Excited Electronic States Research Articles

Unusual Hydrophobic Property of Blue Fluorescent Amino Acid 4-Cyanotryptophan.

It is a common belief that the negative heat capacity change (ΔCp) associated with protein folding, which is a manifestation of the hydrophobic effect, results from a decrease in the solvent accessible hydrophobic surface area. Herein, we investigate the conformational energy landscape and dynamics of a tetrapeptide composed of two glycine and two 4-cyanotryptophan residues using time-resolved fluorescence spectroscopy, molecular dynamics simulations, and density functional theory calculations and find that, contrary to this expectation, the hydrophobic association of two 4-cyanotryptophan side chains leads to a positive ΔCp (approximately 543 J K-1 mol-1). Furthermore, we find that promoting one of the 4-cyanotryptophans to its excited electronic state strengthens this self-association. Taken together, our results provide not only insight into how modification of an aromatic amino acid can affect its hydrophobicity but also a potential strategy for designing protein sequences that can fold (unfold) at high (low) temperatures.

Probing the Electronic Manifold of MgCl with Millimeter-Wave Spectroscopy and Theory: (3)2Σ+ and (4)2Σ+ States.

The millimeter/submillimeter spectrum of magnesium chloride (MgCl) has been observed in two new electronic excited states, (3)2Σ+ and (4)2Σ+, using direct absorption methods. The molecule was synthesized in a mixture of Cl2, argon, and magnesium vapor. For the (3)2Σ+ state, multiple rotational transitions were measured in the v = 0 level for all six isotopologues (24Mg35Cl, 24Mg37Cl, 25Mg35Cl, 25Mg37Cl, 26Mg35Cl, and 26Mg37Cl), as well as up to v = 13 for 24Mg35Cl. For the (4)2Σ+ state, less intense spectra were recorded for 24Mg35Cl (v = 0-2). Equilibrium rotational parameters were determined for both states for 24Mg35Cl, as well as rotational constants and 25Mg hyperfine parameters for the other isotopologues. A perturbation was observed between rotational levels of the two states due to an avoided crossing. Computations were also carried out at the CASPT2 and MRCISD+Q levels, and the resulting bond lengths for (3)2Σ+ and (4)2Σ+ states agree well with the experimental values of re = 2.536 and 2.361 Å. The computations show that the (3)2Σ+ state has a double-well potential; however, the state behaves as a single well with unperturbed vibrational levels up to v = 13 due to nonadiabatic interactions with the (4)2Σ+ state.

Nonadiabatic Excited-State Molecular Dynamics with an Explicit Solvent: NEXMD-SANDER Implementation.

In this article, the nonadiabatic excited-state Molecular dynamics (NEXMD) package is linked with the SANDER package, provided by AMBERTOOLS. The combination of these software packages enables the simulation of photoinduced dynamics of large multichromophoric conjugated molecules involving several coupled electronic excited states embedded in an explicit solvent by using the quantum/mechanics/molecular mechanics (QM/MM) methodology. The fewest switches surface hopping algorithm, as implemented in NEXMD, is used to account for quantum transitions among the adiabatic excited-state simulations of the photoexcitation and subsequent nonadiabatic electronic transitions, and vibrational energy relaxation of a substituted polyphenylenevinylene oligomer (PPV3-NO2) in vacuum and methanol as an explicit solvent has been used as a test case. The impact of including specific solvent molecules in the QM region is also analyzed. Our NEXMD-SANDER QM/MM implementation provides a useful computational tool to simulate qualitatively solvent-dependent effects, like electron transfer, stabilization of charge-separated excited states, and the role of solvent reorganization in the molecular optical properties, observed in solution-based spectroscopic experiments.

Enabling Visible Light Sensitization of YbIII, NdIII and ErIII in Dimeric LnIII/GaIII Metallacrowns through Functionalization with RuII Complexes for NIR‐II Multiplex Imaging

AbstractMultiplex imaging in the second near‐infrared window (NIR‐II, 1000–1700 nm) provides exciting opportunities for more precise understanding of biological processes and more accurate diagnosis of diseases by enabling real‐time acquisition of images with improved contrast and spatial resolution in deeper tissues. Today, the number of imaging agents suitable for this modality remains very scarce. In this work, we have synthesized and fully characterized, including theoretical calculations, a series of dimeric LnIII/GaIII metallacrowns bearing RuII polypyridyl complexes, LnRu‐3 (Ln=YIII, YbIII, NdIII, ErIII). Relaxed structures of YRu‐3 in the ground and the excited electronic states have been calculated using dispersion‐corrected density functional theory methods. Detailed photophysical studies of LnRu‐3 have demonstrated that characteristic emission signals of YbIII, NdIII and ErIII in the NIR‐II range can be sensitized upon excitation in the visible range through RuII‐centered metal‐to‐ligand charge transfer (MLCT) states. We have also showed that these NIR‐II signals are unambiguously detected in an imaging experiment using capillaries and biological tissue‐mimicking phantoms. This work opens unprecedented perspectives for NIR‐II multiplex imaging using LnIII‐based molecular compounds.

Magnetic Circular Dichroism of Oxide Films: Study of Electronic, Magnetic and Charge States

Semiconductor materials based on ZnO and RE3+MnO3 oxides are considered as potential candidates for spintronics. This article presents the methodology and results of studying the effect of magnetic circular dichroism for Zn1-xCoxO, Zn1-x-yCoxAlyO and RE1-x 3+Ax 2+MnO3 film structures in the visible radiation range. It has been shown that the magnetic circular dichroism behavior of the manganite films reflects not only the magnetic, but also the charge component of the material. This indicates the possibility of studying the magnetic and transport characteristics of the films using the magnetic circular dichroism spectroscopy. Since the magnetic circular dichroism effect also directly probes the ground and excited electronic states of the film, it has been obtained data that update calculated parameters for describing the manganites band structure. In the case of the Zn1-xCoxO and Zn1-x-yCoxAlyO films, the magnetic circular dichroism spectroscopy acts as a tool for detecting Co nanoparticles in the solid solution matrix of ZnO:Co and ZnO:(Co+Al).

Theoretical Insights into Ultrafast Separation of Photogenerated Charges in a Push-Pull Polarized Molecular Triad.

Herein, we propose a purely-organic donor-acceptor (D-A) molecular triad, with a light-absorbing polarized molecular wire (PMW) used as a central linkage, as a proof of concept for the possible future applications of the D-PMW-A arrangement in molecular photovoltaics. This work builds upon our earlier study on the PMW unit itself, which proved to be highly promising for the ultrafast photogeneration of free charge carriers. Quantum-chemical calculations performed for the D-PMW-A triad at a semi-empirical level of theory reveal a large electric dipole moment of the system, and show strong charge-transfer (CT) character of its lowest-energy excited electronic states, including the S1, which favours efficient dissociation of an exciton initially formed upon the absorption of light. The confirmation for this effect was found with nonadiabatic molecular dynamics simulations, revealing an ultrafast relaxation from higher, bright excited states to S1, completed on a subpicosecond timescale. The architecture of the proposed molecular triad enables its electronic coupling to the surrounding environment through chemical bonds, or noncovalent stacking interactions, which might open way for synthesis of a new class of D-PMW-A efficient molecular organic photovoltaic materials.

Vibrational assignments and energy analyses of 3,4-difluorophenylacetylene using resonance-enhanced multiphoton ionization and slow electron velocity-map imaging techniques

Here, we report spectroscopic investigations of 3,4-difluorophenylacetylene applying two-color resonant two-photon ionization (2C-R2PI) and slow electron velocity-map imaging (SEVI) techniques. With the assistance of density functional theory (DFT) calculations, vibrational modes of the S0 neutral ground state, S1 first electronic excited state, and D0 cationic ground state were assigned. The adiabatic excitation energy of the S1 ← S0 electronic transition was determined to be 35639 ± 5 cm−1 from the resonance-enhanced multiphoton ionization (REMPI) spectroscopy. Additionally, the adiabatic ionization potential was found to be 72398 ± 5 cm−1 based on the SEVI spectra.

The Hidden Mechanism: Excited-State Proton-Electron Pair Transfer in Metal Nanocluster Emission.

Comprehending the underlying factors that govern photoluminescence (PL) in metal nanoclusters (NCs) under physiological conditions remains a highly intriguing and unresolved challenge, particularly for their biomedical applications. In this study, we evaluate the critical role of excited-state proton-coupled electron transfer in the emission of metal NCs. Our findings demonstrate that hydronium ion (H3O+) binding can trigger a nonlinear, pH-dependent excited-state concerted electron proton transfer (CEPT) reaction. This involves simultaneous electron transfer from the Au(0) core to the Au(I)-ATT (ATT denotes 6-aza-2-thiothymidine) surface and proton transfer from H3O+ to the ATT ligand in a single step, greatly promoting vibrations and rotations of the Au(I)-ATT surface, resulting in substantial PL quenching of Au10(ATT)6 NCs. Further analyses show that the unique CEPT dynamics are strongly influenced by the opposing effects of increased reorganization energy and a larger pre-exponential factor on the electron transfer rate. Moreover, the proposed excited-state CEPT process is found to be prevalent in core-shell relaxation metal NCs, such as Au25(SR)18 (SR denotes thiolate) NCs, and serves as an important factor in limiting their PL emission. By simply controlling the pKa of the ligands, the emission performance of Au25(SR)18 can be easily regulated in physiological environments.

Photocatalytic H2O2 production over boron-doped g-C3N4 containing coordinatively unsaturated FeOOH sites and CoOx clusters

Graphitic carbon nitride (g-C3N4) has gained increasing attention in artificial photosynthesis of H2O2, yet its performance is hindered by sluggish oxygen reduction reaction (ORR) kinetics and short excited-state electron lifetimes. Here we show a B-doped g-C3N4 (BCN) tailored with coordinatively unsaturated FeOOH and CoOx clusters for H2O2 photosynthesis from water and oxygen without sacrificial agents. The optimal material delivers a 30-fold activity enhancement compared with g-C3N4 under visible light, with a solar-to-chemical conversion efficiency of 0.75%, ranking among the forefront of reported g-C3N4-based photocatalysts. Additionally, an electron transfer efficiency reaches 34.1% for the oxygen reduction reaction as revealed by in situ microsecond transient absorption spectroscopy. Experimental and theoretical results reveal that CoOx initiates hole–water oxidation and prolongs the electron lifetime, whereas FeOOH accepts electrons and promotes oxygen activation. Intriguingly, the key to the direct one-step two-electron reaction pathway for H2O2 production lies in coordinatively unsaturated FeOOH to adjust the Pauling-type adsorption configuration of O2 to stabilize peroxide species and restrain the formation of superoxide radicals.

Elevating Nonlinear Optical Response Through D-Electron Modulation in Metal-Organic Frameworks.

Electronic structure and excited state behavior is of pronounced influence on regulation of nonlinear optical (NLO) response. Herein, a serials of transition metal ions bearing different d-electron numbers were in situ coordinated within porphyrinic metal-organic frameworks (MOFs), creating NLO-responsive M-metal (metal=Fe, Co, Ni, Cu, and Zn) frameworks. It demonstrated that the NLO properties can be optimized with the increased occupancy of the d-shell, which enhances the degree of delocalization. Specifically, the full-filled (d10) electron configuration of Zn2+ stabilizes the electronic structure, combination with π-π* local excitation character of M-Zn, promoting charge transfer process and resulting in outstanding NLO properties. Moreover, parameters related to the nonlinear process (β, n2, Imχ(3), Reχ(3) and χ(3)) of M-Zn are calculated to be higher than those of other materials, consistent with theoretical calculations. This work paves the way for NLO modulation based on electronic analysis and provides a promising approach for constructing high-performance NLO materials.

Monovalent nickel ion as ionization probe in matrix-assisted laser desorption/ionization mass spectrometry

We have developed NiO/HM20, a matrix composed of NiO nanoparticles (NiO) loaded on zeolite surface, for matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS). By photoexcitation, monovalent nickel ion (Ni+) was dominantly observed with high intensity. The mechanism of Ni+ production was studied by picosecond time-resolved emission spectroscopy. By loading NiO on the zeolite surface, a new relaxation pathway to other electronic excited states was observed, which increased the lifetime of electron–hole pairs and promoted the reduction of nickel. The long-lived charge-separated electronic excited state corresponding to the large polarization of NiO was confirmed by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction spectroscopy (XRD). The correlation between the Auger parameter related to the polarization energy and the Ni+ peak intensity in the mass spectrum was confirmed. By applying the developed NiO/HM20 matrix to the MS measurement of small molecules, we found that molecules were ionized through complex formation with Ni+ using the coordination of lone electron pairs or π-electrons in the analyte molecules.

Engineering Rydberg-pair interactions in divalent atoms with hyperfine-split ionization thresholds

Quantum information processing with neutral atoms relies on Rydberg excitation for entanglement generation. While the use of heavy divalent or open-shell elements, such as strontium or ytterbium, has benefits due to their optically active core and a variety of possible qubit encodings, their Rydberg structure is generally complex. For some isotopes in particular, hyperfine interactions are relevant even for highly excited electronic states. We employ multichannel quantum defect theory to infer the Rydberg structure of isotopes with nonzero nuclear spin and perform nonperturbative Rydberg-pair interaction calculations. We find that due to the high level density and sensitivities to external fields, experimental parameters must be precisely controlled. Specifically in Sr87, we study an intrinsic Förster resonance, unique to divalent atoms with hyperfine-split thresholds, which simultaneously provides line stability with respect to external field fluctuations and enhanced long-range interactions. Additionally, we provide parameters for pair states that can be effectively described by single-channel Rydberg series. The explored pair states provide exciting opportunities for applications in the blockade regime, as well as for more exotic long-range interactions such as largely flat, distance-independent potentials. Published by the American Physical Society 2024

Ancillary Ligand-Promoted Charge Transfer in Bis-indole Pyridine Ligand-Based Nickel Complexes.

There is growing demand for the utilization of first-row transition metal complexes in light-driven processes instead of their conventional noble metal counterparts due to the greater sustainability of first-row transition metal complexes. However, their major drawback is the ultrafast lifetime of the electronic excited states of these first-row transition metal complexes, particularly those of d8 square-planar systems such as Ni(II) complexes, wherein low-lying metal-centered (MC) states provide the deactivation pathway. To increase the excited-state lifetime and broaden their applications, it is important to develop sterically bulky, strong field ligands with low-lying π* orbitals and a highly σ-donating nature to augment the energy of MC states. The current strategy relies on synthetically carbene-based ligands, which are substitutionally cumbersome and act as σ-donors only. In this work, we introduce a bis-indole pyridine (H2BIP) ligand framework, whose dianionic congener (BIP) demonstrates the ability to form stronger covalent bonds with a Ni(II) center compared to neutral donors like carbene and its effect on the complex to produce a less distorted excited-state structure. When conjoined with ancillary ligands such as pyridine or lutidine, the BIP ligand orchestrates the formation of low-energy 3CT states, which decay in ∼40 ps.

Tracking the Electron Density Changes in Excited States: A Computational Study of Pyrazine.

The development of X-ray free-electron lasers has enabled ultrafast X-ray diffraction (XRD) experiments, which are capable of resolving electronic and vibrational transitions and structural changes in molecules or capturing molecular movies. While time-resolved XRD has attracted more attention, the extraction of information from signals is challenging and requires theoretical support. In this work, we combined X-ray scattering theory and a trajectory surface hopping approach to resolve dynamical changes in the electronic structure of photoexcited molecules by studying the time evolution of electron density changes between electronic excited states and ground state. Using the pyrazine molecule as an example, we show that key features of reaction pathways can be identified, enabling the capture of structural changes associated with electronic transitions for a photoexcited molecule.

Intramolecular benzene excimer formation in 13,14-diphenyldibenzo[b,j][4,7]phenanthroline.

13,14-diphenyldibenzo[b,j][4,7]phenanthroline (DBP3) in various solvents was studied by time-resolved fluorescence and fs transient absorption (fs-TA) spectroscopy. An intramolecular benzene excimer is demonstrated to form within DBP3; it exhibits strong redshifted emission with maximum at 540-640nm. "Intrinsic" fluorescence from DBP3 is dramatically quenched down to τ = 50-400fs in all the solvents studied. Fs-TA and time-resolved fluorescence spectra have proved that relaxed intramolecular benzene excimer is formed from S1 state via hot excimer state with three lifetime components: 50fs, ∼3.5ps, and ∼25ps, which are of the inertial (electronic) and diffusive parts of the relaxation due to solute-solvent interaction. Formation of triplet states via intersystem crossing was observed directly from the upper excited electronic states of DBP3.

Role of Dark States and Stokes Shift Simulations for Tetraphenylpyrazine Compared to Other Donor-Acceptor Photosensitizers.

An excellent agreement for simulated and measured absorption and emission spectra is found for four donor-acceptor aromatic molecules (tetraphenylpyrazine, tetraphenylethene, distirylanthracene and hexaphenylsilole) whose derivatives serve as solid state photosensitizers. After comparing several hybrid TDDFT functionals, EOM-CCSD, and experiments, the best agreement was found with TD-B3LYP and double zeta basis sets (6-31G** and def2-SVP) for one molecule in gas phase. A full characterisation of twelve to twenty electronic excited states was performed in every system. Symmetry-forbidden bands are found in the absorption spectra by sampling fifty to hundred geometries from a Wigner distribution. The density of states in the region 2-6 eV was also analysed, showing a very packed region of excited states and suggesting that dark electronic states may play a role in the dynamics of some of the photoexcited systems. Further calculations were done with QM/xTB at geometries extracted from previously published X-ray data to evaluate the influence of the environment on the excitations of the four aggregated molecular crystals.

A Constraint-Based Orbital-Optimized Excited State Method (COOX).

In this work, we present a novel method to directly calculate targeted electronic excited states within a self-consistent field calculation based on constrained density functional theory (cDFT). The constraint is constructed from the static occupied-occupied and virtual-virtual parts of the excited state difference density from (simplified) linear-response time-dependent density functional theory calculations (LR-TDDFT). Our new method shows a stable convergence behavior, provides an accurate excited state density adhering to the Aufbau principle, and can be solved within a restricted SCF for singlet excitations to avoid spin contamination. This also allows the straightforward application of post-SCF electron-correlation methods like MP2 or direct RPA methods. We present the details of our constraint-based orbital-optimized excited state method (COOX) and compare it to similar schemes. The accuracy of excitation energies will be analyzed for a benchmark of systems, while the quality of the resulting excited state densities is investigated by evaluating excited state nuclear forces and excited state structure optimizations. We also investigate the performance of the proposed COOX method for long-range charge transfer excitations and conical intersections with the ground-state.

The optical properties of 3 + 3 macrocyclic Schiff base thin material obtained by the Molecular Beam Epitaxy method

3 + 3 optically active macrocyclic Schiff bases were synthesized in the reaction between 4-tert-butyl-2,6-diformylphenol with (1R,2R)-(+)-1,2-diphenylethylenediamine (S1) or (1S,2S)-(−)-1,2-diphenylethylenediamine (S1a). The new compounds were spectroscopically characterised by NMR, IR, X-ray (S1a), UV–Vis and fluorescence spectroscopy. The S1a molecule creates channels with distances between oxygen atoms ranging from 5.8-6.3 Å and sufficiently large to host acetonitrile molecule. Both compounds exhibit green-yellow emission in solution and solid state. Thin layers of the S1 compound obtained via Molecular Beam Epitaxy (MBE) were characterised by scanning electron microscopy with energy-dispersive X-ray spectroscopy SEM/EDS and atomic force microscopy (AFM). The optical properties of the S1/Si thin material were analysed using spectroscopic ellipsometry (SE), fluorescence spectroscopy and synchrotron radiation (SR). The time constant for the decay investigated under SR, denoted by τ1, was determined to be approximately 1.02 ns, suggesting a fast deactivation process of the excited electronic state in the S1/Si material. The ellipsometric analysis of the S1/Si layer showed semiconducting behaviour with pronounced absorption features in the UV range, attributed to π → π* and n → π* transitions, characteristic of Schiff bases. The band-gap energy, determined using the Tauc method, is 3.46 ± 0.01 eV. These analyses highlight the material’s potential in applications requiring precise control of optical properties. In the emission spectrum of S1a, a significant emission peak of approximately 561 nm indicates the presence of a prominent emissive process within this wavelength. The S1a compound is emissive in the yellow-green region of the spectrum and has a longer decay time, which suggests that it can be used in sensing optical technologies.

Analytical potential energy functions for CO in its ground and excited electronic states.

Accurate functions to analytically represent the potential energy interactions of CO diatomic system in , , and electronic states are proposed. The new functions depend upon only four parameters directly obtained from experimental data, without any fitting procedure. These functions have been developed from the modified generalized potential proposed by Araújo and Ballester. The function for the electronic state represents a significant improvement to the previously proposed model. To quantify the accuracy of the potential energy functions, the Lippincont test is used. The novel potential was also compared with the classical Morse potential and with the recently proposed Improved Generalized Pöschl-Teller potential. Furthermore, the main spectroscopic constants and vibrational energy levels are calculated and compared for all potentials. The present results agree excellently with the experiment Rydberg-Klein-Rees (RKR) potentials. The rovibrational energy levels of the proposed diatomic potentials were asserted by solving radial the Schrödinger equation of the nuclear motion with the aid of the LEVEL program.

Rapid Quantification of Oxytetracycline Based on Fluorescence Enhancement Influenced by pH.

Accurate quantification of antibiotics in environmental samples is typically challenging due to the low antibiotic concentrations and the complexity of environmental matrices. This paper presents a fluorescence spectrometry method for determining oxytetracycline under alkaline conditions. The ionic distribution of the oxytetracycline solution was analyzed based on its dissociation constant. The dimethylamino group plays a crucial role in this method, as it promotes intramolecular charge transfer in the electronic excited state through its electron-donating capability with a lone electron pair. The presented method is straightforward, cost-effective, and holds potential for analyzing oxytetracycline in water sample after further investigation.