mid-IR Pulses Research Articles

Structural Characterization of Single-Stranded DNA Monolayers Using Two-Dimensional Sum Frequency Generation Spectroscopy

DNA-covered materials are important in technological applications such as biosensors and microarrays, but obtaining structural information on surface-bound biomolecules is experimentally challenging. In this paper, we structurally characterize single-stranded DNA monolayers of poly(thymine) from 10 to 25 bases in length with an emerging surface technique called two-dimensional sum frequency generation (2D SFG) spectroscopy. These experiments are carried out by adding a mid-IR pulse shaper to a femtosecond broad-band SFG spectrometer. Cross peaks and 2D line shapes in the 2D SFG spectra provide information about structure and dynamics. Because the 2D SFG spectra are heterodyne detected, the monolayer spectra can be directly compared to 2D infrared (2D IR) spectra of poly(thymine) in solution, which aids interpretation. We simulate the 2D SFG spectra using DFT calculations and an excitonic Hamiltonian that relates the molecular geometry to the vibrational coupling. Intrabase cross peaks help define the orientation of the bases and interbase cross peaks, created by coupling between bases, and resolves features not observed in 1D SFG spectra that constrain the relative geometries of stacked bases. We present a structure for the poly(T) oligomer that is consistent with the 2D SFG data. These experiments provide insight into the DNA monolayer structure and set precedent for studying complex biomolecules on surfaces with 2D SFG spectroscopy.

Origins of Very-Low and Zero-Energy Electron Structures in Strong-Field Ionization with Intense Mid-IR Pulses

SynopsisIntense long wavelength (λ ≥ 2 μm) laser pulses enable experiments in the tunneling ionization regime (γ ≪ 1) and reveal surprising low electron energy features, which can not be described with the strong-field approximation (SFA). These features, universal for all target species, include the low-energy structure (LES), the very-low-energy structure (VLES) and the zero-energy structure (ZES). Using full 3D electron-ion coincidence detection in combination with our ultrafast 160 kHz mid-IR source, we reveal the entire 3D momentum spectrum well below 1 eV. Quantum and classical simulations allow for an interpretation of the LES, VLES and of the newly identified ZES.

Time-resolved detection of structural change in polyethylene films using mid-infrared laser pulses

Some of the vibrational modes of crystalline organic polymers are known to be sensitive to the structural change from the crystalline phase to the amorphous phase, and vice versa. Using a mid-infrared (mid-IR) pulse from a free-electron laser as a probe, we demonstrate the time-resolved detection of structural change in crystalline polymer (polyethylene) films upon laser heating by a Q-switched Nd:YAG laser. Transmittance of the resonant mid-IR pulse almost instantaneously changes before and after the Nd:YAG laser pulse if its fluence is sufficient to induce the structural change in the film. The developed technique would be useful to study the time-dependent dynamics of the structural change in various materials.

Wide-field FTIR microscopy using mid-IR pulse shaping.

We have developed a new table-top technique for collecting wide-field Fourier transform infrared (FTIR) microscopic images by combining a femtosecond pulse shaper with a mid-IR focal plane array. The pulse shaper scans the delay between a pulse pair extremely rapidly for high signal-to-noise, while also enabling phase control of the individual pulses to under-sample the interferograms and subtract background. Infrared absorption images were collected for a mixture of W(CO)₆ or Mn₂(CO)₁₀ absorbed polystyrene beads, demonstrating that this technique can spatially resolve chemically distinct species. The images are sub-diffraction limited, as measured with a USAF test target patterned on CaF₂ and verified with scalar wave simulations. We also find that refractive, rather than reflective, objectives are preferable for imaging with coherent radiation. We discuss this method with respect to conventional FTIR microscopes.

Stimulated Raman gas sensing by backward UV lasing from a femtosecond filament.

We perform a proof-of-principle demonstration of chemically specific standoff gas sensing, in which a coherent stimulated Raman signal is detected in the direction anticollinear to a two-color laser excitation beam traversing the target volume. The proposed geometry is intrinsically free space as it does not involve back-scattering (reflection) of the signal or excitation beams at or behind the target. A beam carrying an intense mid-IR femtosecond (fs) pulse and a parametrically generated picosecond (ps) UV Stokes pulse is fired in the forward direction. A fs filament, produced by the intense mid-IR pulse, emits a backward-propagating narrowband ps laser pulse at the 337 and 357 nm transitions of excited molecular nitrogen, thus supplying a counter-propagating Raman pump pulse. The scheme is linearly sensitive to species concentration and provides both transverse and longitudinal spatial resolution.

Measuring Coherently Coupled Intramolecular Vibrational and Charge-Transfer Dynamics with Two-Dimensional Vibrational-Electronic Spectroscopy.

We demonstrate Fourier transform (FT) 2D vibrational-electronic (2D VE) spectroscopy employing a novel mid-IR and optical pulse sequence. This new femtosecond third-order nonlinear spectroscopy provides the high time and frequency resolutions of existing 2D FT techniques; however, resulting 2D VE spectra contain IR and electronic dipole moment cross terms. We use 2D VE spectroscopy to help understand the vibrational-electronic couplings in the cyanide-bridged transition-metal mixed valence complex [(CN)5Fe(II)CNRu(III)(NH3)5](-) dissolved in formamide. The amplitudes of the cross-peaks in the 2D VE spectra reveal that three of the intramolecular cyanide stretching vibrations lying along the charge-transfer axis are coherently coupled to the metal-to-metal charge-transfer electronic transition with differing strengths. Analysis of the 2D VE line shapes reveals positive and negative correlations of the cyanide stretching modes with the charge-transfer transition depending on the physical orientation of the vibration in the molecule and its interaction with the solvent. The insights found thus far into the vibronic couplings in the mixed valence model system indicate that the 2D VE technique will be a valuable addition to the existing multidimensional spectroscopy toolbox.

Three-octave-spanning supercontinuum generation and sub-two-cycle self-compression of mid-infrared filaments in dielectrics.

We experimentally and numerically investigate the spectral and temporal structure of mid-infrared (mid-IR) filaments in bulk dielectrics with normal and anomalous group velocity dispersion (GVD) pumped by a 2.1μm optical parametric chirped-pulse amplifier (OPCPA). The formation of stable and robust filaments with several microjoules of pulse energy is observed. We demonstrate a supercontinuum that spans more than three octaves from ZnS in the normal GVD regime and self-compression of the mid-IR pulse to sub-two-cycle duration in CaF2 in the anomalous GVD regime. The experimental observations quantitatively agree well with the numerical simulations based on a three-dimensional nonlinear wave equation that reveals the detailed spatio-temporal dynamics of mid-IR filaments in dielectrics.

Energetic mid-IR femtosecond pulse generation by self-defocusing soliton-induced dispersive waves in a bulk quadratic nonlinear crystal.

Generating energetic femtosecond mid-IR pulses is crucial for ultrafast spectroscopy, and currently relies on parametric processes that, while efficient, are also complex. Here we experimentally show a simple alternative that uses a single pump wavelength without any pump synchronization and without critical phase-matching requirements. Pumping a bulk quadratic nonlinear crystal (unpoled LiNbO(3) cut for noncritical phase-mismatched interaction) with sub-mJ near-IR 50-fs pulses, tunable and broadband (∼ 1,000 cm(-1)) mid-IR pulses around 3.0 μm are generated with excellent spatio-temporal pulse quality, having up to 10.5 μJ energy (6.3% conversion). The mid-IR pulses are dispersive waves phase-matched to near-IR self-defocusing solitons created by the induced self-defocusing cascaded nonlinearity. This process is filament-free and the input pulse energy can therefore be scaled arbitrarily by using large-aperture crystals. The technique can readily be implemented with other crystals and laser wavelengths, and can therefore potentially replace current ultrafast frequency-conversion processes to the mid-IR.

Investigation of giant Kerr nonlinearity in quantum cascade lasers using mid-infrared femtosecond pulses

We study the Kerr nonlinearity of quantum cascade lasers (QCLs) by coupling resonant and off-resonant mid-infrared (mid-IR) femtosecond (fs) pulses into an active QCL waveguide. We observe an increase in the spectral width of the transmitted fs pulses as the coupled mid-infrared (mid-IR) pulse power increases. This is explained by the self-phase modulation effect due to the large Kerr nonlinearity of QCL waveguides. We further confirm this effect by observing the intensity dependent far-field profile of the transmitted mid-IR pulses, showing the pulses undergo self-focusing as they propagate through the active QCL due to the intensity dependent refractive index. We experimentally estimate the nonlinear refractive index n2 of a QCL to be ∼8 × 10−9 cm2/W using the far-field beam profile of the transmitted pulses. The finite-difference time-domain simulations of QCL waveguides with Kerr nonlinearity incorporated show similar behavior to the experimental results.

Formation of very-low-energy states crossing the ionization threshold of argon atoms in strong mid-infrared fields

Atomic ionization by intense mid-infrared (mid-IR) pulses produces low-electron-energy features that the strong-field approximation, which is expected to be valid in the tunneling ionization regime characterized by small Keldysh parameters $(\ensuremath{\gamma}\ensuremath{\ll}1)$, cannot describe. These features include the low-energy structure (LES), the very-low-energy structure (VLES), and the more recently found zero-energy structure (ZES). They result from the interplay between the laser electric field and the atomic Coulomb field which controls the low-energy spectrum also for small $\ensuremath{\gamma}$. In the present joint experimental and theoretical study we investigate the vectorial momentum spectrum of photoelectrons emitted from an Ar gas target at very low energies. Using a reaction microscope optimized for the detection of very-low-energy electrons, we have performed a thorough study of the three-dimensional momentum spectrum well below 1 eV. Our measurements are complemented by quantum and classical simulations, which allow for an interpretation of the LES and VLES and of the ZES in terms of two-dimensional Coulomb focusing and recapture into Rydberg states, respectively.

A 41-W ZnGeP₂ optical parametric oscillator pumped by a Q-switched Ho:YAG laser.

We reported a high-power ZnGeP₂ (ZGP) optical parametric oscillator (OPO) pumped by a Q-switched Ho:YAG laser. The maximum output power of the ZGP OPO was 41.2 W at 107.0 W incident Ho pump power, corresponding to a slope efficiency of 44.6%. The ZGP OPO produced 16-ns mid-IR pulse laser in the 3.74-3.98 μm and 4.38-4.76 μm spectral regions simultaneously. The beam quality was measured to be M²<4.37. The continuous wave maximum average output power of the Ho:YAG laser was 128 W, corresponding to a slope efficiency of 65.8%.

Laser ablation sample transfer for mass spectrometry imaging.

Infrared laser ablation sample transfer (IR-LAST) is a novel ambient sampling technique for mass spectrometry. In this technique, a pulsed mid-IR laser is used to ablate materials that are collected for mass spectrometry analysis; the material can be a solid sample or deposited on a sample target. After collection, the sample can be further separated or analyzed directly by mass spectrometry. For IR-LAST sample transfer tissue imaging using MALDI mass spectrometry, a tissue section is placed on a sample slide and material transferred to a target slide by scanning the tissue sample under a focused laser beam using transmission-mode (back side) IR laser ablation. After transfer, the target slide is analyzed using MALDI imaging. The spatial resolution is approximately 400 μm and limited by the spread of the laser desorption plume. IR-LAST for MALDI imaging provides several new capabilities including ambient sampling, area to spot concentration of ablated material, multiple ablation and analysis from a single section, and direct deposition on matrix-free nanostructured targets.

Kinematically complete measurements of strong field ionization with mid-IR pulses

Recent observations of three unique peaks near 1 eV, 100 meV and 1 meV in the electron spectra generated by ionization using intense mid-IR pulses have challenged the current understanding of strong-field (SF) ionization. The results came as a surprise as they could not be reproduced by the standard version of the commonly used SF approximation. We present results showing the simultaneous measurement of all three low energy ranges at high resolution. This capability is possible due to a unique experimental combination of a high repetition rate mid-IR source, which allows probing deep in the quasi-static regime at high data rates, with a reaction microscope, which allows high resolution three dimensional imaging of the electron momentum distribution.

Spectrally resolved intraband transitions on two-step photon absorption in InGaAs/GaAs quantum dot solar cell

Two-step photon absorption processes in a self-organized In0.4Ga0.6As/GaAs quantum dot (QD) solar cell have been investigated by monitoring the mid-infrared (IR) photoinduced modulation of the external quantum efficiency (ΔEQE) at low temperature. The first step interband and the second step intraband transitions were both spectrally resolved by scanning photon energies of visible to near-IR CW light and mid-IR pulse lasers, respectively. A peak centered at 0.20 eV corresponding to the transition to virtual bound states and a band above 0.42 eV probably due to photoexcitation to GaAs continuum states were observed in ΔEQE spectra, when the interband transition was above 1.4 eV, directly exciting wetting layers or GaAs spacer layers. On the other hand, resonant excitation of the ground state of QDs at 1.35 eV resulted in a reduction of EQE. The sign of ΔEQE below 1.40 eV changed from negative to positive by increasing the excitation intensity of the interband transition. We ascribe this to the filling of higher energy trap states.

Ultrabroadband XFROG of few-cycle mid-infrared pulses by four-wave mixing in a gas

Cross-correlation frequency-resolved optical gating (XFROG) based on four-wave mixing (FWM) in a gas medium is shown to enable dispersion-free characterization of few-cycle mid-infrared (mid-IR) pulses tunable within a spectral range of more than two octaves. The FWM XFROG technique is used to measure spectra and pulse shapes, as well as to retrieve the phase of a few-cycle output of difference-frequency generation (DFG) tunable from 3 to 11&#xA0;&#x3BC;m. With Ti:sapphire laser pulses used as a reference, this FWM process maps the entire tunability range of the DFG source, spanning over more than two octaves, onto a wavelength region of only 50&#xA0;nm in the visible, allowing convenient XFROG measurements and revealing the reshaping of few-cycle mid-IR field waveforms by molecular rovibrational modes.

Difference-frequency generation of fs and ps mid-IR pulses in LiInSe(2) based on Yb-fiber laser pump sources.

Difference-frequency generation between signal and idler of Yb-fiber laser synchronously pumped femtosecond and picosecond optical parametric oscillators (SPOPOs) operating at 53 and 80 MHz, respectively, is investigated in the wide bandgap chalcogenide crystal LiInSe(2). Single pulse energies in excess of 1 nJ are demonstrated, and the continuous tuning extends from 5 to 12 μm.

Design of efficient single-stage chirped pulse difference frequency generation at 7 μm, driven by a dual wavelength Ti:sapphire laser

We present a design for a high-energy single stage mid-IR difference frequency generation adapted to a two-color Ti:sapphire amplifier system. The optimized mixing process is based on chirped pulse difference frequency generation (CP-DFG), allowing for a higher conversion efficiency, larger bandwidth and reduced two photon absorption losses. The numerical start-to-end simulations include stretching, chirped pulse difference frequency generation and pulse compression. Realistic design parameters for commercially available non linear crystals (GaSe, AgGaS2, LiInSe2, LiGaSe2) are considered. Compared to conventional un-chirped DFG directly pumped by Ti:sapphire technology we report a threefold increase of the quantum efficiency. Our CP-DFG scheme provides up to 340 {\mu}J pulse energy directly at 7.2 {\mu}m when pumped with 3 mJ and supports a bandwidth of up to 350 nm. The resulting 240 fs mid-IR pulses are inherently phase stable.

Graphene mode-locked Cr:ZnS laser with 41 fs pulse duration

We report the ultrashort-pulse Cr:ZnS laser mode-locked by graphene-based saturable absorber mirror. Using the combination of bulk material and a chirped mirror, we demonstrate the shortest reported so far mid-IR pulses of only 5.1 optical cycles (41 fs) centered at 2.4 µm with 190 nm spectral bandwidth. The pulse spectrum almost completely fills the water-free atmospheric window. The output parameters reach 2.3 nJ pulse energy and 250 mW average output power at 108 MHz repetition rate.

High peak-power mid-infrared ZnGeP_2 optical parametric oscillator pumped by a Tm:fiber master oscillator power amplifier system

We report on the utilization of a novel Tm:fiber laser source for mid-IR ZnGeP2 (ZGP) optical parametric oscillator (OPO) pumping. The pump laser is built in a master oscillator power-amplifier configuration delivering up to 3.36 W of polarized, diffraction limited output power with 7 ns pulse duration and 4 kHz repetition rate. This corresponds to a peak power of ∼121 kW and a pulse energy of ∼0.84 mJ. With this source, we generated 27.9 kW of total mid-IR peak power in a doubly resonant oscillator (DRO) configuration. This is, to the best of our knowledge, the highest ever demonstrated mid-IR peak power from a directly Tm:fiber laser pumped ZGP OPO. Moreover, a DRO output with about 284 μJ of total mid-IR pulse energy was demonstrated using 100 ns pump pulses. The wavelength tuning of the idler was extended to 6 μm with lower output power in another OPO experiment.

Two-Dimensional Sum-Frequency Generation Reveals Structure and Dynamics of a Surface-Bound Peptide

Surface-bound polypeptides and proteins are increasingly used to functionalize inorganic interfaces such as electrodes, but their structural characterization is exceedingly difficult with standard technologies. In this paper, we report the first two-dimensional sum-frequency generation (2D SFG) spectra of a peptide monolayer, which are collected by adding a mid-IR pulse shaper to a standard femtosecond SFG spectrometer. On a gold surface, standard FTIR spectroscopy is inconclusive about the peptide structure because of solvation-induced frequency shifts, but the 2D line shapes, anharmonic shifts, and lifetimes obtained from 2D SFG reveal that the peptide is largely α-helical and upright. Random coil residues are also observed, which do not themselves appear in SFG spectra due to their isotropic structural distribution, but which still absorb infrared light and so can be detected by cross-peaks in 2D SFG spectra. We discuss these results in the context of peptide design. Because of the similar way in which the spectra are collected, these 2D SFG spectra can be directly compared to 2D IR spectra, thereby enabling structural interpretations of surface-bound peptides and biomolecules based on the well-studied structure/2D IR spectra relationships established from soluble proteins.