Quantum State-Dependent Fragmentation Dynamics of D2S Molecules Following Excitation at Wavelengths ∼ 129.1 and ∼ 139.1 nm.

The first high-resolution translational spectroscopy studies of D atom photoproducts following excitation to the Rydberg states of D2S are reported. Excitation at wavelengths λ ∼ 139.1 nm reveals an unusual 'inverse' isotope effect; the 1B1(3da1←2b1) Rydberg state of D2S predissociates much faster than its counterpart in H2S. This is attributed to accidental near resonance with a vibrationally excited level of a lower-lying, more heavily predissociated Rydberg state of D2S that boosts the probability of nonadiabatic coupling to the dissociation continuum with 1A″ symmetry. Excitation at λ ∼ 129.1 nm populates the 1B1(4da1←2b1) Rydberg state, which predissociates more slowly and allows the study of ways in which the branching into different quantum states of the SD products varies with the choice of parent excited (JKaKc) level. All excited parent levels yield both ground (X) and electronically excited (A) state SD fragments. The former are distributed over a wide range of rovibrational (v″, N″) levels, while the population of levels with low v' and high N' is favored in the latter. These trends reflect the topographies of the dissociative 1A″ (1A') potential energy surfaces that correlate with the respective dissociation limits. Rotational motion about the b-inertial axis in the excited state molecule increases the relative yield of SD(A) products, consistent with dissociation by rotationally (Coriolis-) induced coupling from the photoexcited Rydberg level to the 1A' continuum. Molecules excited to the rotationless (JKaKc = 000) level also yield some SD(A) products, however, confirming the operation of a rival fragmentation pathway wherein photoexcited molecules decay by initial vibronic coupling to the 1A″ continuum, with subsequent nonadiabatic coupling between the 1A″ and 1A' continua enabling access to the D + SD(A) limit.

Pressure-Induced Changes in the Phase Distribution and Carrier Dynamics of Quasi-Two-Dimensional Ruddlesden-Popper Perovskites.

Quasi-two-dimensional (quasi-2D) perovskites hold significant potential for diverse design strategies due to their tunable structures, exceptional optical properties, and environmental stability. Due to the complexity of the structure and carrier dynamics, characterization methods such as photoluminescence and absorption spectroscopy can observe but cannot precisely distinguish or identify the phase distribution within quasi-2D perovskite films or correlate phases with carrier dynamics. In this study, we used pressure to modulate the intralayer and interlayer structures of (PEA)2Csn-1PbnBr3n+1 quasi-2D perovskite films, investigating charge carrier dynamics. Steady-state spectroscopy revealed phase transitions at 1.62, 3, and 8 GPa, with free excitons transforming into self-trapped excitons after 8 GPa. Transient absorption spectroscopy elucidated the structural evolution, energy transfer, and pressure-induced transition mechanisms. The results demonstrate that combining pressure and spectroscopy enables the precise identification of phase distribution and pressure response ranges and reveals photophysical mechanisms, providing new insights for optimizing optoelectronic materials.

Modulating Carrier Dynamics in PdSe2: The Role of Pressure in Electronic and Phononic Interactions.

PdSe2 is a puckered transition metal dichalcogenide that has been reported to undergo a two-dimensional to three-dimensional structural transition under pressure. Here, we investigated the electronic and phononic evolution of PdSe2 under high pressure using pump-probe spectroscopy. We observed the electronic intraband and interband transitions occurring in the d orbitals of Pd, revealing the disappearance of the Jahn-Teller effect under high pressure. Furthermore, we found that the decay rates of interband recombination and intraband relaxation lifetimes change at 3 and 7 GPa, respectively. First-principles calculations suggest that the bandgap closure slows the decay rate of interband recombination after 3 GPa, while the saturation of phonon-phonon scattering is the main reason for the relatively constant intraband relaxation lifetime. Our work provides a novel perspective for understanding the evolution of the electron and modulation of the carrier dynamics by phonons under pressure.

Real-time observation of two distinctive non-thermalized hot electron dynamics at MXene/molecule interfaces.

The photoinduced non-thermalized hot electrons at an interface play a pivotal role in determining plasmonic driven chemical events. However, understanding non-thermalized electron dynamics, which precedes electron thermalization (~125 fs), remains a grand challenge. Herein, we simultaneously captured the dynamics of both molecules and non-thermalized electrons in the MXene/molecule complexes by femtosecond time-resolved spectroscopy. The real-time observation allows for distinguishing non-thermalized and thermalized electron responses. Differing from the thermalized electron/heat transfer, our results reveal two non-thermalized electron dynamical pathways: (i) the non-thermalized electrons directly transfer to attached molecules at an interface within 50 fs; (ii) the non-thermalized electrons scatter at the interface within 125 fs, inducing adsorbed molecules heating. These two distinctive pathways are dependent on the irradiating wavelength and the energy difference between MXene and adsorbed molecules. This research sheds light on the fundamental mechanism and opens opportunities in photocatalysis and interfacial heat transfer theory.

Unraveling the Rich Fragmentation Dynamics Associated with S-H Bond Fission Following Photoexcitation of H2S at Wavelengths ∼129.1 nm.

H2S is being detected in the atmospheres of ever more interstellar bodies, and photolysis is an important mechanism by which it is processed. Here, we report H Rydberg atom time-of-flight measurements following the excitation of H2S molecules to selected rotational (JKaKc') levels of the 1B1 Rydberg state associated with the strong absorption feature at wavelengths of λ ∼ 129.1 nm. Analysis of the total kinetic energy release spectra derived from these data reveals that all levels predissociate to yield H atoms in conjunction with both SH(A) and SH(X) partners and that the primary SH(A)/SH(X) product branching ratio increases steeply with ⟨Jb2⟩, the square of the rotational angular momentum about the b-inertial axis in the excited state. These products arise via competing homogeneous (vibronic) and heterogeneous (Coriolis-induced) predissociation pathways that involve coupling to dissociative potential energy surfaces (PES(s)) of, respectively, 1A″ and 1A' symmetries. The present data also show H + SH(A) product formation when exciting the JKaKc' = 000 and 111 levels, for which ⟨Jb2⟩ = 0 and Coriolis coupling to the 1A' PES(s) is symmetry forbidden, implying the operation of another, hitherto unrecognized, route to forming H + SH(A) products following excitation of H2S at energies above ∼9 eV. These data can be expected to stimulate future ab initio molecular dynamic studies that test, refine, and define the currently inferred predissociation pathways available to photoexcited H2S molecules.

Photodissociation dynamics of SO2 via the G̃1B1 state: The O(1D2) and O(1S0) product channels.

Produced by both nature and human activities, sulfur dioxide (SO2) is an important species in the earth's atmosphere. SO2 has also been found in the atmospheres of other planets and satellites in the solar system. The photoabsorption cross sections and photodissociation of SO2 have been studied for several decades. In this paper, we reported the experimental results for photodissociation dynamics of SO2 via the G̃1B1 state. By analyzing the images from the time-sliced velocity map ion imaging method, the vibrational state population distributions and anisotropy parameters were obtained for the O(1D2) + SO(X3Σ-, a1Δ, b1Σ+) and O(1S0) + SO(X3Σ-) channels, and the branching ratios for the channels O(1D2) + SO(X3Σ-), O(1D2) + SO(a1Δ), and O(1D2) + SO(b1Σ+) were determined to be ∼0.3, ∼0.6, and ∼0.1, respectively. The SO products were dominant in electronically and rovibrationally excited states, which may have yet unrecognized roles in the upper planetary atmosphere.

Identification of Binding Sites in Copper(II)-Peptide Complexes Using Infrared Spectroscopy.

Complex formation of the copper(II) ion (CuII) with histidine (H) and H-containing peptides plays a crucial role in various metallo-enzymatic reactions. To elucidate the nature of coordinate bonding in CuII complexes, Fourier-transform infrared spectroscopy and 2D IR spectroscopy were employed to investigate the coordination geometries of CuII with diglycine, l-histidylglycine (HG), glycyl-l-histidine (GH), and glycylglycyl-l-histidine. The coordination of CuII to different peptide groups, including the peptide N- and C-termini, the amide group, and the imidazole of the H side chain, exhibits distinct spectral features. The derived molecular structure of the CuII-HG complex based on these spectral features significantly differs from that of CuII-GH, suggesting a preference of the N-terminus and the steric hindrance of the H side chain in CuII chelation.

Roaming in highly excited states: The central atom elimination of triatomic molecule decomposition.

Chemical reactions are generally assumed to proceed from reactants to products along the minimum energy path (MEP). However, straying from the MEP-roaming-has been recognized as an unconventional reaction mechanism and found to occur in both the ground and first excited states. Its existence in highly excited states is however not yet established. We report a dissociation channel to produce electronically excited fragments, S(1D)+O2(a1Δg), from SO2 photodissociation in highly excited states. The results revealed two dissociation pathways: One proceeds through the MEP to produce vibrationally colder O2(a1Δg) and the other yields vibrationally hotter O2(a1Δg) by means of a roaming pathway involving an intramolecular O abstraction during reorientation motion. Such roaming dynamics may well be the rule rather than the exception for molecular photodissociation through highly excited states.

Time-Resolved Dynamics of Metal Halide Perovskite under High Pressure: Recent Progress and Challenges.

Metal halide perovskites have garnered significant attention in the scientific community for their promising applications in optoelectronic devices. The application of pressure engineering, a viable technique, has played a crucial role in substantially improving the optoelectronic characteristics of perovskites. Despite notable progress in understanding ground-state structural changes under high pressure, a comprehensive exploration of excited-state dynamics influencing luminescence remains incomplete. This Perspective delves into recent advances in time-resolved dynamics studies of photoexcited metal halide perovskites under high pressure. With a focus on the intricate interplay between structural alterations and electronic properties, we investigate electron-phonon interactions, carrier transport mechanisms, and the influential roles of self-trapped excitons (STEs) and coherent phonons in luminescence. However, significant challenges persist, notably the need for more advanced measurement techniques and a deeper understanding of the phenomena induced by high pressure in perovskites.

Evidence of Surface-Mediated Carrier-Phonon Scattering in MXene.

In a two-dimensional (2D) metallic nanostructure, when a sample's thickness is shorter than a carrier mean free path, the ultrathin thickness may influence carrier and energy transport, owing to surface scattering. However, to date, for metallic 2D transition-metal carbides (MXenes), experiments and calculations related to surface scattering have not been performed. The contribution of ultrathin structures to carrier surface scattering in MXene is yet to be explored. Herein, to reveal this effect, we design various models, including metal/MXene, dielectric/MXene, and bulk structure, and analyze their carrier dynamics via ultrafast spectroscopy. The results related to carrier dynamics indicate that the influence of the dielectric/MXene interface and the temperature is negligible. In contrast, the carrier dynamic lifetimes are prolonged owing to weakened surface scattering in metal/MXene, which is supported by ab initio calculations. These results suggest that the carrier-phonon scattering is dominated by surface scattering. These findings can help guide effective energy transport and enhance energy conversion and catalysis.

A high-quality chromosome-level wild rice genome of Oryza coarctata.

Oryza coarctata (2n = 4X = 48, KKLL) is an allotetraploid, undomesticated relative of rice and the only species in the genus Oryza with tolerance to high salinity and submergence. Therefore, it contains important stress and tolerance genes/factors for rice. The initial draft genome published was limited by data and technical restrictions, leading to an incomplete and highly fragmented assembly. This study reports a new, highly contiguous chromosome-level genome assembly and annotation of O. coarctata. PacBio high-quality HiFi reads generated 460 contigs with a total length of 573.4 Mb and an N50 of 23.1 Mb, which were assembled into scaffolds with Hi-C data, anchoring 96.99% of the assembly onto 24 chromosomes. The genome assembly comprises 45,571 genes, and repetitive content contributes 25.5% of the genome. This study provides the novel identification of the KK and LL genome types of the genus Oryza, leading to valuable insights into rice genome evolution. The chromosome-level genome assembly of O. coarctata is a valuable resource for rice research and molecular breeding.

Multiple Dissociation Pathways in HNCO Decomposition Governed by Potential Energy Surface Topography.

The exquisite features of molecular photochemistry are key to any complete understanding of the chemical processes governed by potential energy surfaces (PESs). It is well established that multiple dissociation pathways relate to nonadiabatic transitions between multiple coupled PESs. However, little detail is known about how the single PES determines reaction outcomes. Here we perform detailed experiments on HNCO photodissociation, acquiring the state-specific correlations of the NH (a1Δ) and CO (X1Σ+) products. The experiments reveal a trimodal CO rotational distribution. Dynamics simulations based on a full-dimensional machine-learning-based PES of HNCO unveil three dissociation pathways exclusively occurring on the S1 excited electronic state. One pathway, following the minimum energy path (MEP) via the transition state, contributes to mild rotational excitation in CO, while the other two pathways deviating substantially from the MEP account for relatively cold and hot CO rotational state populations. These peculiar dynamics are unambiguously governed by the S1 state PES topography, i.e., a narrow acceptance cone in the vicinity of the transition state region. The dynamical picture shown in this work will serve as a textbook example illustrating the importance of the PES topography in molecular photochemistry.

Manipulating Lone-Pair-Driven Luminescence in 0D Tin Halides by Pressure-Tuned Stereochemical Activity from Static to Dynamic.

The excellent luminescence properties and structural dynamics driven by the stereoactivity of the lone pair in a variety of low-dimensional ns2 metal halides have attracted growing investigations for optoelectronic applications. However, the structural and photophysical aspects of the excited state associated with the lone pair expression are currently open questions. Herein, zero-dimensional Sn-based halides with static stereoactive 5 s2 lone pairs are selected as a model system to understand the correlations between the distinctive lone pair expression and the excited-state structural relaxation and charge carrier dynamics by continuous lattice manipulation. Lattice compression drives 5 s2 lone pair active switching and self-trapped exciton (STE) redistribution by suppressing excited-state structural deformation of the isolated SnBr4 2- units. Our results demonstrate that the static expression of the 5 s2 lone pair results in a red broadband triplet STE emission with a large Stokes shift, while its dynamic expression creates a sky-blue narrowband emission dominated by the radiative recombination of singlet STEs. Our findings and the photophysical mechanism proposed highlight the stereochemical effects of lone pair expression in controlling light emission properties and offer constructive guidelines for tuning the optoelectronic properties in diverse ns2 metal halides.

Exploring the vacuum ultraviolet photochemistry of astrochemically important triatomic molecules.

The recently constructed vacuum ultraviolet (VUV) free electron laser (FEL) at the Dalian Coherent Light Source (DCLS) is yielding a wealth of new and exquisitely detailed information about the photofragmentation dynamics of many small gas-phase molecules. This Review focuses particular attention on five triatomic molecules-H2O, H2S, CO2, OCS and CS2. Each shows excitation wavelength-dependent dissociation dynamics, yielding photofragments that populate a range of electronic and (in the case of diatomic fragments) vibrational and rotational quantum states, which can be characterized by different translational spectroscopy methods. The photodissociation of an isolated molecule from a well-defined initial quantum state provides a lens through which one can investigate how and why chemical reactions occur, and provides numerous opportunities for fruitful, synergistic collaborations with high-level ab initio quantum chemists. The chosen molecules, their photofragments and the subsequent chemical reaction networks to which they can contribute are all crucial in planetary atmospheres and in interstellar and circumstellar environments. The aims of this Review are 3-fold: to highlight new photochemical insights enabled by the VUV-FEL at the DCLS, notably the recently recognized central atom elimination process that is shown to contribute in all of these triatomic molecules; to highlight some of the potential implications of this rich photochemistry to our understanding of interstellar chemistry and molecular evolution within the universe; and to highlight other and future research directions in areas related to chemical reaction dynamics and astrochemistry that will be enabled by increased access to VUV-FEL sources.

Highly Efficient Photosensitizers with Molecular Vibrational Torsion for Cancer Photodynamic Therapy.

The development of highly effective photosensitizers (PSs) for photodynamic therapy remains a great challenge at present. Most PSs rely on the heavy-atom effect or the spin-orbit charge-transfer intersystem crossing (SOCT-ISC) effect to promote ISC, which brings about additional cytotoxicity, and the latter is susceptible to the interference of solvent environment. Herein, an immanent universal property named photoinduced molecular vibrational torsion (PVT)-enhanced spin-orbit coupling (PVT-SOC) in PSs has been first revealed. PVT is verified to be a widespread intrinsic property of quinoid cyanine (QCy) dyes that occurs on an extremely short time scale (10-10 s) and can be captured by transient spectra. The PVT property can provide reinforced SOC as the occurrence of ISC predicted by the El Sayed rules (1ππ*-3nπ*), which ensures efficient photosensitization ability for QCy dyes. Hence, QTCy7-Ac exhibited the highest singlet oxygen yield (13-fold higher than that of TCy7) and lossless fluorescence quantum yield (ΦF) under near-infrared (NIR) irradiation. The preeminent photochemical properties accompanied by high biosecurity enable it to effectively perform photoablation in solid tumors. The revelation of this property supplies a new route for constructing high-performance PSs for achieving enhanced cancer phototherapy.

Vacuum ultraviolet photodissociation of sulfur dioxide and its implications for oxygen production in the early Earth's atmosphere.

The emergence of molecular oxygen (O2) in the Earth's primitive atmosphere is an issue of major interest. Although the biological processes leading to its accumulation in the Earth's atmosphere are well understood, its abiotic source is still not fully established. Here, we report a new direct dissociation channel yielding S(1D) + O2(a1Δg/X3Σg-) products from vacuum ultraviolet (VUV) photodissociation of SO2 in the wavelength range between 120 and 160 nm. Experimental results show O2 production to be an important channel from SO2 VUV photodissociation, with a branching ratio of 30 ± 5% at the H Lyman-α wavelength (121.6 nm). The relatively large amounts of SO2 emitted from volcanic eruptions in the Earth's late Archaean eon imply that VUV photodissociation of SO2 could have provided a crucial additional source term in the O2 budget in the Earth's primitive atmosphere. The results could also have implications for abiotic oxygen formation on other planets with atmospheres rich in volcanically outgassed SO2.

Exploring the Potential Applications of Lanthanide-Based Double Perovskite in Remote Pressure and Temperature Sensing.

Remote optical sensing with nondestructive, fast, and accurate detection capabilities is a powerful noncontact method widely used in natural, industrial, and biological fields. In this work, Cs2NaErCl6 double perovskite was synthesized via a hydrothermal method. The pressure-dependent photoluminescence (PL) lifetime of Er3+ in the range of 0-20 GPa was investigated, demonstrating its potential for pressure monitoring. The high-pressure relative sensitivity (SR) is ∼18.45% GPa-1. Temperature measurements were conducted using the fluorescence intensity ratio (FIR) of the thermal couple energy level (TCEL) and the nonthermal couple energy level (NTCEL) of Er3+ across a temperature range of 100-660 K, with a maximum SR of 5.36% K-1. By combining MXene with Cs2NaErCl6 and recording the FIR of Cs2NaErCl6 under 1550 nm excitation, the photothermal conversion temperature of MXene can be accurately determined. These findings highlight the potential of Cs2NaErCl6 for remote pressure and temperature sensing, particularly in the biomedical field.

Photodissociation dynamics of SO2 between 193 and 201 nm.

The nonadiabatic interactions between the C̃ state and neighboring electronic states of SO2 have attracted much attention; however, the predissociation mechanisms are not yet completely understood. In this work, the predissociation dynamics of SO2 via its C̃ state have been investigated at λ = 193-201 nm by using the time-sliced velocity map ion imaging technique. The translational energy distributions and the branching ratios of the O(3PJ=2,1,0) spin-orbit products at six photolysis wavelengths have been acquired. The SO(3Σ-) product population gradually decreases in v = 0 and increases in v = 2 as the photolysis wavelength decreases. The branching ratios of O(3P J=2,1,0) products are almost similar at most wavelengths, except at 194.8 nm. Our data suggest that the predissociation between 193 and 201 nm is via an avoided crossing between the C̃ state and the repulsive triplet 23A' state. The state-to-state dynamical pictures shown in this work provide a rigorous test of the potential energy surfaces (PESs) of the SO2 and the nonadiabatic couplings between these PESs.

Slice imaging study of NO2 photodissociation via the 12B2 and 22B2 states: the NO(X2Π) + O(3PJ) product channel.

The state-resolved photodissociation of NO2via the 12B2 and 22B2 excited states has been investigated by using time-sliced velocity-mapped ion imaging technique. The images of the O(3PJ=2,1,0) products at a series of excitation wavelengths are measured by employing a 1 + 1' photoionization scheme. The total kinetic energy release (TKER) spectra, NO vibrational state distributions and anisotropy parameters (ß) are derived from the O(3PJ=2,1,0) images. For the 12B2 state photodissociation of NO2, the TKER spectra mainly present a non-statistical vibrational state distribution of the NO co-products, and the profiles of most vibrational peaks display a bimodal structure. The ß values show a gradual decrease with the photolysis wavelength increasing except for a sudden increase at 357.38 nm. The results suggest that the NO2 photodissociation via the 12B2 state proceeds via the non-adiabatic transition between the 12B2 and X̃2A1 states, leading to the NO(X2Π) + O(3PJ) products with wavelength-dependent rovibrational distributions. As for photodissociation of NO2via the 22B2 state, the NO vibrational state distribution is relatively narrow with the main peak shifting from v = 1, 2 at 235.43-249.22 nm to v = 6 at 212.56 nm. The ß values exhibit two distinctly different angular distributions, i.e., near isotropic at 249.22 and 246.09 nm and anisotropic at the rest of the excitation wavelengths. These results are consistent with the fact that the 22B2 state potential energy surface has a barrier, and the dissociation process is fast when the initial populated level is above this barrier. A bimodal vibrational state distribution is clearly observed at 212.56 nm, in which the main distribution (peaking at v = 6) is ascribed to dissociation via an avoided crossing with the higher electronically excited state while the subsidiary distribution (peaking at v = 11) likely arises due to dissociation via the internal conversion to the 12B2 state or to the X̃ ground state.

Tailoring the high-brightness "warm" white light emission of two-dimensional perovskite crystals via a pressure-inhibited nonradiative transition.

Efficient warm white light emission is an ideal characteristic of single-component materials for light-emitting applications. Although two-dimensional hybrid perovskites are promising candidates for light-emitting diodes, as they possess broadband self-trapped emission and outstanding stability, they rarely achieve a high photoluminescence quantum yield of warm white light emissions. Here, an unusual pressure-induced warm white emission enhancement phenomenon from 2.1 GPa to 9.9 GPa was observed in two-dimensional perovskite (2meptH2)PbCl4, accompanied by a large increase in the relative quantum yield of photoluminescence. The octahedral distortions, accompanied with the evolution of organic cations, triggered the structural collapse, which caused the sudden emission enhancement at 2.1 GPa. Afterwards, the further intra-octahedral collapse promotes the formation of self-trapped excitons and the substantial suppression of nonradiative transitions are responsible for the continuous pressure-induced photoluminescence enhancement. This study not only clearly illustrates the relationship between crystal structure and photoluminescence, but also provides an experimental basis for the synthesis of high-quality warm white light-emitting 2D metal halide perovskite materials.