-frequency modes of 1,529.1 and 1,568.1 cm-1 Quantum chemistry calculations further verify that the strong vibronic couplings of the two vibrations promote the transition from the S2 state to the lower excited state S1 We believe that this development of 2D-EVSFG opens up an avenue of understanding excited-state dynamics related to interfaces and surfaces.

Development of interface-/surface-specific two-dimensional electronic spectroscopy.

Structures, kinetics, and chemical reactivities at interfaces and surfaces are key to understanding many of the fundamental scientific problems related to chemical, material, biological, and physical systems. These steady-state and dynamical properties at interfaces and surfaces require even-order techniques with time-resolution and spectral-resolution. Here, we develop fourth-order interface-/surface-specific two-dimensional electronic spectroscopy, including both two-dimensional electronic sum frequency generation (2D-ESFG) spectroscopy and two-dimensional electronic second harmonic generation (2D-ESHG) spectroscopy, for structural and dynamics studies of interfaces and surfaces. The 2D-ESFG and 2D-ESHG techniques were based on a unique laser source of broadband short-wave IR from 1200 nm to 2200 nm from a home-built optical parametric amplifier. With the broadband short-wave IR source, surface spectra cover most of the visible light region from 480 nm to 760 nm. A translating wedge-based identical pulses encoding system (TWINs) was introduced to generate a phase-locked pulse pair for coherent excitation in the 2D-ESFG and 2D-ESHG. As an example, we demonstrated surface dark states and their interactions of the surface states at p-type GaAs (001) surfaces with the 2D-ESFG and 2D-ESHG techniques. These newly developed time-resolved and interface-/surface-specific 2D spectroscopies would bring new information for structure and dynamics at interfaces and surfaces in the fields of the environment, materials, catalysis, and biology.

Singlet Fission Driven by Anisotropic Vibronic Coupling in Single-Crystalline Pentacene.

Vibronic coupling is believed to play an important role in siglet fission, wherein a photoexcited singlet exciton is converted into two triplet excitons. In the present study, we examine the role of vibronic coupling in singlet fission using polarized transient absorption microscopy and ab initio simulations on single-crystalline pentacene. It was found that singlet fission in pentacene is greatly facilitated by the vibrational coherence of a 35.0 cm-1 phonon, where anisotropic coherence persists extensively for a few picoseconds. This coherence-preserving phonon that drives the anisotropic singlet fission is made possible by a unique cross-axial charge-transfer intermediate state. In the same fashion, this phonon was also found to predominantly drive the quantum decohence of a correlated triplet pair to form a decoupled triplet dimer. Moreover, our transient kinetic experimental data illustrates notable directional anisotropicity of the singlet fission rate in single-crystalline pentacene.

In Situ Spectroscopic Probing of Polarity and Molecular Configuration at Aerosol Particle Surfaces.

The growth of aerosol particles in the atmosphere is related to chemical reactions in the gas and particle phases and at aerosol particle surfaces. While research regarding the gas and particle phases of aerosols is well-documented, physical properties and chemical reactivities at aerosol particle surfaces have not been studied extensively but have long been recognized. In particular, in situ measurements of aerosol particle surfaces are just emerging. The main reason is a lack of suitable surface-specific analytical techniques for direct measurements of aerosol particles under ambient conditions. Here we develop in situ surface-specific electronic sum frequency scattering (ESFS) to directly identify spectroscopic behaviors of molecules at aerosol particle surfaces. As an example, we applied an ESFS probe, malachite green (MG). We examined electronic spectra of MG at aerosol particle surfaces and found that the polarity of the surfaces is less polar than that in bulk. Our quantitative orientational analysis shows that MG is orientated with a polar angle of 25°-35° at the spherical particle surfaces of aerosols. The adsorption free energy of MG at the aerosol surfaces was found to be -20.75 ± 0.32 kJ/mol, which is much lower than that at the air/water interface. These results provide new insights into aerosol particle surfaces for further understanding the formation of secondary organic aerosols in the atmosphere.

Interface-Specific Two-Dimensional Electronic Sum Frequency Generation Spectroscopy.

High even-order surface/interface specific spectroscopy has the potential to provide more structural and dynamical information about surfaces and interfaces. In this work, we developed a novel fourth-order interface-specific two-dimensional electronic sum frequency generation (2D-ESFG) for structures and dynamics at surfaces and interfaces. A translating wedge-based identical pulses encoding system (TWINs) was introduced to generate phase-locked pulse pairs for coherent pump beams in 2D-ESFG. As a proof-of-principle experiment, fourth-order 2D-ESFG spectroscopy was used to demonstrate couplings of surface states for both n-type and p-type GaAs (100). We found surface dark state within the bandgap of the GaAs in 2D-ESFG spectra, which could not be observed in one-dimensional ESFG spectra. To our best knowledge, this is a first demonstration of interface-specific two-dimensional electronic spectroscopy. The development of the 2D-ESFG spectroscopy will provide new structural probes of spectral diffusion, conformational dynamics, energy transfer, and charge transfer for surfaces and interfaces.

Anisotropic Geminate and Non-Geminate Recombination of Triplet Excitons in Singlet Fission of Single Crystalline Hexacene.

Singlet fission is believed to improve the efficiency of solar energy conversion by breaking up the Shockley-Queisser thermodynamic limit. Understanding of triplet excitons generated by singlet fission is essential for solar energy exploitation. Here we employed transient absorption microscopy to examine dynamical behaviors of triplet excitons. We observed anisotropic recombination of triplet excitons in hexacene single crystals. The triplet exciton relaxations from singlet fission proceed in both geminate and non-geminate recombination. For the geminate recombination, the different rates were attributed to the significant difference in their related energy change based on the Redfield quantum dissipation theory. The process is mainly governed by the electron-phonon interaction in hexacene. On the other hand, the non-geminate recombination is of bimolecular origin through energy transfer. In the triplet-triplet bimolecular process, the rates along the two different optical axes in the a-b crystalline plane differ by a factor of 4. This anisotropy in the triplet-triplet recombination rates was attributed to the interference in the coupling probability of dipole-dipole interactions in the different geometric configurations of hexacene single crystals. Our experimental findings provide new insight into future design of singlet fission materials with desirable triplet exciton exploitations.

Ordered-to-Disordered Transformation of Enhanced Water Structure on Hydrophobic Surfaces in Concentrated Alcohol-Water Solutions.

The effects of hydrophobic solutes on the structure of the surrounding water have been a topic of debate for almost 70 years. However, a consistent description of the physical insight into the causes of the anomalous thermodynamic properties of alcohol-water mixtures is lacking. Here we report experimental results that combined temperature-dependent linear and femtosecond infrared spectroscopy measurements to explore the water structural transformation in concentrated alcohol-water solutions. Experiments show that the enhancement of water structure arises around microhydrophobic interfaces at room temperature in the solutions. As temperature increases, this ordered water structure disappears and a surface topography-dependent new disordered water structure arises at concentrated solutions of large alcohols. The water structural transformation is dependent on not only the length of the alkyl chain but also the clustering of the alcohols. A more-ordered-than-water structure can transform into a less-ordered-than-water structure.

Anisotropic Singlet Fission in Single Crystalline Hexacene.

Singlet fission is known to improve solar energy utilization by circumventing the Shockley-Queisser limit. The two essential steps of singlet fission are the formation of a correlated triplet pair and its subsequent quantum decoherence. However, the mechanisms of the triplet pair formation and decoherence still remain elusive. Here we examined both essential steps in single crystalline hexacene and discovered remarkable anisotropy of the overall singlet fission rate along different crystal axes. Since the triplet pair formation emerges on the same timescale along both crystal axes, the quantum decoherence is likely responsible for the directional anisotropy. The distinct quantum decoherence rates are ascribed to the notable difference on their associated energy loss according to the Redfield quantum dissipation theory. Our hybrid experimental/theoretical framework will not only further our understanding of singlet fission, but also shed light on the systematic design of new materials for the third-generation solar cells.

Interfaces of Gas-Aerosol Particles: Relative Humidity and Salt Concentration Effects.

The growth of aerosol particles is intimately related to chemical reactions in the gas phase and particle phase and at gas-aerosol particle interfaces. While chemical reactions in gas and particle phases are well documented, there is very little information regarding interface-related reactions. The interface of gas-aerosol particles not only facilitates a physical channel for organic species to enter and exit but also provides a necessary lane for culturing chemical reactions. The physical and chemical properties of gas-particle interfaces have not been studied extensively, nor have the reactions occurring at the interfaces been well researched. This is mainly due to the fact that there is a lack of suitable in situ interface-sensitive analytical techniques for direct measurements of interfacial properties. The motivation behind this research is to understand how interfaces play a role in the growth of aerosol particles. We have developed in situ interface-specific second harmonic scattering to examine interfacial behaviors of molecules of aerosol particles under different relative humidity (RH) and salt concentrations. Both the relative humidity and salt concentration can change the particle size and the phase of the aerosol. RH not only varies the concentration of solutes inside aerosol particles but also changes interfacial hydration in local regions. Organic molecules were found to exhibit distinct behaviors at the interfaces and bulk on NaCl particles under different RH levels. Our quantitative analyses showed that the interfacial adsorption free energies remain unchanged while interfacial areas increase as the relative humidity increases. Furthermore, the surface tension of NaCl particles decreases as the RH increases. Our experimental findings from the novel nonlinear optical scattering technique stress the importance of interfacial water behaviors on aerosol particles in the atmosphere.

Molecular rotation in 3 dimensions at an air/water interface using femtosecond time resolved sum frequency generation.

This paper presents the first study of the rotations of rigid molecules in 3 dimensions at the air/water interface, using the femtosecond time resolved sum frequency generation (SFG) technique. For the purpose of this research, the aromatic dye molecule C153 was chosen as an example of a molecule having two functional groups that are SFG active, one being the hydrophilic -C=O group and the other the hydrophobic -CF3 group. From polarized SFG measurements, the orientations of the two chromophores with respect to the surface normal were obtained. On combining these results with the known relative orientation of the two chromophores in the molecule yields the absolute orientation of C153 at the air/water interface. It was found that the -CF3 axis projected towards the bulk air at an angle of 59° with respect to the interface normal and the -C=O group projected towards the bulk water at an angle of 144°. In order to observe the rotational motions of C153 at the air/water interface, the approach was used to perturb the ground electronic state equilibrium orientational distribution using a polarized resonant pump pulse, which preferentially excites ground state molecules that have their electronic S0 → S1 transition moment aligned closely to the electric field of the incident pump pulse. As a consequence of the photoselection perturbation, the orientational distribution of the remaining ground state molecules was not the equilibrium distribution. Similarly, the orientational distribution of the excited state molecules that were created by the polarized pump pulse was not in their final equilibrium orientational distribution. The rotational motions of the interfacial molecules towards equilibrium were obtained from time dependent measurements of the intensities of the SFG signal generated by the simultaneous incidence at the air/water interface of a visible probe pulse plus an IR probe pulse. In this way, the recovery times to achieve the orientational equilibrium of the two chromophores including the orientation of the normal of the C153 plane with respect to the interface were obtained. The photo-selection process shifts the average orientation angle of the hydrophilic -C=O group by an increase of 4° ± 0.6° with a rotational recovery time constant of 130 ± 20 ps, which is the time to return to an orientational equilibrium distribution. The hydrophobic -CF3 group undergoes a shift that increases its angle by 8° ± 1.5° with a rotational recovery time constant of 210 ± 38 ps. We find that the orientational change of the molecular normal is 4° ± 0.5° and has a rotational recovery time constant of 125 ± 26 ps. The interface-specific time-dependent polarized measurements allowed us to monitor the orientational motions of molecules at interfaces, both in 3 dimensions and in real time.

Development of ultrafast broadband electronic sum frequency generation for charge dynamics at surfaces and interfaces.

Understandings of population and relaxation of charges at surfaces and interfaces are essential to improve charge collection efficiency for energy conversion, catalysis, and photosynthesis. Existing time-resolved surface and interface tools are limited to either under ultrahigh vacuum or in a narrow wavelength region with the loss of spectral information. There lacks an efficient time-resolved surface/interface-specific electronic spectroscopy under ambient conditions for the ultrafast surface/interface dynamics. Here we developed a novel technique for surface/interface-specific broadband electronic sum frequency generation (ESFG). The broadband ESFG was based on a stable two-stage BiB3O6 crystal-based optical parametric amplifier, which generates a strong broadband short-wave infrared (SWIR) from 1200 nm to 2400 nm. A resultant surface spectrum covers almost all visible light from 480 nm to 760 nm, combined a broadband electronic second harmonic generation (ESHG) with the ESFG from the SWIR laser source. We further developed the steady-state and transient broadband ESFG and ESHG techniques to investigate the structure and dynamics of charges at oxidized p-type GaAs (100) semiconductor surfaces, as an example. Both the steady-state and transient experiments have shown that two surface states exist inside the bandgap of the GaAs. The kinetic processes at the GaAs surface include both the population and recombination of the surface states after photoexcitation, in addition to the build-up of the space photo-voltage (SPV). The build-up SPV occurs with a rate of 0.56 ± 0.07 ps-1, while the population rate of the surface states exhibits a two-body behavior with a rate constant of (0.012 ± 0.002) × 1012 s-1 cm2. The photo-generated electron-hole pairs near the surface recombine with a rate of 0.002 ± 0.0002 ps-1 for the oxidized p-type GaAs (100). All the methodologies developed here are readily applied to any optically accessible interfaces and surfaces, in particular buried interfaces under ambient conditions.

In Situ Chemical Analysis of the Gas-Aerosol Particle Interface.

The gas-aerosol particle interface is believed to contribute to the growth of secondary organic aerosols in the atmosphere. Despite its importance, the chemical composition of the interface has not been probed directly because of a lack of suitable interface-specific analytical techniques. The preliminary result in our early work has demonstrated direct observations of molecules at the gas-aerosol particle interface with the development of second harmonic scattering (SHS). However, the SHS technique is far away from being an analytical tool of chemical compositions at the gas-aerosol particle interface. In this work, we continued to develop the interface-specific SHS for in situ chemical analysis of molecules at the gas-aerosol particle interface. As an example, we demonstrated coherent SHS signal of a new SHS probe, crystal violet (CV), from interfaces of aerosol particles. The development of the SHS technique includes: (1) Optimization for a more efficient femtosecond laser system in the generation of SHS from aerosol particles. A near 5 MHz repetition rate of a femtosecond laser was found to be optimal for the generation of SHS; (2) exploration of a more effective detector for SHS of aerosol particles. We found that both a CCD detector and a single-photon counter produce similar signal-to-noise ratios of the interfacial SHS signals from aerosol particles. The CCD detector is a more effective option for the detection of SHS and could greatly reduce sampling time of the interfacial responses; (3) combination of the optimal laser system with the CCD detector, which has greatly improved the detection sensitivity of interfacial molecules by more than 2 orders of magnitude and could potentially detect interfacial SHS from a single aerosol particle. These experimental results not only provided a thorough analysis of the SHS technique but also built a solid foundation for further development of a new vibrational sum frequency scattering (SFS) technique for chemical structures at the gas-aerosol particle interface.

The molecular rotational motion of liquid ethanol studied by ultrafast time resolved infrared spectroscopy.

In this report, ultrafast time-resolved infrared spectroscopy is used to study the rotational motion of the liquid ethanol molecule. The results showed that the methyl, methylene, and CO groups have close rotational relaxation times, 1-2 ps, and the rotational relaxation time of the hydroxyl group (-OH) is 8.1 ps. The fast motion of the methyl, methylene and CO groups, and the slow motion of the hydroxyl group suggested that the ethanol molecules experience anisotropic motion in the liquid phase. The slow motion of the hydroxyl group also shows that the hydrogen bonded network could be considered as an effective molecule. The experimental data provided in this report are helpful for theorists to build models to understand the molecular rotational motion of liquid ethanol. Furthermore, our experimental method, which can provide more data concerning the rotational motion of sub groups of liquid molecules, will be useful for understanding the complicated molecular motion in the liquid phase.

Solvation structure around the Li(+) ion in succinonitrile-lithium salt plastic crystalline electrolytes.

Herein, we discuss the study of solvation dynamics of lithium-succinonitrile (SN) plastic crystalline electrolytes by ultrafast vibrational spectroscopy. The infrared absorption spectra indicated that the CN stretch of the Li(+) bound and unbound succinonitrile molecules in a same solution have distinct vibrational frequencies (2276 cm(-1)vs. 2253 cm(-1)). The frequency difference allowed us to measure the rotation decay times of solvent molecules bound and unbound to Li(+) ion. The Li(+) coordination number of the Li(+)-SN complex was found to be 2 in the plastic crystal phase (22 °C) and 2.5-3 in the liquid phase (80 °C), which is independent of the concentration (from 0.05 mol kg(-1) to 2 mol kg(-1)). The solvation structures along with DFT calculations of the Li(+)-SN complex have been discussed. In addition, the dissociation percentage of lithium salt was also determined. In 0.5 mol kg(-1) LiBF4-SN solutions at 80 °C, 60% ± 10% of the salt dissociates into Li(+), which is bound by 2 or 3 solvent molecules. In the 0.5 mol kg(-1) LiClO4-SN solutions at 80 °C, the salt dissociation ratio can be up to 90% ± 10%.

Negligible Isotopic Effect on Dissociation of Hydrogen Bonds.

Isotopic effects on the formation and dissociation kinetics of hydrogen bonds are studied in real time with ultrafast chemical exchange spectroscopy. The dissociation time of hydrogen bond between phenol-OH and p-xylene (or mesitylene) is found to be identical to that between phenol-OD and p-xylene (or mesitylene) in the same solvents. The experimental results demonstrate that the isotope substitution (D for H) has negligible effects on the hydrogen bond kinetics. DFT calculations show that the isotope substitution does not significantly change the frequencies of vibrational modes that may be along the hydrogen bond formation and dissociation coordinate. The zero point energy differences of these modes between hydrogen bonds with OH and OD are too small to affect the activation energy of the hydrogen bond dissociation in a detectible way at room temperature.

Observation of the interference between the intramolecular IR-visible and visible-IR processes in the doubly resonant sum frequency generation vibrational spectroscopy of Rhodamine 6G adsorbed at the air/water interface.

Using the picosecond visible light at 532.1 nm and infrared light at 2800-3100 cm(-1), we observed the interference between the intramolecular IR-visible and visible-IR processes in the doubly resonant sum frequency generation vibrational spectroscopy of Rhodamine 6G adsorbed at the air/water interface. The interference phenomenon exists for both the C-H stretching vibrations in the 2800-3100 cm(-1) region and the skeleton vibrations in the 1450-1700 cm(-1) region. The relative strength of the visible-IR process at different wavelengths is the result of the electronic structure of the molecule. This is the first direct observation of the visible-IR sum frequency generation process in the electronically excited state of a model molecular system.