Narrow homogeneous linewidths and slow cooling dynamics across infrared intra-band transitions in n-doped HgSe colloidal quantum dots.

Intra-band transitions in colloidal quantum dots (QDs) are promising for opto-electronic applications in the mid-IR spectral region. However, such intra-band transitions are typically very broad and spectrally overlapping, making the study of individual excited states and their ultrafast dynamics very challenging. Here, we present the first full spectrum two-dimensional continuum infrared (2D CIR) spectroscopy study of intrinsically n-doped HgSe QDs, which exhibit mid-infrared intra-band transitions in their ground state. The obtained 2D CIR spectra reveal that underneath the broad absorption line shape of ∼500 cm-1, the transitions exhibit surprisingly narrow intrinsic linewidths with a homogeneous broadening of 175-250 cm-1. Furthermore, the 2D IR spectra are remarkably invariant, with no sign of spectral diffusion dynamics at waiting times up to 50 ps. Accordingly, we attribute the large static inhomogeneous broadening to the distribution of size and doping level of the QDs. In addition, the two higher-lying P-states of the QDs can be clearly identified in the 2D IR spectra along the diagonal with a cross-peak. However, there is no indication of cross-peak dynamics indicating that, despite the strong spin-orbit coupling in HgSe, transitions between the P-states must be longer than our maximum waiting time of 50 ps. This study illustrates a new frontier of 2D IR spectroscopy enabling the study of intra-band carrier dynamics in nanocrystalline materials across the entire mid-infrared spectrum.

Wedge-Based Design for Phase Stable and Phase Accurate Heterodyne-Detected Sum-Frequency Generation Spectroscopy.

Phase sensitive and heterodyne-detected (HD) sum-frequency generation (SFG) spectroscopy offers the ability to separate the nonlinear susceptibility into its real and imaginary components. This provides information about the absolute orientation of molecules at interfaces while also producing an absorptive spectrum that is linear in spectral composition and can easily be decomposed into different spectral components. However, simultaneously obtaining phase accuracy and phase stability remains a challenge in SFG. Here we present a new experimental design for HD-SFG spectroscopy that incorporates a wedge pair to accurately control the timing between the local oscillator and the sample signal. This experimental approach provides high phase accuracy and long-time phase stability in a compact and flexible configuration.

Full spectrum 2D IR spectroscopy reveals below-gap absorption and phonon dynamics in the mid-IR bandgap semiconductor InAs.

While the mid-infrared spectral region spans more than 3000 cm-1, ultrafast mid-IR spectroscopies are normally limited to the spectral bandwidth that can be generated in optical parametric amplifiers-typically a few hundred cm-1. As such, the spectral coverage in conventional two dimensional infrared (2D IR) spectroscopy captures only about 1% of the full potential 2D mid-IR spectrum. Here, we present 2D IR spectra using a continuum source as both the excitation and probe pulses, thus capturing close to the full 2D IR spectrum. While the continuum pulses span the entire mid-IR range, they are currently too weak to efficiently excite molecular vibrational modes but strong enough to induce electronic responses and excite phonons in semiconductors. We demonstrate the full spectrum 2D IR spectroscopy of the mid-IR bandgap semiconductor indium arsenide with a bandgap at 2855 cm-1. The measured response extends far below the bandgap and is due to field-induced band-shifting, causing probe absorption below the bandgap. While the band-shifting induces an instantaneous response that exists only during pulse overlap, the 2D IR spectra reveal additional off-diagonal features that decay on longer timescales. These longer-lived off-diagonal features result from coherent phonons excited via a Raman-like process at specific excitation frequencies. This study illustrates that the full spectrum 2D IR spectroscopy of electronic states in the mid-IR is possible with current continuum pulse technology and is effective in characterizing semiconductor properties.

Interpreting Quasi-Thermal Effects in Ultrafast Spectroscopy of Hydrogen-Bonded Systems.

Vibrational excitation of molecules in the condensed phase relaxes through vibrational modes of decreasing energy to ultimately generate an equilibrium state in which the energy is distributed among low-frequency modes. In ultrafast vibrational spectroscopy, changes in the vibrational features of hydrogen-bonded NH and OH stretch modes are typically observed to persist long after these high-frequency vibrations have relaxed. Due to the resemblance to the spectral changes caused by heating the sample, these features are typically described as arising from a hot ground state. However, these spectral features appear on ultrafast time scales that are much too fast to result from a true thermal state, and significant differences between the thermal difference spectrum and the induced quasi-thermal changes in ultrafast spectroscopy are often observed. Here, we examine and directly compare the thermal and quasi-thermal responses of the hydrogen-bonded homodimer of 7-azaindole with temperature-dependent FTIR spectroscopy and ultrafast mid-IR continuum spectroscopy. We find that the thermal difference spectra contain contributions from both dissociation of the hydrogen bonds and from frequency shifts due to changes in the thermal population of low-frequency modes. The transient spectra in ultrafast vibrational spectroscopy are also found to contain two contributions: initial frequency shifts over 2.3 ± 0.11 ps associated with equilibration of the initial excitation, and frequency shifts associated with the excitation of several fingerprint modes, which decay over 21.8 ± 0.11 ps, giving rise to a quasi-thermal response caused by a distribution of fingerprint modes being excited within the sample ensemble. This resembles the thermal frequency shifts due to population changes of low-frequency modes, but not the overall thermal spectrum, which is dominated by features caused by dimer dissociation. These findings provide insight into the changes in the vibrational spectrum from different origins and are important for assigning, analyzing, and comparing features in thermal and ultrafast vibrational spectroscopy of hydrogen-bonded complexes.

Interferometric 2D Sum Frequency Generation Spectroscopy Reveals Structural Heterogeneity of Catalytic Monolayers on Transparent Materials.

Molecular monolayers exhibit structural and dynamical properties that are different from their bulk counterparts due to their interaction with the substrate. Extracting these distinct properties is crucial for a better understanding of processes such as heterogeneous catalysis and interfacial charge transfer. Ultrafast nonlinear spectroscopic techniques such as 2D infrared (2D IR) spectroscopy are powerful tools for understanding molecular dynamics in complex bulk systems. Here, we build on technical advancements in 2D IR and heterodyne-detected sum frequency generation (SFG) spectroscopy to study a CO2 reduction catalyst on nanostructured TiO2 with interferometric 2D SFG spectroscopy. Our method combines phase-stable heterodyne detection employing an external local oscillator with a broad-band pump pulse pair to provide the first high spectral and temporal resolution 2D SFG spectra of a transparent material. We determine the overall molecular orientation of the catalyst and find that there is a static structural heterogeneity reflective of different local environments at the surface.

Couplings Across the Vibrational Spectrum Caused by Strong Hydrogen Bonds: A Continuum 2D IR Study of the 7-Azaindole-Acetic Acid Heterodimer.

Strongly hydrogen-bonded motifs provide structural stability and can act as proton transfer relays to drive chemical processes in biological and chemical systems. However, structures with medium and strong hydrogen bonds are difficult to study due to their characteristically broad vibrational bands and large anharmonicity. This is further complicated by strong interactions between the high-frequency hydrogen-bonded vibrational modes, fingerprint modes, and low-frequency intradimer modes that modulate the hydrogen-bonding. Understanding these structures and their associated dynamics requires studying much of the vibrational spectrum. Here, mid-IR continuum spectroscopy of the cyclic 7-azaindole-acetic acid (7AI-AcOH) heterodimer reveals the vibrational relaxation dynamics and couplings of this complex hydrogen-bonded system. Within this dimer, the NH bond of 7AI exhibits a band at 3250 cm-1 caused by a medium strength hydrogen bond, while the strongly hydrogen-bonded OH modes of acetic acid exhibit a broad double-peaked vibrational feature spanning 1750 to 2750 cm-1. Transient IR and 2D IR experiments were performed using three excitation frequencies, centered on the high-frequency OH and NH modes, and probed with a mid-IR continuum to measure the spectral response from 1000 to 3500 cm-1. While the NH stretch is observed to relax in 300 fs, the strongly hydrogen-bonded OH modes relax within the time resolution of the experiment (sub-100 fs). The difference in the strength of the hydrogen bonds is also reflected in the coupling pattern in the fingerprint region observed with 2D IR spectroscopy. Here the NH is strongly coupled to fingerprint modes involving the 7AI monomer, while the OH vibrations are strongly coupled to vibrational modes across the entire dimer. Together, the results show strong coupling and rapid energy transfer across the hydrogen-bonded interface and through the structure of the 7-azaindole-acetic acid heterodimer, highlighting the need to study the full vibrational spectrum for strongly hydrogen-bonded systems.

Strong intermolecular vibrational coupling through cyclic hydrogen-bonded structures revealed by ultrafast continuum mid-IR spectroscopy.

Cyclic hydrogen-bonded structures are common motifs in biological systems, providing structural stability and mediating proton transfer for redox reactions. The mechanism of proton transfer across hydrogen-bonded interfaces depends on the strength of the intermolecular coupling between bridging OH/NH vibrational modes. Here we present a novel ultrafast continuum mid-IR spectroscopy experiment to study the vibrational dynamics of the 7-azaindole-acetic acid (7AI-Ac) heterodimer as a model system for asymmetric cyclic hydrogen-bonded structures. In addition to spreading of the excitation across the whole OH band within the time resolution of the experiment, excitation of a 300 cm(-1) region of the ∼1000 cm(-1) broad OH stretching mode of the acetic acid monomer leads to a frequency shift in the NH stretching mode of the 7AI monomer. This indicates that the NH and OH stretching modes located on the two monomers are strongly coupled despite being separated by 750 cm(-1). The strong coupling further causes the OH and NH bands to decay with a common decay time of ∼2.5 ps. This intermolecular coupling is mediated through the hydrogen-bonded structure of the 7AI-Ac heterodimer and is likely a general property of cyclic hydrogen-bonded structures. Characterizing the vibrational dynamics of and the coupling between the high-frequency OH/NH modes will be important for understanding proton transfer across such molecular interfaces.

Ultrafast continuum mid-infrared spectroscopy: probing the entire vibrational spectrum in a single laser shot with femtosecond time resolution.

Until now, ultrafast IR spectroscopy has been limited by the bandwidth of optical parametric amplifiers, typically 100-400 cm(-1). Here we present the first example of transient IR spectroscopy using a continuum laser source to probe the entire mid-IR region with ultrafast time resolution. The continuum source is based on focusing the fundamental, second harmonic, and third harmonic of 1 mJ, 25 fs, 800 nm pulses in air, generating ∼150 fs continuum mid-IR pulses that span the frequency range of <400 to >5000 cm(-1) or, conversely, <2 to >25 µm. We characterize the spectral and temporal properties of dicarbonylacetonato rhodium(I) in hexane. We further demonstrate the versatility of the method by measuring the very fast and broad (>1500 cm(-1)) spectral changes following IR excitation associated with the 7-azaindole-acetic acid heterodimer in carbon tetrachloride.