Accidental Resonances Research Articles

Quantum State-Dependent Fragmentation Dynamics of D2S Molecules Following Excitation at Wavelengths ∼ 129.1 and ∼ 139.1 nm.

The first high-resolution translational spectroscopy studies of D atom photoproducts following excitation to the Rydberg states of D2S are reported. Excitation at wavelengths λ ∼ 139.1 nm reveals an unusual 'inverse' isotope effect; the 1B1(3da1←2b1) Rydberg state of D2S predissociates much faster than its counterpart in H2S. This is attributed to accidental near resonance with a vibrationally excited level of a lower-lying, more heavily predissociated Rydberg state of D2S that boosts the probability of nonadiabatic coupling to the dissociation continuum with 1A″ symmetry. Excitation at λ ∼ 129.1 nm populates the 1B1(4da1←2b1) Rydberg state, which predissociates more slowly and allows the study of ways in which the branching into different quantum states of the SD products varies with the choice of parent excited (JKaKc) level. All excited parent levels yield both ground (X) and electronically excited (A) state SD fragments. The former are distributed over a wide range of rovibrational (v″, N″) levels, while the population of levels with low v' and high N' is favored in the latter. These trends reflect the topographies of the dissociative 1A″ (1A') potential energy surfaces that correlate with the respective dissociation limits. Rotational motion about the b-inertial axis in the excited state molecule increases the relative yield of SD(A) products, consistent with dissociation by rotationally (Coriolis-) induced coupling from the photoexcited Rydberg level to the 1A' continuum. Molecules excited to the rotationless (JKaKc = 000) level also yield some SD(A) products, however, confirming the operation of a rival fragmentation pathway wherein photoexcited molecules decay by initial vibronic coupling to the 1A″ continuum, with subsequent nonadiabatic coupling between the 1A″ and 1A' continua enabling access to the D + SD(A) limit.

Edge treatment for spurious mode suppression in thin-film lithium niobate resonators

Thin-film lithium niobate is an attractive material for RF acoustic devices because of its high electromechanical coupling. However, due to the large coupling and the high anisotropy, thin-film lithium niobate resonators are prone to accidental resonances called spurious modes. These modes compromise the frequency response of the resonators, limiting their use in filter and oscillator applications. In this work, we present a novel method of spurious mode suppression through a special edge treatment etch process. Two thin-film lithium niobate resonators were fabricated, one with smooth sidewalls and one with the edge treatment. It was found that the edge-treated resonators show a weaker spurious mode response. This is potentially a new way to mitigate spurious resonances, a major issue in lithium niobate Lamb wave devices.

Fermi Resonance and the Quantum Mechanical Basis of Global Warming

Although the scientific principles of anthropogenic climate change are well-established, existing calculations of the warming effect of carbon dioxide rely on spectral absorption databases, which obscures the physical foundations of the climate problem. Here, we show how CO2 radiative forcing can be expressed via a first-principles description of the molecule’s key vibrational-rotational transitions. Our analysis elucidates the dependence of carbon dioxide’s effectiveness as a greenhouse gas on the Fermi resonance between the symmetric stretch mode ν 1 and bending mode ν 2. It is remarkable that an apparently accidental quantum resonance in an otherwise ordinary three-atom molecule has had such a large impact on our planet’s climate over geologic time, and will also help determine its future warming due to human activity. In addition to providing a simple explanation of CO2 radiative forcing on Earth, our results may have implications for understanding radiation and climate on other planets.

Fe ii fluorescence in main-sequence K-dwarfs

ABSTRACT Main-sequence K-dwarfs possess strong emission in the form of the H i Ly α line. There is a close coincidence between the energy corresponding to the transitions H i 1s-2p and Fe ii (5D)5s 4D5/2–(5D)5p 4D5/2. Singly ionized iron has been confirmed being pumped by photo-excitation by accidental resonance (PAR) in planetary nebulae, symbiotic stars, K-giants, and active galactic nebulae. I investigate in this work whether PAR can occur in the atmospheres of main-sequence K-dwarfs, which do not possess the large extended atmospheres of the late-type K-giants. Specifically a search for possible Fe ii fluorescence lines is conducted. For the case when I can confirm PAR, I estimate the total flux leaving the stars in the form of Fe ii fluorescence. I search for emission lines from the Fe ii (5D)5p 4D5/2 level. Since those of these lines with the largest branching fractions correspond to lines at wavelengths covered by the Far Ultraviolet Spectroscopic Explorer (FUSE) satellite, a search for archival FUSE spectra from K-dwarfs within 20 ly from the sun is conducted. I retrieve and analyse FUSE spectra for four of these K-dwarfs. In each case I can confirm PAR, I fit the H i Ly α line in Hubble Space Telescope spectra recorded with the Space Telescope Imaging Spectrograph, in order to estimate the efficiency of the PAR mechanism. I can now confirm Fe ii fluorescence in the two closest K-dwarfs, Alpha Centauri B, and Epsilon Eridani. The total power leaving as Fe ii fluorescence are 4.9 × 1017 and 1.30 × 1018 W respectively.

Wavepacket dynamics of the excited (S1) state of 2,5-difluoroaniline by accidental resonance with the Rydberg states.

Coherent nuclear wavepacket behavior obtained by time-resolved spectroscopy is a good choice to capture the real-time evolution of molecular configuration. Using femtosecond time-resolved photoelectron imaging, we investigate the real-time evolution of the vibrational wavepacket of 2,5-difluoroaniline following the coherent excitation of an out-of-plane vibrational mode in the S1 state at 289.8nm. Probed by an accidental resonance with the Rydberg states, the periodic oscillations with the frequency of 99cm-1 are observed from the photoelectron kinetic energy (PKE) distributions, corresponding to the energy difference between the out-of-plane mode X1 0 of C-F bond and the band origin. Moreover, phase reversal of π rad between 0.66-0.75 and 1.00-1.08eV is also observed in the PKE region. Combined with the scan of the potential energy surface in the ground cationic D0 state, the observed two ionization channels corresponding to different phases are attributed to the periodic geometry changes between the planar and the non-planar structures when the coherent wavepacket evolves from the initial vertical Franck-Condon region toward the global minimum of the S1 potential energy surface.

Intersystem Crossing of 2-Methlypyrazine Studied by Femtosecond Photoelectron Imaging.

2-methylpyrazine was excited to the high vibrational dynamics of the S1 state with 260 nm femtosecond laser light, and the evolution of the excited state was probed with 400 nm light. Because it was unstable, the S1 state decayed via intersystem crossing to the triplet state T1, and it may have decayed to the ground state S0 via internal conversion. S1-to-T1 intersystem crossing was observed by combining time-resolved mass spectrometry and time-resolved photoelectron spectroscopy. The crossover time scale was 23 ps. Rydberg states were identified, and the photoelectron spectral and angular distributions indicated accidental resonances of the S1 and T1 states with the 3s and 3p Rydberg states, respectively, during ionization.

Room‐Temperature Multi‐Beam, Multi‐Wavelength Bound States in the Continuum Laser

AbstractA highly polarized multi‐beam, multi‐wavelength III–V semiconductor laser based on the concept of bound states in the continuum (BIC) is reported. By utilizing destructive interferences of guided‐mode resonances in an active slab supported by a grating structure, both symmetry‐protected and accidental BIC resonances are created within the gain spectrum of InGaP multi‐quantum wells and achieve lasing in these modes simultaneously. Well‐defined multi‐lasing beams at different wavelengths (i.e., 664.9 nm @ 0.2°, 656.4 nm @ 2.5°, 646.4 nm @ 5.1°, and 636.7 nm @ 7.6°) with transverse magnetic polarization can be obtained in a single device operating at room temperature. Furthermore, the lasing wavelengths can be precisely tuned by changing the grating parameters. The laser concept presented in this paper is promising for applications in highly directional surface‐emitting lasers, optical communications, bio‐sensing, and signal processing.

Infrared spectra of 16O3 in the 900 - 5600 cm−1 range revisited: Empirical corrections to the S&MPO and HITRAN2020 line lists

The paper presents the results of the analysis of experimental FTS infrared vibration-rotation spectra of 16O3 ozone isotopologue recorded in Reims University in the range from 900 to 5600 cm−1, which was used for the current version of the S&MPO database and web-accessible information system (http://smpo.iao.ru; http://smpo.univ-reims.fr). The majority of the reported data is related to the accurate determination of line positions. New parameters of effective Hamiltonian (EH) models for three polyads of vibrational states {(001), (100)}, {(011), (110)} and {(002), (101), (030), (200)} obtained from accurate fits of observed spectra in 900 – 2200 cm−1 range, have also been described. Further, at the higher wavenumber range 2700 – 5600 cm−1, various perturbations in the observed spectra due to accidental ro-vibrational resonances and which have been at the root of a lack of accuracy in certain regions of the previously published line lists were identified. We have applied empirical corrections to line positions and to corresponding energy levels in cases where the EH models did not provide the target accuracy of 10−3 cm−1 given of more complex polyad structures, which in turn allowed the use of corrected energy levels to compute improved line positions for the hot bands. In terms of line intensities, we publish here the effective dipole moment parameters and the line lists with empirically-determined absolute intensities for the ν1/ν3 dyad which are consistent with recent ab initio calculations for the strongest bands. For the higher wavenumber range, the empirical corrections are applied for relative intensities of some series of individual transitions in order to improve the simulation of observed spectra. A significant part of the reported data is included in the 2020 release of the HITRAN database.

Coherent Exciton Dynamics in Ensembles of Size-Dispersed CdSe Quantum Dot Dimers Probed via Ultrafast Spectroscopy: A Quantum Computational Study

Interdot coherent excitonic dynamics in nanometric colloidal CdSe quantum dots (QD) dimers lead to interdot charge migration and energy transfer. We show by electronic quantum dynamical simulations that the interdot coherent response to ultrashort fs laser pulses can be characterized by pump-probe transient absorption spectroscopy in spite of the inevitable inherent size dispersion of colloidal QDs. The latter, leading to a broadening of the excitonic bands, induce accidental resonances that actually increase the efficiency of the interdot coupling. The optical electronic response is computed by solving the time-dependent Schrodinger equation including the interaction with the oscillating electric field of the pulses for an ensemble of dimers that differ by their size. The excitonic Hamiltonian of each dimer is parameterized by the QD size and interdot distance, using an effective mass approximation. Local and charge transfer excitons are included in the dimer basis set. By tailoring the QD size, the excitonic bands can be tuned to overlap and thus favor interdot coupling. Computed pump-probe transient absorption maps averaged over the ensemble show that the coherence of excitons in QD dimers that lead to interdot charge migration can survive size disorder and could be observed in fs pump-probe, four-wave mixing, or covariance spectroscopy.

Comparing many-body localization lengths via nonperturbative construction of local integrals of motion

Many-body localization (MBL), characterized by the absence of thermalization and the violation of conventional thermodynamics, has elicited much interest both as a fundamental physical phenomenon and for practical applications in quantum information. A phenomenological model, which describes the system using a complete set of local integrals of motion (LIOMs), provides a powerful tool to understand MBL, but can be usually only computed approximately. Here we explicitly compute a complete set of LIOMs with a non-perturbative approach, by maximizing the overlap between LIOMs and physical spin operators in real space. The set of LIOMs satisfies the desired exponential decay of weight of LIOMs in real-space. This LIOM construction enables a direct mapping from the real space Hamiltonian to the phenomenological model and thus enables studying the localized Hamiltonian and the system dynamics. We can thus study and compare the localization lengths extracted from the LIOM weights, their interactions, and dephasing dynamics, revealing interesting aspects of many-body localization. Our scheme is immune to accidental resonances and can be applied even at phase transition point, providing a novel tool to study the microscopic features of the phenomenological model of MBL.

Femtosecond real-time probing of the excited-state intramolecular proton transfer reaction in methyl salicylate.

The excited-state intramolecular proton transfer (ESIPT) process and subsequent electronic relaxation dynamics in methyl salicylate have been investigated using femtosecond time-resolved ion yield spectroscopy combined with time-resolved photoelectron imaging. Excitation with a tunable pump pulse populates the keto tautomer in the first excited electronic state S1(ππ*). As a hydrogen atom transfers from the phenolic group to the carbonyl group within 100 fs, the molecular geometry changes gradually, leading to a variation in the electronic photoionization channel. By virtue of the accidental resonance with some intermediate Rydberg states, the time-dependent photoelectron spectra provide a direct mapping of the ESIPT reaction from the initially populated keto tautomer to the proton-transferred enol tautomer. Subsequently, the population around the enol configuration undergoes intramolecular vibrational redistribution on a subpicosecond time scale, followed by internal conversion to the ground state with a wavelength-dependent lifetime in the picosecond range. Furthermore, the excitation energies of several Rydberg states in methyl salicylate are determined experimentally.

Striking Isotopologue-Dependent Photodissociation Dynamics of Water Molecules: The Signature of an Accidental Resonance.

Investigations of the photofragmentation patterns of both light and heavy water at the state-to-state level are a prerequisite for any thorough understanding of chemical processing and isotope heterogeneity in the interstellar medium. Here we reveal dynamical features of the dissociation of water molecules following excitation to the C̃(010) state using a tunable vacuum ultraviolet source in combination with the high-resolution H(D)-atom Rydberg tagging time-of-flight technique. The action spectra for forming H(D) atoms and the OH(OD) product state distributions resulting from excitation to the C̃(010) states of H2O and D2O both show striking differences, which are attributable to the effects of an isotopologue-specific accidental resonance. Such accidental-resonance-induced state mixing may contribute to the D/H isotope heterogeneity in the solar system. The present study provides an excellent example of competitive state-to-state nonadiabatic decay pathways involving at least five electronic states.

Dinitrogen Coupling to a Terpyridine-Molybdenum Chromophore Is Switched on by Fermi Resonance

Summary The traditional view of a chemical change is inherently local and classical, and such a change relies on a mix of thermodynamic and kinetic parameters to control reactivity. Often, the thermodynamic stability of chemical bonds necessitates significant energy input for activation. One fundamental question is potentially transformative: can quantum mechanics enable selective bond activation? A possible approach involves strategic input of energy to reaction-specific vibrational levels. Toward this goal, our work describes the coupling of vibrational motions in a terpyridine-molybdenum complex hosting a nonreactive substrate—dinitrogen. Ultrafast coherence spectroscopies revealed a Fermi-resonance coupling mechanism connecting in-plane breathing motion of the light-harvesting terpyridines with the stretching motion of the spatially disparate dinitrogen bridge. Notably, the coupling is significantly enhanced in the photoexcited state. This Fermi resonance indicates an energy conduit that drives the two motions in sync and thereby amplifies vibrational energy exchange. Achieving selective bond activation by bridging vibrations could present a quantum-inspired design principle in synthetic chemistry.

Identifying and Modulating Accidental Fermi Resonance: 2D IR and DFT Study of 4-Azido-l-phenylalanine.

Azido-modified aromatic amino acids have been used as powerful infrared probes for the site-specific detection of proteins because of their large transition dipole strengths. However, their complex absorption profiles hinder their wider application. The complicated absorption profile of 4-azido-l-phenylalanine (pN3Phe) in isopropanol was identified and attributed to accidental Fermi resonances (FRs) by means of linear absorption and two-dimensional (2D) IR spectroscopies. The 2D IR results of pN3Phe in H2O and D2O further demonstrate that the FRs are distinctively influenced by the hydrogen-bonding environment. Under the influence of FRs, the 2D IR shape is distorted, indicating that pN3Phe is not a good candidate in spectral diffusion studies. A three-state model and first-principles calculations were used to analyze unperturbed energy levels, unveiling the FRs between the azide asymmetric stretching band and two combination bands. Furthermore, the anharmonic frequency calculations suggest that changing the substitution position of the azide group from para to meta can effectively modulate the FRs by reducing the coupling strength. This work provides a deep understanding of the FRs in azido-modified aromatic amino acids and sheds light on the modification of azido-modified amino acids for wider utilization as vibrational probes.

Real-time observation of cascaded electronic relaxation processes in p-Fluorotoluene

Ultrafast electronic relaxation processes following two photoexcitation of 400nm in p-Fluorotoluene (pFT) have been investigated utilizing time-resolved photoelectron imaging coupled with time-resolved mass spectroscopy. Cascaded electronic relaxation processes started from the electronically excited S2 state are directly imaged in real time and well characterized by two distinct time constants of ~85±10fs and 2.4±0.3ps. The rapid component corresponds to the lifetime of the initially excited S2 state, including the structure relaxation from the Franck-Condon region to the conical intersection of S2/S1 and the subsequent internal conversion to the highly excited S1 state. While, the slower relaxation constant is attributed to the further internal conversion to the high levels of S0 from the secondarily populated S1 locating in the channel three region. Moreover, dynamical differences with benzene and toluene of analogous structures, including, specifically, the slightly slower relaxation rate of S2 and the evidently faster decay of S1, are also presented and tentatively interpreted as the substituent effects. In addition, photoelectron kinetic energy and angular distributions reveal the feature of accidental resonances with low-lying Rydberg states (the 3p, 4s and 4p states) during the multi-photon ionization process, providing totally unexpected but very interesting information for pFT.

Imaging multiphoton ionization and dissociation of rotationally warm CO via the B+Σ1 and EΠ1 electronic states.

Pathways for formation of C+ and O+ ions when applying (2 + 1) resonance enhanced multiphoton ionization (REMPI) of CO via the B1Σ+ and E1Π electronic states are characterized with the velocity map imaging technique. By employing an unskimmed pulsed valve, it was possible to obtain sharp images for a wide range of initial CO J-states. Most of the atomic ion production pathways could be assigned as one- or two-photon dissociation of a series of vibrational levels of the CO+ X2Σ+ and A2Π states. Large enhancements in dissociation of particular CO+ vibrational states in these progressions could be accurately assigned to accidental resonances of the REMPI laser with CO+ X2Σ+-B2Σ+ transitions.

An accidental resonance mediated predissociation pathway of water molecules excited to the electronic C[combining tilde] state.

The predissociation dynamics of water molecules in the electronic C[combining tilde] state were studied using the time-resolved photoelectron imaging method. Both vibrationless and vibrationally excited states in the C[combining tilde] electronic state were studied, with an emphasis on the vibrational excitation effects on the predissociation dynamics of the C[combining tilde] state. Besides the well-known rotationally and non-rotationally mediated predissociation pathways (Proc. Natl. Acad. Sci. U. S. A., 2008, 105, 19148), an accidental resonance mediated predissociation pathway for the first bending mode excited state in the C[combining tilde] electronic state of H2O is revealed, providing an excellent example of competition between non-adiabatic decay pathways involving at least five electronic states.

Broadening parameters of the H2O–He collisional system for astrophysical applications

The water vapor line broadening γ and shift δ coefficients in the ν1+ν2, ν2+ν3, ν1+ν3, 2ν3, 2ν1, 2ν2+ν3, and ν1+2ν2 vibrational bands were obtained from the analysis of the H2O–He absorption spectra, recorded in the region from 5000 to 7500cm−1 with the spectral resolution of 0.01cm−1 using a Bruker IFS 125HR FTIR spectrometer. The vibrational bands 2ν3 and ν1+2ν2 were investigated for the first time. The calculations of γ and δ were performed in the framework of the semi-classical method. The rotational contributions as well as the contributions connected with the accidental resonances were taken into account in the used H2O–He interaction potential. The analytical representation of the broadening coefficients γ at planetary temperatures was introduced and discussed.

Equilibrium and Nonequilibrium Features in a Warm He+H2O Microwave Plasma at Atmospheric Pressure

A microwave surface-wave discharge at atmospheric pressure was generated using a He/H2O mixture and studied by optical emission spectroscopy. The main plasma parameters were determined based on the analysis of the spectra when partial thermodynamic equilibrium could be verified. The analysis showed that the system can be classified as a warm plasma with an average gas temperature of $1.7\times 10^{3}$ K, an axially averaged electron density of $2.4\times 10^{13}$ cm $^{-3}$ , and a semiempirically estimated average electron temperature of $15\times 10^{3}$ K. The experimental evidence and theoretical arguments suggest that the main source of ionization in this plasma is the electronic impact ionization of water molecules. An abnormal intensity in the O I [3p ${\,}^{3}\text{P}_{0,1,2}] \to [3{\mathrm{ s}}{\,}^{3}\text{S}^{\circ }_{1}$ ] transition was observed, revealing an overpopulation of the 3p $^{3}\text{P}_{0,1,2}$ states. This observation—which may be explored to obtain stimulated emission—was explained as an effect of the reabsorption of photons generated in the plasma by the H I Ly $_{\beta }$ emission by oxygen atoms (O $\text{I}{\,}^{3}\text{P}_{\mathrm {\mathbf {2}}} \to 3\text{d}{\,}^{3}{\rm D {^{\circ }}}_{1,2,3}$ transition), an effect generally known as photoexcitation by accidental resonance.

The CW-CRDS spectra of the 16O/18O isotopologues of ozone between 5930 and 6340 cm−1—Part 1: 16O16O18O

The first investigation of the very sensitive CW-Cavity Ring Down Spectra (noise equivalent absorption αmin≈1×10−10cm−1) of 18O enriched ozone isotopologues is reported. The ozone generation from 18O enriched oxygen molecules resulted in six isotopic species. The contributions of the 16O16O18O/16O18O16O and of the 18O18O16O/18O16O18O isotopomers were separated using two partial pressures of 16O2/18O2 mixtures. In the 5930–6340cm−1 range, the four dominant bands of 16O16O18O were vibrationally assigned as 2ν1+2ν2+3ν3_1, 2ν2+5ν3, 5ν1+ν3 and 2ν1+2ν2+3ν3_2. They correspond to the highest vibration excitations observed so far in an asymmetric CS ozone isotopologue. The rovibrational spectra for 18O enriched CS ozone species show specific features related to the nuclear spin statistics and to simultaneous symmetry allowed Coriolis and anharmonic accidental resonances, which are discussed. Altogether for the four new bands, 2155 rovibrational transitions were assigned up to Jmax=32. Observed line positions were fitted with rms deviations ranging from 0.005 to 0.01cm−1 using effective Hamiltonian models accounting for dark state perturbations. The derived band centers and rotational constants are in good agreement with new theoretical calculations from the molecular potential function. The corresponding line lists are provided as Supplementary Material.