The complex refractive index is analyzed by measuring its scattering attenuation , group index , and group velocity dispersion (GVD) for 100 nm diameter silica nanoparticles dispersed in water. The experiments were performed for wavelengths between 410 nm and 930 nm. The experimental results were compared with different mixing models for the complex refractive index of colloidal suspensions. The group index linearly scaled with the volume fraction both in experiment and for all tested models. It was found that the GVD has a nonlinear dependence on volume fraction in agreement with the coupled dipole model of Parola et al. [J. Chem. Phys.141, 124902 (2014)JCPSA60021-960610.1063/1.4895961] The scattering attenuation is in good agreement with both the coupled dipole model and the low frequency quasi-crystalline approximation [J. Electromagn. Waves Appl.2, 757 (1988)JEWAE50920-507110.1163/156939388X00053] that take particle correlations into account. With an iterative fitting procedure of all the data based on both the coupled dipole model and the quasi-crystalline approximation, the refractive index, porosity, and size of the nanoparticles were determined. We determined that the coupled dipole model is in best agreement with the data.
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http://dx.doi.org/10.1364/JOSAA.510603 | DOI Listing |
J Chem Phys
January 2025
Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada.
Typical path integral Monte Carlo approaches use the primitive approximation to compute the probability density for a given path. In this work, we develop the pair discrete variable representation (pair-DVR) approach to study molecular rotations. The pair propagator, which was initially introduced to study superfluidity in condensed helium, is naturally well-suited for systems interacting with a pairwise potential.
View Article and Find Full Text PDFJ Chem Phys
January 2025
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, People's Republic of China.
Vibro-polaritons are hybrid light-matter states that arise from the strong coupling between the molecular vibrational transitions and the photons in an optical cavity. Developing theoretical and computational methods to describe and predict the unique properties of vibro-polaritons is of great significance for guiding the design of new materials and experiments. Here, we present the ab initio cavity Born-Oppenheimer density functional theory (CBO-DFT) and formulate the analytic energy gradient and Hessian as well as the nuclear and photonic derivatives of dipole and polarizability within the framework of CBO-DFT to efficiently calculate the harmonic vibrational frequencies, infrared absorption, and Raman scattering spectra of vibro-polaritons as well as to explore the critical points on the cavity potential energy surface.
View Article and Find Full Text PDFAdv Mater
January 2025
Center for Hybrid Organic-Inorganic Semiconductors for Energy, Golden, Colorado, 80401, USA.
Recent activity in the area of chiroptical phenomena has been focused on the connection between structural asymmetry, electron spin configuration and light/matter interactions in chiral semiconductors. In these systems, spin-splitting phenomena emerge due to inversion symmetry breaking and the presence of extended electronic states, yet the connection to chiroptical phenomena is lacking. Here, we develop an analytical effective mass model of chiral excitons, parameterized by density functional theory.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, State Key Laboratory of Polymer Physics and Chemistry, No.159 Renmin Street, 130022, Changchun, CHINA.
The multiple resonance thermally activated delayed fluorescence (MR-TADF) device has drawn great attention due to their outstanding efficiency and color purity. However, the efficiency of solution-processed MR-TADF devices is still far behind their vacuum-deposited counterparts, due to the uncontrollable horizontal emitting dipole orientation for emitters during solution process, resulting in low light out-coupling efficiency. Here, we proposed a new strategy namely electrostatic interaction between a dendritic host with high positive electrostatic potential (ESP) and dendritic emitter with multiple negative ESP sites, which could induce high horizontal dipole ratio (ΘII) up to 83.
View Article and Find Full Text PDFJ Chem Phys
January 2025
Department of Physics, University of Pretoria, 0002 Pretoria, South Africa.
Much can be learned about molecular aggregates by modeling their fluorescence-type spectra. In this study, we systematically describe the accuracy of various methods for simulating fluorescence-type linear spectra in a dimer system with a complex system-environment interaction, which serves as a model for various molecular aggregates, including most photosynthetic light-harvesting complexes (LHCs). We consider the approximate full cumulant expansion (FCE), complex time-dependent Redfield (ctR), time-independent Redfield, and modified Redfield methods and calculate their accuracy as a function of the site energy gap and coupling, excitonic energy gap, and dipole factor (i.
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