Femtosecond Mid-infrared Pump-probe Spectroscopy Research Articles

Vibrational relaxation of carbon dioxide in water.

The dynamics of vibrational relaxation of carbon dioxide in water has been studied using femtosecond mid-infrared pump-probe spectroscopy with excitation of the anti-symmetric stretching (ν3) fundamental state of the solute. The relaxation dynamics were recorded at a constant pressure of 500 bars and in the temperature range between 300 and 600K, thereby covering the liquid-to-near-critical region of the solvent. The excited state of the ν3-mode is deactivated in two competing pathways: (i) direct relaxation to the ground state with resonant transfer of the excess vibrational energy into the bending-librational continuum of the water solvent and (ii) relaxation to the bending fundamental state with transfer into the intramolecular bending mode of H2O. The rate of pathway (i) decreases with increasing temperature, from ∼1/(9ps) at 300K to ∼(1/16ps) at 600K and obeys Fermi's golden rule strictly, provided that the spectral density of energy-accepting solvent states is derived from the stationary infrared absorption profile of H2O. The rate of pathway (ii) is 1/(23ps) and assumed to be temperature-independent within our data analysis. Finally, the bending fundamental of CO2 can also relax to the ground state by resonantly transferring the remaining excess energy to the librational fundamentals of the solvent.

Adsorbed Water Structure on Acrylate-Based Biocompatible Polymer Surface.

The role of water in the excellent biocompatibility of the acrylate-based polymers widely used for antibiofouling coating material has been realized previously. Here, we report femtosecond mid-infrared pump-probe spectroscopy of the OD stretch band of HOD molecule adsorbed on highly biocompatible poly(2-methoxyethyl) acrylate [PMEA] and poorly biocompatible poly(2-phenoxyethyl) acrylate [PPEA], both of which reveal that there are two water species with significantly different vibrational lifetime. PMEA interacts more strongly with water than PPEA through the H-bonding interaction between carbonyl (C═O) and water. The vibrational lifetime of the OD stretch in PPEA is notably longer by factors of 3 and 7 than those in PMEA and bulk water, respectively. The IR-pump visible-probe photothermal imaging further unravels substantial spatial overlap between polymer CO group and water for hydrated PMEA and a significant difference in surface morphology than those in PPEA, which exhibits the underlying relationships among polymer-water interaction, surface morphology, and biocompatibility.

Confined Water Molecules in Binary Mixtures of Water and 2,6-Lutidine Near Lower Solution Critical Temperature

We study the concentration and temperature dependence of the reorientation dynamics of water molecules in binary mixtures of water and 2,6-lutidine below the lower solution critical temperature (LSCT) with femtosecond mid-infrared pump–probe spectroscopy. The measurements reveal the presence of water molecules interacting with both the hydrophobic groups of lutidine and forming a hydrogen bond with the nitrogen atom of lutidine. Both types of molecules show a strongly decreased rotational mobility in comparison to bulk water. From the temperature dependence of the slow water fraction, we conclude that the lutidine molecules form clusters that decrease in size when the temperature is decreased further below the LSCT.

Vibrational Relaxation Dynamics of the Core and Outer Part of Proton-Hydration Clusters.

We study the ultrafast relaxation dynamics of hydrated proton clusters in acetonitrile using femtosecond mid-infrared pump-probe spectroscopy. We observe a strong dependence of transient absorption dynamics on the frequency of excitation. When we excite the OH vibrations with frequencies ≤3100 cm–1, we observe an ultrafast energy relaxation that leads to the heating of the local environment of the proton. This response is assigned to the OH vibrations of the water molecules in the core of the hydrated proton cluster. When we excite with frequencies ≥3200 cm–1, we observe a relatively slow vibrational relaxation with a T1 time constant ranging from 0.22 ± 0.04 ps at νex = 3200 cm–1 to 0.37 ± 0.02 ps at νex = 3520 cm–1. We assign this response to water molecules in the outer part of the hydrated proton cluster.

Water Structure and Dynamics in the Stern Layer of Micelles: Femtosecond Mid-Infrared Pump-Probe Spectroscopy Study.

Molecular-level understanding of the water structure and dynamics in the Stern layer of micelles is important to elucidate the active role of water in biological processes on membrane surfaces. Micelles and reverse micelles are considered to be excellent membrane model systems. Here, to address the question of whether or not the spatial confinement effect on water in reverse micelles and nanometric water pool systems plays a role in modulating water dynamics, we consider four different aqueous micelle solutions and study the water dynamics in the Stern layer of micelles using a femtosecond mid-infrared pump-probe spectroscopy technique. Vibrational energy relaxation and rotational dynamics of the O?D stretch mode of HDO and the azido stretch mode of hydrazoic acid are critically dependent on the charge, polarity, and chemical structure of the surfactant head group. In particular, water molecules in the Stern layer of micelles, which are not in spatially confined environments, are notably different from those in bulk water. This finding clearly indicates that changes in the vibrational and rotational dynamics of water molecules, even in spatially confined systems, are mainly induced by surface effects instead of spatial confinement effects. We believe that the present experimental results are of importance for understanding water-involved biochemical processes on biological membranes.

Ultrafast vibrational energy relaxation of the water bridge

We report the energy relaxation of the OH stretch vibration of HDO molecules contained in an HDO:D(2)O water bridge using femtosecond mid-infrared pump-probe spectroscopy. We found that the vibrational lifetime is shorter (~630 ± 50 fs) than for HDO molecules in bulk HDO:D(2)O (~740 ± 40 fs). In contrast, the thermalization dynamics following the vibrational relaxation are much slower (~1.5 ± 0.4 ps) than in bulk HDO:D(2)O (~250 ± 90 fs). These differences in energy relaxation dynamics strongly indicate that the water bridge and bulk water differ on a molecular scale.

Structure Dynamics of the Proton in Liquid Water Probed with Terahertz Time-Domain Spectroscopy

We study the hydration of protons in liquid water using terahertz time-domain spectroscopy and polarization-resolved femtosecond midinfrared pump-probe spectroscopy. We observe that the addition of protons leads to a very strong decrease of the dielectric response of liquid water that corresponds to 19+/-2 water molecules per dissolved proton. This depolarization results from water molecules ( approximately 4) that are irrotationally bound to the proton and from the motion of water (corresponding to the response of approximately 15 water molecules) involved in the transfer of the proton charge.

Femtosecond mid-IR pump–probe spectroscopy of photoinduced insulator to metal transition in dimer Mott insulator κ-(BEDT-TTF) 2X

Ultrafast dynamics of the photoinduced insulator (I) to metal (M) transition were investigated using femtosecond mid-infrared pump–probe spectroscopy in two-dimensional organic Mott insulators [bis (ethylenedithio)]-tetrathiafulvalene (BEDT-TTF) salts κ-(BEDT-TTF) 2X ( κ-(ET) 2X, where X denotes anion). In κ-( d-ET) 2Cu[N(CN) 2]Br, a metallic state was photogenerated using a phonon-mediated mechanism: the effective bandwidth increases through the photoinduced molecular rearrangement. The mechanism differs fundamentally from the previously reported photoinduced filling control in one-dimensional Mott insulators.

Orientational dynamics of isotopically diluted H2O and D2O

We use femtosecond midinfrared pump-probe spectroscopy to compare the ultrafast dynamics of HDO dissolved in D2O and H2O. For both systems the vibrational energy relaxation proceeds through an intermediate state. The relaxation leads to heating of the sample, which is observed in the transient spectra. In order to obtain the correct anisotropy decay, the ingrowing heating signal is subtracted from the raw data. For the OD vibration this procedure works well. For the OH vibration, however, we find an additional effect that leads to a severe distortion of the anisotropy. We show that this effect can be explained by a slightly faster reorientation of excited molecules during their relaxation as compared to unexcited molecules. We construct a model that includes this effect and is able to reproduce the experimental data. Using this model we show how the distorted anisotropy can be corrected.

On the orientational relaxation of HDO in liquid water

We use femtosecond mid-infrared pump-probe spectroscopy to study the orientational relaxation of HDO molecules dissolved in H2O. In order to obtain a reliable anisotropy decay we model the effects of heating and correct for these effects. We have measured the reorientation time constant of the OD vibration from 2430 to 2600 cm(-1), and observe a value of 2.5 ps that shows no variation over this frequency interval. Our results are discussed in the context of previous experiments that have been performed on the complementary system of HDO dissolved in D2O.

Energy Transfer in Single Hydrogen‐Bonded Water Molecules

We study the structure and dynamics of hydrogen-bonded complexes of H2O/HDO and acetone dissolved in carbon tetrachloride by probing the response of the O-H stretching vibrations with linear mid-infrared spectroscopy and femtosecond mid-infrared pump-probe spectroscopy. We find that the hydrogen bonds in these complexes break and reform with a characteristic time scale of approximately 1 ps. These hydrogen-bond dynamics are observed to play an important role in the equilibration of vibrational energy over the two O-H groups of the H2O molecule. For both H2O and HDO, the O-H stretching vibrational excitation relaxes with a time constant of 6.3+/-0.3 ps, and the molecular reorientation has a time constant of 6+/-1 ps.

Orientational dynamics of hydrogen-bonded phenol

We use femtosecond mid-infrared pump-probe spectroscopy to study the effects of hydrogen bonding on the orientational dynamics of the OD-stretch vibration of phenol-d. We study two samples: phenol-d in chloroform and phenol-d in chloroform to which we added excess acetone. For phenol-d in chloroform, we observe rotational diffusion of the OD group around the CO bond, with a correlation time of 3.7 ps. For phenol-d hydrogen bonded to acetone, the reorientation time is strongly dependent on the probe frequency, varying from 3 ps on the blue side of the spectrum to more than 30 ps on the red side. (c) 2004 American Institute of Physics.

Vibrational relaxation and coupling of two OH-stretch oscillators with an intramolecular hydrogen bond.

We studied the vibrational dynamics of the OH-stretch oscillators of an alcohol with two vicinal OH groups using femtosecond midinfrared pump-probe spectroscopy. The absorption spectrum of pinacol (2,3-dimethyl-2,3-butanediol) in CDCl3 shows two OH-stretch peaks belonging to hydrogen bonded and free OH groups. The anharmonicities of the hydrogen-bonded and free OH-stretch vibrations are 180 and 160 cm(-1), respectively. The lifetime T1 of the OH-stretch vibration is found to be 3.5 +/- 0.4 ps for the hydrogen bonded and 7.4 +/- 0.5 ps for the free OH group. We observed sidebands in the transient spectra after excitation of the bonded OH group, which we attribute to a progression in a low-frequency hydrogen-bond mode. The sideband is redshifted 60 cm(-1) with respect to the 0 --> 1 transition. Due to the coupling between the two OH groups and the presence of the sidebands, simultaneous excitation of both OH-stretch vibrations leads to oscillations on the pump-probe signal with frequencies of 40 and 60 cm(-1).

Temperature dependence of vibrational relaxation in liquid H2O

We have determined the lifetime of the OH-stretch vibration in pure liquid water as a function of temperature using femtosecond mid-infrared pump–probe spectroscopy. The lifetime T1 increases from 260±18 fs at T=298 K to 320±18 fs at T=358 K. The increase in lifetime with temperature can be quantitatively explained from the decrease in overlap resonance between the OH-stretch vibration and the overtone of the H–O–H bending mode.

Reorientational motion and hydrogen-bond stretching dynamics in liquid water

The reorientational motion of the molecules in liquid water is investigated by measuring the anisotropy decay of the O–H stretching mode of HDO dissolved in D 2O using femtosecond mid-infrared pump–probe spectroscopy. We observe that the anisotropy shows a non-exponential decay with an initial fast component of which the amplitude increases with increasing lengths of the O–H⋯O hydrogen bond. The experimental results can be accurately described with a model in which the dependence of the reorientation rate on the hydrogen-bond length and the stochastic modulation of this length are accounted for. It is found that the O–H group of a water molecule can only reorient after the O–H⋯O hydrogen bond has sufficiently lengthened. As a result, the effective rate of reorientation of the molecules in liquid water is determined by the rate at which the length of the hydrogen bonds is modulated.

Orientational relaxation of liquid water molecules as an activated process

Femtosecond mid-infrared pump–probe spectroscopy is used to study the orientational relaxation of HDO molecules dissolved in liquid D2O. In this technique, the excitation of the O–H stretch vibration is used as a label in order to follow the orientational motion of the HDO molecules. The decay of the anisotropy is nonexponential with a typical time scale of 1 ps and can be described with a model in which the reorientation time depends on frequency and in which the previously observed spectral diffusion is incorporated. From the frequency and temperature dependence of the anisotropy decay, the activation energy for reorientation can be derived. This activation energy is found to increase with increasing hydrogen bond strength.

Vibrational dynamics of hydrogen-bonded HCl-diethyl ether complexes

We studied the relaxation of the H–Cl stretch vibration of hydrogen-bonded HCl-diethyl ether [HCl–(CH3CH2)2O] complexes at room temperature using femtosecond mid-infrared pump-probe spectroscopy. The lifetime of the H–Cl stretch vibration is determined to be 0.9±0.2 ps. The relaxation is found to occur via an intermediate state which causes a transient blue-shift of the H–Cl stretch frequency. This blue-shift indicates that the low-frequency (CH3CH2)2O⋅⋅⋅H–Cl hydrogen bond is the main accepting mode of the vibrational energy. The excited population of this hydrogen-bond mode decays with a time constant of 3.1±0.5 ps to the ground state.

Mechanism for vibrational relaxation in water investigated by femtosecond infrared spectroscopy

We present a study on the relaxation of the O–H stretch vibration in a dilute HDO:D2O solution using femtosecond mid-infrared pump-probe spectroscopy. We performed one-color experiments in which the 0→1 vibrational transition is probed at different frequencies, and two-color experiments in which the 1→2 transition is probed. In the one-color experiments, it is observed that the relaxation is faster at the blue side than at the center of the absorption band. Furthermore, it is observed that the vibrational relaxation time T1 shows an anomalous temperature dependence and increases from 0.74±0.01 ps at 298 K to 0.90±0.02 ps at 363 K. These results indicate that the O–H⋯O hydrogen bond forms the dominant accepting mode in the vibrational relaxation of the O–H stretch vibration.

Femtosecond Mid-Infrared Spectroscopy of Hydrogen-Bonded Liquids

We perform femtosecond mid-infrared pump-probe spectroscopy on hydrogen-bonded ethanol dissolved in CCl4. We find that upon excitation of the OH-stretching vibration the hydrogen bonds are predissociated on a femtosecond time scale, and that the predissociation time constant depends strongly on the hydrogen-bond strength.