Ultrafast structural dynamics of water induced by dissipation of vibrational energy

In the liquid phase, water molecules form a disordered fluctuating network of intermolecular hydrogen bonds. Using both inter- and intramolecular vibrations as structural probes in ultrafast infrared spectroscopy, we demonstrate a two-stage structural response of this network to energy disposal: vibrational energy from individually excited water molecules is transferred to intermolecular modes, resulting in a sub-100 fs nuclear rearrangement that leaves the local hydrogen bonds weakened but unbroken. Subsequent energy delocalization over many molecules occurs on an approximately 1 ps time scale and is connected with the breaking of hydrogen bonds, resulting in a macroscopically heated liquid.     

Ultrafast electronic and vibrational energy relaxation of Fe(acetylacetonate)3 in solution

Transient mid-infrared spectroscopy is used to probe the dynamics initiated by excitation of ligand-to-metal (400 nm) and metal-to-ligand (345 nm) charge transfer states of FeIII complexed with acetylacetonate (Fe(acac)3, where acac stands for deprotonated anion of acetylacetone) in solution. Transient spectra in the 1500-1600 cm-1 range show two broad absorptions red-shifted from the bleach of the nu(CO) (approximately 1575 cm-1) and nu(C=C) (approximately 1525 cm-1) ground state absorptions. Bleach recovery kinetics has a time constant of 12-19 ps in chloroform and tetrachloroethylene and it decreases by 30-40% in a 10% mixture of methanol in tetrachloroethylene. The transient absorptions experience band narrowing simultaneously with blue-shifting of the absorption maxima. Both phenomena have time constants of 3-9 ps with no evident dependence on the solvent. The experimental observations are ascribed to fast conversion of the initially excited charge transfer states to the ligand field manifold, and subsequent vibrational cooling on the lowest ligand field excited state prior to electronic conversion to the ground state. The analysis of time dependent bandwidths and positions of the transient absorptions provides some evidence of mode specific vibrational cooling.     

Ultrafast vibrational dynamics of interfacial water

We report investigations of the vibrational dynamics of water molecules at the water–air and at the water–lipid interface. Following vibrational excitation with an intense femtosecond infrared pulse resonant with the O–H stretch vibration of water, we follow the subsequent relaxation processes using the surface-specific spectroscopic technique of sum frequency generation. This allows us to selectively follow the vibrational relaxation of the approximately one monolayer of water molecules at the interface. Although the surface vibrational spectra of water at the interface with air and lipids are very similar, we find dramatic variations in both the rates and mechanisms of vibrational relaxation. For water at the water–air interface, very rapid exchange of vibrational energy occurs with water molecules in the bulk, and this intermolecular energy transfer process dominates the response. For membrane-bound water at the lipid interface, intermolecular energy transfer is suppressed, and intramolecular relaxation dominates. The difference in relaxation mechanism can be understood from differences in the local environments experienced by the interfacial water molecules in the two different systems.     

Nonperturbative vibrational energy relaxation effects on vibrational line shapes

A general formulation of nonperturbative quantum dynamics of solutes in a condensed phase is proposed to calculate linear and nonlinear vibrational line shapes. In the weak solute-solvent interaction limit, the temporal absorption profile can be approximately factorized into the population relaxation profile from the off-diagonal coupling and the pure-dephasing profile from the diagonal coupling. The strength of dissipation and the anharmonicity-induced dephasing rate are derived in Appendix A. The vibrational energy relaxation (VER) rate is negligible for slow solvent fluctuations, yet it does not justify the Markovian treatment of off-diagonal contributions to vibrational line shapes. Non-Markovian VER effects are manifested as asymmetric envelops in the temporal absorption profile, or equivalently as side bands in the frequency domain absorption spectrum. The side bands are solvent-induced multiple-photon effects which are absent in the Markovian VER treatment. Exact path integral calculations yield non-Lorentzian central peaks in absorption spectrum resulting from couplings between population relaxations of different vibrational states. These predictions cannot be reproduced by the perturbative or the Markovian approximations. For anharmonic potentials, the absorption spectrum shows asymmetric central peaks and the asymmetry increases with anharmonicity. At large anharmonicities, all the approximation schemes break down and a full nonperturbative path integral calculation that explicitly accounts for the exact VER effects is needed. A numerical analysis of the O-H stretch of HOD in D(2)O solvent reveals that the non-Markovian VER effects generate a small recurrence of the echo peak shift around 200 fs, which cannot be reproduced with a Markovian VER rate. In general, the nonperturbative and non-Markovian VER contributions have a stronger effect on nonlinear vibrational line shapes than on linear absorption.     

On the role of nonbonded interactions in vibrational energy relaxation of cyanide in water

The vibrationally excited cyanide ion (CN(-)) in H2O or D2O relaxes back to the ground state within several tens of picoseconds. Pump-probe infrared spectroscopy has determined relaxation times of T1 = 28 ± 7 and 71 ± 3 ps in H2O and D2O, respectively. Atomistic simulations of this process using nonequilibrium molecular dynamics simulations allow determination of whether it is possible at all to describe such a process, what level of accuracy in the force fields is required, and whether the information can be used to understand the molecular mechanisms underlying vibrational relaxation. It is found that, by using the best electrostatic models investigated, absolute relaxation times can be described rather more qualitatively (T1(H2O) = 19 ps and T1(D2O) = 34 ps) whereas the relative change in going from water to deuterated water is more quantitatively captured (factor of 2 vs 2.5 from experiment). However, moderate adjustment of the van der Waals ranges by less than 20% (for NVT) and 7.5% (for NVE), respectively, leads to almost quantitative agreement with experiment. Analysis of the energy redistribution establishes that the major pathway for CN(-) relaxation in H2O or D2O proceeds through coupling to the water-bending plus libration mode.     

Nitrous oxide vibrational energy relaxation is a probe of interfacial water in lipid bilayers

Ultrafast infrared spectroscopy of N 2O is shown to be a sensitive probe of hydrophobic and aqueous sites in lipid bilayers. Distinct rates of VER of the nu 3 antisymmetric stretching mode of N 2O can be distinguished for N 2O solvated in the acyl tail, interfacial water, and bulk water regions of hydrated dioleoylphosphatidylcholine (DOPC) bilayers. The lifetime of the interfacial N 2O population is hydration-dependent. This effect is attributed to changes in the density of intermolecular states resonant with the nu 3 band ( approximately 2230 cm (-1)) resulting from oriented interfacial water molecules near the lipid phosphate. Thus, the N 2O VER rate becomes a novel and experimentally convenient tool for reporting on the structure and dynamics of interfacial water in lipids and, potentially, in other biological systems.     

Ultrafast vibrational energy transfer of polyethylene investigated with picosecond laser pulses

Picosecond Raman scattering after infrared excitation is studied for polyethylene films at room temperature. Ultrafast vibrational energy redistribution (⩽ 5 ps) and a comparatively long population lifetime (T₁ = 260 ± 100 ps) are observed for the CH-stretching modes.     

Ultrafast electronic relaxation and coherent vibrational oscillation of strongly coupled gold nanoparticle aggregates

We report the first direct observation of the ultrafast electronic relaxation and coherent vibrational oscillation of strongly interacting gold nanoparticle aggregates measured by femtosecond laser spectroscopy. The electronic relaxation, reflected as a fast decay component with a time constant of 1.5-2.5 ps, becomes faster with decreasing pump power, similar to earlier observations of isolated gold nanoparticles. Surprisingly, periodic oscillations have been observed in the transient absorption/bleach signal and have been attributed to the coherent vibrational excitation of the gold nanoparticle aggregates. The oscillation period has been found to depend on the probe wavelength. As the probe wavelength is varied from 720 to 850 nm, the period changes from 37 to 55 ps. This suggests that the broad extended plasmon band (EPB) contains contributions from gold nanoparticle aggregates with different sizes and/or different fractal structures. Each of the different probe wavelengths therefore interrogates one subset of the aggregates with similar size or structure. Interestingly, the observed oscillation period for a given aggregate size determined by dynamic light scattering is longer than that predicted based on a elastic sphere model. One possible explanation is that the actual size of the aggregates is larger than what was observed from dynamic light scattering. An alternative, perhaps more likely, explanation is that the vibration of the aggregates is "softer" than that of hard spherical gold nanoparticles possibly because the longitudinal speed of sound is lower in the aggregates than in bulk gold. Persistent spectral hole burning was performed and yielded a hole in the nanoparticle aggregate's extended plasmon band, further supporting that the near-IR band is composed of absorption subbands from differently sized/structured aggregates.     

Temperature dependence of vibrational energy relaxation in liquid oxygen

The energy relaxation of the lowest vibrational level (υ = 1) of liquid oxygen in the electronic ground state was investigated within a wide temperature range (53.4 K ? T ? 96 K). The relaxation time exhibits a peak value of τ′ ≈ 3.1 ms around 65 K and is shorter at lower and higher temperatures. The observed temperature behavior is discussed in view of theoretical models of energy relaxation in liquids.     

Intramolecular relaxation of excess vibrational energy in jet-cooled perylene

The intramolecular redistribution of excess vibrational energy (IVR) in electronically excited perylene is being studied by fluorescence techniques. Analysis has shown, in agreement with the literature, little evidence of relaxation of fundamental modes up to ? 1100 cm^?1. However, it is also shown, contrary to literature assertions, that combination states from 700 to 1100 cm^?1 do not relax significantly on the time-scale of molecular fluorescence. The picture is simplified by reassignment of several key combination bands in the spectrum. Excitation at higher energies reveals differences in behaviour between combination bands involving high-frequency fundamentals and those only using fundamentals < 800 cm^?1. In the latter case, the persistence of narrow-line emission indicates substantially slower relaxation rates. As an example, the 1600 cm^?1 fundamental state appears to relax substantially faster than the 1603 cm^?1 satellite state, which is assigned to 353³550¹. This kind of disparity has been observed up to 2000 cm^?1. These data provide evidence for the importance of anharmonic interactions in determining the relative rates of IVR over short energy ranges.     

Effect of ions on the vibrational relaxation of liquid water

We study the relaxation of the O-H stretch vibration of water in aqueous salt solutions using femtosecond two-color pump-probe spectroscopy. The vibrational lifetimes are measured for a series of salts consisting of the anions Cl(-), Br(-), and I(-) and the cations Li(+), Na(+), and Mg(2+), for a range of concentrations from 0.5 M up to 6 M (chloride salts), 9 M (bromide salts), and 10 M (iodide salts). In addition to the previously found dependence of the vibrational lifetime on the nature of the anion, the lifetime is found to depend on concentration and is observed to show a small but significant dependence on the nature of the cation. We present a model in which all the effects of ions on the vibrational relaxaton of liquid water are accounted for.     

Isomer effects on vibrational energy relaxation in perylene-argon complexes

Fluorescence spectroscopic measurements have been carried out on jet-cooled complexes of perylene with a number of guest species ranging from argon to small hydrocarbons. In the case of argon, a sequence of red-shifted absorption bands is assigned to a group of aggregates involving up to five guest atoms. Calculations using empirical atom-atom pair potentials have allowed unambiguous assignment of eight different perylene-argon complexes. Spectrally dispersed fluorescence measurements have studied the effect of internal energy on the IVR and predissociation processes. In particular, the two perylene diargon isomers are shown to exhibit different rates for IVR.It has been shown that arson forms a series of organised, readily identifiable complexes with perylene in a supersonic jet. On excitation of the different isomeric forms of the 2:1 complex, different rates for vibrational energy redistribution have been found. The greatest difference was observed at low vibrational energies of the parent, which confirmed that low-frequency van der Waals modes were responsible. Although more detailed calculations will appear elsewhere, the most obvious difference between the two isomeric forms is the exchange of two low-frequency x-y plane vibrations (≈5 cm^?1) for a hindered rotation and a substantially higher-frequency (15–30 cm^?1) argon-argon stretching mode. Photodissociation is also readily observed, confirming the computed values for the argon-perylene binding energies. Finally, strong resonance fluorescence is observed, accompanied by (relaxed) emission from the singly dissociated species when either the 1:1 or either 2:1 isomer is excited with a (parent) vibrational energy of 705 cm^?1. Thus, in spite of the presence of the dissociative pathway, all observable emission from the undissociated species appears to originate from a state in the “small molecule” limit, which survives for about 4 ns.     

Role of heme propionates of myoglobin in vibrational energy relaxation

The role of heme propionates of myoglobin in vibrational energy relaxation was studied by time-resolved resonance Raman spectroscopy. Time-resolved anti-Stokes spectra were measured to monitor the vibrational energy relaxation of the heme. The decay rates of the band intensities were compared between wild-type myoglobin and etioheme-substituted myoglobin where the heme lacks hydrogen-bonding side chains. The decay rates of the anti-Stokes intensities of the latter were less than those of the former, providing strong support for a theoretical proposal that the propionates and their coupling to solvent bath play an important role in the dissipation of excess energy of the excited heme in solvated wild-type myoglobin.     

Ultrafast vibrational spectroscopy and relaxation in polyatomic molecules: Potential for molecular parallel computing

The feasibility of controlled ultrafast pumping in the mid IR and the probe of the subsequent intramolecular dynamics is illustrated for vibrational excitation of the two metal carbonyls W(CO)₆ and Mn(CO)₅Br in solution. Pumping and probing is performed by short, 130 fs, pulses centered at about 2000 cm⁻¹. Frequency resolved measurements of the time delayed probe pulse are performed. Measured two dimensional spectra are fitted by a kinetic scheme that models the vibrational dynamics. Fast relaxation is solvent induced with the solvent acting also as a heat bath. The (several) probe signals in the experiment can be thought of as the response of a finite state logic machine. This suggests that the molecular machine can act as an ultrafast (petaHertz) processor. The number of internal (memory) states of the machine is determined by the number of vibrational states in the kinetic scheme that can fit the observed relaxation. The number of outputs of the machine is the number of the several different available probe signals. It is shown that the machine is massively parallel because in each (sub ps) time step it produces an entire vector as an output and that each component of the output vector is, by itself, a transform over the input. Beyond that, the machine can produce a (finite number of) different output vectors in sequential time steps.     

Ultrafast dynamics through conical intersections and intramolecular vibrational energy redistribution in styrene

We report a femtosecond time-resolved photoelectron spectroscopy (TRPES) investigation of internal conversion in the first two excited singlet electronic states of styrene. We find that radiationless decay through an S(1)/S(0) conical intersection occurs on a timescale of ～4 ps following direct excitation to S(1) with 0.6 eV excess energy, but that the same process is significantly slower (～20 ps) if it follows internal conversion from S(2) to S(1) after excitation to S(2) with 0.3 eV excess energy (0.9 eV excess energy in S(1)).     

Ultrafast vibrational spectroscopy of the flavin chromophore

Ultrafast time-resolved infrared (TRIR) spectra of flavin adenine dinucleotide (FAD) and the anion of lumiflavin (Lf-) are described. Ground-state recovery and excited-state decay of FAD reveal a common dominant ultrafast relaxation and a minor slower component. The Lf- transient lacks a fast component. No intermediate species are observed, suggesting that the quenching mechanism is internal conversion promoted by interaction of the adenine and isoalloxazine rings in FAD. Modes are assigned, and the potential for extension of the TRIR method to photoactive proteins is discussed.     

Theoretical studies of solute vibrational energy relaxation at liquid interfaces

Recent advances in the theoretical understanding of solute vibrational energy relaxation at liquid interfaces and surfaces are described. Non-equilibrium molecular dynamics simulations of the relaxation of an initially excited solute molecule are combined with equilibrium force autocorrelation calculations to gain insight into the factors that influence the vibrational relaxation rate. Diatomic and triatomic nonpolar, polar, and ionic solute molecules adsorbed at the liquid/vapor interface of several liquids as well as at the water/CCl(4) liquid/liquid interface are considered. In general, the vibrational relaxation rate is significantly slower (a factor of 3 to 4) at the liquid/vapor and liquid/liquid interface than in the bulk due to the reduced density, which gives rise to a reduced contribution of the repulsive solvent-solute forces on the vibrational mode. The surface effects on the ionic solutes are much smaller (50% or less slower relaxation relative to the bulk). This is due to the fact that ionic solutes at the interface are able to keep part of their solvation shell to a degree that depends on their size. Thus, a significant portion of the repulsive forces is maintained. A high degree of correlation is found between the peak height of the solvent-solute radial distribution function and the vibrational relaxation rate. The relaxation rate at the liquid/liquid interface strongly depends on the location of the solute across the interface and correlates with the change in the density and polarity profile of the interface.     

Fluctuating energy level Landau-Teller theory: application to the vibrational energy relaxation of liquid methanol

State-to-state vibrational energy relaxation (VER) rates of the OH-stretch fundamental to select vibrational modes of liquid methanol are presented. The rates are calculated via a modified, fluctuating Landau-Teller (FLT) theory approach, which allow for dynamical vibrational energy level shifts. These rates are then compared to previously published results from Gulmen and Sibert [J. Phys. Chem. A 2004, 108, 2389] for the traditional Landau-Teller (LT) method as well as results calculated through time-dependent perturbation theory (TD), which naturally allow for the fluctuation. For the first time, this method is applied to a polyatomic molecular system, and the FLT theory greatly reduces the discrepancy between the LT and TD results or, at a minimum, is comparable to the LT approach with very little additional computational cost.     

Ultrafast vibrational dynamics of water at a charged interface revealed by two-dimensional heterodyne-detected vibrational sum frequency generation

Two-dimensional heterodyne-detected vibrational sum frequency generation (2D HD-VSFG) spectroscopy is performed for an aqueous interface for the first time. The 2D HD-VSFG spectra in the OH stretch region are obtained from a positively charged surfactant∕water interface with isotopically diluted water (HOD∕D(2)O) to reveal the femtosecond vibrational dynamics of water at the charged interface. The 2D HD-VSFG spectrum is diagonally elongated immediately after photoexcitation, clearly demonstrating inhomogeneity in the interfacial water. This elongation almost disappears at 300 fs owing to the spectral diffusion. Interestingly, the 2D HD-VSFG spectrum at the 0 fs shows an oppositely asymmetric shape to the corresponding 2D IR spectrum in bulk water: The bandwidth of the bleach signal gets narrower when the pump wavenumber becomes higher. This suggests that the dynamics and mechanism of the hydrogen bond rearrangement at the charged interface are significantly different from those in bulk water.