Design Principles for Two-Dimensional Molecular Aggregates Using Kasha's Model: Tunable Photophysics in Near and Short-Wave Infrared

Technologies which utilize near-infrared (700 – 1000 nm) and short-wave infrared (1000 – 2000 nm) electromagnetic radiation have applications in deep-tissue imaging, telecommunications and satellite telemetry due to low scattering and decreased background signal in this spectral region. It is therefore necessary to develop materials that absorb light efficiently beyond 1000 nm. Transition dipole moment coupling (e.g. J-aggregation) allows for redshifted excitonic states and provides a pathway to highly absorptive electronic states in the infrared. We present aggregates of two cyanine dyes whose absorption peaks redshift dramatically upon aggregation in water from ~800 nm to 1000 nm and 1050 nm respectively with sheet-like morphologies and high molar absorptivities (e ~ 105 M-1cm-1). We use Frenkel exciton theory to extend Kasha’s model for J and H aggregation and describe the excitonic states of 2-dimensional aggregates whose slip is controlled by steric hindrance in the assembled structure. A consequence of the increased dimensionality is the phenomenon of an intermediate “I-aggregate”, one which redshifts yet displays spectral signatures of band-edge dark states akin to an H-aggregate. We distinguish between H-, I- and J-aggregates by showing the relative position of the bright (absorptive) state within the density of states using temperature dependent spectroscopy. I-aggregates hold potential for applications as charge injection moieties for semiconductors and donors for energy transfer in NIR and SWIR. Our results can be used to better design chromophores with predictable and tunable aggregation with new photophysical properties

Polaritons in Large Stochastic Simulations of 2D Molecular Aggregates

We introduce stochastic techniques for simulating polaritons resulting from large molecular aggregate crystals ($10^8$ dyes) in realistic cavities. This enables the study of 2D polaritons that are derived from systems with internal excitonic structure and interact with many modes of cavity light due to their large size, achieving thermodynamic convergence in both the molecular and photonic subsystems. We demonstrate cases where cavity coupling may induce emergent delocalization not present outside of the cavity. Such examples demonstrate the nontrivial role the internal aggregate Hamiltonian can play in polariton properties.Comment: 6 pages, 3 figure

Nonadiabatic derivative couplings through multiple Franck-Condon modes dictate the energy gap law for near and short-wave infrared dye molecules

Near infrared (NIR, 700 - 1,000 nm) and short-wave infrared (SWIR, 1,000 - 2,000 nm) dye molecules exhibit significant nonradiative decay rates from the first singlet excited state to the ground state. While these trends can be empirically explained by a simple energy gap law, detailed mechanisms of the nearly universal behavior have remained unsettled for many cases. Theoretical and experimental results for two representative NIR/SWIR dye molecules reported here clarify an important mechanism of such nature. It is shown that the first derivative nonadiabatic coupling terms serve as major coupling pathways for nonadiabatic decay processes exhibiting the energy gap law behavior and that vibrational modes other than the highest frequency ones also make significant contributions to the rate. This assessment is corroborated by further theoretical comparison with possible alternative mechanisms of intersystem crossing to triplet states and also by comparison with experimental data for deuterated molecules

Stochastically Realized Observables for Excitonic Molecular Aggregates

We show that a stochastic approach enables calculations of the optical properties of large 2-dimensional and nanotubular excitonic molecular aggregates. Previous studies of such systems relied on numerically diagonalizing the dense and disordered Frenkel Hamiltonian, which scales approximately as $\mathcal{O}(N^3)$ for $N$ dye molecules. Our approach scales much more efficiently as $\mathcal{O}(N\log(N))$, enabling quick study of systems with a million of coupled molecules on the micron size scale. We calculate several important experimental observable including the optical absorption spectrum and density of states, and develop a stochastic formalism for the participation ratio. Quantitative agreement with traditional matrix diagonalization methods is demonstrated for both small- and intermediate-size systems. The stochastic methodology enables the study of the effects of spatial-correlation in site energies on the optical signatures of large 2D aggregates. Our results demonstrate that stochastic methods present a path forward for screening structural parameters and validating experiments and theoretical predictions in large excitonic aggregates.Comment: 11 pages, 7 figures, as submitted to JP

Generalized Kasha's Scheme for Classifying Two-Dimensional Excitonic Molecular Aggregates: Temperature Dependent Absorption Peak Frequency Shift

We propose a generalized theoretical framework for classifying two-dimensional (2D) excitonic molecular aggregates based on an analysis of temperature dependent spectra. In addition to the monomer-aggregate absorption peak shift, which defines the conventional J- and H-aggregates, we incorporate the peak shift associated with increasing temperature as a measure to characterize the exciton band structure. First we show that there is a one-to-one correspondence between the monomer-aggregate and the T-dependent peak shifts for Kasha's well-established model of 1D aggregates, where J-aggregates exhibit further redshift upon increasing temperature and H-aggregates exhibit further blueshift. On the contrary, 2D aggregate structures are capable of supporting the two other combinations: blueshifting J-aggregates and redshifting H-aggregates, owing to their more complex exciton band structures. Secondly, using spectral lineshape theory, the T-dependent shift is associated with the relative abundance of states on each side of the bright state. We further establish that the density of states can be connected to the microscopic packing condition leading to these four classes of aggregates by separately considering the short and long-range contribution to the excitonic couplings. In particular the T-dependent shift is shown to be an unambiguous signature for the sign of net short-range couplings: Aggregates with net negative (positive) short-range couplings redshift (blueshift) with increasing temperature. Lastly, comparison with experiments shows that our theory can be utilized to quantitatively account for the observed but previously unexplained T-dependent absorption lineshapes. Thus, our work provides a firm ground for elucidating the structure-function relationships for molecular aggregates and is fully compatible with existing experimental and theoretical structure characterization tools.Comment: 29 pages, 4 figure

Extending the large molecule limit: The role of Fermi resonance in developing a quantum functional group

Polyatomic molecules equipped with optical cycling centers (OCCs), enabling continuous photon scattering during optical excitation, are exciting candidates for advancing quantum information science. However, as these molecules grow in size and complexity the interplay of complex vibronic couplings on optical cycling becomes a critical, but relatively unexplored consideration. Here, we present an extensive exploration of Fermi resonances in large OCC-containing molecules, surpassing the constraints of harmonic approximation. High-resolution dispersed laser-induced fluorescence and excitation spectroscopy reveal Fermi resonances in calcium and strontium phenoxides and their derivatives. This resonance manifests as vibrational coupling leading to intensity borrowing by combination bands near optically active harmonic bands. The resulting additional vibration-changing decays require more repumping lasers for effective optical cycling. To mitigate these effects, we explore altering vibrational energy level spacing through substitutions on the phenyl ring or changes in the OCC itself. While the complete elimination of vibrational coupling in complex molecules remains challenging, our findings underscore the potential for significant mitigation, opening new avenues for optimizing optical cycling in large polyatomic molecules.Comment: 8 pages, 4 figures, 1 table, SI (15 pages

Laser spectroscopy of aromatic molecules with optical cycling centers: strontium (I) phenoxides

We report the production and spectroscopic characterization of strontium (I) phenoxide ($\mathrm{SrOC}_6\mathrm{H}_5$, or SrOPh) and variants featuring electron-withdrawing groups designed to suppress vibrational excitation during spontaneous emission from the electronically excited state. Optical cycling closure of these species, which is the decoupling of vibrational state changes from spontaneous optical decay, is found by dispersed laser-induced fluorescence spectroscopy to be high, in accordance with theoretical predictions. A high-resolution, rotationally-resolved laser excitation spectrum is recorded for SrOPh, allowing the estimation of spectroscopic constants and identification of candidate optical cycling transitions for future work. The results confirm the promise of strontium phenoxides for laser cooling and quantum state detection at the single-molecule level.Comment: Erratum for a correction of an incorrect grant number for the NSF Center for Chemical Innovation, Phase I. The correct number should be CHE-222145

Achieving a quantum smart workforce

Interest in building dedicated Quantum Information Science and Engineering (QISE) education programs has greatly expanded in recent years. These programs are inherently convergent, complex, often resource intensive and likely require collaboration with a broad variety of stakeholders. In order to address this combination of challenges, we have captured ideas from many members in the community. This manuscript not only addresses policy makers and funding agencies (both public and private and from the regional to the international level) but also contains needs identified by industry leaders and discusses the difficulties inherent in creating an inclusive QISE curriculum. We report on the status of eighteen post-secondary education programs in QISE and provide guidance for building new programs. Lastly, we encourage the development of a comprehensive strategic plan for quantum education and workforce development as a means to make the most of the ongoing substantial investments being made in QISE.Comment: 18 pages, 2 figures, 1 tabl