Excited State Absorption Spectra Research Articles

Role of cation nature in crown ether appended 25-Oxasmaragdyrins with second-order NLO responses: As potential and selective metal ions detector

Crown ethers, known for their efficacy as metal ion traps, have garnered significant interest in optoelectronic applications due to their unique cavity structure and special binding ability with metals. Herein, we systematically designed and investigated the second-order nonlinear optical (NLO) properties of an intriguing compound, 18-crown-6 derivative appended with 25-oxasmaragdyrins (Cr-Prs), achieved through the incorporation of diverse metal ions into the crown ether ring. Significantly, the βtot values of compounds with alkaline earth metal ions (Mg2+, Ca2+) are greater than those compounds with alkali metal ions (Na+, K+). Interestingly, the Hg2+@Cr-Prs compound exhibits a tremendous second-order NLO property with the βtot value of 5.34 × 105 au. Further insights into substantial βtot values across all compounds were provided through a comprehensive analysis of the transition energies, the molecular orbitals, and the absorption spectra of the main excited states. The calculation results conclude that the second-order NLO properties of Cr-Prs can be modulated by incorporating metal ions into the crown ether ring. Crown ether emerges as a facilitator in detecting and identifying Hg2+ ions, serving as an effective NLO-based ion detector. These findings not only broaden the scope of cation detection and efficiency but also present innovative applications in analytical and optoelectronic research, encapsulating the essence of our study within a concise framework.

Which Options Exist for NISQ-Friendly Linear Response Formulations?

Linear response (LR) theory is a powerful tool in classic quantum chemistry crucial to understanding photoinduced processes in chemistry and biology. However, performing simulations for large systems and in the case of strong electron correlation remains challenging. Quantum computers are poised to facilitate the simulation of such systems, and recently, a quantum linear response formulation (qLR) was introduced [Kumar et al., J. Chem. Theory Comput. 2023, 19, 9136-9150]. To apply qLR to near-term quantum computers beyond a minimal basis set, we here introduce a resource-efficient qLR theory, using a truncated active-space version of the multiconfigurational self-consistent field LR ansatz. Therein, we investigate eight different near-term qLR formalisms that utilize novel operator transformations that allow the qLR equations to be performed on near-term hardware. Simulating excited state potential energy curves and absorption spectra for various test cases, we identify two promising candidates, dubbed "proj LRSD" and "all-proj LRSD".

Generalization of One-Center Nonorthogonal Configuration Interaction Singles to Open-Shell Singlet Reference States: Theory and Application to Valence-Core Pump-Probe States in Acetylacetone.

We formulate a one-center nonorthogonal configuration interaction singles (1C-NOCIS) theory for the computation of core excited states of an initial singlet state with two unpaired electrons. This model, which we refer to as 1C-NOCIS two-electron open-shell (2eOS), is appropriate for computing the K-edge near-edge X-ray absorption spectra (NEXAS) of the valence excited states of closed-shell molecules relevant to pump-probe time-resolved (TR) NEXAS experiments. With the inclusion of core-hole relaxation effects and explicit spin adaptation, 1C-NOCIS 2eOS requires mild shifts to match experiment, is free of artifacts due to spin contamination, and can capture the high-energy region of the spectrum beyond the transitions into the singly occupied molecular orbitals (SOMOs). Calculations on water and thymine illustrate the different key features of excited-state NEXAS, namely, the core-to-SOMO transitions as well as shifts and spin-splittings in the transitions analogous to those of the ground state. Simulations of the TR-NEXAS of acetylacetone after excitation to its π → π* singlet excited state at the carbon K-edge, an experiment carried out recently, showcase the ability of 1C-NOCIS 2eOS to efficiently simulate NEXAS based on nonadiabatic molecular dynamics simulations.

Excited-state absorption in light-scattering Er:CaSc2O4 ceramic

Excited-state absorption (ESA) in visible from the I13/24 level in the upconversion phosphor Er:CaSc2O4 is investigated. ESA spectra are recorded in the spectral range 400 - 750 nm in ceramic optically-scattering Er(2 at.%):CaSc2O4. The ESA spectra are calibrated to cross-section units and separated from other processes (luminescence, stimulated emission) taking place in this spectral range. ESA from the I11/24 level is also noticed and discussed. The cross-sections of the various ESA processes in the visible spectral range are found. The precision of the calibration method is discussed.

Tm:CALGO lasers at 2.32 µm: cascade lasing and upconversion pumping.

We report on the first laser operation of a disordered Tm:CaGdAlO4 crystal on the 3H4 → 3H5 transition. Under direct pumping at 0.79 µm, it generates 264 mW at 2.32 µm with a slope efficiency of 13.9% and 22.5% vs. incident and absorbed pump power, respectively, and a linear polarization (σ). Two strategies to overcome the bottleneck effect of the metastable 3F4 Tm3+ state leading to the ground-state bleaching are exploited: cascade lasing on the 3H4 → 3H5 and 3F4 → 3H6 transitions and dual-wavelength pumping at 0.79 and 1.05 µm combining the direct and upconversion pumping schemes. The cascade Tm-laser generates a maximum output power of 585 mW at 1.77 µm (3F4 → 3H6) and 2.32 µm (3H4 → 3H5) with a higher slope efficiency of 28.3% and a lower laser threshold of 1.43 W, out of which 332 mW are achieved at 2.32 µm. Under dual-wavelength pumping, further power scaling to 357 mW at at 2.32 µm is observed at the expense of increased laser threshold. To support the upconversion pumping experiment, excited-state absorption spectra of Tm3+ ions for the 3F4 → 3F2,3 and 3F4 → 3H4 transitions are measured for polarized light. Tm3+ ions in CaGdAlO4 exhibit broadband emission at 2.3 - 2.5 µm making this crystal promising for ultrashort pulse generation.

Ab Initio Investigation of Intramolecular Charge Transfer States in DMABN by Calculation of Excited State X-ray Absorption Spectra

Dual fluorescence in 4-(dimethylamino)benzonitrile (DMABN) and its derivatives in polar solvents has been studied extensively for the past several decades. An intramolecular charge transfer (ICT) minimum on the excited state potential energy surface, in addition to the localized low-energy (LE) minimum, has been proposed as a mechanism for this dual fluorescence, with large geometric relaxation and molecular orbital reorganization a key feature of the ICT pathway. Herein, we have used both equation-of-motion coupled-cluster with single and double excitations (EOM-CCSD) and time-dependent density functional (TDDFT) methods to investigate the landscape of excited state potential energy surfaces across a number of geometric conformations proposed as ICT structures. In order to correlate these geometries and valence excited states in terms of potential experimental observables, we have calculated the nitrogen K-edge ground and excited state absorption spectra for each of the predicted "signpost" structures and identified several key spectral features that could be used to interpret a future time-resolved X-ray absorption experiment.

Excited-state absorption and upconversion pumping of Tm3+-doped potassium lutetium double tungstate.

We report on a bulk thulium laser operating on the 3H4 → 3H5 transition with pure upconversion pumping at 1064 nm by an ytterbium fiber laser (addressing the 3F4 → 3F2,3 excited-state absorption (ESA) transition of Tm3+ ions) generating 433 mW at 2291 nm with a slope efficiency of 7.4% / 33.2% vs. the incident / absorbed pump power, respectively, and linear laser polarization representing the highest output power ever extracted from any bulk 2.3 µm thulium laser with upconversion pumping. As a gain material, a Tm3+-doped potassium lutetium double tungstate crystal is employed. The polarized ESA spectra of this material in the near-infrared are measured by the pump-probe method. The possible benefits of dual-wavelength pumping at 0.79 and 1.06 µm are also explored, indicating a positive effect of co-pumping at 0.79 µm on reducing the threshold pump power for upconversion pumping.

Diiodo-BODIPY Sensitizing of the [Mo3S13]2- Cluster for Noble-Metal-Free Visible-Light-Driven Hydrogen Evolution within a Polyampholytic Matrix.

We report on a photocatalytic setup that utilizes the organic photosensitizer (PS) diiodo-BODIPY and the non-precious-metal-based hydrogen evolution reaction (HER) catalyst (NH4)2[Mo3S13] together with a polyampholytic unimolecular matrix poly(dehydroalanine)-graft-poly(ethylene glycol) (PDha-g-PEG) in aqueous media. The system shows exceptionally high performance with turnover numbers (TON > 7300) and turnover frequencies (TOF > 450 h-1) that are typical for noble-metal-containing systems. Excited-state absorption spectra reveal the formation of a long-lived triplet state of the PS in both aqueous and organic media. The system is a blueprint for developing noble-metal-free HER in water. Component optimization, e.g., by modification of the meso substituent of the PS and the composition of the HER catalyst, is further possible.

Near-Infrared Absorption Features of Triplet-Pair States Assigned by Photoinduced-Absorption-Detected Magnetic Resonance.

Singlet fission proceeds through a manifold of triplet-pair states that are exceedingly difficult to distinguish spectroscopically. Here, we introduce a new implementation of photoinduced-absorption-detected magnetic resonance (PADMR) and use it to understand the excited-state absorption spectrum of a tri-2-pentylsilylethynyl pentadithiophene (TSPS-PDT) film. These experiments allow us to directly correlate magnetic transitions driven by RF with electronic transitions in the visible and near-infrared spectrum with high sensitivity. We find that the new near-infrared excited-state transitions that arise in thin films of TSPS-PDT are correlated with the magnetic transitions of T1, not 5TT. Thus, we assign these features to the excited-state absorption of 1TT, which is depleted when T1 states are driven to a spin configuration that forbids subsequent fusion. These results clarify the disputed origin of triplet-associated near-infrared absorption features in singlet-fission materials and demonstrate an incisive general purpose tool for studying the evolution of high-spin excited states.

Transient “cis-Peak” Is Present in Excited-State Absorption of Central-cis Isomers of Carotenoids

Application of femtosecond time-resolved transient absorption spectroscopy on all-trans and central-cis isomers of two exemplary carotenoids, lutein and spirilloxanthin, performed at room and cryogenic temperatures in the spectral range expanded toward UV revealed new spectroscopic transient features for the cis isomers. Notably, particularly for the central-cis spirilloxanthin, a very distinct additional transient absorption band is observed on the short wavelength side of the main excited-state absorption band of the S1 state, having the same temporal characteristics as the latter one. This band is absent in transient absorption spectra of all-trans isomers, suggesting it could be assigned to "transient cis-peak." Overall, the results show that the "transient" counterpart of the spectral marker of cis-isomers of carotenoids, or the so-called cis-peak, is detectable in the excited-state absorption spectrum and could be attributed to electronic transition from the S1 state. This new transient spectral band could be very useful for spectroscopic experiments targeting the dynamics of carotenoid isomers and their severely distorted forms.

Effects of aggregation on the structures and excited-state absorption for zinc phthalocyanine.

In the present paper, the aggregated structures of zinc phthalocyanine (ZnPc) have been investigated by considering its dimers and trimers. Based on the density functional theory calculations, two stable conformations are obtained for the ZnPc dimer and trimer, respectively. The IGMH (independent gradient model based on the Hirshfeld partition of molecular density) analysis reveals that the π-π interaction between the ZnPc molecules causes the aggregation. Normally, stacked structures with a slight displacement are favorable for aggregation. In addition, the planar structure of the ZnPc monomer is largely maintained in the aggregated conformations. For the presently obtained structures, the first singlet excited state absorption (ESA) spectra of these aggregated conformations of ZnPc were calculated based on the linear-response time-dependent density functional theory (LR-TDDFT), which has been well applied by our group. The results of the excited state absorption spectra reveal that the aggregation causes the ESA band to blue shift compared to the ZnPc monomer. By using the conventional description of the interaction between monomer transition dipoles, this blue shift is elucidated by the side-by-side transition dipole moments in the constituted monomers. The present results for the ESA combined with the previously reported results for ground state absorption (GSA) will provide guidelines to tune the window of the optical-limiting effect for the ZnPc based materials.

Numerical analysis and optimization of 2.8 μm lightly-erbium-doped fluoride fiber laser based on cascaded transition

Er<sup>3+</sup>-doped ZBLAN fiber laser is a promising approach to producing 2.8 μm mid-infrared (MIR) laser. The long lifetime of the lower-laser-level <sup>4</sup>I<sub>13/2</sub> often results in serious self-terminating effect which harms the laser power and efficiency significantly, especially for the active fiber with low dopant concentration which is preferred for weak thermal issues but cannot depopulate the lower-laser-level effectively via the up-conversion process. The 1.6 μm lasing (<sup>4</sup>I<sub>13/2 </sub>→ <sup>4</sup>I<sub>15/2</sub>) in Er-ZBLAN fiber could deplete the population on <sup>4</sup>I<sub>13/2</sub>. Therefore, cascaded 2.8 μm and 1.6 μm lasing in Er<sup>3+</sup>-doped ZBLAN fiber provides a promising solution to the self-termination effects on laser power scaling. Moreover, the <sup>4</sup>I<sub>13/2 </sub>→ <sup>4</sup>I<sub>15/2</sub> 1.6 μm laser also has some overlap with the <sup>4</sup>I<sub>13/2 </sub>→ <sup>4</sup>I<sub>9/2</sub> excited state absorption (ESA) spectrum. The ions on the <sup>4</sup>I<sub>9/2</sub> level would then relax to the upper-laser-level of 2.8 μm lasing (<sup>4</sup>I<sub>11/2</sub>), and results in enhanced laser efficiency. In general, the 1.6 μm cascaded lasing in 2.8 μm Er-ZBLAN fiber laser involves both lasing and ESA. The two processes have different spectra and different influences on the 2.8 μm laser gain. Therefore, there should exist an optimal wavelength of the 1.6 μm laser, which would balance the two processes, ensuring the lower-laser-level depopulation while maximizing the ion recycling. Therefore, we develop a comprehensive numerical model of cascaded 2.8 μm and 1.6 μm lasers based on Er-ZBLAN fiber. After the numerical model is verified by the previous experimental results, the effects of MIR and 1.6 μm lasing wavelengths on the power and conversion efficiency of 2.8 μm laser are investigated in depth. The results show that a suitable trade-off between the two processes can be reached with the cascaded lasing wavelength of 1610 nm, for the optimized 2.8 μm laser power/efficiency. Moreover, the influence of 1.6 μm laser cavity feedback on the power/efficiency characteristics of the 2.8 μm laser is also investigated. It is found that the feedback at 1.6 μm is very low, even only 4% is provided by the Fresnel reflection of the fiber facet, which can effectively generate 1.6 μm laser and significantly improve the efficiency of 2.8 μm laser.

Panchromatic Excited-State Absorption in Bis-Cyclometalated Iridium Isocyanide Complexes.

In this work, we introduce a series of cyclometalated iridium complexes and evaluate the suitability of this class of compounds in nonlinear optical (NLO) applications, with an emphasis on long-lived, panchromatic reverse-saturable absorption (RSA). The investigated complexes are represented by the general formula [Ir(C^N)2(CNArdmp)2]+, (C^N = cyclometalating ligand, CNArdmp = 2,6-dimethylphenyl isocyanide). Seven such complexes were synthesized and characterized, including in-depth analysis of their photophysical properties (UV-vis absorption, photoluminescence, and transient absorption). This series of compounds contains seven different cyclometalating ligands (2-phenylbenzothiazole (bt) (Ir1), 5-nitro-2-phenylpyridine (ppyNO2) (Ir2), 5-nitro-2-(9-phenanthryl)pyridine (phenNO2) (Ir3), 2-(benzo[b]thiophen-2-yl)quinoline (btq) (Ir4), 6-(benzo[b]thiophen-2'-yl)phenanthridine (btph) (Ir5), 2,4-diphenylquinoline (dpq) (Ir6), and 6-nitro-2,4-diphenylquinoline (NO2dpq) (Ir7)), which have profound effects on their ground-state and excited-state absorption spectra. To evaluate the effects of the isocyanide ancillary ligands, some heteroleptic bis-cyclometalated iridium(III) acetylacetonate (acac) analogue complexes are included as points of comparison. In the ground state, the bis-isocyanide complexes display UV-vis absorption with the characteristic 1LC (π → π*) band at λ < 350 nm and 1MLCT bands at 350-500 nm. Five of the complexes (Ir1, Ir2, Ir4, Ir5, and Ir6) display broad, intense triplet excited-state absorption with no ground-state bleach (GSB) over the spectral window of 400-900 nm, with excited-state lifetimes spanning three orders of magnitude from ∼32 ns to 12 μs. The photophysical data suggests that the isocyanide ancillary ligand blue-shifts the GSB transient into the UV, which is normally found in the middle of the visible region for cyclometalated iridium complexes. This study demonstrates the applicability of cationic cyclometalated iridium(III) bis-isocyanide complexes as candidate RSA materials.

Accurate Calculation of Excited-State Absorption for Small-to-Medium-Sized Conjugated Oligomers: Multiconfigurational Treatment vs Quadratic Response TD-DFT.

Excited-state absorption (ESA) spectra of π-conjugated compounds are frequently calculated by (quadratic response) time-dependent density functional theory, (QR) TD-DFT, often giving a reasonable representation of the experimental results despite the (known) incomplete electronic description. To investigate whether this is inherent to the method, we calculate here the ESA spectra of small-to-medium-sized oligophenylenevinylenes (nPV) and oligothiophenes (nT) using QR TD-DFT as well as CASPT2 based on CASSCF geometries. CASPT2 gives indeed a reliable, theoretically correct description of the ESA features for all compounds; the computational effort can be reduced without significant loss of accuracy using TD-DFT geometries. QR TD-DFT, based on BHandHLYP and CAM-/B3LYP functionals, fails on short nTs but provides a reasonable description for spectral positions of nPVs and long nTs. The failure on short nTs is, however, only partly due to the incomplete configuration description but, in particular, related to an improper MO description, resulting in an asymmetric energy spacing of the occupied vs unoccupied MOs in the DFT scheme. Longer nTs, on the other side, adapt approximately the MO scheme for alternant hydrocarbons just like in nPVs, while contributions by two triplet excitations combined to a singlet (which inhibits an accurate treatment of polyenes with standard TD-DFT) do not play a relevant role in the current case. For such "well-behaved" systems, a reasonable representation of ESA spectra is found at the QR TD-DFT level due to the rather small energy shifts when including higher-order excitations.

Simulating excited-state absorption spectra in upconverting lanthanide doped nanoparticles: KY3F10:Er3+

High-resolution absorption and laser-excited fluorescence studies of KY3F10:Er3+ core-only nanoparticles are presented. A total of 49 crystal-field energy levels, distributed amongst 13 multiplets of the Er3+ ion, have been deduced for the C4v point group symmetry centre in this material. A parametrized, single-electron crystal-field calculation provides an excellent approximation to the experimental data with optimized crystal fit parameters that are comparable to the bulk KY3F10:Er3+ crystal. Simulated spectra, based upon wavefunctions derived from the crystal-field calculations, unequivocally demonstrate that excited-state absorption is the predominant upconversion mechanism in this material – agreeing well with upconversion excitation spectra obtained for Yb3+ co-doped samples.

Er&lt;sup&gt;3+&lt;/sup&gt;,Yb&lt;sup&gt;3+&lt;/sup&gt;:YGdSiO&lt;sub&gt;5&lt;/sub&gt; Crystal as Gain Media for Lasers Emitting in the Spectral Range of 1.5–1.6 µm

Solid-state erbium lasers, emitting in the spectral range of 1.5–1.6 µm, are of great interest for several industrial applications. Nowadays the Er:glass is the most widespread laser material for obtaining laser radiation at the wavelength near 1.5 µm. However, the maximal output powers of such lasers are restricted by hundreds of milliwatts because low thermal characteristics of the glass host. By this reason the search for new crystalline hosts doped with erbium ions is the actual task.In this article the investigation results of spectroscopic properties of Er3+,Yb3+:YGdSiO5 (YGSO) crystals are reported. Polarized absorption and luminescence spectra were measured. The lifetimes of energy levels were determined. The excited state absorption spectra were measured. It was shown that excited state absorption band does not overlap with gain band in the range 1.5–1.6 µm. The energy transfer efficiency from ytterbium to erbium ions was estimated. The stimulated emission and gain cross-section spectra for Er3+ ions in YGSO were calculated.

Quantum-chemistry study of the ground and excited state absorption of distyrylbenzene: Multi vs single reference methods.

State-of-the-art complete active space self-consistent field/complete active space second order perturbation theory (CASPT2) calculations are used to investigate the role of double excitations on the ground state absorption (GSA) and excited state absorption (ESA) spectra of distyrylbenzene, an important prototype medium-sized π-conjugated organic compound for optoelectronics. The multi-reference results are compared with linear and quadratic response time-dependent density functional theory (DFT) results, revealing an incomplete description of the electronic transitions in the latter. Careful selection of the active space and basis set in the CASPT2 approach allows for a reliable description of the GSA and ESA features; cost-effective DFT-based geometries can be utilized without a significant loss of accuracy. Double excitations are shown to play a pivotal role already for higher excited states in the GSA spectrum, however, without a relevant impact on the discernible spectral features. In the ESA, which shows a much more complex electronic situation, the crucial importance of double (and higher) excitations in all relevant electronic transitions, indeed, mandates a multiconfigurational treatment as done in the present benchmark study.

Influence of electron-withdrawing groups in two-photon absorption of imidazopyridines derivatives

This work investigates the influence of different electron-withdrawing groups (Cl, Br, fluorobenzonitrile), on the two-photon absorption cross-section of six imidazo[4,5-b]pyridine derivatives. The two-photon absorption cross-section spectra were obtained by ultra-fast Z-scan technique from 470 nm up to 700 nm. The Sum-Over-States approach was applied to model the two-photon absorption spectra, using a three-level energy system. Photophysical properties, such as transition dipole moment, the difference of permanent dipole moments, and anisotropy coefficient were determined through the analysis of one-photon absorption spectra, solvatochromism, and fluorescence anisotropy, respectively. Besides, the excited state absorption spectra were measured through ultra-fast transient absorption, allowing the excited state lifetime and spectral position determination. Two-photon absorption cross-sections of about 160 GM were observed when two electron-withdrawing groups are linked to the imidazo[4,5-b]pyridine core, elucidating a path to achieve high optical nonlinearities in imidazopyridine derivatives. Furthermore, a increase in the two-photon cross-section was observed when chloride is linked at the C-6 position (90 GM) instead of the C-5 position (50 GM), which is related to the proximity of a higher excited state.

An assessment of different electronic structure approaches for modeling time-resolved x-ray absorption spectroscopy.

We assess the performance of different protocols for simulating excited-state x-ray absorption spectra. We consider three different protocols based on equation-of-motion coupled-cluster singles and doubles, two of them combined with the maximum overlap method. The three protocols differ in the choice of a reference configuration used to compute target states. Maximum-overlap-method time-dependent density functional theory is also considered. The performance of the different approaches is illustrated using uracil, thymine, and acetylacetone as benchmark systems. The results provide guidance for selecting an electronic structure method for modeling time-resolved x-ray absorption spectroscopy.

Excited-State Absorption of Uracil in the Gas Phase: Mapping the Main Decay Paths by Different Electronic Structure Methods.

We present a computational study of the one-photon and excited-state absorption (ESA) from the two lowest energy excited states of uracil in the gas phase: an nπ* dark state (1n) and the lowest energy bright ππ* state (1π). The predictions of six different linear response electronic structure methods, namely, TD-CAM-B3LYP, EOM-CCSD, EOM-CC3, ADC(2), ADC(2)-x, and ADC(3) are critically compared. In general, the spectral shapes predicted by TD-CAM-B3LYP, EOM-CCSD, EOM-CC3, and ADC(3) are fairly similar, though the quality of TD-CAM-B3LYP slightly deteriorates in the high-energy region. By computing the spectra at some key structures on different potential energy surfaces (PES), that is, the Franck-Condon point, the 1n minimum, and structures representative of different regions of the 1π PES, we obtain important insights into the shift of the ESA spectra, following the motion of the wavepacket on the excited-state PES. Though 1π has larger ESA than 1n, some spectral regions are dominated by these latter signals. Aside from its methodological interest, we thus obtain interesting indications to interpret transient absorption spectra to disentangle the photoactivated dynamics of nucleobases.