Far infrared electronic and vibronic transitions of Nd super 3 super plus in the tysonite lanthanide fluorides.
Far IR electronic and vibronic transitions in single crystals of Nd ions in tysonite lanthanide fluorides
Lowndes, R. P.↗
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Vibronic Transitions of Hexagonal Rare-Earth Trichlorides. I
Phonon spectrum of neodymium trichloride crystal lattice determined from polarized vibronic transition spectra and Zeeman effect of trivalent Pr and Nd impurity ions
VIBRATIONAL SPECTRUM↗
Vibronic transitions of hexagonal rare-earth trichlorides. II.
Absorption spectra of rare earth trichlorides with trivalent Pr, observing vibronic transitions noting assignments of phonon branches
LATTICE VIBRATION↗
Analysis of vibronic transitions in titanium doped sapphire using the temperature of the fluorescence spectra
An analysis of the fluorescence spectra of titanium-doped sapphire crystals for temperatures ranging from 13 to 578 K is made. Zero- and multiphoton assisted electronic transitions are observed at temperatures below 125 K. Zero-phonon transition energies agree with previously reported measured and predicted values. Photon-assisted transitions suggest that two principle modes of lattice vibrations with energies of 220 and 260/cm are coupled to the electronic 2T2g state. A single phonon energy of 173/cm is observed to couple to the 2Eg electronic state. Crossover energy is estimated to be about 11,800/cm using a simple harmonic approximation. Lineshape analysis is performed. The fluorescence lifetime as measured to be a constant 3.9 microsec below 150 k decreasing to 2.9 microsec at 300 K.
Byvik, C. E.↗
Terahertz Circular Dichroism Spectroscopy of Molecular Assemblies and Nanostructures
Chemical, physical, biological and materials engineering disciplines use a variety of chiroptical spectroscopies to probe geometrical and optical asymmetry in molecules and particles. Electronic (ECD) and vibrational (VCD) circular dichroism are the most common of these techniques and collectively enable the studies of electronic and vibronic transitions with energies between 0.1 and 5.0 eV. The vibrational states with characteristic energies in the range of 0.001–0.01 eV carry valuable information about concerted intermolecular motions in molecules and crystals involving multiple atoms. These vibronic transitions located in the terahertz (THz) part of the spectrum become increasingly more important for the chemistry, physics, and biology of complex molecules and materials However, the methodology and hardware of THz circular dichroism (TCD) are much less developed than the chiroptical spectroscopies for ultraviolet, visible, near- and mid infrared photons. In this report we provide theoretical foundations, practical implementations, comparative assessments, and exemplary applications of TCD spectroscopy. We show that the sign, intensity, and position of TCD peaks are highly sensitive to the three-dimensional structure and long-range organization of molecular crystals, which offer unique capabilities to study (bio) molecules, their crystals, and nanoscale assemblies and apply the novel data processing methodologies. TCD also offers a convenient toolbox to identify new physical phenomena, such as chiral phonons and their propagation in nanostructured matter. We also discuss the major challenges, emerging opportunities and promising research directions, including broad investigation of chiral phonons observed in chiral (nano) crystals and emerging machine learning methodologies for TCD in biological and nanoscale structures. Ubiquity of low-frequency vibrations with rotational components in biomolecular structures, combined with sharpness of peaks in TCD spectra, enables a variety of technological translations.
36 MATERIALS SCIENCE↗
Multimode two-dimensional vibronic spectroscopy. II. Simulating and extracting vibronic coupling parameters from polarization-selective spectra
We report experimental demonstrations of polarization-selection two-dimensional Vibrational-Electronic (2D VE) and 2D Electronic-Vibrational (2D EV) spectroscopies aim to map the magnitudes and spatial orientations of coupled electronic and vibrational coordinates in complex systems. The realization of that goal depends on our ability to connect spectroscopic observables with molecular structural parameters. In this paper, we use a model Hamiltonian consisting of two anharmonically coupled vibrational modes in electronic ground and excited states with linear and bilinear vibronic coupling terms to simulate polarization-selective 2D EV and 2D VE spectra. We discuss the relationships between the linear vibronic coupling and two-dimensional Huang–Rhys parameters and between the bilinear vibronic coupling term and Duschinsky mixing. We develop a description of the vibronic transition dipoles and explore how the Hamiltonian parameters and non-Condon effects impact their amplitudes and orientations. Using simulated polarization-selective 2D EV and 2D VE spectra, we show how 2D peak positions, amplitudes, and anisotropy can be used to measure parameters of the vibronic Hamiltonian and non-Condon effects. This paper, along with the first in the series, provides the reader with a detailed description of reading, simulating, and analyzing multimode, polarization-selective 2D EV and 2D VE spectra with an emphasis on extracting vibronic coupling parameters from complex spectra.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Coupling, lifetimes, and “strong coupling” maps for single molecules at plasmonic interfaces
The interaction between excited states of a molecule and excited states of a metal nanostructure (e.g., plasmons) leads to hybrid states with modified optical properties. When plasmon resonance is swept through molecular transition frequency, an avoided crossing may be observed, which is often regarded as a signature of strong coupling between plasmons and molecules. Such strong coupling is expected to be realized when 2|$\langle$U$\rangle$|/ℏΓ > 1, where $\langle$U$\rangle$ and Γ are the molecule–plasmon coupling and the spectral width of the optical transition, respectively. Because both $\langle$U$\rangle$ and Γ strongly increase with decreasing distance between a molecule and a plasmonic structure, it is not obvious that this condition can be satisfied for any molecule–metal surface distance. Here, in this work, we investigate the behavior of $\langle$U$\rangle$ and Γ for several geometries. Surprisingly, we find that if the only contributions to Γ are lifetime broadenings associated with the radiative and nonradiative relaxation of a single molecular vibronic transition, including effects on molecular radiative and nonradiative lifetimes induced by the metal, the criterion 2|$\langle$U$\rangle$|/ℏΓ > 1 is easily satisfied by many configurations irrespective of the metal–molecule distance. This implies that the Rabi splitting can be observed in such structures if other sources of broadening are suppressed. Additionally, when the molecule–metal surface distance is varied keeping all other molecular and metal parameters constant, this behavior is mitigated due to the spectral shift associated with the same molecule–plasmon interaction, making the observation of Rabi splitting more challenging.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Cavity Ring Down Spectroscopy of Cold Neutral Phenanthrene and Phenanthridine in Supersonic Jets
Here we study the effect of nitrogen insertion on the electronic spectra of polycyclic aromatic hydrocarbon (PAH) molecules measured under laboratory conditions that are relevant for comparison with astronomical data. We examine the case of the substitution of carbon atoms by nitrogen atoms in the benzenoid skeleton of phenanthrene (C 14 H 10 ), a prototype non-compact PAH. The vibronic transitions of the 2 1 A 1 (S 1 )←X 1 A 1 (S 0 ) electronic absorption band system of neutral phenanthrene (C 14 H 10 ) and phenanthridine (C 13 H 9 N) molecules seeded in a supersonic free jet expansion of argon gas are measured in the 315-345 nm region using the cavity ring down spectroscopy (CRDS) technique. Additional measurements of the absorption spectra of the phenanthrene, phenanthridine, and 1,10-phenanthroline (C 12 H 8 N 2 ) molecules isolated in 10-K solid argon matrices are also presented. The results obtained confirm that laboratory spectra of cold, isolated molecules obtained under astrophysically relevant conditions are required for a direct, unambiguous comparison with astronomical observations as well as for the understanding of the physical evolution of the interstellar medium.
Absorption band↗
Ab initio study and assignment of electronic states in molecular RaCl
Radium compounds have attracted recently considerable attention due to both development of experimental techniques for high-precision laser spectroscopy of molecules with short-lived nuclei and amenability of certain radium compounds for direct cooling with lasers. Currently, radium monofluoride (RaF) is one of the most studied molecules among the radium compounds, both theoretically and recently also experimentally. Complementary studies of further diatomic radium derivatives are highly desired to assess the influence of chemical substitution on diverse molecular parameters, especially on those connected with laser cooling, such as vibronic transition probabilities, and those related to violations of fundamental symmetries. Here in this article high-precision ab initio studies of electronic and vibronic levels of diatomic radium monochloride (RaCl) are presented. Recently developed approaches for treating electronic correlation with Fock-space coupled cluster methods are applied for this purpose. Theoretical results are compared to an early experimental investigation by Lagerqvist and used to partially reassign the experimentally observed transitions and molecular electronic levels of RaCl. Effective constants of $\mathscr{P}$-odd hyperfine interaction W a and $\mathscr{P, T}$-odd scalar-pseudoscalar nucleus-electron interaction Ws in the ground electronic state of RaCl are estimated within the framework of a quasirelativistic Zeroth-Order Regular Approximation approach and compared to parameters in RaF and RaOH.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Analysis of vibronic coupling in a 4f molecular magnet with FIRMS
Vibronic coupling, the interaction between molecular vibrations and electronic states, is a fundamental effect that profoundly affects chemical processes. In the case of molecular magnetic materials, vibronic, or spin-phonon, coupling leads to magnetic relaxation, which equates to loss of magnetic memory and loss of phase coherence in molecular magnets and qubits, respectively. The study of vibronic coupling is challenging, and most experimental evidence is indirect. Here we employ far-infrared magnetospectroscopy to directly probe vibronic transitions in [Yb(trensal)] (where H 3 trensal = 2,2,2-tris(salicylideneimino)trimethylamine). We find intense signals near electronic states, which we show arise due to an “envelope effect” in the vibronic coupling Hamiltonian, which we calculate fully ab initio to simulate the spectra. We subsequently show that vibronic coupling is strongest for vibrational modes that simultaneously distort the first coordination sphere and break the C 3 symmetry of the molecule. With this knowledge, vibrational modes could be identified and engineered to shift their energy towards or away from particular electronic states to alter their impact. Hence, these findings provide new insights towards developing general guidelines for the control of vibronic coupling in molecules.
36 MATERIALS SCIENCE↗
Explicit environmental and vibronic effects in simulations of linear and nonlinear optical spectroscopy
Accurately simulating the linear and nonlinear electronic spectra of condensed phase systems and accounting for all physical phenomena contributing to spectral line shapes presents a significant challenge. Vibronic transitions can be captured through a harmonic model generated from the normal modes of a chromophore, but it is challenging to also include the effects of specific chromophore–environment interactions within such a model. We work to overcome this limitation by combining approaches to account for both explicit environment interactions and vibronic couplings for simulating both linear and nonlinear optical spectra. We present and show results for three approaches of varying computational cost for combining ensemble sampling of chromophore–environment configurations with Franck–Condon line shapes for simulating linear spectra. We present two analogous approaches for nonlinear spectra. Simulated absorption spectra and two-dimensional electronic spectra (2DES) are presented for the Nile red chromophore in different solvent environments. Furthermore, employing an average Franck–Condon or 2DES line shape appears to be a promising method for simulating linear and nonlinear spectroscopy for a chromophore in the condensed phase.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
IR pumped third-harmonic generation and sum-frequency generation in diatomic molecules
The potential efficiency of using nonlinear up-conversion techniques for the high efficiency type lasers (CO,CO2, and chemical) is assessed. Results indicate that: the small pump photon energy necessitates the use of molecular media for conversion if resonance enhancement is to be used and that molecular systems present several problems. These difficulties include: their levels are complex; their transition probabilities are often unknown; and the oscillator strengths among vibrational levels in the ground electronic state of a molecule are much smaller than those among electronic states of an atom, thus limiting the magnitude of nonlinear interactions. It is shown that this problem can be eliminated by making use of vibronic transitions which, being primarily electronic transitions have much larger matrix elements and efficient conversion can be achieved with molecular systems.
She, C. Y.↗
Vibronic and Environmental Effects in Simulations of Optical Spectroscopy
Including both environmental and vibronic effects is important for accurate simulation of optical spectra, but combining these effects remains computationally challenging. We outline two approaches that consider both the explicit atomistic environment and the vibronic transitions. Both phenomena are responsible for spectral shapes in linear spectroscopy and the electronic evolution measured in nonlinear spectroscopy. The first approach utilizes snapshots of chromophore-environment configurations for which chromophore normal modes are determined. We outline various approximations for this static approach that assumes harmonic potentials and ignores dynamic system-environment coupling. The second approach obtains excitation energies for a series of time-correlated snapshots. This dynamic approach relies on the accurate truncation of the cumulant expansion but treats the dynamics of the chromophore and the environment on equal footing. Both approaches show significant potential for making strides toward more accurate optical spectroscopy simulations of complex condensed phase systems.
Chemistry↗
Infrared-pumped third-harmonic and sum-frequency generation in diatomic molecules
Using molecular hydrogen as a model system, we present a calculation which demonstrates the feasibility of efficient third-harmonic and sum-frequency generation of IR laser radiation by diatomic molecular gases. A conversion efficiency of 10% without phase matching is achievable with a modest laser intensity of about 20 MW/sq cm. In addition to a two-photon resonance, the efficient conversion depends on a mechanism which makes use of virtual vibronic transitions exclusively. Possible methods for phase matching are also suggested.
She, C. Y.↗
Two-photon excitation of nitric oxide fluorescence as a temperature indicator in unsteady gas-dynamic processes
A laser induced fluorescence technique, suitable for measuring fluctuating temperatures in cold turbulent flows containing very low concentrations of nitric oxide is described. Temperatures below 300 K may be resolved with signal to noise ratios greater than 50 to 1 using high peak power, tunable dye lasers. The method relies on the two photon excitation of selected ro-vibronic transitions. The analysis includes the effects of fluorescence quenching and shows the technique to be effective at all densities below ambient. Signal to noise ratio estimates are based on a preliminary measurement of the two photon absorptivity for a selected rotational transition in the NO gamma (0,0) band.
Mckenzie, R. L.↗
Single-pulse gas thermometry at low temperatures using two-photon laser-induced fluorescence in NO/N2 mixtures
A technique suitable for measuring fluctuating temperatures in supersonic turbulent flows of N2 seeded with NO has been demonstrated in a nonflowing cell. The method relies on the two photon excitation of two selected ro-vibronic transitions in the NO gamma (alpha 2 sigma+, v prime = 0 yields ch1zp1, v double prime = 0).
Gross, K. P.↗
Single-pulse gas thermometry at low temperatures using two-photon laser-induced fluorescence in NO-N2 mixtures
A technique suitable for measuring fluctuating temperatures in supersonic turbulent flows of N2 seeded with NO has been demonstrated in a nonflowing cell. The method relies on the two photon excitation of two selected ro-vibronic transitions in the NO gamma (alpha 2 sigma+, v prime = 0 yields ch1zp1, v double prime = 0). Previously announced in STAR as N83-20079
Gross, K. P.↗