Spectroscopy Of Excited States Research Articles

Spectroscopy of excited quarkonium states in the light-front quark model

Abstract We have investigated the ground state ($1S$), radially excited states ($2S$) and ($3S$) along with the orbitally excited state ($1P$) for the heavy charmonia ($c \bar c$) and bottomonia ($b \bar b$) mesons in the light-front quark model (LFQM). The light-front wave functions have been successful in explaining various physical properties of meson states in the past, especially for the $1S$ and $2S$ states. However, studies regarding the radially excited state $3S$ and orbitally excited state $1P$ have hardly been pursued before. In this study, we take up these two excited states and investigate the electromagnetic form factors (EMFFs), charge radii, decay constants, parton distribution functions (PDFs) and the distribution amplitudes (DAs) for the quarkonia system. For the sake of completeness, we have also included the study of the ground and the first excited states of quarkonia mesons. We have also illustrated the 3D wave functions for the radially excited states in order to study their nodal structures. Content from this work may be used under the terms of the Creative Commons Attribution 3.0 licence. Any further distribution of this work must maintain attribution to the author(s) and the title of the work, journal citation and DOI. Article funded by SCOAP3 and published under licence by Chinese Physical Society and the Institute of High Energy Physics of the Chinese Academy of Science and the Institute of Modern Physics of the Chinese Academy of Sciences and IOP Publishing Ltd.

Controlled single-electron transfer enables time-resolved excited-state spectroscopy of individual molecules.

An increasing number of scanning-probe-based spectroscopic techniques provides access to diverse electronic properties of single molecules. Typically, these experiments can only study a subset of all electronic transitions, which obscures the unambiguous assignment of measured quantities to specific quantum transitions. Here we develop a single-molecule spectroscopy that enables the access to many quantum transitions of different types, including radiative, non-radiative and redox, that is, charge-related, transitions. Our method relies on controlled alternating single-charge attachment and detachment. For read-out, the spin states are mapped to charge states, which we can detect by atomic force microscopy. We can determine the relative energies of ground and excited states of an individual molecule and can prepare the molecule in defined excited states. After a proof-of-principle demonstration of the technique on pentacene, we apply it to PTCDA, the scanning-probe luminescence of which has been interpreted controversially. The method may be used to guide, understand and engineer tip-induced chemical reactions as well as phosphorescence and fluorescence of individual molecules.

Extending the Tavis-Cummings model for molecular ensembles-Exploring the effects of dipole self-energies and static dipole moments.

Strong coupling of organic molecules to the vacuum field of a nanoscale cavity can be used to modify their chemical and physical properties. We extend the Tavis-Cummings model for molecular ensembles and show that the often neglected interaction terms arising from the static dipole moment and the dipole self-energy are essential for a correct description of the light-matter interaction in polaritonic chemistry. On the basis of a full quantum description, we simulate the excited-state dynamics and spectroscopy of MgH+ molecules resonantly coupled to an optical cavity. We show that the inclusion of static dipole moments and the dipole self-energy is necessary to obtain a consistent model. We construct an efficient two-level system approach that reproduces the main features of the real molecular system and may be used to simulate larger molecular ensembles.

Enhanced intramolecular charge transfer and near-infrared fluorescence in 4-dimethylamino-chalcone analogues through extended conjugation: synthesis, photophysical properties, and theoretical modelling.

The distinctive characteristics of near-infrared fluorescent organic molecules render them indispensable across diverse applications, from energy harvesting to bioimaging and sensing technologies. In this work, we continue our investigation on the chalcone derivative, 4-dimethylamino-2'-hydroxychalcone (nDHC, n = 1; where n is the number of olefinic bonds), by expanding the number of central double bonds (n = 2 (2DHC) and n = 3 (3DHC)). Additionally, we also synthesized the structurally related chalcones lacking the OH group (DC, 2DC, 3DC) in order to obtain a comprehensive understanding of their effects on the intramolecular charge transfer (ICT). The results show remarkable bathochromic shifts in absorption and fluorescence peaks in solution as n increases. These shifts, 20 nm and 35 nm for absorption and 100 nm and 200 nm for fluorescence in 2DHC and 3DHC, respectively, signify enhanced ICT and a significant increase in the excited state's dipole moment. The presence of OH groups notably amplifies these shifts due to additional electron donation, influencing solute-solvent interactions in solution. Femtosecond fluorescence upconversion and transient absoprtion techniques unraveled distinct dynamics in these derivatives, exhibiting the dominance of vibrational cooling, solvation, and intramolecular motions, particularly in the larger conjugated systems 3DHC and 3DC. The observed changes in the femtosecond transinet absorption spectra suggest the existence of new active states in extended conjugation systems, indicating diverse intramolecular conformational states contributing to their relaxation dynamics. The results of this study provide invaluable insights into excited-state spectroscopy, offering a roadmap for tailoring chalcone derivatives for specific applications.

Chalcone derivatives' interaction with human serum albumin and cyclooxygenase-2.

Chalcone derivatives are an extremely valuable class of compounds, primarily due to the keto-ethylenic group, CO-CH[double bond, length as m-dash]CH-, they contain. Moreover, the presence of a reactive α,β-unsaturated carbonyl group confers upon them a broad range of pharmacological properties. Recent developments in heterocyclic chemistry have led to the synthesis of chalcone derivatives, which have been biologically investigated for their activity against certain diseases. In this study, we investigated the binding of new chalcone derivatives with COX-2 (cyclooxygenase-2) and HSA (Human Serum Albumin) using spectroscopic and molecular modeling studies. COX-2 is commonly found in cancer and plays a role in the production of prostaglandin E (2), which can help tumors grow by binding to receptors. HSA is the most abundant protein in blood plasma, and it transports various compounds, including hormones and fatty acids. The conformation of chalcone derivatives in the HSA complex system was established through fluorescence steady and excited state spectroscopy techniques and FTIR analyses. To gain a more comprehensive understanding, molecular docking, and dynamics were conducted on the target protein (COX-2) and transport protein (HSA). In addition, we conducted density-functional theory (DFT) and single-point DFT to understand intermolecular interaction in protein active sites.

Diphenyl ditelluride assisted synthesis of noble metal-based silver-telluride 2D organometallic nanofibers with enhanced aggregation-induced emission (AIE) after oleylamine treatment

Silver-Telluride 2D organometallic nanofibers (NFs), using diphenyl ditelluride (DPDT) as a precursor, were synthesized. The synthesis was carried out by reacting DPDT with AgNO3 in acetonitrile at room temperature (RT) under an inert atmosphere. The resulting material was fully characterized using various techniques, including UV-VIS-NIR spectroscopy, steady-state and excited-state fluorescence spectroscopy, IR-FTIR-ATR spectroscopy, HR-ESI MS spectrometry, high-resolution transmission electron microscopy (HRTEM), BF-STEM or HAADF-STEM, confocal fluorescence microscopy images and conductivity measurements. Initially, the nanofibers were almost non-emissive. However, a remarkable modification was observed after treating the nanofibers with oleylamine under ultrasound treatment. This methodology induced an aggregation emission effect (AIE) in the solution and in the solid state, resulting in the formation of a highly red emissive fluorescent nanomaterial. This research provides valuable insights for developing new fluorescent materials with potential applications in various optical fields.

Microsecond Isomer at the N=20 Island of Shape Inversion Observed at FRIB.

Excited-state spectroscopy from the first experiment at the Facility for Rare Isotope Beams (FRIB) is reported. A 24(2)-μs isomer was observed with the FRIB Decay Station initiator (FDSi) through a cascade of 224- and 401-keV γ rays in coincidence with ^{32}Na nuclei. This is the only known microsecond isomer (1 μs≤T_{1/2}<1 ms) in the region. This nucleus is at the heart of the N=20 island of shape inversion and is at the crossroads of the spherical shell-model, deformed shell-model, and abinitio theories. It can be represented as the coupling of a proton hole and neutron particle to ^{32}Mg, ^{32}Mg+π^{-1}+ν^{+1}. This odd-odd coupling and isomer formation provides a sensitive measure of the underlying shape degrees of freedom of ^{32}Mg, where the onset of spherical-to-deformed shape inversion begins with a low-lying deformed 2^{+} state at 885keV and a low-lying shape-coexisting 0_{2}^{+} state at 1058keV. We suggest two possible explanations for the 625-keV isomer in ^{32}Na: a 6^{-} spherical shape isomer that decays by E2 or a 0^{+} deformed spin isomer that decays by M2. The present results and calculations are most consistent with the latter, indicating that the low-lying states are dominated by deformation.

Rapid-Scan Resonant Two-Dimensional Impulsive Stimulated Raman Spectroscopy of Excited States.

Photochemical reactions occur in the electronically excited state, which is effectively represented by a multidimensional potential energy surface (PES) with a vast degree of freedom of nuclear coordinates. The elucidation of the intricate shape of the PES constitutes an important topic in the field of photochemistry and has long been studied both experimentally and theoretically. Recently, fully time-domain resonant two-dimensional Raman spectroscopy has emerged as a potentially powerful tool to provide unique information about the coupling between vibrational manifolds in the excited state. However, the wide application of this technique has been significantly hampered by the technical difficulties associated with experimental implementation and remains challenging. Herein, we demonstrate time-domain resonant two-dimensional impulsive stimulated Raman spectroscopy (2D-ISRS) of excited states using sub-10 fs pulses based on the rapid scan of the time delay, which facilitates the efficient collection of time-domain vibrational signals with high sensitivity. As a proof-of-principle experiment, we performed 2D-ISRS of 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene) in solution. Through 2D Fourier transformation of the high-quality time-time oscillatory signal, we obtained a 2D frequency-frequency correlation map of excited-state TIPS-pentacene in the broad frequency window of 0-2000 cm-1. The data clearly resolve a number of cross peaks that signify the correlations among excited-state vibrational manifolds. The high capability of the rapid-scan-based 2D-ISRS spectrometer presented in this study enables the systematic investigation of various photochemical reaction systems, thereby further promoting the understanding and applications of this new multidimensional spectroscopy.

Efficient pathway to NaCs ground state molecules

We present a study of two-photon pathways for the transfer of NaCs molecules to their rovibrational ground state. Starting from NaCs Feshbach molecules, we perform bound-bound excited state spectroscopy in the wavelength range from 900 nm to 940 nm, covering more than 30 vibrational states of the , , and electronic states. Analyzing the rotational substructure, we identify the highly mixed state as an efficient bridge for stimulated Raman adiabatic passage. We demonstrate transfer into the NaCs ground state with an efficiency of up to 88(4)%. Highly efficient transfer is critical for the realization of many-body quantum phases of strongly dipolar NaCs molecules and high fidelity detection of single molecules, for example, in spin physics experiments in optical lattices and quantum information experiments in optical tweezer arrays.

Effect of electron-donating groups on the excited state spectroscopy and dynamics of 2′-hydroxychalcone derivatives

We investigated the effect of different electron-donating groups on the intramolecular charge transfer (ICT) process in three hydroxychalcone derivatives. More efficient ICT was observed when replacing N(Me)2 by pyrrolidine due to less hydrogen bonding with solvent. Adding NH2 to the structure caused more planarity that was detected as a larger fluorescence quantum yield and narrower fluorescence peak. This was confirmed by femtosecond transient absorption in which the intramolecular twisting process, observed in the other derivatives, was absent in the presence of NH2. This work should be a useful step toward understanding and tailoring the excited state spectroscopy of chalcone derivatives.

Excited state spectroscopy and spin splitting in single layer MoS2 quantum dots.

Semiconducting transition metal dichalcogenides (TMDCs) are very promising materials for quantum dots and spin-qubit implementation. Reliable operation of spin qubits requires the knowledge of the Landé g-factor, which can be measured by exploiting the discrete energy spectrum on a quantum dot. However, the quantum dots realized in TMDCs are yet to reach the required control and quality for reliable measurement of excited state spectroscopy and the g-factor, particularly in atomically thin layers. Quantum dot sizes reported in TMDCs so far are not small enough to observe discrete energy levels on them. Here, we report on electron transport through discrete energy levels of quantum dots in a single layer MoS2 isolated from its environment using a dual gate geometry. The quantum dot energy levels are separated by a few (5-6) meV such that the ground state and the first excited state transitions are clearly visible, thanks to the low contact resistance of ∼700 Ω and relatively low gate voltages. This well-resolved energy separation allowed us to accurately measure the ground state g-factor of ∼5 in MoS2 quantum dots. We observed a spin-filling sequence in our quantum dots under a perpendicular magnetic field. Such a system offers an excellent testbed to measure the key parameters for evaluation and implementation of spin-valley qubits in TMDCs, thus accelerating the development of quantum systems in two-dimensional semiconducting TMDCs.

Excited-state resonance Raman spectroscopy probes the sequential two-photon excitation mechanism of a photochromic molecular switch.

Some diarylethene molecular switches have a low quantum yield for cycloreversion when excited by a single photon, but react more efficiently following sequential two-photon excitation. The increase in reaction efficiency depends on both the relative time delay and the wavelength of the second photon. This paper examines the wavelength-dependent mechanism for sequential excitation using excited-state resonance Raman spectroscopy to probe the ultrafast (sub-30fs) dynamics on the upper electronic state following secondary excitation. The approach uses femtosecond stimulated Raman scattering (FSRS) to measure the time-gated, excited-state resonance Raman spectrum in resonance with two different excited-state absorption bands. The relative intensities of the Raman bands reveal the initial dynamics in the higher-lying states, Sn, by providing information on the relative gradients of the potential energy surfaces that are accessed via secondary excitation. The excited-state resonance Raman spectra reveal specific modes that become enhanced depending on the Raman excitation wavelength, 750 or 400nm. Many of the modes that become enhanced in the 750nm FSRS spectrum are assigned as vibrational motions localized on the central cyclohexadiene ring. Many of the modes that become enhanced in the 400nm FSRS spectrum are assigned as motions along the conjugated backbone and peripheral phenyl rings. These observations are consistent with earlier measurements that showed higher efficiency following secondary excitation into the lower excited-state absorption band and illustrate a powerful new way to probe the ultrafast dynamics of higher-lying excited states immediately following sequential two-photon excitation.

Ab initio study of the low-lying states of PS molecule

Quantum chemical calculations on the low-lying electronic states of PS correlating with the lowest four dissociation limits are performed by utilizing the internally contracted multireference configuration interaction method (icMRCI) with all-electron Gaussian basis sets. The potential energy curves (PECs) and spectroscopic constants of low-lying bound states are computed. It is of interest to compare the spectroscopic constants of low-lying bound states for the PS molecule with experimental and theoretical results. The detailed information on the properties of the emission 22Π1/2-X12Π1/2, 22Π3/2-X22Π3/2, 12Σ−1/2-X12Π3/2 and 12Σ−1/2-X12Π1/2 bands of PS system, including the transition dipole moments (TDMs), permanent dipole moments (PDMs), Franck-Condon factors (FCFs) and radiative lifetimes, has been identified. We first calculated the f value and radiative lifetime of this radical. Whether the C state is 12Σ− or 12Δ is discussed. According to the calculation results, it is confirmed that the experimental C state is redistributed to 12Δ. Our study should be valuable for further experimental works understanding the spectroscopy and dynamics of the electronic excited states for PS.

MRCI+Q study on SnF+ including spin-orbit coupling

The low-lying electronic states correlated to the lowest dissociation limit of SnF+ are investigated using the multireference configuration interaction method including the core-valence correlations and the spin-orbit coupling effects. Based on the computed potential energy curves of the Λ–S and Ω states, the spectroscopic constants of the bound states of SnF+ are determined. The Λ–S components of the five Ω states (X1Σ+0+, a3Π0+, a3Π0-, a3Π1 and a3Π2) are shown as a function of bond length considering the avoided crossing rules. The a3Π-X1Σ+ transition properties have been reported in detail. Our study is expected to be helpful for understanding the spectroscopy and dynamics of electronic excited states of the SnF+ ion.

Two novel “release-on-demand” fluorescent biosensors for probing UV-induced DNA damage induced in single stranded and double stranded DNA: Comparative study

Light in the UVC spectral region damages both single-strand (ssDNA) and double-strand DNA (dsDNA), and contributes to the formation of mutagenic photoproducts. In-vivo studies show greater damage for ssDNA compared to dsDNA. However, excited-state spectroscopy shows that dsDNA has longer excited-state lifetime than ssDNA, which increases the probability of damage for dsDNA. However, lack of a direct comparison of in-vitro ssDNA and dsDNA damage rates precludes the development of a model that elucidates the molecular factors responsible for damage. In this work, two novel sensitive “release-on-demand” biosensors are developed for the selective probing of DNA-damage and comparing the rate of DNA damage in ssDNA and dsDNA. The two biosensors involve the use of EvaGreen and Hoechst dyes for the sensitive probing of DNA-damage. The results show that ssDNA is damaged at a faster rate than dsDNA in the presence of UVC light (200–295 nm). Furthermore, we examined the effect of G/C composition on the damage rate for mostly A/T ssDNA and dsDNA oligonucleotides. Our results show that DNA damage rates are highly dependent on the fraction of guanines in the sequence, but that in-vitro dsDNA always exhibits an overall slower rate of damage compared to ssDNA, essentially independent of sequence.

Excited-State Spectroscopy of Spin Defects in Hexagonal Boron Nitride.

A negatively charged boron vacancy (VB-) color center in hexagonal boron nitride has recently been proposed as a promising quantum sensor due to its excellent properties. However, the spin level structure of the VB- color center is still unclear, especially for the excited state. Here we measured and confirmed the excited-state spin transitions of VB- using an optically detected magnetic resonance (ODMR) technique. The zero-field splitting of the excited state is 2.06 GHz, the transverse splitting is 93.1 MHz, and the g factor is 2.04. Moreover, negative peaks in fluorescence intensity and ODMR contrast at the level anticrossing point were observed, and they further confirmed that the spin transitions we measured came from the excited state. Our work deepens the understanding of the excited-state structure of VB- and promotes VB--based quantum sensing applications.

Excited State Spectroscopy of Boron Vacancy Defects in Hexagonal Boron Nitride Using Time-Resolved Optically Detected Magnetic Resonance.

We report optically detected magnetic resonance (ODMR) measurements of an ensemble of spin-1 negatively charged boron vacancies in hexagonal boron nitride. The photoluminescence decay rates are spin-dependent, with intersystem crossing rates of 1.02 ns-1 and 2.03 ns-1 for the mS = 0 and mS = ±1 states, respectively. Time gating the photoluminescence enhances the ODMR contrast by discriminating between different decay rates. This is particularly effective for detecting the spin of the optically excited state, where a zero-field splitting of |DES| = 2.09 GHz is measured. The magnetic field dependence of the photoluminescence exhibits dips corresponding to the ground (GSLAC) and excited-state (ESLAC) anticrossings and additional anticrossings due to coupling with nearby spin-1/2 parasitic impurities. Comparison to a model suggests that the anticrossings are mediated by the interaction with nuclear spins and allows an estimate of the ratio of the singlet to triplet spin-dependent relaxation rates of κ0/κ1 = 0.34.

Excited-State Switching in Rhenium(I) Bipyridyl Complexes with Donor-Donor and Donor-Acceptor Substituents.

The optical properties of two Re(CO)3(bpy)Cl complexes in which the bpy is substituted with two donor (triphenylamine, TPA, ReTPA2) as well as both donor (TPA) and acceptor (benzothiadiazole, BTD, ReTPA-BTD) groups are presented. For ReTPA2 the absorption spectra show intense intraligand charge-transfer (ILCT) bands at 460 nm with small solvatochromic behavior; for ReTPA-BTD the ILCT transitions are weaker. These transitions are assigned as TPA → bpy transitions as supported by resonance Raman data and TDDFT calculations. The excited-state spectroscopy shows the presence of two emissive states for both complexes. The intensity of these emission signals is modulated by solvent. Time-resolved infrared spectroscopy definitively assigns the excited states present in CH2Cl2 to be MLCT in nature, and in MeCN the excited states are ILCT in nature. DFT calculations indicated this switching with solvent is governed by access to states controlled by spin-orbit coupling, which is sufficiently different in the two solvents, allowing to select out each of the charge-transfer states.

Microwave-Resonator-Detected Excited-State Spectroscopy of a Double Quantum Dot

As an application in circuit quantum electrodynamics (cQED) coupled systems, superconducting resonators play an important role in high-sensitivity measurements in a superconductingsemiconductor hybrid architecture. Taking advantage of a high-impedance NbTiN resonator, we perform excited-state spectroscopy on a GaAs double quantum dot (DQD) by applying voltage pulses to one gate electrode. The pulse train modulates the DQD energy detuning and gives rise to charge state transitions at zero detuning. Benefiting from the outstanding sensitivity of the resonator, we distinguish different spin-state transitions in the energy spectrum according to the Pauli exclusion principle. Furthermore, we experimentally study how the interdot tunneling rate modifies the resonator response. The experimental results are consistent with the simulated spectra based on our model.

Spin Readout of a CMOS Quantum Dot by Gate Reflectometry and Spin-Dependent Tunneling

Silicon spin qubits are promising candidates for realizing large-scale quantum processors, benefitting from a magnetically quiet host material and the prospects of leveraging the mature silicon device fabrication industry. We report the measurement of an electron spin in a singly occupied gate-defined quantum dot, fabricated using CMOS-compatible processes at the 300-mm wafer scale. For readout, we employ spin-dependent tunneling combined with a low-footprint single-lead quantum-dot charge sensor, measured using rf gate reflectometry. We demonstrate spin readout in two devices using this technique, obtaining valley splittings in the range 0.5–0.7 meV using excited-state spectroscopy, and measure a maximum electron-spin relaxation time (T1) of 9±3 s at 1 T. These long lifetimes indicate the silicon-nanowire geometry and fabrication processes employed here show a great deal of promise for qubit devices, while the spin-readout method demonstrated here is well suited to a variety of scalable architectures.4 MoreReceived 16 May 2020Revised 12 October 2020Accepted 24 February 2021DOI:https://doi.org/10.1103/PRXQuantum.2.010353Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI.Published by the American Physical SocietyPhysics Subject Headings (PhySH)Research AreasQuantum computationPhysical SystemsQuantum dotsCondensed Matter, Materials & Applied Physics