Sustainable high-strength and dimensionally stable composites through in situ regulation and reconstitution of bamboo-derived lignin and hemicellulose contents.

The development of modern construction and transportation industries demands increasingly high requirements for thin, lightweight, high-strength, and highly tough composite materials, such as metal carbides and concrete. Bamboo is a green, low-carbon, fast-growing, renewable, and biodegradable material with high strength and toughness. However, the density of its inner layer is low due to the functional gradient (the volume fraction of vascular bundles decreases from the outer layer to the inner layer), resulting in low performance, high compressibility, and significant amounts of bamboo waste. We utilized chemical and mechanical treatments of bamboo's low-density, low-strength inner layers to create lightweight, ultra-thin, high-strength, and high-toughness composites. The treatment included the partial removal of lignin and hemicellulose to alter the chemical components, followed by mechanical drying and hot pressing. The treated bamboo had 100.8 % higher tensile strength (150.35 MPa), 47.7 % higher flexural strength (97.67 MPa), and 132.0 % higher water resistance and was approximately 68.9 % thinner than the natural bamboo. The excellent physical and mechanical properties of the treated bamboo are attributed to the contraction of parenchyma cells during delignification, the interlocking due to the collapse of parenchyma cells during mechanical drying, and an increase in the density of hydrogen bonds between cellulose molecular chains during hot pressing. Our research provides a new strategy for obtaining sustainable, ultra-thin, lightweight, high-strength, and high-toughness composite materials from bamboo for construction and transportation applications.

Quantum Dynamics of Photodissociation: Recent Advances and Challenges.

Recent advances in constructing accurate potential energy surfaces and nonadiabatic couplings from high-level ab initio data have revealed detailed potential landscapes in not only the ground electronic state but also excited ones. They enabled quantitatively accurate characterization of photoexcited reactive systems using quantum mechanical methods. In this Perspective, we survey the recent progress in quantum mechanical studies of adiabatic and nonadiabatic photodissociation dynamics, focusing on initial state control and product energy disposal. These new insights helped to understand quantum effects in small prototypical systems, and the results serve as benchmarks for developing more approximate theoretical methods.

Imaging of the charge-transfer reaction of spin-orbit state-selected Ar+(2P3/2) with N2 reveals vibrational-state-specific mechanisms.

Charge-transfer reactions are ubiquitous and play important roles in various gaseous environments, but, despite a long history of extensive research, our understanding of their dynamics at the quantum state-to-state level is still lacking. Here we report quantum-state-resolved experiments for the paradigmatic charge-transfer reaction Ar+ + N2 → Ar + N2+ using a three-dimensional velocity-map imaging crossed-beam apparatus with the Ar+ beam prepared exclusively in the spin-orbit state 2P3/2. High-resolution scattering images show strong dependence of rotational and angular distributions on the vibrational quantum number of the N2+ product. Trajectory surface-hopping calculations, which semi-quantitatively reproduce the experimental observations, support the existence of two distinct charge-transfer mechanisms. One of these, in the dominant N2+(v' = 1) channel, is the well-known long-distance harpooning mechanism. However, the highly rotationally excited products in the forward direction are attributed to a hard-collision glory scattering mechanism, which occurs on account of the strong attraction between the collisional partners counterbalanced by the short-range repulsive interaction.

Nonadiabatic Reactive Quenching of OH(A2Σ+) by H2: Origin of High Vibrational Excitation in the H2O Product.

The nonadiabatic dynamics of the reactive quenching channel of the OH(A2Σ+) + H2/D2 collisions is investigated with a semiclassical surface hopping method, using a recently developed four-state diabatic potential energy matrix (DPEM). In agreement with experimental observations, the H2O/HOD products are found to have significant vibrational excitation. Using a Gaussian binning method, the H2O vibrational state distribution is determined. The preferential energy disposal into the product vibrational modes is rationalized by an extended Sudden Vector Projection model, in which the h and g vectors associated with the conical intersection are found to have large projections with the product normal modes. However, our calculations did not find significant insertion trajectories, suggesting the need for further improvement of the DPEM.

Bamboo-Inspired Renewable, Lightweight, and Vibration-Damping Laminated Structural Materials for the Floor of a Railroad Car.

It is important for the floor of railroad cars to be fitted with vibration- and noise-reducing, fire-resistant, and durable materials. In this study, inspired by a delicate and ordered bamboo gradient structure and excellent multilevel interfaces, we fabricated a laminated composite with characteristics similar to those of the bamboo structure using a simple and effective "top-down" method by laminating fast-growing wood, waste rubber, and bamboo charcoal plastic sheets made of bamboo processing residues. This composite material combines the unique advantages of a laminated structure design and composite interface bionics. The low density (0.73 g/cm3) of the laminated composite results in a specific modulus of 13.03 GPa cm3/g, a vibration damping ratio of 6.61%, and an impact toughness of 14.16 J/cm2, which is significantly higher than that of other wood-based composites used for high-speed rail floors, such as Birch plywood (BP). In addition, we also investigated the laminated composite bonding property, fire resistance, and fatigue performance. This biomimetic bamboo-wood composite material has great potential for application in fitting the floor of eco-friendly railway cars.

Unimolecular dissociation dynamics of electronically excited HCO(Ã2A''): rotational control of nonadiabatic decay.

The photoinduced unimolecular decay of the electronically excited HCO(Ã2A'') is investigated in a combined experimental-theoretical study. The molecule is excited to the (1, n2, 0) combination bands, which decay via Renner-Teller coupling to the ground electronic state. The rovibrational state distribution of the CO fragment was measured via the high-n Rydberg H-atom time-of-flight method and calculated using a wave packet method on an accurate set of potential energy surfaces. It is shown that the non-adiabatic decay rate is strongly modulated by the HCO rotational angular momentum, which leaves unique signatures in the product state distribution. The experimentally observed bimodal rotational distribution of the dominant CO(v = 0) fragment is likely due to decay of different vibronic states populated by the excitation and modulated by the excited state lifetime, which is in turn controlled by the parent rotational quantum number.

Representation of Diabatic Potential Energy Matrices for Multiconfiguration Time-Dependent Hartree Treatments of High-Dimensional Nonadiabatic Photodissociation Dynamics.

Conventional quantum mechanical characterization of photodissociation dynamics is restricted by steep scaling laws with respect to the dimensionality of the system. In this work, we examine the applicability of the multi-configurational time-dependent Hartree (MCTDH) method in treating nonadiabatic photodissociation dynamics in two prototypical systems, taking advantage of its favorable scaling laws. To conform to the sum-of-product form, elements of the ab initio diabatic potential energy matrix (DPEM) are re-expressed using the recently proposed Monte Carlo canonical polyadic decomposition method, with enforcement of proper symmetry. The MCTDH absorption spectra and product branching ratios are shown to compare well with those calculated using conventional grid-based methods, demonstrating its promise for treating high-dimensional nonadiabatic photodissociation problems.

Semiclassical Trajectory Studies of Reactive and Nonreactive Scattering of OH(A 2 Σ+ ) by H2 Based on an Improved Full-Dimensional Ab Initio Diabatic Potential Energy Matrix.

We present a new full-dimensional diabatic potential energy matrix (DPEM) for electronically nonadiabatic collisions of OH(A 2 Σ+ ) with H2 , and we calculate the probabilities of electronically adiabatic inelastic collisions, nonreactive quenching, and reactive quenching to form H2 O+H. The DPEM was fitted using a many-body expansion with permutationally invariant polynomials in bond-order functions to represent the many-body part. The dynamics calculations were carried out with the fewest-switches with time uncertainty and stochastic decoherence (FSTU/SD) semiclassical trajectory method. We present results both for head-on collisions (impact parameter b equal to zero) and for a full range of impact parameters. The results are compared to experiment and to earlier FSTU/SD and quantum dynamics calculations with a previously published DPEM. The various theoretical results all agree that nonreactive quenching dominates reactive quenching, but there are quantitative differences between the two DPEMs and between the b=0 results and the all-b results, especially for the probability of reactive quenching.

Full-dimensional quantum stereodynamics of the non-adiabatic quenching of OH(A2Σ+) by H2.

The Born-Oppenheimer approximation, assuming separable nuclear and electronic motion, is widely adopted for characterizing chemical reactions in a single electronic state. However, the breakdown of the Born-Oppenheimer approximation is omnipresent in chemistry, and a detailed understanding of the non-adiabatic dynamics is still incomplete. Here we investigate the non-adiabatic quenching of electronically excited OH(A2Σ+) molecules by H2 molecules using full-dimensional quantum dynamics calculations for zero total nuclear angular momentum using a high-quality diabatic-potential-energy matrix. Good agreement with experimental observations is found for the OH(X2Π) ro-vibrational distribution, and the non-adiabatic dynamics are shown to be controlled by stereodynamics, namely the relative orientation of the two reactants. The uncovering of a major (in)elastic channel, neglected in a previous analysis but confirmed by a recent experiment, resolves a long-standing experiment-theory disagreement concerning the branching ratio of the two electronic quenching channels.

Rotational Modulation of Ã2A″-State Photodissociation of HCO via Renner-Teller Nonadiabatic Transitions.

By examining the product-state distribution of a prototypical nonadiabatic predissociation system, HCO(Ã2A″-X̃2A'), we demonstrate that the dissociation dynamics is strongly modulated by parent rotational quantum numbers. The predissociation of the nominal (νC-H = 0, νbend, νC-O = 1) vibronic levels of the Ã2A″ state surprisingly gives rise to both vibrational ground and excited states of the CO product, despite the assumed spectator nature of the CO moiety. This anomaly is attributed to the dependence of the lifetime of the vibronic resonance facilitated by the Renner-Teller interaction on the parent rotational angular momentum quantum numbers coupled with transient intensity borrowing from nearby vibronic resonances with νC-O = 0. This unique phenomenon is a purely quantum mechanical behavior that has no classical analogue.

Impact of Diabolical Singular Points on Nonadiabatic Dynamics and a Remedy: Photodissociation of Ammonia in the First Band.

Several recent publications have pointed out a potentially severe drawback in some widely used diabatization methods based on the electronic properties of molecules. In a diabatic representation defined by a property-based method, artificial singularities may arise due to the defining equation of the adiabatic-to-diabatic (AtD) transformation. Such diabolical singular points (DSPs) may seriously affect nuclear dynamics if they lie in the relevant configuration space. Their impact is demonstrated here using the A-band photodissociation of ammonia as an example. To this end, quantum dynamics calculations are performed based on a diabatic potential energy matrix (DPEM) constructed using the generalized Mulliken-Hush method, which is based on dipoles. These property-based results are compared with the results obtained with a DPEM determined using derivative coupling explicitly. A DSP seam is found near the Franck-Condon region, which results in a complete failure to reproduce the absorption spectrum. A modification of the generalized Mulliken-Hush method is proposed to remove the DSPs while preserving the conical intersection, which leads to an accurate reproduction of the absorption spectrum and the NH2(Ã)/NH2(X̃) product branching ratio.

Origin of the "odd" behavior in the ultraviolet photochemistry of ozone.

The origin of the even-odd rotational state population alternation in the 16O2(a1Δg) fragments resulting from the ultraviolet (UV) photodissociation of 16O3, a phenomenon first observed over 30 years ago, has been elucidated using full quantum theory. The calculated 16O2(a1Δg) rotational state distribution following the 266-nm photolysis of 60 K ozone shows a strong even-odd propensity, in excellent agreement with the new experimental rotational state distribution measured under the same conditions. Theory indicates that the even rotational states are significantly more populated than the adjacent odd rotational states because of a preference for the formation of the A' Λ-doublet, which can only occupy even rotational states due to the exchange symmetry of the two bosonic 16O nuclei, and thus not as a result of parity-selective curve crossing as previously proposed. For nonrotating ozone, its dissociation on the excited B1A' state dictates that only A' Λ-doublets are populated, due to symmetry conservation. This selection rule is relaxed for rotating parent molecules, but a preference still persists for A' Λ-doublets. The A''/A' ratio increases with increasing ozone rotational quantum number, and thus with increasing temperature, explaining the previously observed temperature dependence of the even-odd population alternation. In light of these results, it is concluded that the previously proposed parity-selective curve-crossing mechanism cannot be a source of heavy isotopic enrichment in the atmosphere.

First-principles dynamics of collisional intersystem crossing: resonance enhanced quenching of C(1D) by N2.

Intersystem crossing is a common and important nonadiabatic process in molecular systems, and its first-principles characterization requires accurate descriptions of both the electronic structure and nuclear dynamics. Here, we report an accurate full-dimensional quantum dynamical investigation of collisional quenching of the excited state C(1D) atom to its ground state C(3P) counterpart by N2, which is an important process in both combustion and interstellar media, using full-dimensional ab initio potential energy surfaces and spin-orbit couplings. Satisfactory agreement with experimental rate coefficients is obtained. Despite relatively small spin-orbit couplings, it is shown that intersystem crossing is efficient because of multiple passages via long-lived collisional resonances.

Dynamical interference in the vibronic bond breaking reaction of HCO.

First-principles treatments of quantum molecular reaction dynamics have reached the level of quantitative accuracy even in cases with strong non-Born-Oppenheimer effects. This achievement permits the interpretation of puzzling experimental phenomena related to dynamics governed by multiple coupled potential energy surfaces. We present a combined experimental and theoretical study of the photodissociation of formyl radical (HCO). Oscillations observed in the distribution of product states are found to arise from the interference of matter waves-a manifestation analogous to Young's double-slit experiment.

Modified Gaussian Wave Packet Method for Calculating Initial State Wave Functions in Photodissociation.

A modified Gaussian wave packet relaxation method is proposed to calculate the ground state wave function using an expansion of frozen Gaussian wave packets. This new procedure consists of two steps. In the first step, a multidimensional Gaussian product placed at the ground state equilibrium geometry is propagated in imaginary time. The relaxation optimizes the widths of the one-dimensional Gaussians. In the second step, additional Gaussian wave packets with the same widths are placed near the equilibrium geometry, and the corresponding expansion coefficients are optimized using the same relaxation method. This new algorithm is tested in photodissociation of NOCl and NH3, and the results show good agreement with the exact results in the energy, wave function, and absorption spectrum. In particular, the highly structured absorption spectrum of NH3 is reproduced, underscoring the accuracy of both the initial wave packet and the excited state propagation.

An experimental and theoretical investigation of the N(4S) + C2(¹Σg⁺) reaction at low temperature.

Rate constants for the N((4)S) + C2((1)Σg(+)) reaction have been measured in a continuous supersonic flow reactor over the range 57 K ≤T≤ 296 K by the relative rate technique employing the N((4)S) + OH(X(2)Π) → H((2)S) + NO(X(2)Π) reaction as a reference. Excess concentrations of atomic nitrogen were produced by the microwave discharge method and C2 and OH radicals were created by the in situ pulsed laser photolysis of precursor molecules C2Br4 and H2O2 respectively. In parallel, quantum dynamics calculations were performed based on an accurate global potential energy surfaces for the three lowest lying quartet states of the C2N molecule. The 1(4)A'' potential energy surface is barrierless, having two deep potential wells corresponding to the NCC and CNC intermediates. Both the experimental and theoretical work show that the rate constant decreases to low temperature, although the experimentally measured values fall more rapidly than the theoretical ones except at the lowest temperatures. Astrochemical simulations indicate that this reaction could be the dominant source of CN in dense interstellar clouds.