Quantum mechanical solution to spectral lineshape in strongly-coupled atomnanocavity system

The strongly coupled system composed of atoms, molecules, molecule aggregates, and semiconductor quantum dots embedded within an optical microcavity/nanocavity with high quality factor and/or low modal volume has become an excellent platform to study cavity quantum electrodynamics (CQED), where a prominent quantum effect called Rabi splitting can occur due to strong interaction of cavity-mode single-photon with the two-level atomic states. In this paper, we build a new quantum model that can describe the optical response of the strongly-coupled system under the action of an external probing light and the spectral lineshape. We take the Hamiltonian for the strongly-coupled photon-atom system as the unperturbed Hamiltonian H 0 and the interaction Hamiltonian of the probe light upon the coupled-system quantum states as the perturbed Hamiltonian V. The theory yields a double Lorentzian lineshape for the permittivity function, which agrees well with experimental observation of Rabi splitting in terms of spectral splitting. This quantum theory will pave the way to construct a complete understanding for the microscopic strongly-coupled system that will become an important element for quantum information processing, nano-optical integrated circuits, and polariton chemistry.

Water Capture Mechanisms at Zeolitic Imidazolate Framework Interfaces

Water capture mechanisms of zeolitic imidazolate framework ZIF-90 are revealed by differentiating the water clustering and the center pore filling step, using vibrational sum-frequency generation spectroscopy (VSFG) at a one-micron spatial resolution and state-of-the-art molecular dynamics (MD) simulations. Through spectral lineshape comparison between VSFG and IR spectra, the relative humidity dependence of VSFG intensity, and MD simulations, based on MB-pol, we found water clustering and center pore filling happen nearly simultaneously within each pore, with water filling the other pores sequentially. The integration of nonlinear optics with MD simulations provides critical mechanistic insights into the pore filling mechanism and suggests that the relative strength of the hydrogen bonds governs the water uptake mechanisms. This molecular-level detailed mechanism can inform the rational optimization of metal-organic frameworks for water harvesting.

Anharmonic DFT Study of Near-Infrared Spectra of Caffeine: Vibrational Analysis of the Second Overtones and Ternary Combinations

Anharmonic quantum chemical calculations were employed to simulate and interpret a near-infrared (NIR) spectrum of caffeine. First and second overtones, as well as binary and ternary combination bands, were obtained, accurately reproducing the lineshape of the experimental spectrum in the region of 10,000–4000 cm−1 (1000–2500 nm). The calculations enabled performing a detailed analysis of NIR spectra of caffeine, including weak bands due to the second overtones and ternary combinations. A highly convoluted nature of NIR spectrum of caffeine was unveiled, with numerous overlapping bands found beneath the observed spectral lineshape. To properly reflect that intrinsic complexity, the band assignments were provided in the form of heat maps presenting the contributions to the NIR spectrum from various kinds of vibrational transitions. These contributions were also quantitatively assessed in terms of the integral intensities. It was found that the combination bands provide the decisively dominant contributions to the NIR spectrum of caffeine. The first overtones gain significant importance between 6500–5500 cm−1, while the second overtones are meaningful in the higher wavenumber regions, particularly in the 10,000–7000 cm−1 region. The obtained detailed band assignments enabled deep interpretation of the absorption regions of caffeine identified in the literature as meaningful for analytical applications of NIR spectroscopy focused on quantitative analysis of caffeine content in drugs and natural products.

The Einstein A and B coefficients

The Einstein A and B coefficients for atom–photon reactions are defined: they describe absorption, stimulated emission, and spontaneous emission. We calculate B and consequently find A by the Einstein trick. The procedure is validated by application of detailed balance. Separating out frequencies permits introduction of the spectral lineshape function (normalized line profile). A reformulation describes transitions involving single atomic states and single field modes. This points to a link with quantum electrodynamics.

Charge Carrier Relaxation in Colloidal FAPbI3 Nanostructures Using Global Analysis

We study the hot charge carrier relaxation process in weakly confined hybrid lead iodide perovskite colloidal nanostructures, FAPbI3 (FA = formaminidium), using femtosecond transient absorption (TA). We compare the conventional analysis method based on the extraction of the carrier temperature (Tc) by fitting the high-energy tail of the band-edge bleach with a global analysis method modeling the continuous evolution of the spectral lineshape in time using a simple sequential kinetic model. This practical approach results in a more accurate way to determine the charge carrier relaxation dynamics. At high excitation fluence (density of charge carriers above 1018 cm−3), the cooling time increases up to almost 1 ps in thick nanoplates (NPs) and cubic nanocrystals (NCs), indicating the hot phonon bottleneck effect. Furthermore, Auger heating resulting from the multi-charge carrier recombination process slows down the relaxation even further to tens and hundreds of picoseconds. These two processes could only be well disentangled by analyzing simultaneously the spectral lineshape and amplitude evolution.

Low-frequency (gigahertz to terahertz) depolarized Raman scattering off n-alkanes, cycloalkanes, and six-membered rings: a physical interpretation

Molecular liquids have long been known to undergo various distinct and simple intermolecular motions, from fast librations and cage rattling oscillations to slow orientational and translational diffusion. However, their resultant gigahertz to terahertz spectra are far from simple, appearing as broad shapeless bands that span many orders of magnitude of frequency making meaningful interpretation troublesome. <i>Ad hoc</i> spectral lineshape fitting has become a notoriously fine art in the field; a unified approach to handling such spectra is long overdue. Here we apply ultrafast optical Kerr-effect (OKE) spectroscopy to study the intermolecular dynamics of room temperature <i>n</i>-alkanes, cycloalkanes, and six-carbon rings, as well as liquid methane and propane. This work provides stress-tests and converges upon an experimentally robust model across simple molecular series and temperatures, providing a blueprint for the interpretation of the dynamics of van der Waals liquids. This will enable the interpretation of low frequency spectra of more complex liquids.

Low-frequency (gigahertz to terahertz) depolarized Raman scattering off n-alkanes, cycloalkanes, and six-membered rings: a physical interpretation

Molecular liquids have long been known to undergo various distinct and simple intermolecular motions, from fast librations and cage rattling oscillations to slow orientational and translational diffusion. However, their resultant gigahertz to terahertz spectra are far from simple, appearing as broad shapeless bands that span many orders of magnitude of frequency making meaningful interpretation troublesome. <i>Ad hoc</i> spectral lineshape fitting has become a notoriously fine art in the field; a unified approach to handling such spectra is long overdue. Here we apply ultrafast optical Kerr-effect (OKE) spectroscopy to study the intermolecular dynamics of room temperature <i>n</i>-alkanes, cycloalkanes, and six-carbon rings, as well as liquid methane and propane. This work provides stress-tests and converges upon an experimentally robust model across simple molecular series and temperatures, providing a blueprint for the interpretation of the dynamics of van der Waals liquids. This will enable the interpretation of low frequency spectra of more complex liquids.

Modeling multidimensional spectral lineshapes from first principles: application to water-solvated adenine

We theoretically describe spectral lineshape from first principles, providing insight into solvent–solute interactions in terms of static and dynamic disorder and how these shape experimental signals in linear and non-linear optical spectroscopies.