2D IR Spectrometer Research Articles

Direct comparison of amplitude and geometric measures of spectral inhomogeneity using phase-cycled 2D-IR spectroscopy.

Two-dimensional infrared (2D-IR) spectroscopy provides access to equilibrium dynamics with the extraction of the frequency-fluctuation correlation function (FFCF) from the measured spectra. Several different methods of obtaining the FFCF from experimental spectra, such as the center line slope (CLS), ellipticity, phase slope, and nodal line slope, all depend on the geometrical nature of the 2D line shape and necessarily require spectral extent in order to achieve a measure of the FFCF. Amplitude measures, on the other hand, such as the inhomogeneity index, rely only on signal amplitudes and can, in principle, be computed using just a single point in a 2D spectrum. With a pulse shaper-based 2D-IR spectrometer, in conjunction with phase cycling, we separate the rephasing and nonrephasing signals used to determine the inhomogeneity index. The same measured data provide the absorptive spectrum, needed for the CLS. Both methods are applied to two model molecular systems: tungsten hexacarbonyl (WCO6) and methylcyclopentadienyl manganese tricarbonyl [Cp'Mn(CO)3, MCMT]. The three degenerate IR modes of W(CO)6 lack coherent modulation or noticeable intramolecular vibrational redistribution (IVR) and are used to establish a baseline comparison. The two bands of the MCMT tripod complex include intraband coherences and IVR as well as likely internal torsional motion on a few-picosecond time scale. We find essentially identical spectral diffusion, but faster, non-equilibrium dynamics lead to differences in the FFCFs extracted with the two methods. The inhomogeneity index offers an advantage in cases where spectra are complex and energy transfer can mimic line shape changes due to frequency fluctuations.

Shot-to-shot 2D IR spectroscopy at 100 kHz using a Yb laser and custom-designed electronics.

The majority of 2D IR spectrometers operate at 1-10 kHz using Ti:Sapphire laser technology. We report a 2D IR spectrometer designed around Yb:KGW laser technology that operates shot-to-shot at 100 kHz. It includes a home-built OPA, a mid-IR pulse shaper, and custom-designed electronics with optional on-chip processing. We report a direct comparison between Yb:KGW and Ti:Sapphire based 2D IR spectrometers. Even though the mid-IR pulse energy is much lower for the Yb:KGW driven system, there is an 8x improvement in signal-to-noise over the 1 kHz Ti:Sapphire driven spectrometer to which it is compared. Experimental data is shown for sub-millimolar concentrations of amides. Advantages and disadvantages of the design are discussed, including thermal background that arises at high repetition rates. This fundamental spectrometer design takes advantage of newly available Yb laser technology in a new way, providing a straightforward means of enhancing sensitivity.

Ultrafast pH-jump two-dimensional infrared spectroscopy.

We present a pH-jump two-dimensional infrared (2D IR) spectrometer to probe pH-dependent conformational changes from nanoseconds to milliseconds. The design incorporates a nanosecond 355nm source into a pulse-shaper-based 2D IR spectrometer to trigger dissociation of a caged proton prior to probing subsequent conformational changes with femtosecond 2D IR spectroscopy. We observe a blue shift in the amide I mode (C═O stretch) of diglycine induced by protonation of the terminal amine. This method combines the bond-specific structural sensitivity of ultrafast 2D IR with triggered conformational dynamics, providing structural access to multiscale biomolecular transformations such as protein folding.

A 100 kHz Pulse Shaping 2D-IR Spectrometer Based on Dual Yb:KGW Amplifiers

A high-speed, high-sensitivity and compact two-dimensional infrared (2D-IR) spectrometer based on 100 kHz Yb:KGW regenerative amplifier technology is described and demonstrated. The setup is three color, using an independent pump OPA and two separately tunable probe OPAs. The spectrometer uses 100 kHz acousto-optic pulse shaping on the pump beam for rapid 2D-IR acquisitions. The shot-to-shot stability of the laser system yields excellent signal-to-noise figures (∼10 μOD noise on 5000 laser shots). We show that the reduced bandwidth of the Yb:KGW amplifiers in comparison with conventional Ti:sapphire systems does not compromise the ability of the setup to generate high-quality 2D-IR data. Instrument responses of <300 fs are demonstrated and 2D-IR data presented for several systems of interest to physical chemists, showing spectral diffusion in NaSCN, amide I and II bands of a β sheet protein and DNA base-pair-backbone couplings. Overall, the increased data acquisition speed, intrinsic stability, and robustness of the Yb:KGW lasers are a significant step forward for 2D-IR spectroscopy.

General noise suppression scheme with reference detection in heterodyne nonlinear spectroscopy.

We devised a novel two-step reference scheme that can greatly suppress the additive and convolutional noises in heterodyne nonlinear spectroscopy. To optimally remove additive noise, we fully utilized the spectral correlation in multi-channel reference data through a linear combination and regression algorithm. Using our pump-probe 2D IR spectrometer, we demonstrated that our scheme can improve the signal-to-noise ratio by 10-30 times and reach the noise floor of the signal detector. The new algorithm is guaranteed to reduce noise, enables the use of unmatched reference detectors, and does not introduce baseline shift or signal distortion. This scheme is applicable to many heterodyne spectroscopic techniques.

High-Throughput Two-Dimensional Infrared (2D IR) Spectroscopy Achieved by Interfacing Microfluidic Technology with a High Repetition Rate 2D IR Spectrometer.

The precision control of microfluidic technology was successfully interfaced with a 100 kHz two-dimensional infrared (2D IR) spectrometer to observe the sensitivity of the anion cyanate (OCN-) to the surrounding solvent environment in a high-throughput manner. Producing high-throughput 2D IR spectroscopy measurements allows us to observe the vibrational response of cyanate in mixed solvent environments. Changes in solvation environment around the cyanate ion yield frequency shifts from 2150 to 2165 cm-1 when moving from a pure dimethylformamide solvent environment to a pure methanol environment. 2D IR spectra were captured laterally across microfluidic devices tailored to produce a tunable gradient to observe the OCN- vibrational response to mixed solvent environments. These experiments reveal that there is no preferential solvation of cyanate in this system; instead, a more complex local solvent environment is observed.

2D IR spectroscopy at 100 kHz utilizing a Mid-IR OPCPA laser source.

We present a 100 kHz 2D IR spectrometer. The system utilizes a ytterbium all normal dispersion fiber oscillator as a common source for the pump and seed beams of a MgO:PPLN OPCPA. The 1030 nm OPCPA pump is generated by amplification of the oscillator in cryocooled Yb:YAG amplifiers, while the 1.68 μm seed is generated in a OPO pumped by the oscillator. The OPCPA outputs are used in a ZGP DFG stage to generate 4.65 μm pulses. A mid-IR pulse shaper delivers pulse pairs to a 2D IR spectrometer allowing for data collection at 100 kHz.

Fully automated dual-frequency three-pulse-echo 2DIR spectrometer accessing spectral range from 800 to 4000 wavenumbers.

A novel dual-frequency two-dimensional infrared instrument is designed and built that permits three-pulse heterodyned echo measurements of any cross-peak within a spectral range from 800 to 4000 cm(-1) to be performed in a fully automated fashion. The superior sensitivity of the instrument is achieved by a combination of spectral interferometry, phase cycling, and closed-loop phase stabilization accurate to ~70 as. The anharmonicity of smaller than 10(-4) cm(-1) was recorded for strong carbonyl stretching modes using 800 laser shot accumulations. The novel design of the phase stabilization scheme permits tuning polarizations of the mid-infrared (m-IR) pulses, thus supporting measurements of the angles between vibrational transition dipoles. The automatic frequency tuning is achieved by implementing beam direction stabilization schemes for each m-IR beam, providing better than 50 μrad beam stability, and novel scheme for setting the phase-matching geometry for the m-IR beams at the sample. The errors in the cross-peak amplitudes associated with imperfect phase matching conditions and alignment are found to be at the level of 20%. The instrument can be used by non-specialists in ultrafast spectroscopy.

Fully absorptive 3D IR spectroscopy using a dual mid-infrared pulse shaper.

This paper presents the implementation of 3D IR spectroscopy by adding a second pump beam to a two-beam 2D IR spectrometer. An independent mid-IR pulse shaper is used for each pump beam, which can be programmed to collect its corresponding dimension in either the frequency or time-domains. Due to the phase matching geometry employed here, absorptive 3D IR spectra are automatically obtained, since all four of the rephasing and non-rephasing signals necessary to generate absorptive spectra are collected simultaneously. Phase cycling is used to isolate the fifth-order from the third-order signals. The method is demonstrated on tungsten hexacarbonyl (W(CO)6) and dicarbonylacetylacetonato rhodium (I), for which the eigenstates are extracted up to the third excited state. Pulse shaping affords a high degree of control over 3D IR experiments by making possible mixed time- and frequency-domain experiments, fast data acquisition and straightforward implementation.

Comparisons of 2D IR measured spectral diffusion in rotating frames using pulse shaping and in the stationary frame using the standard method

Multidimensional visible spectroscopy using pulse shaping to produce pulses with stable controllable phases and delays has emerged as an elegant tool to acquire electronic spectra faster and with greatly reduced instrumental and data processing errors. Recent migration of this approach using acousto-optic modulator (AOM) pulse shaping to the mid-infrared region has proved useful for acquiring two dimensional infrared (2D IR) vibrational echo spectra. The measurement of spectral diffusion in 2D IR experiments hinges on obtaining accurate 2D line shapes. To date, pulse shaping 2D IR has not been used to study the time-dependent spectral diffusion of a vibrational chromophore. Here we compare the spectral diffusion data obtained from a standard non-collinear 2D IR spectrometer using delay lines to the data obtained from an AOM pulse shaper based 2D IR spectrometer. The pulse shaping experiments are performed in stationary, partially rotating, and fully rotating reference frames and are the first in the infrared to produce 2D spectra collected in a fully rotating frame using a phase controlled pulse sequence. Rotating frame experiments provide a dramatic reduction in the number of time points that must be measured to obtain a 2D IR spectrum, with the fully rotating frame giving the greatest reduction. Experiments were conducted on the transition metal carbonyl complex tricarbonylchloro(1,10-phenanthroline)rhenium(I) in chloroform. The time dependent data obtained from the different techniques and with different reference frames are shown to be in agreement.

Automated 2D IR spectrometer mitigates the influence of high optical densities

Two-dimensional infrared spectroscopy is a powerful tool for studying molecular structure and kinetics. However, standard ways of implementing the technique are not amenable to samples with high optical densities. In this paper, we demonstrate that a shaper-based automated 2D IR spectrometer largely compensates for most of the distortions caused by high optical densities. By comparing a series of 2D IR spectra collected with varying concentrations and sample thicknesses, we find that high quality 2D IR spectra can be obtained at optical densities of >1.2 when these spectra are collected using a pulse shaping method recently developed in our lab. Furthermore, distortions due to high OD primarily appear along the pump axis and are largely absent along the probe axis. Using this knowledge, we have applied our approach to study a high optical density sample of a truncated form of the human islet amyloid peptide that is involved in Type 2 diabetes. Our methodology promises to aid in the interpretation of 2D IR lineshapes for systems where the optical density cannot be controlled, such as in protein folding or chemical reactions where large changes in optical density occur during the kinetics.