2 research outputs found
Large Room Temperature Bulk DNP of <sup>13</sup>C via P1 Centers in Diamond
We use microwave-induced dynamic nuclear polarization
(DNP) of
the substitutional nitrogen defects (P1 centers) in diamond to hyperpolarize
bulk 13C nuclei in both single crystal and powder samples
at room temperature at 3.34 T. The large (>100-fold) enhancements
demonstrated correspond to a greater than 10 000-fold improvement
in terms of signal averaging of the 1% abundant 13C spins.
The DNP was performed using low-power solid state sources under static
(nonspinning) conditions. The DNP spectrum (DNP enhancement as a function
of microwave frequency) of diamond powder shows features that broadly
correlate with the EPR spectrum. A well-defined negative Overhauser
peak and two solid effect peaks are observed for the central (mI = 0) manifold of the 14N spins. Previous low temperature measurements in diamond
had measured a positive Overhauser enhancement in this manifold. Frequency-chirped
millimeter-wave excitation of the electron spins is seen to significantly
improve the enhancements for the two outer nuclear spin manifolds
(mI = ±1) and to blur some of the
sharper features associated with the central manifold. The outer lines
are best fit using a combination of the cross effect and the truncated
cross effect, which is known to mimic features of an Overhauser effect.
Similar features are also observed in experiments on single crystal
samples. The observation of all of these mechanisms in a single material
system under the same experimental conditions is likely due to the
significant heterogeneity of the high pressure, high temperature (HPHT)
type Ib diamond samples used. Large room temperature DNP enhancements
at fields above a few tesla enable spectroscopic studies with better
chemical shift resolution under ambient conditions
Plexcitons: The Role of Oscillator Strengths and Spectral Widths in Determining Strong Coupling
Strong
coupling interactions between plasmon and exciton-based
excitations have been proposed to be useful in the design of optoelectronic
systems. However, the role of various optical parameters dictating
the plasmon-exciton (plexciton) interactions is less understood. Herein,
we propose an inequality for achieving strong coupling between plasmons
and excitons through appropriate variation of their oscillator strengths
and spectral widths. These aspects are found to be consistent with
experiments on two sets of free-standing plexcitonic systems obtained
by (i) linking fluorescein isothiocyanate on Ag nanoparticles of varying
sizes through silane coupling and (ii) electrostatic binding of cyanine
dyes on polystyrenesulfonate-coated Au nanorods of varying aspect
ratios. Being covalently linked on Ag nanoparticles, fluorescein isothiocyanate
remains in monomeric state, and its high oscillator strength and narrow
spectral width enable us to approach the strong coupling limit. In
contrast, in the presence of polystyrenesulfonate, monomeric forms
of cyanine dyes exist in equilibrium with their aggregates: Coupling
is not observed for monomers and H-aggregates whose optical parameters
are unfavorable. The large aggregation number, narrow spectral width,
and extremely high oscillator strength of J-aggregates of cyanines
permit effective delocalization of excitons along the linear assembly
of chromophores, which in turn leads to efficient coupling with the
plasmons. Further, the results obtained from experiments and theoretical
models are jointly employed to describe the plexcitonic states, estimate
the coupling strengths, and rationalize the dispersion curves. The
experimental results and the theoretical analysis presented here portray
a way forward to the rational design of plexcitonic systems attaining
the strong coupling limits