Michael L. Cowan

Ultrafast memory loss and energy redistribution in the hydrogen bond network of liquid H2O.

Many of the unusual properties of liquid water are attributed to its unique structure, comprised of a random and fluctuating three-dimensional network of hydrogen bonds that link the highly polar water molecules. One of the most direct probes of the dynamics of this network is the infrared spectrum of the OH stretching vibration, which reflects the distribution of hydrogen-bonded structures and the intermolecular forces controlling the structural dynamics of the liquid. Indeed, water dynamics has been studied in detail, most recently using multi-dimensional nonlinear infrared spectroscopy for acquiring structural and dynamical information on femtosecond timescales. But owing to technical difficulties, only OH stretching vibrations in D2O or OD vibrations in H2O could be monitored. Here we show that using a specially designed, ultrathin sample cell allows us to observe OH stretching vibrations in H2O. Under these fully resonant conditions, we observe hydrogen bond network dynamics more than one order of magnitude faster than seen in earlier studies that include an extremely fast sweep in the OH frequencies on a 50-fs timescale and an equally fast disappearance of the initial inhomogeneous distribution of sites. Our results highlight the efficiency of energy redistribution within the hydrogen-bonded network, and that liquid water essentially loses the memory of persistent correlations in its structure within 50 fs.

Temperature dependence of the two-dimensional infrared spectrum of liquid H2O

Two-dimensional infrared photon-echo measurements of the OH stretching vibration in liquid H2O are performed at various temperatures. Spectral diffusion and resonant energy transfer occur on a time scale much shorter than the average hydrogen bond lifetime of ≈1 ps. Room temperature measurements show a loss of frequency and, thus, structural correlations on a 50-fs time scale. Weakly hydrogen-bonded OH stretching oscillators absorbing at high frequencies undergo slower spectral diffusion than strongly bonded oscillators. In the temperature range from 340 to 274 K, the loss in memory slows down with decreasing temperature. At 274 K, frequency correlations in the OH stretch vibration persist beyond ≈200 fs, pointing to a reduction in dephasing by librational excitations. Polarization-resolved pump-probe studies give a resonant intermolecular energy transfer time of 80 fs, which is unaffected by temperature. At low temperature, structural correlations persist longer than the energy transfer time, suggesting a delocalization of OH stretching excitations over several water molecules.

Ultrafast Mid-IR Laser Scalpel: Protein Signals of the Fundamental Limits to Minimally Invasive Surgery

Lasers have in principle the capability to cut at the level of a single cell, the fundamental limit to minimally invasive procedures and restructuring biological tissues. To date, this limit has not been achieved due to collateral damage on the macroscale that arises from thermal and shock wave induced collateral damage of surrounding tissue. Here, we report on a novel concept using a specifically designed Picosecond IR Laser (PIRL) that selectively energizes water molecules in the tissue to drive ablation or cutting process faster than thermal exchange of energy and shock wave propagation, without plasma formation or ionizing radiation effects. The targeted laser process imparts the least amount of energy in the remaining tissue without any of the deleterious photochemical or photothermal effects that accompanies other laser wavelengths and pulse parameters. Full thickness incisional and excisional wounds were generated in CD1 mice using the Picosecond IR Laser, a conventional surgical laser (DELight Er:YAG) or mechanical surgical tools. Transmission and scanning electron microscopy showed that the PIRL laser produced minimal tissue ablation with less damage of surrounding tissues than wounds formed using the other modalities. The width of scars formed by wounds made by the PIRL laser were half that of the scars produced using either a conventional surgical laser or a scalpel. Aniline blue staining showed higher levels of collagen in the early stage of the wounds produced using the PIRL laser, suggesting that these wounds mature faster. There were more viable cells extracted from skin using the PIRL laser, suggesting less cellular damage. β-catenin and TGF-β signalling, which are activated during the proliferative phase of wound healing, and whose level of activation correlates with the size of wounds was lower in wounds generated by the PIRL system. Wounds created with the PIRL systsem also showed a lower rate of cell proliferation. Direct comparison of wound healing responses to a conventional surgical laser, and standard mechanical instruments shows far less damage and near absence of scar formation by using PIRL laser. This new laser source appears to have achieved the long held promise of lasers in minimally invasive surgery.

Laser selective cutting of biological tissues by impulsive heat deposition through ultrafast vibrational excitations

Mechanical and thermodynamic responses of biomaterials after impulsive heat deposition through vibrational excitations (IHDVE) are investigated and discussed. Specifically, we demonstrate highly efficient ablation of healthy tooth enamel using 55 ps infrared laser pulses tuned to the vibrational transition of interstitial water and hydroxyapatite around 2.95 microm. The peak intensity at 13 GW/cm(2) was well below the plasma generation threshold and the applied fluence 0.75 J/cm(2) was significantly smaller than the typical ablation thresholds observed with nanosecond and microsecond pulses from Er:YAG lasers operating at the same wavelength. The ablation was performed without adding any superficial water layer at the enamel surface. The total energy deposited per ablated volume was several times smaller than previously reported for non-resonant ultrafast plasma driven ablation with similar pulse durations. No micro-cracking of the ablated surface was observed with a scanning electron microscope. The highly efficient ablation is attributed to an enhanced photomechanical effect due to ultrafast vibrational relaxation into heat and the scattering of powerful ultrafast acoustic transients with random phases off the mesoscopic heterogeneous tissue structures.

High-power femtosecond infrared laser source based on noncollinear optical parametric chirped pulse amplification

The optical parametric chirped pulse amplication (OPCPA) concept has been extended to the infrared range, providing a new approach, to our knowledge, to high-power femtosecond pulses in the 1.5 μm range. This amplifier is based on 1.05 μm pumping of bulk KTiOAsO4 with broadband phase matching in a noncollinear geometry. The output pulse energy of 1 mJ was generated with 50 nm of bandwidth by 3.8 mJ of pump energy from a 100 ps, 1 kHz Nd:YLF amplified laser. Total gain of 108 was achieved in three stages with 32% conversion of the pump energy in the final amplifier stage. Amplified pulses were compressed to 130 fs with peak intensities of 3.85 GW.

Ultrafast noncollinear optical parametric chirped pulse amplification in KTiOAsO 4

Amplification of femtosecond pulses at 1.56 microm based on noncollinear parametric chirped pulse amplification in a potassium titanyl arsenate (KTA) crystal with pumping at 1.05 microm is reported. The 100 fs pulses of an erbium fiber laser are parametrically amplified while synchronously pumped by an amplified mode-locked Nd:YLF laser. This amplifier has a saturated gain of 65 dB with 30% conversion efficiency and has produced 160 fs pulses with peak powers of up to 0.75 GW. The system produced 380 mW before compression and can be readily scaled to the multiwatt range with bandwidths to support sub-100 fs pulses.

2D-IR Photon Echo Spectroscopy of Pure Liquid Water--Combination of Novel Nanofluidics and Diffractive Optics Deciphers Ultrafast Structural Dynamics

2D-IR photon echo studies of the OH stretching vibration in pure liquid water are presented. At room temperature, a 50-fs decay of structural correlations is found. The temperature dependence of the vibrational dynamics is investigated.

Heterodyne 2D-IR Photon Echo Spectroscopy of Multi-Level OH Stretching Coherences in Hydrogen Bonds

We explore the multilevel structure and vibrational couplings of hydrogen bonded O-H stretching transitions in acetic acid dimer using femtosecond 2D-IR photon echo spectroscopy. Anharmonic coupling with low-frequency modes and Fermi resonances with overtone/combination levels dominate the complex ultrafast dynamics.