Relative Excitation Energies Research Articles

Spin Coupling Effect on Geometry-Dependent X-Ray Absorption of Diradicals.

We theoretically investigate the influence of diradical electron spin coupling on the time-resolved X-ray absorption spectra of the photochemical ring opening of furanone. We predict geometry-dependent carbon K-edge signals involving transitions from core orbitals to both singly and unoccupied molecular orbitals. The most obvious features of the ring opening come from the carbon atom directly involved in the bond breaking through its transition to both the newly formed singly occupied and the available lowest unoccupied molecular orbitals (SOMO and LUMO, respectively). In addition to this primary feature, the singlet spin coupling of four unpaired electrons that arises in the core-to-LUMO states creates additional geometry dependence in some spectral features with both oscillator strengths and relative excitation energies varying observably as a function of the ring opening. We attribute this behavior to a spin-occupancy-induced selection rule, which occurs when singlet spin coupling is enforced in the diradical state. Notably, one of these geometry-sensitive core-to-LUMO transitions excites core electrons from a backbone carbon not involved in the bond breaking, providing a novel nonlocal X-ray probe of chemical dynamics arising from electron spin coupling.

Excited state dynamics of a double ESIPT unit comprising fluorophore

A comprehensive experimental and computational analysis on the photophysical characteristics of a double ESIPT unit based fluorescent molecule, 2,2′-(1,4-phenylenebis(1H-benzo[d]imidazole-1,2-diyl))diphenol (PBIDP), was carried out. Photoluminescence spectra and lifetime decays have been measured in various polar and nonpolar solvents to explore the fluorescence properties. Furthermore, time-resolved area normalized emission spectra are exploited to identify the different conformers to the unsymmetrical keto emission band correlating with their lifetime values. To corroborate the experimental observations, computations have been enacted by calculating the relative energy, excitation and emission energies of different conformers. Especially, the simulation facilitates to trace the reason behind the triple emissions, uncovering the proton transfer dynamics in the double ESIPT based PBIDP system. Additionally, to understand the ESIPT mechanism in the fluorophore, the potential energy curve and transition state in the ground, and excited state were calculated.

Highly Emissive Luminogens in Both Solution and Aggregate States

Highly Emissive Luminogens in Both Solution and Aggregate States

Benchmarking time-dependent density functional theory for singlet excited states of thermally activated delayed fluorescence chromophores

Thermally activated delayed fluorescence (TADF) is the internal conversion of triplet excitons into singlet excitons via reverse intersystem crossing. TADF can significantly enhance the efficiency of organic light-emitting diodes (OLEDs). In order for a chromophore to display TADF the energy difference between its lowest singlet and lowest triplet states, ${S}_{1}$ and ${T}_{1}$, should be as small as possible. This requirement is facilitated by spatial separation between the frontier orbitals. Computer simulations based on time-dependent density functional theory (TDDFT) have been used extensively to predict the excited state properties of TADF chromophores. However, the accuracy of TDDFT largely depends on the choice of exchange-correlation functional. Here, we present a benchmark study of the performance of TDDFT based on different classes of hybrid functionals for 16 TADF chromophores consisting of different donor and acceptor moieties. We find that only the range-separated double hybrid functionals, $\ensuremath{\omega}\mathrm{B}2\mathrm{PLYP}$ and $\ensuremath{\omega}\mathrm{B}2\mathrm{GP}\text{\ensuremath{-}}\mathrm{PLYP}$, provide qualitatively correct predictions of the relative singlet excitation energies of different molecules, the spectral composition of excited states, and the energy ordering of intramolecular charge-transfer versus valence excited states. Therefore, we recommend using these functionals to assess prospective TADF chromophores. Nevertheless, further development is needed to improve the quantitative performance of TDDFT. These findings are important for our ability to computationally screen and design candidate TADF chromophores and advance the development of highly efficient OLEDs.

Complexation of Green and Red Kaede Fluorescent Protein Chromophores by a Zwitterion to Probe Electrostatic and Induction Field Effects.

The photophysics of green fluorescent protein (GFP) and red Kaede fluorescent protein (rKFP) are defined by the intrinsic properties of the light-absorbing chromophore and its interaction with the protein binding pocket. This work deploys photodissociation action spectroscopy to probe the absorption profiles for a series of synthetic GFP and rKFP chromophores as the bare anions and as complexes with the betaine zwitterion, which is assumed as a model for dipole microsolvation. Electronic structure calculations and energy decomposition analysis using Symmetry-Adapted Perturbation Theory are used to characterize gas-phase structures and complex cohesion forces. The calculations reveal a preponderance for coordination of betaine to the phenoxide deprotonation site predominantly through electrostatic forces. Calculations using the STEOM-DLPNO-CCSD method are able to reproduce absolute and relative vertical excitation energies for the bare anions and anion-betaine complexes. On the other hand, treatment of the betaine molecule with a point-charge model, in which the charges are computed from some common electron density population analysis schemes, show that just electrostatic and point-charge induction interactions are unable to account for the betaine-induced spectral shift. The present methodology could be applied to investigate cluster forces and optical properties in other gas-phase ion-zwitterion complexes.

Effects of three-nucleon force on the low-lying states of <sup>28</sup>F and<sup>29</sup>Ne within <italic>ab initio</italic> calculations

One of the most interesting anomalies in nuclear physics is the island of inversion (IOI), which indicates that the magic numbers disappear. It provides a good platform to understand single-particle motion, many-body correlation, and nucleon-nucleon interaction. In neutron-rich isotopes near N =20 area, many experiments have found that the spectra, electromagnetic transitions, radii, and two-neutron separation energies of these nuclei are abnormal. This region is called the N =20 IOI, because it is characterized by neutron particle-hole excitations related to deformation from the 1s0d shell into the 1p0f shell across the N =20 shell gap. Recent experiments show that the ground states of 29Ne and 28F have negative parities, indicating that these two nuclei are within the N =20 IOI. This provides new opportunities and challenges for theoretical models in this area. With the standard shell model, the N =20 IOI has been proved by many works to have a strong cross-shell effect between 1s0d and 1p0f shells. They proposed that the tensor force and three-nucleon force should have an important influence on the microscopic description of neutron-rich nuclei in this area, especially in Ne and Mg isotopes. However, the N =20 IOI is still rarely studied in ab initio calculations. Recently, an extension of the ab initio valence-space in-medium similarity renormalization group method was presented to study the physics of neutron-rich nuclei by Miyagi et al. In the present paper, based on chiral force including nucleon-nucleon and three-nucleon force, we have performed ab initio calculations for the low-lying states of 28F and 29Ne, focusing on the relative excitation energies of the positive- and negative-parity states in these nuclei. In order to study the effect of three-nucleon force on the N =20 IOI, we use nucleon-nucleon force at N3LO with or without three-nucleon force at N2LO in our calculations. Using the open-shell many-body perturbation theory, the cross shell sd-pf realistic effective Hamiltonian, including single-particle energies and effective two-body interactions, is constructed self-consistently without introducing parameters. The constructed effective Hamiltonian is diagonalized with the shell model method. In shell model calculation, we use a truncation with up to five nucleons (including protons and neutrons) occupying the pf orbit. The low-lying states of 28F and 29Ne are calculated with NN and NN+3N interactions. The results show that three-nucleon force is important in the descriptions of low-lying states of 28F and 29Ne, especially in 29Ne while the first negative state turned to be ground state due to the three-nucleon force. Our calculations give that three-nucleon force gives large effects for the relative position between the 0d3/2 and 1p3/2 single-particle orbitals, causing the two orbitals to reverse. Furthermore, the configurations of low-lying states of 28F and 29Ne are calculated within our ab initio calculations with NN+3N interaction. The results give that the lowest positive and negative parity states in 28F and 29Ne are dominated by 2 ℏ ω and 1 ℏ ω components, respectively. We have also calculated the configurations of the ground state in neutron-rich even-even Ne isotopes, and the results indicate that the three-nucleon force could enhance the cross-shell excitations in the nuclei in the vicinity of IOI, which is essential for the exotic properties of these nuclei. Furthermore, we have also performed the phenomenological shell model calculations with SDPF-MU effective interactions, and the results are similar to our ab initio calculations including three-nucleon force.

CSP-Z[formula omitted]: Application of the controlled single particle concept for the prolate to oblate nuclear shape phase transition in odd-A nuclei

In this paper, we study the prolate to oblate nuclear shape phase transition in odd-A nuclei with the help of the controlled single particle (CSP) concept. At first, we construct the corresponding Hamiltonian of the system, and related energy eigenvalue and eigenfunction are derived analytically. Then, according to the concept of the CSP, appropriate angular momenta of the even-even core inside of the odd-A nuclei are determined for 189Ir, the experimental candidate of this model. To examine the results, relative excitation energy and B(E2) transition rates of 189Ir are reproduced and compared with experimental data. The results show a good agreement with them.

Role of quantum phase transition in spontaneous fission

A systematic study of quantum phase (i.e., nuclear shape) transition has been carried out from the standpoint of spontaneous fission. The quantum phase transition is defined by the ratio of relative excitation energies of IΠ=4+ to IΠ=2+ states between heavier and lighter fission fragments and its extremum value fixes the most probable pair of fission fragments. This ratio provides an effective order parameter which is not only easy to measure, but also distinguishes between first and second order phase transitions and takes on a special value in the critical region. Its (i.e., the energy ratio) variation is mainly controlled by the relative inertia tensors of the correlated pair of fission fragment and is fully supported by our cranking mass parameter calculations based on the asymmetric two center shell model bases.Once the fission fragment pair is governed by the quantum phase transition, its validity is tested by F-spin selection rule that is based on valence nucleons which are responsible for determining the nuclear shape transition. It implies that if a pair of conjugate fission fragments together with appropriate neutron emission have total F-spin equal to 12 with projections F0=±12 then and only then the fission proceeds, provided both the valence shell nucleons in either of the fission fragments are treated as particles like and is valid for the even-even decay modes. The goodness of F-spin selection rule extends further to extract all the allowed pairs of neutron-rich fission fragments. The validity of F-spin selection rule has been tested in various decay modes of spontaneous fission and seems to be a milestone in deciding the appropriate decay channels. These findings have important consequences in the formation and discovery of drip-line exotic nuclei.

Cluster embedding of ionic systems: Point charges and extended ions.

The embedding of cluster models of oxides with point charges and with extensions of the embedding which take into account the spatial extent of the cations is examined with an emphasis on the consequences of this embedding for the relative ionization and excitation energies that are measured in core-level spectroscopies. It is found that the dependence of the electronic structure of the oxides and the relative energies of different levels depend only weakly on the embedding and that relatively simple embeddings may be sufficient to provide an adequate model for determining core-level spectra. This is different from absolute values of the ionizations which, as expected, depend strongly on the details of the extended crystal; however, relative values of binding energies, as measured in photoemission, are of greater interest than the absolute values.

Effects of one valence proton on seniority and angular momentum of neutrons in neutron-rich Sb51122–131 isotopes

The neutron-rich $^{122-131}$Sb isotopes were produced as fission fragments in the reaction $^{9}$Be($^{238}$U,~f) with 6.2 MeV/u beam energy. An unique setup, consisting of AGATA, VAMOS++ and EXOGAM detectors, was used which enabled the prompt-delayed gamma-ray ($\gamma$) spectroscopy of fission fragments in the time range of 100 ns - 200 $\mu$s. New isomers, prompt and delayed transitions were established in the even-A $^{122-130}$Sb isotopes. In the odd-A $^{123-131}$Sb isotopes, new prompt and delayed $\gamma$-ray transitions were identified, in addition to the confirmation of the previously known isomers. The half-lives of the isomeric states and the $B(E2)$ transition probabilities of the observed transitions depopulating these isomers were extracted. The experimental data was compared with the theoretical results obtained in the framework of Large-Scale Shell-Model (LSSM) calculations in a restricted model space. Modifications of several components of the shell model interaction were introduced to obtain a consistent agreement with the excitation energies and the $B(E2)$ transition probabilities in neutron-rich Sn and Sb isotopes. The isomeric configurations in Sn and Sb were found to be relatively pure. Further, the calculations revealed that the presence of a single valence proton, mainly in the $g_{7/2}$ orbital in Sb isotopes, leads to significant mixing (due to the $\nu\pi$ interaction) of: (i) the neutron seniorities ($\upsilon_{\nu}$) and (ii) the neutron angular momentum ($I_{\nu}$). The above features have a weak impact on the excitation energies, but have an important impact on the $B(E2)$ transition probabilities. In addition, a constancy of the relative excitation energies irrespective of neutron seniority and neutron number in Sn and Sb was observed.

High-resolution study of the Gamow-Teller ( GT− ) strength in the Zn64(He3,t)Ga64 reaction

Gamow-Teller (GT) transitions starting from the ${T}_{z}=+2$ nucleus $^{64}\mathrm{Zn}$ to the ${T}_{z}=+1$ nucleus $^{64}\mathrm{Ga}$ were studied in a ($p,n$)-type ($^{3}\mathrm{He},t$) charge-exchange reaction at a beam energy of 140 MeV/nucleon and scattering angles close to ${0}^{\ensuremath{\circ}}$. Here, ${T}_{z}$ is the $z$ component of the isospin $T$. The experiment was conducted at the Research Center for Nuclear Physics (RCNP) in Osaka, Japan. An energy resolution of $\ensuremath{\approx}34$ keV was achieved by applying beam matching techniques to the Grand Raiden magnetic spectrometer system. With our good resolution, we could observe GT strength fragmented in many states up to an excitation energy of $\ensuremath{\approx}11$ MeV. By performing angular distribution analysis, we could identify states in $^{64}\mathrm{Ga}$ excited by GT transitions. The reduced GT transition strengths [$B$(GT) values] were calculated assuming the proportionality between the cross sections and the $B$(GT) values. Shell-model calculations using the GXPF1J interaction reproduced the $B$(GT) strength distribution throughout the spectrum. States with isospin $T=3$ were identified by comparing the $^{64}\mathrm{Zn}\text{(}{}^{3}\text{He,}t{\text{)}}^{64}\text{Ga}$ spectrum with a $^{64}\mathrm{Zn}(d,^{2}\mathrm{He})^{64}\mathrm{Cu}$ spectrum. Relative excitation energies of the corresponding structures are in good agreement, supporting the robustness of isospin symmetry in the mass number $A=64$ nuclei.

Computational Characterization of "Dark" Intermediates in the Ultrafast Deactivation of Photoexcited Bilirubin.

The characterization of various intermediates in the ultrafast deactivation of photoexcited ( Z, Z)-bilirubin-IXα was carried out using different computational methods. Various excited states of ( Z, Z)-bilirubin-IXα and their respective vertical excitation energies were calculated using time-dependent density functional theory (TD-DFT) employing the Coulomb-attenuating method (CAM) combined with the B3LYP functional, which is known to predict accurate results on the charge transfer excitation process. Optimized geometries and absorption spectra were determined in chloroform solvent using the polarizable continuum model incorporating the integral equation formalism. The optimized geometries of different conformers of bilirubin ( ZZ, ZE, EZ, and EE) along with their relative energies and vertical excitation energies were obtained. The geometry of the first excited state, S1, for the ZZ conformer was optimized using TD-DFT. The computational study suggests that excited-state intramolecular proton transfer (ESIPT) plays a major role in the deactivation process of ( Z, Z)-bilirubin-IXα on a shorter time scale. The lactam-lactim tautomerism that arises from the ESIPT process gives rise to various intermediates of ( Z, Z)-bilirubin-IXα. The computational results nicely corroborate the experimental findings available in the literature.

Robust and Fragile Quantum Effects in the Transfer Kinetics of Delocalized Excitons between B850 Units of LH2 Complexes.

Aggregates of light harvesting 2 (LH2) complexes form the major exciton-relaying domain in the photosynthetic unit of purple bacteria. Application of a generalized master equation to pairs of the B850 units of LH2 complexes, where excitons predominantly reside, provides quantitative information on how the inter-LH2 exciton transfer depends on the distance, relative rotational angle, and the relative energies of the two LH2s. The distance dependence demonstrates significant enhancement of the rate due to quantum delocalization of excitons, the qualitative nature of which remains robust against the disorder. The angle dependence reflects isotropic nature of exciton transfer, which remains similar for the ensemble of disorder. The variation of the rate on relative excitation energies of LH2 exhibits resonance peaks, which, however, is fragile as the disorder becomes significant. Overall, the average transfer times between two LH2s are estimated to be in the range of 4-25 ps for physically plausible inter-LH2 distances.

Empirical signatures of shape phase transitions in nuclei with odd nucleon numbers

Nuclear level density at low excitation energies is proposed as an indicator of the first order phase transitions in nuclei. The new signature, a maximum value of the level density at the critical point, appears to be sensitive to the detailed way the phase transition takes place in different nuclear regions: it is consistent with phase coexistence in the N=90 region, and with a rapid crossing of the two phases, without their coexistence/mixing at the critical point in the N=60 region, respectively. Candidates for critical point nuclei are proposed for odd-mass and odd-odd nuclei, using correlations between relative excitation energies, and their ratios, for structures (bands) based on unique-parity orbitals.

Optical properties of donor–acceptor conjugated copolymers: A computational study

TDDFT calculations are associated to an extrapolation scheme to predict the optical properties of twelve donor-acceptor copolymers, in which carbazole, benzodithiophene or cyclopentadithiophene donor subunits are combined to benzofurazane, benzothiadiazole or diketopyrrolopyrrole acceptor moieties. Relative excitation energies and absorption strengths are rationalized in terms of geometrical, electronic and optical descriptors. It is shown that the combination of a cyclopentadithiophene with a diketopyrrolopyrrole leads to the lowest excitation energy and highest light absorption efficiency within the series. However, combining cyclopentadithiophene and benzodithiophene subunits appears as more efficient for solar cell applications due to better energy level alignment with respect to PCBM.

A robust empirical parametrization of proton stopping power using dual energy CT.

In this study the authors present a new method for estimation of proton stopping power ratios (SPRs) using dual energy CT (DECT), which is robust toward CT noise. The authors propose a parametrization for SPR based directly on the CT numbers in a DECT image set, whereby the intermediate steps of estimating the relative electron density, ρe, and mean excitation energy, I, are avoided. The SPR parametrization proposed in this study is a purely empirical fit based on the theoretical SPR values for a list of 34 reference human tissues. To investigate the SPR estimation made with this new method the authors performed a calibration and an evaluation with the method. The authors initially calculated CT numbers using CT energy spectrum characterization parameters obtained from calibration based on a Gammex 467 electron density calibration phantom. These CT numbers were fitted to the theoretical SPR for the reference human tissues using the new SPR parametrization presented in this study. The method was evaluated based on theoretical CT numbers for the reference human tissues. The root-mean-square error (RMSE) of the SPR and the proton range error from the continuous slowing down approximation were calculated for the reference human tissues. To test the stability of the parametrization the authors varied the density and elemental composition of the reference human tissues and calculated their new SPR estimates. Further, clinically realistic noise values were added to the theoretical CT numbers to investigate how CT noise affected the estimated water equivalent range through 10 cm of the reference human tissues. All results for the new SPR parametrization were compared to the results obtained using two previously published DECT methods for SPR estimation. Comparisons were also made to a single energy CT (SECT) SPR estimation method, the stoichiometric method, which is commonly used in clinical practise for proton therapy treatment planning. The RMSE for the SPR of the 34 reference human tissues using the new SPR parametrization was 0.12%, compared to 0.19% and 0.28% for the two previously published DECT methods. The SPR parametrization was more stable toward variations of the calcium content in the reference human tissues, but less stable toward density variations and changes to the hydrogen content than the two other DECT methods. When adding noise to the theoretical CT numbers the SPR parametrization gave the lowest water equivalent range errors of all four tested SPR estimation methods (maximum error reduced to 0.4 mm). In all cases tested, the new SPR parametrization outperformed the SECT stoichiometric method. The new SPR parametrization gave lower RMSEs than the two other published DECT methods, and was in particular more robust against added noise. The method has potential for reducing range uncertainty margins in treatment planning of proton therapy.

Structure Prediction of Self-Assembled Dye Aggregates from Cryogenic Transmission Electron Microscopy, Molecular Mechanics, and Theory of Optical Spectra.

Cryogenic transmission electron microscopy (cryo-TEM) studies suggest that TTBC molecules self-assemble in aqueous solution to form single-walled tubes with a diameter of about 35 Å. In order to reveal the arrangement and mutual orientations of the individual molecules in the tube, we combine information from crystal structure data of this dye with a calculation of linear absorbance and linear dichroism spectra and molecular dynamics simulations. We start with wrapping crystal planes in different directions to obtain tubes of suitable diameter. This set of tube models is evaluated by comparing the resulting optical spectra with experimental data. The tubes that can explain the spectra are investigated further by molecular dynamics simulations, including explicit solvent molecules. From the trajectories of the most stable tube models, the short-range ordering of the dye molecules is extracted and the optimization of the structure is iteratively completed. The final structural model is a tube of rings with 6-fold rotational symmetry, where neighboring rings are rotated by 30° and the transition dipole moments of the chromophores form an angle of 74° with respect to the symmetry axis of the tube. This model is in agreement with cryo-TEM images and can explain the optical spectra, consisting of a sharp red-shifted J-band that is polarized parallel to to the symmetry axis of the tube and a broad blue-shifted H-band polarized perpendicular to this axis. The general structure of the homogeneous spectrum of this hybrid HJ-aggregate is described by an analytical model that explains the difference in redistribution of oscillator strength inside the vibrational manifolds of the J- and H-bands and the relative intensities and excitation energies of those bands. In addition to the particular system investigated here, the present methodology can be expected to aid the structure prediction for a wide range of self-assembled dye aggregates.

Combining linear interpolation with extrapolation methods in range-separated ensemble density functional theory

ABSTRACTThe combination of a recently proposed linear interpolation method (LIM), which enables the calculation of weight-independent excitation energies in range-separated ensemble density functional approximations, with the extrapolation scheme of Savin is presented in this work. It is shown that LIM excitation energies vary quadratically with the inverse of the range-separation parameter μ when the latter is large. As a result, the extrapolation scheme, which is usually applied to long-range interacting energies, can be adapted straightforwardly to LIM. This extrapolated LIM (ELIM) has been tested on a small test set consisting of He, Be, H2 and HeH+. Relatively accurate results have been obtained for the first singlet excitation energies with the typical μ = 0.4 value. The improvement of LIM after extrapolation is remarkable, in particular for the doubly excited 21Σ+g state in the stretched H2 molecule. Three-state ensemble calculations in H2 also show that ELIM does not necessarily improves relative excitation energies, even though individual excitation energies are more accurate after extrapolation. Finally, an alternative decomposition of the short-range ensemble exchange–correlation energy is proposed in order to correct for ghost-interaction errors in multi-determinant range-separated ensemble density functional theory calculations. The implementation and calibration of such a scheme arecurrently in progress.

Systematics on the low-lying spectra in N = 78 ~ 80 isotones

Combining the new spectroscopy results of 144 Tb and previous spectroscopy studies of neighboring nuclei, a systematic investigation on the low-lying spectra in N = 78 ~ 80 isotones is performed. Good systematics have been found for the coupling patterns which couple the odd nucleon(s), such as πh11/2, [Formula: see text], to the 2+, 4+, 6+ and 3- core excitations. It is found that the relative excitation energies of the states formed by coupling h11/2 proton(s) to the 2+, 4+ core excitations are pushed up, in contrast with those formed by coupling h11/2 neutron hole(s) to the 2+, 4+ core excitations, which are pulled down. According to the systematics, the interpretation that the 17/2+ states observed in 141 Sm and 143 Gd are the fully aligned member of coupling the odd h11/2 neutron hole to the octupole 3- core excitation, is explored to the isotones 145 Dy , 142 Eu , and 144 Tb .

Hybrid femtosecond/picosecond coherent anti‐Stokes Raman scattering for high‐speed CH4/N2 measurements in binary gas mixtures

Hybrid femtosecond/picosecond (fs/ps) vibrational coherent anti‐Stokes Raman scattering was demonstrated for high‐speed, in‐situ measurements of CH4/N2 mole fractions in binary gas mixtures with temporal nonresonant suppression. A single broadband, 100‐fs laser source was used to simultaneously excite CH4 and N2 vibrational Raman transitions, characterized by a spectral separation of ~584 cm−1, followed by frequency‐domain detection with a time‐delayed ps probe pulse. In this manner, the temporal evolution of the nonresonant background and vibrational wavepackets of CH4 and N2 could be evaluated to maximize signal and minimize interferences. A typical accuracy of ~95% was achieved for experimental CH4 mole fractions between 0.02 and 0.70, and a precision of ~4% was achieved by maximizing relative excitation energy through induced chirp in the pump and Stokes pulses. It was further shown that mole‐fraction measurements were not affected by variations in bi‐molecular broadened linewidths over a wide range of mixture fractions. Copyright © 2013 John Wiley & Sons, Ltd.