Andrei Tokmakoff

Local hydrogen bonding dynamics and collective reorganization in water: Ultrafast infrared spectroscopy of HOD/D2O

We present an investigation into hydrogen bonding dynamics and kinetics in water using femtosecond infrared spectroscopy of the OH stretching vibration of HOD in D(2)O. Infrared vibrational echo peak shift and polarization-selective pump-probe experiments were performed with mid-IR pulses short enough to capture all relevant dynamical processes. The experiments are self-consistently analyzed with a nonlinear response function expressed in terms of three dynamical parameters for the OH stretching vibration: the frequency correlation function, the lifetime, and the second Legendre polynomial dipole reorientation correlation function. It also accounts for vibrational-relaxation-induced excitation of intermolecular motion that appears as heating. The long time, picosecond behavior is consistent with previous work, but new dynamics are revealed on the sub-200 fs time scale. The frequency correlation function is characterized by a 50 fs decay and 180 fs beat associated with underdamped intermolecular vibrations of hydrogen bonding partners prior to 1.4 ps exponential relaxation. The reorientational correlation function observes a 50 fs librational decay prior to 3 ps diffusive reorientation. Both of these correlation functions compare favorably with the predictions from classical molecular dynamics simulations. The time-dependent behavior can be separated into short and long time scales by the 340 fs correlation time for OH frequency shifts. The fast time scales arise from dynamics that are mainly local: fluctuations in hydrogen bond distances and angles within relatively fixed intermolecular configurations. On time scales longer than the correlation time, dephasing and reorientations reflect collective reorganization of the liquid structure. Since the OH transition frequency and dipole are only weakly sensitive to these collective coordinates, this is a kinetic regime which gives an effective rate for exchange of intermolecular structures.

Characterization of spectral diffusion from two-dimensional line shapes

The analysis of line shapes in two-dimensional optical and infrared spectroscopies is a powerful approach to characterizing the dynamics of molecules in the condensed phase. Changes in line shape from diagonally elongated to symmetric as a function of waiting time arise from evolution of the transition frequency. We describe a number of quantitative measures of frequency fluctuations and spectral diffusion through the analysis of two-dimensional (2D) line shapes. These metrics are identical to the systems frequency correlation function and independent of population relaxation in the limit of a short time approximation for the 2D response. We also test the broader applicability of these expressions for analyzing three-level vibrational systems and experiments with finite pulses.

Multidimensional infrared spectroscopy of water. I. Vibrational dynamics in two-dimensional IR line shapes

In this and the following paper, we describe the ultrafast structural fluctuations and rearrangements of the hydrogen bonding network of water using two-dimensional (2D) infrared spectroscopy. 2D IR spectra covering all the relevant time scales of molecular dynamics of the hydrogen bonding network of water were studied for the OH stretching absorption of HOD in D2O. Time-dependent evolution of the 2D IR line shape serves as a spectroscopic observable that tracks how different hydrogen bonding environments interconvert while changes in spectral intensity result from vibrational relaxation and molecular reorientation of the OH dipole. For waiting times up to the vibrational lifetime of 700 fs, changes in the 2D line shape reflect the spectral evolution of OH oscillators induced by hydrogen bond dynamics. These dynamics, characterized through a set of 2D line shape analysis metrics, show a rapid 60 fs decay, an underdamped oscillation on a 130 fs time scale induced by hydrogen bond stretching, and a long time decay constant of 1.4 ps. 2D surfaces for waiting times larger than 700 fs are dominated by the effects of vibrational relaxation and the thermalization of this excess energy by the solvent bath. Our modeling based on fluctuations with Gaussian statistics is able to reproduce the changes in dispersed pump-probe and 2D IR spectra induced by these relaxation processes, but misses the asymmetry resulting from frequency-dependent spectral diffusion. The dynamical origin of this asymmetry is discussed in the companion paper.

Two-dimensional Fourier transform spectroscopy in the pump-probe geometry

Two-dimensional (2D) Fourier transform (FT) infrared spectroscopy is performed by using a collinear pulse-pair pump and probe geometry with conventional optics. Simultaneous collection of the third-order response and pulse-pair timing permit automated phasing and rapid acquisition of 2D absorptive spectra. To demonstrate the ability of this method to capture molecular dynamics, couplings and structure found in the conventional boxcar 2D FT spectroscopy, a series of 2D spectra of a metal carbonyl, and a beta-sheet protein are acquired.

Two-dimensional Raman spectroscopy of the intermolecular modes of liquid CS2

The two-dimensional response of the intermolecular modes of CS2 has been measured using nonresonant fifth order Raman spectroscopy. Whereas third order Raman spectroscopies only observe the spatially averaged spectrum of solvent motions, the fifth order experiment allows the microscopic composition of this spectral density to be probed. Within the limitations of the theory, the results confirm a picture of the liquid CS2 in which dynamics are dictated by a distribution of fixed structures at short times ( 700 fs). The data suggest that the microscopic dynamics show highly damped oscillatory behavior at intermediate times. The full sensitivity to the details of the molecular dynamics is obtained by virtue of the full two-dimensional response. The ability to make such observations has important general implications for understanding the broad range of time scales in the study of dynamics in complex condensed phases.

Multidimensional infrared spectroscopy of water. II. Hydrogen bond switching dynamics

We use multidimensional infrared spectroscopy of the OH stretch of HOD in D2O to measure the interconversion of different hydrogen bonding environments. The OH stretching frequency distinguishes hydrogen bonded (HB) and non-hydrogen-bonded (NHB) configurations by their absorption on the low (red) and high (blue) sides of the line shape. Measured asymmetries in the two dimensional infrared OH line shapes are manifestations of the fundamentally different spectral relaxations of HB and NHB. HB oscillators exhibit coherent oscillations within the hydrogen-bonded free energy well before undergoing activated barrier crossing, resulting in the exchange of hydrogen bonded partners. Conversely, NHB oscillators rapidly return to HB frequencies within 150 fs. These results support a picture where NHB configurations are only visited transiently during large fluctuations about a hydrogen bond or during the switching of hydrogen bonding partners. The results are not consistent with the presence of entropically stabilized dangling hydrogen bonds or a conceptual picture of water as a mixture of environments with varying hydrogen bond strength separated by barriers >kT.

Vibrational coherence transfer characterized with Fourier-transform 2D IR spectroscopy

Two-dimensional infrared (2D IR) spectroscopy of the symmetric and asymmetric C[Triple Bond]O stretching vibrations of Rh(CO)(2)acac in hexane has been used to investigate vibrational coherence transfer, dephasing, and population relaxation in a multilevel vibrational system. The transfer of coherence between close-lying vibrational frequencies results in extra relaxation-induced peaks in the 2D IR spectrum, whose amplitude depends on the coherence transfer rate. Coherence transfer arises from the mutual interaction of the bright CO stretches with dark states, which in this case reflects the mutual d-pi(*) back bonding of the Rh center to both the terminal carbonyls and the acetylacenonate ligand. For 2D IR relaxation experiments with variable waiting times, coherent dynamics lead to the modulation of peak amplitudes, while incoherent population relaxation and exchange results in the growth of the relaxation-induced peaks. We have modeled the data by propagating the density matrix with the Redfield equation, incorporating all vibrational relaxation processes during all three experimental time periods and including excitation reorientation effects arising from relaxation. Coherence and population transfer time scales from the symmetric to the asymmetric stretch were found to be 350 fs and 3 ps, respectively. We also discuss a diagrammatic approach to incorporating all vibrational relaxation processes into the nonlinear response function, and show how coherence transfer influences the analysis of structural variables from 2D IR spectroscopy.

Structural Rearrangements in Water Viewed Through Two-Dimensional Infrared Spectroscopy

Compared with other molecular liquids, water is highly structured because of its ability to form up to four hydrogen bonds, resulting in a tetrahedral network of molecules. However, this underlying intermolecular structure is constantly in motion, exhibiting large fluctuations and reorganizations on time scales from femtoseconds to picoseconds. These motions allow water to play a key role in a number of chemical and biological processes. By exploiting the fact that the OH stretching frequency of dilute HOD in liquid D(2)O is highly dependent upon the configuration of the neighbor nearest to the proton, researchers have been able to track waters time-dependent structure using two-dimensional infrared (2D IR) spectroscopy, which tags molecules at an initial frequency and then watches as that frequency evolves with respect to time. Recent advances in molecular dynamics simulation techniques allow for the calculation of 2D IR spectra, providing an atomistic interpretation tool of 2D IR spectra in terms of the underlying dynamics of the liquid. In this Account, we review recent ultrafast 2D IR studies at MIT that provide new information on the mechanism of hydrogen-bond rearrangements in liquid water. The 2D IR spectra of the OH stretching vibration of HOD in D(2)O appear highly asymmetric. In the frequency range indicative of hydrogen-bonded molecules (<3300 cm(-1)), the 2D spectra remain fairly compact. By contrast, in the frequency range in which molecules having weak or broken hydrogen bonds absorb (>3500 cm(-1)), the 2D spectra broaden over a time scale of approximately 60 fs, consistent with librations (hindered rotations) of water molecules. This broadening indicates that molecules forming weak or broken hydrogen bonds are unstable and reorient rapidly to return to a hydrogen-bonded configuration. These conclusions are supported by the results of molecular dynamics simulations, which suggest that water molecules undergo a large-angle reorientation during the course of hydrogen-bond exchange. The transition state for hydrogen-bond rearrangements is found to resemble a bifurcated hydrogen bond. Roughly half of the hydrogen-bond exchange events in the simulation are found to involve the insertion of a water molecule across a hydrogen bond, suggesting that hydrogen-bond exchange in water involves the correlated motion of water molecules as far away as the second solvation shell. The combination of ultrafast 2D IR spectroscopy with simulation-based modeling is leading to self-consistent descriptions of the underlying dynamics in liquid water. Moreover, these results also demonstrate a more general, unique characteristic of the spectroscopy: if a spectral signature of the transition state exists, then 2D IR can effectively serve as a transition-state spectroscopy.

Coupling and orientation between anharmonic vibrations characterized with two-dimensional infrared vibrational echo spectroscopy

Two-dimensional vibrational spectroscopy has been used to characterize transient molecular structure by measuring the couplings and projection angles between two strongly coupled anharmonic vibrations. Two-dimensional Fourier-transform infrared spectra of the coupled carbonyl stretches of Rh(CO)2(C5H7O2) in hexane have been obtained from femtosecond vibrational echo signals detected with spectral interferometry. The eight resonances in the two-dimensional spectrum can be interpreted as two diagonal peaks and two cross peaks, each split into a pair. The splitting between the peak pairs is directly related to the diagonal and off-diagonal anharmonicity of the symmetric and asymmetric carbonyl stretches. The ratio of the amplitude of the cross peaks for two different polarization geometries determines the projection angle between the coupled transition dipoles. The experimental characterization of the vibrational eigenstates allows the local carbonyl structure to be modeled as bilinearly coupled cubic anharm...

Water vibrations have strongly mixed intra- and intermolecular character

The ability of liquid water to dissipate energy efficiently through ultrafast vibrational relaxation plays a key role in the stabilization of reactive intermediates and the outcome of aqueous chemical reactions. The vibrational couplings that govern energy relaxation in H2O remain difficult to characterize because of the limitations of current methods to visualize inter- and intramolecular motions simultaneously. Using a new sub-70 fs broadband mid-infrared source, we performed two-dimensional infrared, transient absorption and polarization anisotropy spectroscopy of H2O by exciting the OH stretching transition and characterizing the response from 1,350 cm(-1) to 4,000 cm(-1). These spectra reveal vibrational transitions at all frequencies simultaneous to the excitation, including pronounced cross-peaks to the bend vibration and a continuum of induced absorptions to combination bands that are not present in linear spectra. These observations provide evidence for strong mixing of inter- and intramolecular vibrations in liquid H2O, and illustrate the shortcomings of traditional relaxation models.