John D. Hybl

Bio: John D. Hybl is an academic researcher from Massachusetts Institute of Technology. The author has contributed to research in topics: Fourier transform & Femtosecond. The author has an hindex of 15, co-authored 26 publications receiving 1779 citations. Previous affiliations of John D. Hybl include Ford Motor Company & University of Colorado Boulder.

Two-dimensional Fourier transform electronic spectroscopy

Abstract: Two-dimensional Fourier transform electronic spectra of the cyanine dye IR144 in methanol are used to explore new aspects of optical 2D spectroscopy on a femtosecond timescale The experiments reported here are pulse sequence and coherence pathway analogs of the two-dimensional magnetic resonance techniques known as COSY (correlated spectroscopy) and NOESY (nuclear Overhauser effect spectroscopy) Noncollinear three pulse scattering allows selection of electronic coherence pathways by choice of phase matching geometry, temporal pulse order, and Fourier transform variables Signal fields and delays between excitation pulses are measured by spectral interferometry Separate real (absorptive) and imaginary (dispersive) 2D spectra are generated by measuring the signal field at the sample exit, performing a 2D scan that equally weights rephasing and nonrephasing coherence pathways, and phasing the 2D spectra against spectrally resolved pump–probe signals A 3D signal propagation function is used to correct the 2D spectra for excitation pulse propagation and signal pulse generation inside the sample At relaxation times greater than all solvent and vibrational relaxation timescales, the experimental 2D electronic spectra can be predicted from linear spectroscopic measurements without any adjustable parameters The 2D correlation spectra verify recent computational predictions of a negative region above the diagonal, a displacement of the 2D peak off the diagonal, and a narrowing of the 2D cross-width below the vibrational linewidth The negative region arises from 4-level four-wave mixing processes with negative transition dipole products, the displacement off the diagonal arises from a dynamic Stokes shift during signal radiation, and the narrow 2D cross-width indicates femtosecond freezing of vibrational motion

Laser-induced breakdown spectroscopy detection and classification of biological aerosols.

Abstract: Laser-induced breakdown spectroscopy (LIBS) is examined as a potential method for detecting airborne biological agents. A spectrally broadband LIBS system was used for laboratory measurements on some common biological agent simulants. These measurements were compared to those of common, naturally occurring biological aerosol components (pollen and fungal spores) to determine the potential of LIBS for discriminating biological agents from natural background aerosols. A principal components analysis illustrates that linear combinations of the detected atomic lines, which are present in different ratios in each of the samples tested, can be used to discriminate biological agent simulants from other biological matter. A more sensitive, narrowband LIBS instrument was used to demonstrate the detection of single simulant (Bg) particles in the size range 1-5 μm. Ca, Mg, and Na, which are present in varying concentrations between 0.3 and 11% (by mass) in the Bg particles, were observed in single particles using LIBS.

Laser induced breakdown spectroscopy for the detection and classification of biological aerosols

Abstract: Laser-induced breakdown spectroscopy (LIBS) is examined as a potential method for detecting airborne biological agents. A spectrally broadband LIBS system was used for laboratory measurements on some common biological agent simulants. These measurements were compared to those of common, naturally occurring biological aerosol components (pollen and fungal spores) to determine the potential of LIBS for discriminating biological agents from natural background aerosols. A principal components analysis illustrates that linear combinations of the detected atomic lines, which are present in different ratios in each of the samples tested, can be used to discriminate biological agent simulants from other biological matter. A more sensitive, narrowband LIBS instrument was used to demonstrate the detection of single simulant (Bg) particles in the size range 1–5 μm. Ca, Mg, and Na, which are present in varying concentrations between 0.3 and 11% (by mass) in the Bg particles, were observed in single particles using LIBS.

Heterodyne detection of the complete electric field of femtosecond four-wave mixing signals

Abstract: A novel optimized heterodyne method that recovers the complete electric field of any four-wave mixing signal at its point of origin is demonstrated. A tracer pulse is sent along the signal path and characterized at the sample by frequency-resolved optical gating. Spectral interferometry is used to determine the phase difference between the tracer and a reference pulse, the absorptive change in tracer phase in the sample, and the reference-signal phase difference. Together, these measurements allow calculation of the signal phase at the sample. The phase of three pulse-scattering signals from solutions of the infrared dye IR 144 in methanol determines the absolute signal-emission time within 0.5 fs.

Laser-induced breakdown spectroscopy (LIBS), part II: review of instrumental and methodological approaches to material analysis and applications to different fields.

Abstract: The first part of this two-part review focused on the fundamental and diagnostics aspects of laser-induced plasmas, only touching briefly upon concepts such as sensitivity and detection limits and largely omitting any discussion of the vast panorama of the practical applications of the technique. Clearly a true LIBS community has emerged, which promises to quicken the pace of LIBS developments, applications, and implementations. With this second part, a more applied flavor is taken, and its intended goal is summarizing the current state-of-the-art of analytical LIBS, providing a contemporary snapshot of LIBS applications, and highlighting new directions in laser-induced breakdown spectroscopy, such as novel approaches, instrumental developments, and advanced use of chemometric tools. More specifically, we discuss instrumental and analytical approaches (e.g., double- and multi-pulse LIBS to improve the sensitivity), calibration-free approaches, hyphenated approaches in which techniques such as Raman and fluorescence are coupled with LIBS to increase sensitivity and information power, resonantly enhanced LIBS approaches, signal processing and optimization (e.g., signal-to-noise analysis), and finally applications. An attempt is made to provide an updated view of the role played by LIBS in the various fields, with emphasis on applications considered to be unique. We finally try to assess where LIBS is going as an analytical field, where in our opinion it should go, and what should still be done for consolidating the technique as a mature method of chemical analysis.

Two-dimensional femtosecond spectroscopy

Abstract: The simplest two-dimensional (2D) spectra show how excitation with one (variable) frequency affects the spectrum at all other frequencies, thus revealing the molecular connections between transitions. Femtosecond 2D Fourier transform (2D FT) spectra are more flexible and share some of the remarkable properties of their conceptual parent, 2D FT nuclear magnetic resonance. When 2D FT spectra are experimentally separated into real absorptive and imaginary refractive parts, the time resolution and frequency resolution can both reach the uncertainty limit set for each resonance by the sample itself. Coherent four-level contributions to the signal provide new molecular phase information, such as relative signs of transition dipoles. The nonlinear response can be picked apart by selecting a single coherence pathway (e.g., specifying the relative signs of energy level difference frequencies during different time intervals as in the photon echo). Because molecules are frozen on the femtosecond timescale, femtosecond 2D FT experiments can separate a distribution of instantaneous molecular environments and intramolecular geometries as inhomogeneous broadening. This review provides an introduction to two-dimensional Fourier transform experiments exploiting second- and third-order vibrational and electronic nonlinearities.

Long-lived quantum coherence in photosynthetic complexes at physiological temperature

Abstract: Photosynthetic antenna complexes capture and concentrate solar radiation by transferring the excitation to the reaction center that stores energy from the photon in chemical bonds. This process occurs with near-perfect quantum efficiency. Recent experiments at cryogenic temperatures have revealed that coherent energy transfer—a wave-like transfer mechanism—occurs in many photosynthetic pigment-protein complexes. Using the Fenna–Matthews–Olson antenna complex (FMO) as a model system, theoretical studies incorporating both incoherent and coherent transfer as well as thermal dephasing predict that environmentally assisted quantum transfer efficiency peaks near physiological temperature; these studies also show that this mechanism simultaneously improves the robustness of the energy transfer process. This theory requires long-lived quantum coherence at room temperature, which never has been observed in FMO. Here we present evidence that quantum coherence survives in FMO at physiological temperature for at least 300 fs, long enough to impact biological energy transport. These data prove that the wave-like energy transfer process discovered at 77 K is directly relevant to biological function. Microscopically, we attribute this long coherence lifetime to correlated motions within the protein matrix encapsulating the chromophores, and we find that the degree of protection afforded by the protein appears constant between 77 K and 277 K. The protein shapes the energy landscape and mediates an efficient energy transfer despite thermal fluctuations.

Primary biological aerosol particles in the atmosphere: a review

Abstract: Atmospheric aerosol particles of biological origin are a very diverse group of biological materials and structures, including microorganisms, dispersal units, fragments and excretions of biological organisms. In recent years, the impact of biological aerosol particles on atmospheric processes has been studied with increasing intensity, and a wealth of new information and insights has been gained. This review outlines the current knowledge on major categories of primary biological aerosol particles (PBAP): bacteria and archaea, fungal spores and fragments, pollen, viruses, algae and cyanobacteria, biological crusts and lichens and others like plant or animal fragments and detritus. We give an overview of sampling methods and physical, chemical and biological techniques for PBAP analysis (cultivation, microscopy, DNA/RNA analysis, chemical tracers, optical and mass spectrometry, etc.). Moreover, we address and summarise the current understanding and open questions concerning the influence of PBAP on the atmosphere and climate, i.e. their optical properties and their ability to act as ice nuclei (IN) or cloud condensation nuclei (CCN). We suggest that the following research activities should be pursued in future studies of atmospheric biological aerosol particles: (1) develop efficient and reliable analytical techniques for the identification and quantification of PBAP; (2) apply advanced and standardised techniques to determine the abundance and diversity of PBAP and their seasonal variation at regional and global scales (atmospheric biogeography); (3) determine the emission rates, optical properties, IN and CCN activity of PBAP in field measurements and laboratory experiments; (4) use field and laboratory data to constrain numerical models of atmospheric transport, transformation and climate effects of PBAP. Keywords: primary biological atmospheric aerosol; climate; cloud condensation nuclei; biology; atmospheric ice nuclei (Published: 22 February 2012) Citation: Tellus B 2012, 64 , 15598, DOI: 10.3402/tellusb.v64i0.15598