Engineering topics

Hess, Wayne P.

Publications and source records attributed to Hess, Wayne P..

6 records

DOE OSTI2018

Time Domain Simulations of Single Molecule Raman Scattering

Non-equilibrium chemical phenomena are known to play an important role in single molecule microscopy and spectroscopy. Herein, we explore these effects through ab initio molecular dynamics (AIMD)-based Raman spectral simulations. We target an isolated aromatic thiol (thiobenzonitrile, TBN) as a prototypical molecular system. We first show that the essential features contained in the ensemble-averaged Raman spectrum of TBN can be reproduced by averaging over 18 short AIMD trajectories spanning a total simulation time of ~60 ps. This involved more than 90,000 polarizability calculations at the B3LYP/def2-TZVP level of theory. We then illustrate that the short trajectories (~3.3 ps total simulation time), where the accessible phase space is not fully sampled, provide a basis set for understanding key features that are often observed in measurements targeting single molecules. Our results suggest that a complete understanding of single molecule Raman scattering needs to account for molecular conformational flexibility and non-equilibrium chemical phenomena. These effects are well-captured using the described AIMD-based single molecule Raman spectral simulations.

Apra, Edoardo↗

DOE OSTI2018

Tip-Enhanced Raman Scattering from Nanopatterned Graphene and Graphene Oxide

Tip-enhanced Raman spectroscopy (TERS) is particularly sensitive to analytes residing at plasmonic tip-sample nanojunctions, where the incident and scattered optical fields may be localized and optimally enhanced. However, the enhanced local electric fields in this so-called gap-mode TERS configuration are nominally orthogonal to the sample plane. As such, any given Raman active vibrational Eigenstate needs to have projections (of its polarizability derivative tensor elements) along the sample normal to be detectable via TERS. The faint TERS signals observed from two prototypical systems, namely, pristine graphene and graphene oxide are a classical example of the aforementioned rather restrictive TERS selection rules in this context. In this study, we demonstrate that nano-indentation, herein achieved using pulsed-force lithography with a sharp single-crystal diamond atomic force microscope probe, may be used to locally enhance TERS signals from graphene and graphene oxide flakes on gold. Nano-indentation locally perturbs the otherwise flat graphene structure and introduces out-of-plane protrusions that generate enhanced TERS. Although our approach is nominally invasive, we illustrate that the introduced nano-defects are highly localized, as evidenced by TERS nanoscale chemical mapping. As such, the described protocol may be used to extend and generalize the applicability of TERS for the rapid identification of two-dimensional material systems on the nanoscale. KEYWORDS

Bhattarai, Ashish↗

DOE OSTI2017

Multimodal hyperspectral optical microscopy

We describe a unique and convenient approach to multimodal hyperspectral optical microscopy, herein achieved by coupling a portable and transferable hyperspectral imager to various optical microscopes. The experimental and data analysis schemes involved in recording spectrally and spatially resolved fluorescence, dark field, and optical absorption micrographs are illustrated through prototypical measurements targeting selected model systems. Namely, hyperspectral fluorescence micrographs of isolated fluorescent beads are employed to ensure spectral calibration of our detector and to gauge the attainable spatial resolution of our measurements; the recorded images are diffraction-limited. Moreover, spatially over-sampled absorption spectroscopy of a single lipid (18:1 Liss Rhod PE) layer reveals that optical densities on the order of 10-3 may be resolved by spatially averaging the recorded optical signatures. We also briefly illustrate two applications of our setup in the general areas of plasmonics and cell biology. Most notably, we deploy hyperspectral optical absorption microscopy to identify and image algal pigments within a single live Tisochrysis lutea cell. Overall, this work paves the way for multimodal multidimensional spectral imaging measurements spanning the realms of several scientific disciples.

47 OTHER INSTRUMENTATION↗

NASA NTRS1987

Absolute I(asterisk) quantum yields for the ICN A state by diode laser gain-vs-absorption spectroscopy

Absolute I(asterisk) quantum yields have been measured as a function of wavelength for room temperature photodissociation of the ICN A state continuum. The yields are obtained by the technique of time-resolved diode laser gain-vs-absorption spectroscopy. Quantum yields are evaluated at seven wavelengths from 248 to 284 nm. The yield at 266 nm is 66.0 + or - 2 percent and it falls off to 53.4 + or - 2 percent and 44.0 + or - 4 percent at 284 and 248 nm, respectively. The latter values are significantly higher than those obtained by previous workers using infrared fluorescence. Estimates of I(asterisk) quantum yields obtained from analysis of CN photofragment rotational distributions, as discussed by other workers, are in good agreement with the I(asterisk) yields reported here. The results are considered in conjunction with recent theoretical and experimental work on the CN rotational distributions and with previous I(asterisk) quantum yield results.

Hess, Wayne P.↗

NASA NTRS1987

Absolute 1* quantum yields for the ICN A state by diode laser gain versus absorption spectroscopy

Absolute I* quantum yields were measured as a function of wavelength for room temperature photodissociation of the ICN A state continuum. The temperature yields are obtained by the technique of time-resolved diode laser gain-versus-absorption spectroscopy. Quantum yields are evaluated at seven wavelengths from 248 to 284 nm. The yield at 266 nm is 66.0 +/- 2% and it falls off to 53.4 +/- 2% and 44.0 +/- 4% at 284 and 248 respectively. The latter values are significantly higher than those obtained by previous workers using infrared fluorescence. Estimates of I* quantum yields obtained from analysis of CN photofragment rotational distributions, as discussed by other workers, are in good agreement with the I* yields. The results are considered in conjunction with recent theoretical and experimental work on the CN rotational distributions and with previous I* yield results.

Hess, Wayne P.↗

NASA NTRS1986

Transient gain-versus-absorption laser probing of spin-orbit states, kinetics and dynamics

The spin-orbit populations of excited (2P1/2) and ground (2P3/2) state Br atoms at 2714 nm and I atoms at 1315 nm are examined using a tunable F-center laser and a diode laser. The transient laser gain-versus-absorption measurements are utilized to estimate quantum yields of the spin-orbit states in the photodissociation of Br- and I-containing compounds; the continuum yields for Br2 are investigated in terms of temperature. The collisional release, Doppler velocity effects, and differing reactivity of the spin-orbit excited and ground state atoms are studied. It is noted that the transient gain versus absorption technique is applicable to the analysis of kinetic phenomena due to its high sensitivity and excellent time resolution.

Smedley, John E.↗