The influence of stereodynamical control on the nonadiabatic effects in the D + HD (v = 1, j = 2) → D2 + H reaction.

Stereodynamics is a field that studies the influence of the alignment or orientation of colliding partners on the results of collisions. At present, the intersection of nonadiabatic effects and stereodynamics remains to be explored. In this study, we theoretically demonstrate significant stereodynamical effects in the D + HD (v = 1, j = 2) → D2 + H reaction within the collision energy range of 0.01-2.99 eV by using the time-dependent wave packet method. It is found that the stereodynamical control not only facilitates the reaction but also allows precise control of the products over a range of different scattering angles. The analysis at the state-to-state level reveals that the nonadiabatic effects are stronger in the parallel configuration than in the perpendicular configuration. By topological approach to separate the two reaction pathways at the conical intersection, the scattering amplitude of the roaming pathway in the parallel configuration is larger than that of the perpendicular configuration, which leads to more dramatic nonadiabatic features in the collision with parallel configuration.

Unveiling Quantum Interference in the D+ + H2 Nonadiabatic Reaction Dynamics at Low Collision Energies.

Fully converged nonadiabatic dynamics calculations of the D+ + H2 → H+ + HD reaction are performed at low temperatures using the time-dependent wave packet approach based on a set of precise 3 × 3 diabatic potential energy surfaces (PESs) ( Phys. Chem. Chem. Phys., 2021, 23, 7735-7747, DOI: 10.1039/D0CP04100A). The D+ + H2 reaction is mediated by a dense manifold of resonances associated with the deep potential well on the ground-state PES. The calculated results show that the nonadiabatic coupling can affect the resonance positions, deviating from the expectation based solely on adiabatic considerations. Furthermore, significant forward-backward asymmetry in total differential cross sections (DCSs) is revealed, which is markedly influenced by nonadiabatic effects. The nonadiabatic effects not only affect the contribution of partial waves in the reaction but also make the interference patterns in the DCSs change significantly.

Theoretical study on photoinduced charge transfer in one-photon and two-photon absorption of branching oligofluorenes.

Oligofluorenes have been identified as very promising two-photon absorption (TPA) materials and present great application potential for the fabrication of nonlinear optical devices, but the TPA mechanism and corresponding electron excitation properties have not been studied. Here, the photoinduced charge transfer characteristics of V-shaped and Y-shaped branching oligofluorenes that consist of two and three fluorene units in each branch during one-photon absorption (OPA) and TPA processes are analyzed theoretically using the density functional theory and visualization sum-over-states model. The calculated results show that the OPA intensity and TPA cross-section are significantly enhanced by increasing the branch length or changing the structure from V-shaped to Y-shaped. The long-distance charge transfer only occurs on the second transition of TPA at high excited states. Compared to Y-shaped molecules, V-shaped structures exhibit a stronger cooperative effect among the different branches.

An effective approximation of Coriolis coupling in reactive scattering: application to the time-dependent wave packet calculations.

Coriolis coupling plays a crucial role in reactive scattering, but dynamics calculations including the complete Coriolis coupling significantly increase the difficulty of numerical evolution due to the corresponding expensive matrix processing. The coupled state approximation that completely ignores the off-diagonal Coriolis coupling saves computational cost significantly but its error is usually unacceptable. In this paper, an improved coupled state approximation inspired by recently published results [D. Yang, X. Hu, D. H. Zhang and D. Xie, J. Chem. Phys., 2018, 148, 084101.] of the inelastic scattering problem is extended to deal with the reactive scattering. The calculations using the time-dependent wave packet method reveal that the new method can accurately reproduce the rigorous results of the H + HD (j0 < 3) → D + H2 reaction and immensely improve the computational efficiency. Additionally, we extend the new method to the non-adiabatic Li(2p) + H2 (v0 = 0, j0 = 0, 1) → H + LiH reaction, showcasing its advantages of low computational cost and high accuracy.

Globally Accurate Gaussian Process Potential Energy Surface and Quantum Dynamics Studies on the Li(2S) + Na2 → LiNa + Na Reaction at Low Collision Energies.

The LiNa2 reactive system has recently received great attention in the experimental study of ultracold chemical reactions, but the corresponding theoretical calculations have not been carried out. Here, we report the first globally accurate ground-state LiNa2 potential energy surface (PES) using a Gaussian process model based on only 1776 actively selected high-level ab initio training points. The constructed PES had high precision and strong generalization capability. On the new PES, the quantum dynamics calculations on the Li(2S) + Na2(v = 0, j = 0) → LiNa + Na reaction were carried out in the 0.001-0.01 eV collision energy range using an improved time-dependent wave packet method. The calculated results indicate that this reaction is dominated by a complex-forming mechanism at low collision energies. The presented dynamics data provide guidance for experimental research, and the newly constructed PES could be further used for ultracold reaction dynamics calculations on this reactive system.

A neural network potential energy surface and quantum dynamics studies for the Ca+(2S) + H2 → CaH+ + H reaction.

Reactive collisions of Ca+ ions with H2 molecules play a crucial role in ultracold chemistry, quantum information and other cutting-edge fields, and have been widely studied experimentally, but the corresponding theoretical studies have not been reported due to the lack of an applicable potential energy surface (PES). Herein, a globally accurate PES of the ground-state CaH2+ is constructed using the permutation invariant polynomial neural network method based on 27 780 ab initio points calculated at the multi-reference configuration interaction level. On the new PES, the quantum time-dependent wave packet calculations are performed to study the dynamics mechanisms of the Ca+(2S) + H2(ν0 = 0, j0 = 0) → CaH+ + H reaction. The calculated results suggest that the reaction follows a direct abstraction process when the collision energy is below 5.0 eV. The dynamics results would have a great reference significance for the experimental research of this reactive system at a finer level, and further dynamics studies, such as the effects of isotope substitution and rovibrational excitations of the reactant molecule, could be carried out on this newly constructed PES.

Electronically Nonadiabatic Effects on the Quantum Dynamics of the Ha + BeHb+ → Be+ + HaHb; Hb + BeHa+ Reactions.

Nonadiabatic effects are ubiquitous and play an important role in many chemical processes. Here, the adiabatic and nonadiabatic quantum scattering calculations of the H + BeH+ reaction are performed using the time-dependent wave packet method based on an accurate diabatic potential energy matrix that includes the lowest two electronic states and their couplings. The resulting integral cross sections reveal that the nonadiabatic effect significantly inhibits the reactivity of the BeH+-depletion channel but enhances that of the H-exchange channel. The vibrational excitation is suppressed, but the translational excitation is promoted for the H2 product in the BeH+-depletion channel when the nonadiabatic coupling is included. However, the nonadiabatic coupling has a mild effect on the H-exchange product-state distribution. When the nonadiabatic effect is considered, the differential cross sections of the H2 product become less polarized because of the formation of an excited-state complex, whereas the corresponding results of the H-exchange channel only present an increase in the magnitude at the backward region.

Time-dependent wave packet dynamics study of the resonances in the H + LiH+(v = 0, j = 0) → Li+ + H2 reaction at low collision energies.

The depletion process of LiH+ by H collision plays an important role in the evolution of the early universe and astrophysical processes, including the eventual charge-states, abundances of atomic and molecular species and ensuing astrochemistry. Here, a quantum dynamics study on the H + LiH+(v = 0, j = 0) → Li+ + H2 reaction is performed at the low collision energy range from 0.1 meV to 10 meV using the time-dependent wave packet method. A Feshbach resonance peak is observed near 0.8 meV collision energy on the total reaction probability curves. This resonance originates from the coupling with the v = 0, j = 1 energy level of the reactant LiH+, and it is dominated by the contributions of J = 0-4 partial waves. Another partial wave resonance is also found on the total integral cross section at 1.2 meV, which is closely connected to the opening of the J = 7 partial wave. The opening of the J = 7 partial wave generates a notable forward scattering peak, and the Feshbach resonance can promote both the forward and backward scatterings. Moreover, the total and product vibrational state-resolved rate coefficients for the temperature range of 1-100 K are also reported.

Wave Packet Approach to Adiabatic and Nonadiabatic Dynamics of Cold Inelastic Scatterings.

Due to the extremely large de Broglie wavelength of cold molecules, cold inelastic scattering is always characterized by the time-independent close-coupling (TICC) method. However, the TICC method is difficult to apply to collisions of large molecular systems. Here, we present a new strategy for characterizing cold inelastic scattering using wave packet (WP) method. In order to deal with the long de Broglie wavelength of cold molecules, the total wave function is divided into interaction, asymptotic and long-range regions (IALR). The three regions use different numbers of ro-vibrational basis functions, especially the long-range region, which uses only one function corresponding to the initial ro-vibrational state. Thus, a very large grid range can be used to characterize long de Broglie wavelengths in scattering coordinates. Due to its better numerical scaling law, the IALR-WP method has great potential in studying the inelastic scatterings of larger collision systems at cold and ultracold regimes.

Representing globally accurate reactive potential energy surfaces with complex topography by combining Gaussian process regression and neural networks.

There has been increasing attention in using machine learning technologies, such as neural networks (NNs) and Gaussian process regression (GPR), to model multi-dimensional potential energy surfaces (PESs). A PES constructed using NNs features high accuracy and generalization capability, but a single NN cannot actively select training points as GPR does, resulting in expensive ab initio calculations as the molecular complexity increases. However, a PES constructed using GPR has a slow speed of evaluation and it is difficult to accurately describe a fast-changing potential. Herein, an efficient scheme for representing globally accurate reactive PESs with complex topography based on as few points as possible by incorporating active data selection of GPR into NN fitting is proposed. The validity of this strategy is tested using the BeH2+ system, and only 1270 points are automatically sampled. The generalization performance and speed of evaluation of the generated PES are much better than those of the GPR PES constructed using the same dataset. Moreover, an accurate NN PES is fitted by 12 122 points as a benchmark for comparison to further test the global accuracy of the PES obtained using this scheme, and the corresponding results present extremely consistent topography characteristics and calculated Be+(2S) + H2 reaction probabilities.

Stereodynamics-Controlled Product Branching in the Nonadiabatic H + NaD → Na(3s, 3p) + HD Reaction at Low Temperatures.

Nonadiabatic processes play an important role at energies near or higher than conical intersection of adiabatic potential energy surfaces in chemical reactions. In this work, dynamics of the nonadiabatic H + NaD reaction at low temperatures are studied by using the quantum wave packet method based on an improved L-shaped grid. The nonadiabatic H + NaD reaction has two exothermic reaction channels: Na(3s) + HD and Na(3p) + HD; the latter can only occur via nonadiabatic transition. The dynamics results show that the product branching of the H + NaD reaction at collision energies ranging from 20 to 80 cm-1 is controlled by stereodynamics. The Na(3s) and Na(3p) reaction channels occur through collinear collision and side-on collision, respectively. When the collision energy is lower than 20 cm-1, the resonance-mediated reaction mechanism is dominant in both the Na(3s) and Na(3p) reaction channels.

Quantum Wave Packet Treatment of Cold Nonadiabatic Reactive Scattering at the State-To-State Level.

Cold and ultracold collisions are dominated by quantum effects, such as resonances, tunneling, and nonadiabatic transitions between different electronic states. Due to the extremely long de Broglie wavelength in such processes, quantum reactive scattering is most conveniently characterized using the time-independent close-coupling (TICC) methods. However, the TICC approach is difficult for systems with a large number of channels because of its steep numerical scaling laws. Here, a recently proposed quantum wave packet (WP) approach for solving adiabatic reactive scattering problems at low collision energies is extended to include nonadiabatic transitions. To impose the outgoing boundary conditions, the total scattering wavefunction is split into three parts, the interaction, the asymptotic, and the long-range regions. Each region is associated with a different set of basis functions, which could be optimized separately. In this way, an extremely long grid can be used to accommodate the characteristic long de Broglie wavelengths in the scattering coordinate. The better numerical scaling laws of the WP approach have the potential for handling larger nonadiabatic reactive systems at low temperatures in the future.

Feshbach resonances in D + HD(v = 1, j = 0) reaction at low collision energies.

Feshbach resonances in D + HD(v = 1, j = 0) reaction are studied by using the time-independent quantum method. The integral cross section (ICS) results present three Feshbach resonance peaks, which are different from H + HD(v = 1, j = 0) reaction dominated by only one peak. These resonances are attributed to coupling with adiabatic effective potentials of D + HD(v = 1, j = 1) reaction, and the most obvious peak is contributed by J = 1 at 83.16 cm-1 collision energy. For J = 0 and 2, the resonances are related with the same L partial wave and present a double-peak structure in total ICS. The characteristics of product angular distribution show that the resonance of J = 1 is long-lived, while the lifetimes are relatively shorter for the resonance of J = 0 and 2.

Noble Metallic Pyramidal Substrate for Surface-Enhanced Raman Scattering Detection of Plasmid DNA Based on Template Stripping Method.

In this paper, a new method for manufacturing flexible and repeatable sensors made of silicon solar cells is reported. The method involves depositing the noble metal film directly onto the Si template and stripping out the substrate with a pyramid morphology by using an adhesive polymer. In order to evaluate the enhancement ability of the substrate, Rhodamine 6G (R6G) were used as surface-enhanced Raman scattering (SERS) probe molecules, and the results showed a high sensitivity and stability. The limit of detection was down to 10-12 M for R6G. The finite-difference time domain (FDTD) was used to reflect the distribution of the electromagnetic field, and the electric field was greatly enhanced on the surface of the inverted pyramidal substrate, especially in pits. The mechanism of Raman enhancement of two types of pyramidal SERS substrate, before and after stripping of the noble metal film, is discussed. By detecting low concentrations of plasmid DNA, the identification of seven characteristic peaks was successfully realized using a noble metallic pyramidal substrate.

Accurate electronic properties and non-linear optical response of two-dimensional MA2Z4.

Two-dimensional MA2Z4 (M = Mo, W, V, Nb, Ta, Ti, Zr, Hf, or Cr; A = Si or Ge; Z = N, P, or As) is a new lead in the 2D family, because it exhibits versatile properties by tuning the components M, A and Z. However, theoretical studies on MA2Z4 are quite limited, and electronic properties are mainly studied by standard DFT levels, which seriously underestimates the band gap. Here, we systematically investigated the electronic properties and nonlinear optical response of MA2Z4 using a hybrid HSE06 functional. It was found that replacing component Z changes the lattice constant most, while the lattice influence by component M substitution is only slight. We showed that the gap difference between PBE and HSE06 is generally about 30% but can be up to 101%. (MIV = Hf, Ti, or Zr)Si2N4 possesses multi-valley characteristics. Furthermore, the second-harmonic generation (SHG) responses of various MA2Z4 composites were also calculated. Three non-zero elements of second order non-linear susceptibilities are revealed for MA2Z4 with the relationship: d16 = d21 = d22, indicating that MA2Z4 belongs to the D3H1 space group. HfSi2N4 possesses a multi-valley characteristic, and exhibits the largest susceptibility under broad wavelengths and the value of d21 reaches 3697.04 pm V-1 at band gap resonance energy. Intriguingly, the non-linear coefficients of MoSi2P4 and MoSi2As4 in the IR region are two orders of magnitude larger than those of other well-known non-linear crystals, such as LiGaS2 and BaAl4S7. We further explored the anisotropic SHG response by the polar plot of intensity under different incident light into MA2Z4. Our work provides theoretical guidelines for further experimental explorations of MA2Z4 and paves the way for its utilization in non-linear optic devices.

Quantum Dynamics Studies of the Significant Intramolecular Isotope Effects on the Nonadiabatic Be+(2P) + HD → BeH+/BeD+ + D/H Reaction.

Quantum time-dependent wave packet dynamics studies on the nonadiabatic Be+(2P) + HD → BeH+/BeD+ + D/H reaction are performed for the first time employing recently constructed diabatic potential energy surfaces. Strong intramolecular isotope effects and unusual results are presented, which are attributed to the dynamic effects of shallow wells induced by avoided crossing on the diagonal V22d surface. The BeH+ + D and BeD+ + H channels are dominated by high-J and low-J partial waves, respectively. The BeD+/BeH+ branching ratio is larger than 10 at low energy and gradually decreases with increasing collision energy. The BeH+ product is primarily distributed at low vibrational states, whereas there exists an obvious population inversion of vibrational states on the BeD+ product. The results of differential cross sections suggest that the formation of the BeH+ + D channel favors a direct reaction process, while the BeD+ + H channel is mainly generated by the complex-forming mechanism.

Temperature- and pressure-dependent rate coefficient measurement for the reaction of CH2OO with CH3CH2CHO.

Propionaldehyde is one of the most abundant aldehydes, which are an important class of volatile organic compounds. In this work, the rate coefficient of the reaction of the simplest Criegee intermediate CH2OO with propionaldehyde (CH3CH2CHO) was measured for the first time in a flash photolysis reaction tube by using the OH laser-induced fluorescence (LIF) method at temperature and pressure in the range of 283 to 318 K and 5 to 200 Torr. This reaction is observed to be pressure- and temperature-dependent. The measured rate coefficient at 50 Torr is in the vicinity of the high-pressure limit value of (3.23 ± 0.49) × 10-12 cm3 s-1 at 298 K, which is in agreement with a previously reported theoretical result of 2.44 × 10-12 cm3 s-1. The Arrhenius plot of the temperature-dependent rate coefficients yields an activation energy of (-1.99 ± 0.23) kcal mol-1.

Competition between tubular, planar and cage geometries: a complete picture of structural evolution of Bn (n = 31-50) clusters.

Stimulated by the early theoretical prediction of B80 fullerene and the experimental finding of the B40 cage, the structures of medium-sized boron clusters have attracted intensive research interest during the last decade, but a complete picture of their size-dependent structural evolution remains a puzzle. Using a genetic algorithm combined with density-functional theory calculations, we have performed a systematic global search for the low-lying structures of neutral Bn clusters with n = 31-50. Diverse structural patterns, including tubular, quasi-planar, cage, core-shell, and bilayer, are demonstrated for the ground-state Bn clusters; for certain cluster sizes, unprecedented geometries are predicted for the first time. Their stabilities at finite temperatures are evaluated, and the competition mechanism between various patterns is elucidated. Chemical bonding analysis reveals that the availability of localized σ bonds and delocalized π bonds in the Bn clusters play a key role in their structural stability. Our results provide important insights into the bonding pattern and growth behavior of medium-sized boron clusters, which lay the foundation for experimental design and synthesis of boron nanostructures.

Theoretical study of surface-enhanced Raman scattering mechanism of scandium-doped copper/silver clusters.

Rare earth metals exhibit strong chemical activity and have many unique properties in the aspects of magnetic susceptibility, photo-absorption, catalytic activity and electrical property. Precious metals have strong chemical stability and great surface-enhanced Raman scattering (SERS) enhancing activity, providing a good platform for detecting SERS signals from molecules. Combining precious metals with rare earth metals could form new composite materials, providing more possibilities for SERS substrates. In this work, the SERS and absorption spectra of the probe molecule adsorbed on scandium-doped silver/copper clusters are theoretically simulated by time-dependent density functional theory. The contributions of charge-transfer (CT) enhancement and electromagnetic enhancement are treated uniformly in calculations based on a short-time approximation for the Raman scattering cross-section, and distinguished by using visualization of electron transitions. The largest Raman enhancement factor of the probe molecule adsorbed on Sc@Cu7 and Sc@Ag7 alloy clusters could reach the order of 105, due to the enhancement of resonance excitation to the CT transition. The factors influencing SERS are systematically investigated, including the composition of the substrate, local chemical environment of the binding site, form of electron transition, oscillator strength of excitation and excitation wavelength.

Quantum dynamics studies of isotope effects in the Mg+(3p) + HD → MgH+/MgD+ + D/H insertion reaction.

The time-dependent wave packet quantum dynamics studies for the Mg+(3p) + HD → MgH+/MgD+ + D/H diabatic reaction are carried out for the first time on recently developed diabatic YHWCH potential energy surfaces [Phys. Chem. Chem. Phys., 2018, 20, 6638-6647]. The results of reaction probabilities and total integral cross sections show a dramatic preference to the formation of MgD+ over MgH+ owing to the insertion reaction mechanism in the title reaction. The MgD+/MgH+ branching ratio witnesses a monotonic decrease from 10.58 to 3.88 at collision energy range of 0.01 to 0.20 eV, and at the collision energy of 0.114 eV, it is close to the experimental value of 5. The rovibrational state-resolved ICSs of the two channels show the products MgD+ have higher vibrational excitation and hotter rotational state distributions. The opacity function P(J) suggests that the MgH+ + D channel and MgD+ + H channel are dominated by high-b and low-b collisions, respectively. Both forward and backward scattering peaks are found in the differential cross section curves, whereas the angle distributions of products are not strictly forward-backward symmetric because of the short lifetime of the complex in the reaction.