Excitation Energy Research Articles

High-Precision Mass Measurements of Neutron Deficient Silver Isotopes Probe the Robustness of the N=50 Shell Closure.

High-precision mass measurements of exotic ^{95-97}Ag isotopes close to the N=Z line have been conducted with the JYFLTRAP double Penning trap mass spectrometer, with the silver ions produced using the recently commissioned inductively heated hot cavity catcher laser ion source at the Ion Guide Isotope Separator On-Line facility. The atomic mass of ^{95}Ag was directly determined for the first time. In addition, the atomic masses of β-decaying 2^{+} and 8^{+} states in ^{96}Ag have been identified and measured for the first time, and the precision of the ^{97}Ag mass has been improved. The newly measured masses, with a precision of ≈1 keV/c^{2}, have been used to investigate the N=50 neutron shell closure, confirming it to be robust. Empirical shell-gap and pairing energies determined with the new ground-state mass data are compared with the state-of-the-art abinitio calculations with various chiral effective field theory Hamiltonians. The precise determination of the excitation energy of the ^{96m}Ag isomer in particular serves as a benchmark for abinitio predictions of nuclear properties beyond the ground state, specifically for odd-odd nuclei situated in proximity to the proton dripline below ^{100}Sn. In addition, density functional theory calculations and configuration-interaction shell-model calculations are compared with the experimental results. All theoretical approaches face challenges to reproduce the trend of nuclear ground-state properties in the silver isotopic chain across the N=50 neutron shell and toward the proton dripline.

Metastable Evaporation of Molecules from Water Clusters.

We probe the stability of water clusters by means of their metastable decay probability extracted from two-dimensional reflectron time-of-flight mass spectra. Two different methods are used to ionize and potentially excite the clusters and trigger the evaporation: (i) attachment of electrons with near-zero energies, producing negatively charged clusters, and (ii) electron impact ionization, producing protonated (H2O)nH+ clusters. The electron attachment is a soft ionization and therefore provides information about the size distribution of the neutral clusters in the beam due to a very limited amount of post-ionization loss of water molecules. A dependence of metastable fractions on the conditions of neutral clusters production prior to the electron attachment is reported. For the cations, the higher energy electron impact ionization leads to a more extensive metastable loss of water molecules. The results are discussed in the light of neutral cluster excitation energy distributions and, for negative clusters, also in terms of binding energies. The experiments demonstrate clearly the role of the excess electron vs the excess proton in the two different charge states of the clusters around sizes N = 50-55, for which binding energies of the anions are derived from the data.

Triple Electron Attachments with a New Intermediate-Hamiltonian Fock-Space Coupled-Cluster Method.

The implementation of a new intermediate-Hamiltonian Fock-space coupled-cluster (IHFSCC) scheme for the (3,0) sector of the Fock space is reported. In this IHFSCC approach, the three-body contributions in the cluster operator S(3,0) corresponding to the (3,0) sector of the Fock space are considered, while S(1,0) and S(2,0) at the (1,0) and (2,0) level only include one- and two-body operators. By introducing a suitable partition of the wave operator, the intermediate Hamiltonian, which only depends on the two-body operator of S(1,0), is obtained. S(2,0) and S(3,0) are not required within this new IHFSCC scheme, and a large reference space can be possibly employed. The performance of this (3,0) IHFSCC method in calculating triple ionization potentials and excitation energies for atoms and cations with a ground p3 configuration as well as adiabatic excitation energies for some molecules is investigated. The effect of the number of active virtual orbitals and three different types of orbitals, i.e., reference orbitals, restricted open-shell Hartree-Fock orbitals (ROHF) of the target systems, and canonicalized ROHF orbitals, on IHFSCC results, is also studied. Our calculations indicate that reasonable results can be achieved with this (3,0) IHFSCC method when a minimal reference space is employed. Further increasing the number of active orbitals does not necessarily improve the results. In addition, the IHFSCC results using canonicalized ROHF orbitals generally agree well with reference values, and they are not very sensitive to the number of active orbitals compared with results using the reference orbitals. The new (3,0) IHFSCC method can be applied to open-shell systems with three unpaired electrons with reasonable accuracy at a relatively low computational cost.

Bonding and Interactions in UO22+ for Ground and Core Excited States: Extracting Chemistry from Molecular Orbital Calculations.

Theoretical analyses of actinyls are necessary in order to understand and correctly interpret the chemical and physical properties of these molecules. Here, wave functions of Uranyl, UO22+, are considered for the ground state and for the core excited states where an electron is promoted from the U 3d5/2 shell into a low-lying unoccupied orbital that is U 5f antibonding with the ligand, O, orbitals. A focus is on the application of novel theoretical methods to the analysis of these wave functions so that measurements, especially with X-ray absorption, can be related to the UO22+ chemical bonding. The bond covalency is examined with these theoretical methods. The study includes how the covalent character is different for the ground and excited configurations and how this character changes as the U-O distance is changed. Furthermore, analyses are mode of how many-body effects may modify excitation energies and X-ray adsorption intensities. This includes determining the extent to which a single configuration provides a satisfactory model for the UO22+ wave functions. Two distinct types of many-body effects are considered. One involves the angular momentum coupling of the open shell electrons in the excited states to yield correct multiplets. The second adds excitations from shells that are bonding into the antibonding open shell space. These excitations are essential to properly describe the X-ray adsorption. While these many-body effects must be taken into account, their importance and their role can be explained and understood using orbitals and orbital occupations.

Inverse Design of Singlet-Fission Materials with Uncertainty-Controlled Genetic Optimization.

Singlet fission has shown potential for boosting the efficiency of solar cells, but the scarcity of suitable molecular materials hinders its implementation. We introduce an uncertainty-controlled genetic algorithm (ucGA) based on ensemble machine learning predictions from different molecular representations that concurrently optimizes excited state energies, synthesizability, and exciton size for the discovery of singlet fission materials. The ucGA allows us to efficiently explore the chemical space spanned by the reFORMED fragment database, which consists of 45,000 cores and 5,000 substituents derived from crystallographic structures assembled in the FORMED repository. Running the ucGA in an exploitative setup performs local optimization on variations of known singlet fission scaffolds, such as acenes. In an explorative mode, hitherto unknown candidates displaying excellent excited state properties for singlet fission are generated. We suggest a class of heteroatom-rich mesoionic compounds as acceptors for charge-transfer mediated singlet fission. When included in larger donor-acceptor systems, these units exhibit localization of the triplet state, favorable diradicaloid character and suitable triplet energies for exciton injection into semiconductor solar cells.

Calculations of Dissociation Dynamics of CH3OH on a Global Potential Energy Surface Reveal the Mechanism for the Formation of HCOH; Roaming Plays a Role.

The experimental observation of hydroxymethylene, HCOH, following excitation of methanol at 193 nm, was reported recently (Hockey, E. K.; McLane, N.; Martí, C.; Duckett, L.; Osborn, D. L.; Dodson, L. G. Direct Observation of Gas-Phase Hydroxymethylene: Photoionization and Kinetics Resulting from Methanol Photodissociation. J. Am. Chem. Soc. 2024, 146, 14416-14421, 10.1021/jacs.4c03090). This stimulated us to investigate a dynamic mechanism for its formation using a global potential energy surface for the ground electronic state (S0) of methanol. We show via quasi-classical trajectory calculations that hydroxymethylene is indeed formed under the reasonable assumption that the initially excited state undergoes rapid internal conversion to S0. From the trajectories, fractional yields of the six major product channels are determined as a function of excitation energy, and the rate of production of each is determined from the fractions and rate of methanol disappearance. Roaming is observed in trajectories leading to the OH and CH3 products as well as in those leading to CH2OH + H and non-reactive trajectories. A "frustrated" roaming accounts for roughly 20% of the HCOH production.

Structural and spectroscopic characterization of the peridinin-chlorophyll a-protein (PCP) complex from Heterocapsa pygmaea (HPPCP)

Light harvesting proteins are optimized to efficiently collect and transfer light energy for photosynthesis. In eukaryotic dinoflagellates these complexes utilize chlorophylls and a special carotenoid, peridinin, and arrange them for efficient excitation energy transfer. At the same time, the carotenoids protect the system by quenching harmful chlorophyll triplet states. Here we use advanced spectroscopic techniques and X-ray structure analysis to investigate excitation energy transfer processes in the major soluble antenna, the peridinin chlorophyll a protein (PCP) from the free living dinoflagellate Heterocapsa pygmaea. We determined the 3D-structure of this complex at high resolution (1.2 Å). For better comparison, we improved the reference structure of this protein from Amphidinium carterae to a resolution of 1.15 Å. We then used fs and ns time-resolved absorption spectroscopy to study the mechanisms of light harvesting, but also of the photoprotective quenching of the chlorophyll triplet state. The photoprotection site was further characterized by Electron Spin Echo Envelope Modulation (ESEEM) spectroscopy to yield information on water molecules involved in triplet-triplet energy transfer.Similar to other PCP complexes, excitation energy transfer from peridinin to chlorophyll is found to be very efficient, with transfer times in the range of 1.6–2.1 ps. One of the four carotenoids, the peridinin 614, is well positioned to quench the chlorophyll triplet state with high efficiency and transfer times in the range of tens of picoseconds. Our structural and dynamic data further support, that the intrinsic water molecule coordinating the chlorophyll Mg ion plays an essential role in photoprotection.

Extended perturbative approach including Redfield and Förster limits for qualitative analysis of exciton dynamics in any photosynthetic light harvesting and reaction center

According to many reports, the various structures of photosynthetic light-harvesting/reaction-center complexes and their molecular-dynamics simulations necessitate a numerically efficient and quality-conserved theory of excitation energy transfer and exciton relaxation in large pigment systems. Although exciton dynamics depend on various parameters, such as exciton coupling strength, exciton–phonon coupling, site energy values for each pigment, and temperature, classifying the transition mechanism for any Hamiltonian into perturbatively delocalized or localized theories is challenging. In this study, perturbative quantum master equations of a reduced density matrix for any orthogonal transformation similar to the coherent modified Redfield theory are derived. Our approach qualitatively conserves the dynamics of relevant perturbative approximations in each limiting case. As an application, any orthogonal transformation of a relevant system is optimized using the average of the square of interactions between orthogonal state transitions. The numerical results for two pigment systems are compared with the limiting formalisms of the modified Redfield and Förster theory.

Nucleation of baryons in relativistic hadron-nucleus collisions

We suggest a new theoretical method to describe the baryon clusterization of nuclei in hadron-nucleus reactions. As an example we have explored the nuclei production in π−+C and π−+W collisions at plab=1.7 GeV by using the hybrid approach consisting of the Ultra Relativistic Quantum Dynamics Model (UrQMD) and the Statistical Multifragmentation Model (SMM). The UrQMD describes the production of new baryons, and the propagation toward the subnuclear densities with the fluctuations leading to the formation of excited baryonic clusters. The SMM describes the production of final nuclei and hypernuclei after interaction of baryons inside these clusters. We demonstrate the transverse momenta, rapidity, mass distributions and excitation energies of both primary clusters and final nuclei (including hypernuclei). The results of the UrQMD and UrQMD+SMM model calculations for different clusterization parameters are compared with the available HADES experimental data on baryon production, providing a very promising window for future research on nuclei and hypernuclei formation in these reactions.

Mono- and Binuclear Complexes in a Centrifuge-Less Cloud-Point Extraction System for the Spectrophotometric Determination of Zinc(II).

The hydrophobic reagent 6-hexyl-4-(2-thiazolylazo)resorcinol (HTAR) was investigated as part of a cloud-point extraction (CPE) system for the spectrophotometric determination of Zn(II). In the system, complexes with different stoichiometries, including 1:1 and 2:2 (Zn:HTAR), are formed. Their ground-state equilibrium geometries were optimized at the B3LYP/6-31G level of theory. The obtained structures were then used to calculate vertical excitation energies in order to generate theoretical UV/Vis absorption spectra. The comparison between theoretical and experimental spectra demonstrated that, under optimal conditions, a binuclear complex containing oxygen-bridging atoms is the dominant species. The absorbance was found to be linearly dependent on the concentration of Zn(II) within the range of 15.7 to 209 ng mL-1 (R2 = 0.9996). The fraction extracted (%E), logarithm of the conditional extraction constant (log Kex), and molar absorption coefficient (ε) at λmax = 553 nm were calculated to be 98.3%, 15.9, and 4.47 × 105 L mol-1 cm-1, respectively. The method developed is characterized by simplicity, convenience, profitability, sensitivity, and ecological friendliness. It has been successfully applied to the analysis of pharmaceutical and industrial samples.

Equation-of-motion regularized orbital-optimized second-order perturbation theory with the density-fitting approximation.

The density-fitted equation-of-motion (EOM) orbital-optimized second-order perturbation theory (DF-EOM-OMP2) method is presented for the first time. In addition, κ-DF-EOM-MP2 and κ-DF-EOM-OMP2 methods are implemented with the addition of κ-regularization. The accuracy of the DF-EOM-OMP2, κ-DF-EOM-MP2, and κ-DF-EOM-OMP2 methods are compared to the density-fitted EOM-MP2 (DF-EOM-MP2), EOM coupled-cluster (CC) singles and doubles (DF-EOM-CCSD), and EOM-CCSD with the triples excitation correction model [EOM-CCSD(fT)] for excitation energies of many closed- and open-shell chemical systems. The excitation energies computed using different test cases and methods were compared to the EOM-CCSD(fT) method and mean absolute errors (MAEs) are presented. The MAE values of closed- and open-shell cases (closed-shell organic chromophores set, open-shell set, peptide radicals set, and radical set) according to the EOM-CCSD(fT) method show that the κ-regularization technique yields highly accurate results for the first excited states. Our results indicate that the κ-DF-EOM-MP2 and κ-DF-EOM-OMP2 methods perform noticeably better than the DF-EOM-MP2 and DF-EOM-OMP2 methods. They approach the EOM-CCSD quality, at a significantly reduced cost, for the computation of excitation energies. Especially, the κ-DF-EOM-MP2 method provides outstanding results for most test cases considered. Overall, we conclude that the κ-versions of DF-EOM-MP2 and DF-EOM-OMP2 emerge as a useful computational tool for the study of excited-state molecular properties.

Integrating simulated and experimental studies on novel single crystal bis(guanidininium) n-carboxylatephenylalanine towards enhanced antitumor effect

A novel organic crystal bis(guanidininium) n-carboxylatephenylalanine (GUPA) was synthesized and X-ray diffraction outcomes exposed P21, triclinic space group with cell dimensions a = 6.6492(3) Å, b = 16.2440(7) Å, c = 7.8985(3) Å, β = 0.127(2) °, V = 853.11(6) Å3, Z = 2 and possess good agreement with experimental data. Intermolecular interactions were revealed through hirshfeld and major contribution from O-H interaction confirms the presence of intermolecular hydrogen bonds. Through B3LYP algorithm with set 6–311++ G (d, p), chemical reactivity forms and molecular structure of GUPA was investigated, confirming a good stability and hard electrophilic nature. While first order hyperpolarizability value (35.37 × 10−31 esu) was indicative of good nonlinear optical material and hyperconjugate interactions and charge delocalization was further confirmed by natural bond orbitals. To further investigate the electronic properties theoretical (TD-DFT) and experimental absorption wavelengths were compared and excitation energies, oscillator strength and type of electronic transition with contributions have also been studied. The topological properties were evaluated using ELF/LOL maps and RDG with NCI were used to establish the type of interaction present in the GUPA molecular system. The anti-breast cancer effect of GUPA was computationally studied through molecular docking against p53 gene and was further investigated through in vitro MDA-MB-231 cell line studies and GUPA showed better inhibition of cancer cells and their expression.

Accurate determination of excitation energy: An equation-of-motion approach over a bi-exponential coupled cluster theory.

The calculation of molecular excited states is critically important to decipher a plethora of molecular properties. In this paper, we develop an equation of motion formalism on top of a bi-exponentially parameterized ground state wavefunction toward the determination of excited states. While the ground state bi-exponential parameterization ensures an accurate description of the wavefunction through the inclusion of high-rank correlation effects, the excited state is parameterized by a novel linear response operator with an effective excitation rank beyond two. To treat the ground and excited states in the same footings, in addition to the conventional one- and two-body response operators, we introduced certain two-body "generalized" response operators with an effective excitation rank of one. We introduce a projective formulation for determining the perturbed amplitudes for the set of "generalized" operators. Our formulation entails a significantly small number of unknown parameters and is shown to be highly accurate compared to allied methods for several difficult chemical systems.

Temperature ratio RT = TL/TH of fully accelerated complementary fragments (used for TXE partition) obtained independently of prompt emission model calculations

Several refined prompt emission model codes, nowadays employed, use the partition of total excitation energy (TXE) according to the temperature ratio RT = TL/TH of fully accelerated fragments. In such codes RT is given as input, either as an unique value for all fragmentations or as a function of AH; This temperature ratio RT being obtained by fitting the experimental ν(A) data with the respective prompt emission model code. This paper proposes a method for obtaining “experimental RT(AH)” (also based on experimental ν(A)), but without resorting to prompt emission model calculations for the fit of ν(A) data. So that this is an independent method providing RT(AH) which can be employed by any prompt emission model code in which the TXE partition is done at the full acceleration according to RT given as input. A procedure which facilitates the parameterization of RT(AH) is proposed, too. A prediction of the RT(AH) shape at very high excitation energies of the fissioning nucleus is also reported. The comparison of RT(AH) ratios obtained from any TXE partition based on modeling at scission with those provided by the present method can constitute a supplementary validation of the respective modeling at scission.

Accelerated Computer-Aided Screening of Optical Materials: Investigating the Potential of Δ-SCF Methods to Predict Emission Maxima of Large Dye Molecules.

Accurate simulation of electronic excited states of large chromophores is often difficult due to the computationally expensive nature of existing methods. Common approximations such as fragmentation methods that are routinely applied to ground-state calculations of large molecules are not easily applicable to excited states due to the delocalized nature of electronic excitations in most practical chromophores. Thus, special techniques specific to excited states are needed. Δ-SCF methods are one such approximation that treats excited states in a manner analogous to that for ground-state calculations, accelerating the simulation of excited states. In this work, we employed the popular initial maximum overlap method (IMOM) to avoid the variational collapse of the electronic excited state orbitals to the ground state. We demonstrate that it is possible to obtain emission energies from the first singlet (S1) excited state of many thousands of dye molecules without any external intervention. Spin correction was found to be necessary to obtain accurate excitation and emission energies. Using thousands of dye-like chromophores and various solvents (12,318 combinations), we show that the spin-corrected initial maximum overlap method accurately predicts emission maxima with a mean absolute error of only 0.27 eV. We further improved the predictive accuracy using linear fit-based corrections from individual dye classes to achieve an impressive performance of 0.17 eV. Additionally, we demonstrate that IMOM spin density can be used to identify the dye class of chromophores, enabling improved prediction accuracy for complex dye molecules, such as dyads (chromophores containing moieties from two different dye classes). Finally, the convergence behavior of IMOM excited state SCF calculations is analyzed briefly to identify the chemical space, where IMOM is more likely to fail.

Excitation energies of 21+ and 41+ states of neutron deficient U and Pu isotopes

Excitation energies of 21+ and 41+ states of neutron deficient U and Pu isotopes

Post-Neutron Mass Yield Distribution in the Epi-Cadmium Neutron-Induced Fission of 235U

Cumulative and independent yields of various fission products within the mass ranges of 78 to 117 and 123 to 155 have been measured in the epi-cadmium reactor neutron-induced fission of 235U by using an off-line gamma-ray spectrometric technique. The average neutron energy <En> of the epi-cadmium reactor spectrum is 1.9 MeV. From the cumulative yields, post-neutron mass chain yields were obtained by applying the charge distribution correction. In the mass yield distribution, values of the full-width at tenth-maximum of light and heavy mass wings, average light mass <AL> and heavy mass <AH>, and average number of neutrons <ν> were obtained. The peak-to-valley ratio in the epi-cadmium neutron-induced fission of 235U was obtained for the first time. The present data in the 235U(n,f) reaction were compared with the literature data in the 235U(nth,f) reaction to examine the role of excitation energy on the mass yield distribution parameters and nuclear structure effect. The role of the standard I and standard II asymmetric modes of fission was also discussed.

A study on the synthesis of superheavy element Mc (Z = 115) using lead, bismuth and actinide targets

The evaporation residue cross sections in synthesizing isotopes of superheavy element Mc (Z = 115) by the hot fusion reactions 48Ca+241,243Am→289,291Mc, 45Sc+240,242,244Pu→285,287,289Mc, 50Ti+236,237Np→286,287Mc, 51V+238U→289Mc, 36S+253Es→289Mc, 46K+248Cm→294Mc, and by the cold fusion reactions 78As+208Pb→286Mc, 76Ge+209Bi→285Mc have been systematically investigated using the phenomenological model for production cross section. We have predicted the most effective projectile-target combinations for synthesizing Mc isotopes among these reactions. Our result shows that the 3n- channel cross section is larger for the reaction 48Ca+243Am→291Mc, and the 4n- channel cross section is larger for the reaction 46K+248Cm→294Mc. This study also examines the effect of the use of mass values and shell corrections by the Möller and Warsaw groups. Using our predicted combinations and the cross section values at a range of excitation energies, we hope these isotopes of Mc can be synthesized in near-future experiments.

Experimental and Computational Evaluation of Lipidomic In-Source Fragmentation as a Result of Postionization with Matrix-Assisted Laser Desorption/Ionization.

Matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI-MSI) can provide spatially resolved molecular information about a sample. Recently, a postionization approach (MALDI-2) has been commercially integrated with MALDI-MSI, allowing for bettered sensitivity and consequent improved spatial resolution. While advantages of MALDI-2 have previously been established, we demonstrate here statistically increased in-source fragmentation (ISF) results from postionization with a commercial instrument. Via lipid standard analyses, known MALDI ISF pathways (e.g., loss of trimethylamine) were statistically increased in MALDI-2 compared to MALDI-1 (65-172% increase in fragmentation). Gas phase molecular modeling with density functional theory estimated that the most-weighted virtual orbitals to excite within lipids involve ester and phosphate bonds. Protonated lipid excitation energies are furthermore red-shifted compared to those of other adduct types [e.g., 254 nm for protonated PC(16:0/18:1)] and approach the MALDI-2 laser energy (266 nm). Analysis of rat brain homogenate detected statistically more positive-ion mode peaks with MALDI-2 (1090) than that with MALDI-1 (719), where Kernel density estimations showed that the majority of this enhancement occurs with low m/z ions (i.e., m/z 75-500). Taken together with the lipid standard data, these observations may indicate ISF due to postionization. While artifact contributions from matrix blanks were also noted, both experimental and computational data sets suggest that the overall extent of ISF is statistically increased in MALDI-2 compared to MALDI-1.

Why Does the Optimal Tuning Method of the Range Separation Parameter of a Long-Range Corrected Density Functional Fail in Intramolecular Charge Transfer Excitation Calculations?

We performed intra- and intermolecular charge transfer (CT) excitation energy calculations of (a) conjugated carbon chain [H2N-(CH=CH)n-X] and (b) its equidistant H2NH∙∙∙HX (n = 2~8) with various electron acceptors (X = NH2, OH, Cl, CHO, CN, and NO2) using EOM-CCSD, time-dependent (TD) Hartree-Fock (HF) and various density functional theory (DFT) functionals, such as BLYP, B3LYP, long-range corrected (LC) DFT, and LC-DFT with an optimally tuned (OT) range separation parameter (µ) using Koopman's theorem to investigate the effect of the electron-withdrawing (or -donating) strength of end-capped functional group (X) and CT distance (R) on intra- and intermolecular CT excitation energies. As the electron-withdrawing strength of X increases, both intra- and intermolecular CT excitation energies tend to decrease, since energy gaps between orbitals corresponding to CT excitations (e.g., HOMO and LUMO) decrease. However, the effect of the electron-withdrawing group on intramolecular CT excitation energy is negligible (at most 0.5 eV). OT-LC-DFT shows accurate intermolecular CT excitation energy, but worse results in intramolecular CT excitation energy than LC-DFT with the default µ value (0.47). Therefore, we conclude that the optimal tuning method is not effective in predicting intramolecular CT excitation energy. While intermolecular CT excitation energy has excitonic binding energy with asymptotic behavior to CT distance that is not affected by the choice of range separation parameter, intramolecular CT excitation energy is affected by orbital relaxation energy, which strongly depends on the choice of range separation parameter, which makes the OT method of range separation parameter ineffective in predicting intramolecular CT excitation energy as well as local excitation with high accuracy.