In nearly all applications of ultrafast multidimensional infrared spectroscopy, the spectral degrees of freedom (e.g., transition frequency) and the orientation of the transition dipole are assumed to be decoupled. We present experimental results which confirm that frequency fluctuations can be caused by rotational motion and observed under appropriate conditions. A theory of the frequency-frequency correlation function (FFCF) observable under various polarization conditions is introduced, and model calculations are found to reproduce the qualitative trends in FFCF rates. The FFCF determined with polarization-selective two-dimensional infrared (2D IR) spectroscopy is a direct reporter of the frequency-rotational coupling. For the solute methanol in a room temperature ionic liquid, the FFCF of the hydroxyl (O-D) stretch decays due to spectral diffusion with different rates depending on the polarization of the excitation pulses. The 2D IR vibrational echo pulse sequence consists of three excitation pulses that generate the vibrational echo, a fourth pulse. A faster FFCF decay is observed when the first two excitation pulses are polarized perpendicular to the third pulse and the echo, 〈XXY Y〉, than in the standard all parallel configuration, 〈XXXX〉, in which all four pulses have the same polarization. The 2D IR experiment with polarizations 〈XY XY〉 ("polarization grating" configuration) gives a FFCF that decays even more slowly than in the 〈XXXX〉 configuration. Polarization-selective 2D IR spectra of bulk water do not exhibit polarization-dependent FFCF decays; spectral diffusion is effectively decoupled from reorientation in the water system.
The structural elasticity of metal-organic frameworks (MOFs) is a key property for their functionality. Here, we show that 2D IR spectroscopy with pulse-shaping techniques can probe the ultrafast structural fluctuations of MOFs. 2D IR data, obtained from a vibrational probe attached to the linkers of UiO-66 MOF in low concentration, revealed that the structural fluctuations have time constants of 7 and 670 ps with no solvent. Filling the MOF pores with dimethylformamide (DMF) slows the structural fluctuations by reducing the ability of the MOF to undergo deformations, and the dynamics of the DMF molecules are also greatly restricted. Methodology advances were required to remove the severe light scattering caused by the macroscopic-sized MOF particles, eliminate interfering oscillatory components from the 2D IR data, and address Förster vibrational excitation transfer.2D IR spectroscopy | metal-organic framework | UiO-66 MOF | ultrafast structural fluctuations | solvent confinement effect M etal-organic frameworks (MOFs) are molecular architectures in which metal clusters are connected by organic linkers to yield relatively regular 3D coordination polymers with nanometer-sized pores (1, 2). MOFs have been investigated for a wide variety of chemical applications, such as adsorption of gases (3) and heterogeneous catalysts (4). Among many types of porous materials, MOFs are unique because of their structural elasticity coexisting with a high degree of spatial regularity. In some sense, MOFs are like crystals and polymers. They have relatively regular structures like a crystal, but the metal clusters are joined by organic linkers that, in some systems, produce significant structural mobility. The elasticity of MOFs is intimately related to their physical properties and behavior (5).An important goal for understanding the nature of MOFs and how their chemical composition influences their properties and applications is to develop and apply an experimental method that can measure the ultrafast structural motions of MOFs. The relatively slow motions of the framework occurring in submicrosecond to millisecond scales have been studied by NMR and neutron scattering (6). However, until now, quantitative measurements that can characterize the time dependence of MOF structural motions in ultrafast regimes have not been possible because of the lack of appropriate techniques. Here, we have accomplished the goal by applying ultrafast 2D IR spectroscopy (7) to the study of MOF structural dynamics. 2D IR is akin to 2D NMR, but it operates on the ultrafast timescales necessary to characterize the time dependence of MOF structural motions. In addition, there is the important question of the effects on MOF dynamics when guest molecules fill the MOF nanopores. The guest molecules will affect the structural fluctuations of the framework by interacting with the linkers and the metal units. Furthermore, because of the confinement of guest molecules in MOF nanopores, the dynamics of these molecules are expected to be very different from t...
The room-temperature ionic liquid EmimNTf2 (1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) was studied with two-dimensional infrared (2D IR) spectroscopy and polarization selective pump–probe (PSPP) experiments using low-concentration selenocyanate (SeCN–) as the vibrational probe. SeCN– was added as EmimSeCN, which keeps the cation the same. KSeCN was also used, so K+ was added. Two 2D IR polarization configurations were employed: ⟨XXXX⟩ (all pulses have the same polarization) and ⟨XXYY⟩ (the first two pulse polarizations are perpendicular to that of the third pulse and the echo). The spectral diffusion differs for the two configurations, demonstrating that reorientation-induced spectral diffusion, in addition to structural spectral diffusion (SSD), plays a role in the observed dynamics. The SSD was extracted from the 2D IR time-dependent data. The samples with EmimSeCN have dynamics on several fast time scales; however, when KSeCN is used, both the PPSP anisotropy decay and the 2D IR decays have low amplitude offsets (nondecaying values at long times). The size of the offsets increased with increased K+ concentration. These results are explained in terms of a two-ensemble model. A small fraction of the SeCN– is located in the regions modified by the presence of K+, causing a substantial slowing of the SeCN– orientational relaxation and spectral diffusion. Having a small ensemble of SeCN– that undergoes very slow dynamics is sufficient to explain the offsets. For the major ensemble, the dynamics with and without K+ are the same.
Ionic liquids (ILs), which have widely tunable structural motifs and intermolecular interactions with solutes, have been proposed as possible carbon capture media. To inform the choice of an optimal ionic liquid system, it can be useful to understand the details of dynamics and interactions on fundamental time scales (femtoseconds to picoseconds) of dissolved gases, particularly carbon dioxide (CO2), within the complex solvation structures present in these uniquely organized materials. The rotational and local structural fluctuation dynamics of CO2 in the room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EmimNTf2) were investigated by using ultrafast infrared spectroscopy to interrogate the CO2 asymmetric stretch. Polarization-selective pump probe measurements yielded the orientational correlation function of the CO2 vibrational transition dipole. It was found that reorientation of the carbon dioxide occurs on 3 time scales: 0.91 ± 0.03, 8.3 ± 0.1, 54 ± 1 ps. The initial two are attributed to restricted wobbling motions originating from a gating of CO2 motions by the IL cations and anions. The final (slowest) decay corresponds to complete orientational randomization. Two-dimensional infrared vibrational echo (2D IR) spectroscopy provided information on structural rearrangements, which cause spectral diffusion, through the time dependence of the 2D line shape. Analysis of the time-dependent 2D IR spectra yields the frequency-frequency correlation function (FFCF). Polarization-selective 2D IR experiments conducted on the CO2 asymmetric stretch in the parallel- and perpendicular-pumped geometries yield significantly different FFCFs due to a phenomenon known as reorientation-induced spectral diffusion (RISD), revealing strong vector interactions with the liquid structures that evolve slowly on the (independently measured) rotation time scales. To separate the RISD contribution to the FFCF from the structural spectral diffusion contribution, the previously developed first order Stark effect RISD model is reformulated to describe the second order (quadratic) Stark effect--the first order Stark effect vanishes because CO2 does not have a permanent dipole moment. Through this analysis, we characterize the structural fluctuations of CO2 in the ionic liquid solvation environment, which separate into magnitude-only and combined magnitude and directional correlations of the liquid's time dependent electric field. This new methodology will enable highly incisive comparisons between CO2 dynamics in a variety of ionic liquid systems.
The dynamic nature of hydrogen bonding between a molecular anion, selenocyanate (SeCN(-)), and water in aqueous solution (D2O) is addressed using FT-IR spectroscopy, two-dimensional infrared (2D IR) vibrational echo spectroscopy, and polarization selective IR pump-probe (PSPP) experiments performed on the CN stretching mode. The CN absorption spectrum is asymmetric with a wing on the low frequency (red) side of the line in contrast to the spectrum in the absence of hydrogen bonding. It is shown that the red wing is the result of an increase in the CN stretch transition dipole moment due to the effect of hydrogen bonding (non-Condon effect). This non-Condon effect is similar in nature to observations on pure water and other nonionic systems where hydrogen bonding enhances the extinction coefficient. The 2D IR measurements of spectral diffusion (solvent structural evolution) yield a time constant of 1.5 ps, which is within error the same as that of the OH stretch of HOD in D2O (1.4 ps). The orientational relaxation of SeCN(-) measured by PSPP experiments is long (4.04 ps) compared to the spectral diffusion time. The population decay at or near the absorption line center is a single-exponential decay of 37.4 ± 0.3 ps, the vibrational lifetime. However, on the red side of the line the decay is biexponential with a low amplitude, fast component; on the blue side of the line there is a low amplitude, fast growth followed by the lifetime decay. Both of the fast components have 1.5 ps time constants, which is the spectral diffusion time. The fast components of the population decays are the results of the non-Condon effect that causes the red side of the line to be over pumped by the pump pulse. Spectral diffusion then produces the fast decay component on the red side of the line and the growth on the blue side of the line as the excess initial population on the red side produces a net population flow from red to blue.
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