Effects of Atypical Hydrogen Bonds and π-π Interactions on Nonlinear Optical Properties: Dimers of Triangular Structures Based on Perylene, Naphthalene, and Pyromellitic Diimides.

Nonlinear optical (NLO) materials have become important materials in the field of high-speed optical devices due to the changes in light absorption and refraction caused by the photoelectric field. Compounds tend to exist as aggregates rather than single molecules, so intermolecular interactions are crucial to the nature of aggregates. Therefore, to study the effects of intermolecular interactions on nonlinear optical properties, we use a dimer simplified model and adopt the methods of controlling variables, which are the different intermolecular interactions resulting from the different stacking patterns of dimers based on the same monomer structures (2PMDI-1NDI and 2NDI-1PDI). It is found that compared with dimers involving π-π interactions, dimers involving C-H···O interactions have shorter intermolecular distances, larger intermolecular interaction energies, and smaller highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) energy gaps. Moreover, the C-H···O interactions are more conducive to the intermolecular charge transfers and more beneficial for increasing the nonlinear optical response values of aggregates with respect to π-π interactions. This work provides an important basis for the influence of intermolecular interactions on nonlinear optical properties.

Electron-phonon coupling, bipolar effects, and thermoelectric performance of the CuSbS2 monolayer.

The thermoelectric performance of the CuSbS2 monolayer is determined using the relaxation times obtained from electron-phonon coupling calculations and the transport properties of phonons and electrons. Based on the fully relaxed structure, the lattice thermal conductivity and the electronic transport coefficients are evaluated by solving the Boltzmann transport equation for phonons and electrons under relaxation time approximation, respectively. The tendencies of the transport coefficients depending on the carrier concentrations and temperatures are studied to understand the thermoelectric performance. Based on the bipolar effect, the transport coefficients and intrinsic carrier concentrations, we determined the dimensionless figure of merit ZT in the 300-800 K range. The results demonstrate that the CuSbS2 monolayer should be an p-type semiconductor, and the maximum ZT of 1.36 is obtained, indicating that the monolayer is a good candidate for high-temperature thermoelectric devices. Substantial bipolar effects are observed, and the ones in the x-direction are stronger in comparison to those in the y-direction, which is responsible for the smaller ZT in the x-direction.

Efficient photocatalytic hydrogen evolution and CO2 reduction by HfSe2/GaAs3 and ZrSe2/GaAs3 heterostructures with direct Z-schemes.

The elaborate configuration of the heterostructure is crucial and challenging to achieve high solar-to-hydrogen efficiency or CO2 reduction efficiency . Here, we predict two heterostructures composed of HfSe2, ZrSe2, and GaAs3 monolayers. The maximum of 42.71%/35.12% with the heterostructures can be reached with the perfect match between the bandgap and band edges. The configurations of the heterostructures are discovered from 12 possible stacking types of the three monolayers. The formation energy, potentials of band edges, carrier mobilities, and optical absorption were used to identify the feasibility of the CO2 reduction reaction (CO2RR), the hydrogen evolution reaction (HER), and the oxygen evolution reaction (OER). The and based on overpotentials and bandgaps and the Gibbs free energies (ΔGs) are evaluated to quantificationally access the photocatalytic performance of the constructed heterostructures. The results demonstrate that high can be obtained for the solar photocatalytic Z-schemes with the HfSe2/GaAs3 and ZrSe2/GaAs3 heterostructures, and these values can be further enhanced through strain engineering. Moreover, small changes in ΔGs were observed for HER, OER, and CO2RR. Therefore, the two heterostructures have excellent performance in photocatalytic hydrogen evolution and CO2 reduction. The results of the electronic properties revealed that the delicate matching of the projected band edges of the monolayers in the heterostructures is responsible for the high photocatalytic performance.

Effect of intermolecular interaction of the charge-transfer complex between molecular "tweezers" and C60/C70 on second-order nonlinear optical properties.

To enhance understanding of the correlation between the intermolecular interaction and second-order nonlinear optical (NLO) properties, we studied a "molecular tweezer" with two corannulene substituents linked by a tetrahydro[5]helicene imide, which enabled highly sensitive and selective complexation of C60/C70 through convex-concave π-π interactions. The geometric structure, molecular orbitals, intermolecular interactions, electron absorption spectra and second-order NLO properties of the charge-transfer (CT) complexes formed by molecular tweezers and C60/C70 were studied by density functional theory. Larger fullerenes helped to increase the intermolecular interaction and CT, thereby increasing the first hyperpolarizabilities of CT complexes. Embedding of lithium ions helped to enhance the electron-absorption ability of fullerenes, thereby increasing the intermolecular interaction and intermolecular CT and, thus, enhancing their first hyperpolarizability significantly. Our data indicated that, through structure adjustment (including increasing the volume of fullerene and embedding alkali metal ions), we could enhance intermolecular interactions and improve intermolecular CT significantly. These actions could improve the second-order NLO properties of CT complexes.

The organic co-crystals formed using naphthalenediimide-based triangular macrocycles and coronene: intermolecular charge transfers and nonlinear optical properties.

Formation of organic co-crystals is an effective strategy to synthesize near infrared emission and nonlinear optical (NLO) materials, which often show "1 + 1 > 2" performance. Moreover, the crystallization process can be effectively regulated through supramolecular interactions; thus the properties of co-crystal materials can also be flexibly regulated. Here, in order to further understand the nature and formation mechanism of co-crystals from the perspective of theoretical research, we studied the structures, intermolecular interactions, absorption spectra, charge transfer (CT) characteristics and nonlinear optical (NLO) properties of the newly synthesized organic co-crystals formed between naphthalenediimide based triangles (NDI, acceptor) and coronene (COR, donor). According to the analysis of decomposition of intermolecular interaction energy, dispersion energy played a major role, so the co-crystal properties can be regulated by regulating the intermolecular dispersion energy. More importantly, the formation of co-crystals NDI-COR and NDI-2COR reduced the Egap values with respect to those of their components. And there was significant intermolecular CT from COR to NDI and the degree of CT in NDI-COR was larger than that in NDI-2COR, so that the αtot and γtot values of NDI-COR and NDI-2COR were significantly greater than those of their components. Thus, the NLO properties of organic co-crystals can be further improved by enhancing the electron-donating ability of the donor and the electron-withdrawing ability of the acceptor to enhance the degree of intermolecular interaction energy and CT.

Assembling of Perylene, Naphthalene, and Pyromellitic Diimide-Based Materials and Their Third-Order Nonlinear Optical Properties.

π-conjugated aromatic diimides with chemical stability, heat resistance, and redox activity have attracted more attention due to their excellent fluorescence quantum yield in solution. The planar perylene diimide (PDI) derivatives generally have aggregation-induced emission quenching in the solid state, while the cyclic trimers based on pyromellitic diimides (PMDIs), naphthalene diimides (NDIs), and PDIs can increase the fluorescence quantum yield in the solid state and have large two-photon absorption cross section, which can be used as excellent nonlinear optical (NLO) materials. Therefore, this paper will study the effects of multiple assembly modes of the three monomers on the NLO responses of materials. It was found that the assembly modes of 2PMDI-1NDI and 2NDI-1PDI exhibit larger third-order NLO response (γ) values, which was due to the larger conjugate surface of PDI effectively reducing the energy gap between the HOMO and LUMO. Compared with other assembly methods, 2PMDI-1NDI and 2NDI-1PDI were conducive to causing redshifts (150 nm) in the absorption spectrum. Therefore, the larger conjugate surface of PDI and the assembly mode of the isosceles triangle were more favorable for intramolecular charge transfer, thus improving its NLO properties.

The high power conversion efficiency of a two-dimensional GeSe/AsP van der Waals heterostructure for solar energy cells.

Constructing a van der Waals heterostructure is a practical way to promote the conversion efficiency of solar energy. Here, we demonstrate the efficient performance of a GeSe/AsP heterostructure in solar energy cells based on the first-principles calculations. The electronic properties, optical absorption, and optoelectronic properties are calculated to evaluate the efficiency of the newly designed heterostructure. The results indicate that the GeSe/AsP heterostructure possesses a type-II band alignment with an indirect bandgap of 1.10 eV, which greatly promotes the effective separation of photogenerated carriers. Besides, an intrinsic electric field is formed in the direction from the AsP to GeSe monolayer, which is beneficial to prevent the recombination of the photogenerated electron-hole pair. Simultaneously, a strong optical absorption is observed in the visible light range. The predicted power conversion efficiency (PCE) of the GeSe/AsP heterostructure is 16.0% and can be promoted to 17.3% by applying 1% biaxial compression strain. The present results indicate that the GeSe/AsP heterostructure is a promising candidate material for high-performance solar cells.

Direct laser cooling schemes for the triatomic SOH and SeOH molecules based on ab initio electronic properties.

Direct laser cooling is a very promising method to obtain cold molecules for various applications. However, a molecule with satisfactory electronic and optical properties for the optical scheme is difficult to identify. By suggesting criteria for the qualified molecules, we develop a method to identify the suitable polyatomic molecules for direct laser cooling. The new criteria from the equilibrium geometrical structures and fundamental frequencies of the ground and low-lying excited states are used to replace the past ones based on Franck-Condon factors. The new method can rapidly identify the preferable one among many candidate polyatomic molecules based on ab initio calculations because the new criteria are free from the construction of potential energy surfaces. The method is testified by using triatomic molecules containing OH. All the reported and two new molecules suitable for direct laser cooling are identified by comparing 168 electronic states of 28 molecules with the new criteria. The newly found molecules have been confirmed using the Franck-Condon factors from the construction of potential energy surfaces. Finally, the optical schemes for the direct laser cooling of the SOH and SeOH molecules are established.

The shape selectivity of corannulene dimers based on concave-convex and convex-convex shape complementarity as hosts for C60 and C70.

In the formation of noncovalent complexes, the stacking arrangements of corannulene and fullerene are diverse, most of which are combinations of multiple corannulenes and fullerene. Here, a composition ratio of 2 : 1 was selected for the complex between corannulene and fullerene (C60 and C70) to investigate the effects of different superposition modes, including concave-convex and convex-convex interactions, on the stability and third-order nonlinear optical (NLO) properties of the composite materials. It was found that the concave-convex interaction was stronger and it was reported to stabilize the charge-transfer (CT) complex more effectively than the convex-convex interaction. The dispersion range of the concave-convex interaction was larger than that of the convex-convex interaction, which is consistent with the interaction energy results. The packing design with the double convex-convex interactions exhibited the largest linear optical response and third-order NLO response, which showed that the convex-convex interaction was more likely to be excited and cause intermolecular CT as compared to the concave-convex interaction. This work confirmed that the packing arrangement significantly affected the NLO response and will advance the development of NLO crystals.

Nonadiabatic ab initio molecular dynamics study of photoisomerization in N-salicilydenemethylfurylamine (SMFA).

The photoisomerization mechanisms of N-salicilydenemethylfurylamine upon excitation to the first singlet state are investigated by means of surface-hopping dynamics simulations based on the Zhu-Nakamura theory. Due to different orientations of the methyl-furyl part with respect to the salicylaldimine part and different orientations of hydroxy group with respect to the benzene ring, various stable structures are obtained in the optimization. The enol isomer, S0-ENOL-5a, is the most stable conformer. An ultrafast excited-state intramolecular proton transfer is observed after photoexcitation of the most stable enol conformer and then the molecule reaches the excited-state minimum. After the internal conversion around a conical intersection, the system relaxes to either the cis-keto or trans-keto region in the ground state. The potential energy profiles of the ground and the first excited singlet state are also calculated. According to full-dimensional nonadiabaticdynamics simulations and potential energy profiles, the trans-keto and cis-keto photoproducts can be responsible for the photochromic effect of N-salicilydenemethylfurylamine.

Ab initio studies on the spin-forbidden cooling transitions of the LiRb molecule.

The spin-forbidden cooling of the LiRb molecule is investigated based on ab initio quantum chemistry calculations. The multireference configuration interaction method is used to generate the potential energy curves (PECs) of the ground state X(1)Σ(+) and the low-lying excited states a(3)Σ(+), B(1)Π, and b(3)Π. The spin-orbit coupling effects for the PECs and the transition dipole moments (TDMs) between the X(1)Σ(+), b(3)Π and a(3)Σ(+) states are also calculated. The analytical functions for the PECs are deduced. The rovibrational energy levels, the spectroscopic parameters and the Franck-Condon factors (FCF) are determined by solving the Schrödinger equation of nuclear movement with the obtained analytical functions. The b(3)Π0 ↔ X(1)Σ(+) and b(3)Π1 ↔ X(1)Σ(+) transitions have highly diagonal distributed FCFs and non-zero TDMs, demonstrating that the LiRb molecule could be a very promising candidate for laser cooling. Therefore, a three-cycle laser cooling scheme for the molecule has been proposed based on these two spin-forbidden transitions. Using the radiative lifetime and linewidth calculated from the obtained TDM functions, we present further analysis of the cooling of LiRb and the corresponding KRb molecule. The transition b(3)Π0 ↔ X(1)Σ(+) is found to be a practical transition to cool the LiRb molecule, and a sub-microkelvin cool temperature could be reached for the KRb molecule using a similar laser cooling scheme.

FACS selection of valuable mutant mouse round spermatids and strain rescue via round spermatid injection.

Round spermatid injection (ROSI) into mammalian oocytes can result in the development of viable embryos and offspring. One current limitation to this technique is the identification of suitable round spermatids. In the current paper, round spermatids were selected from testicular cells with phase contrast microscopy (PCM) and fluorescence-activated cell sorting (FACS), and ROSI was performed in two strains of mice. The rates of fertilization, embryonic development and offspring achieved were the same in all strains. Significantly, round spermatids selected by PCM and FACS were effectively used to rescue the infertile Pten-null mouse. The current results indicate that FACS selection of round spermatids can not only provide high-purity and viable round spermatids for use in ROSI, but also has no harmful effects on the developmental capacity of subsequently fertilized embryos. It was concluded that round spermatids selected by FACS are useful for mouse strain rederivation and rescue of infertile males; ROSI should be considered as a powerful addition to the armamentarium of assisted reproduction techniques applicable in the mouse.

Ab initio study on the ground and low-lying states of BAlk (Alk = Li, Na, K) molecules.

The potential energy curves (PECs) and dipole moment functions of (1)Π, (3)Π, (1)Σ(+), and (3)Σ(+) states of BAlk (Alk = Li, Na, K) are calculated using multireference configuration interaction method and large all-electron basis sets. The effects of inner-shell correlation electron for BAlk are considered. The ro-vibrational energy levels are obtained by solving the Schrödinger equation of nuclear motion based on the ab initio PECs. The spectroscopic parameters are determined from the ro-vibrational levels with Dunham expansion. The PECs are fitted into analytical potential energy functions using the Morse long-range potential function. The dipole moment functions for the states of BAlk are presented. The transition dipole moments for (1)Σ(+) → (1)Π and (3)Σ(+) → (3)Π states of BAlk are obtained. The interactions between the outermost electron of Alk and B 2p electrons for (1)Π, (3)Π, (1)Σ(+), and (3)Σ(+) states are also analyzed, respectively.

Quasi-classical trajectory study of the N(2D) + H2(X1ΣG+) → NH(X3Σ-) + H(2S) reaction based on an analytical potential energy surface.

Using the multireference configuration interaction method with the Davidson correction and a large orbital basis set (aug-cc-pV5Z), we obtain an energy grid that includes 17,500 points for the construction of a new analytical potential energy surface (APES) for the N((2)D) + H(2)(X(1)Σ(g)(+)) → NH(X(3)Σ(-)) + H((2)S) reaction. The APES, which contains 145 parameters and is represented with a many-body expansion and a new switch function, is fitted from the ab initio energies using an adaptive nonlinear least-squares algorithm. The geometric characteristics of the reported APES in the literature and those of our APES are also compared. On the basis of the APES that we obtained, reaction cross sections are computed by means of quasi-classical trajectory calculations and compared with the experimental and theoretical values available in the literature.

An ab initio study of the ground and low-lying excited states of KBe with the effect of inner-shell electrons.

The potential energy curves (PECs) of 1(2)Σ(+), 2(2)Σ(+), 1(2)Π, and 2(2)Π states of KBe are calculated using multireference configuration interaction method and large all-electron basis sets. Four sets of frozen core orbitals (FCOs) are considered to examine the effect of inner-shell correlation electrons on the molecular properties. The ro-vibrational energy levels are obtained by solving the Schrödinger equation of nuclear motion based on the ab initio PECs. The spectroscopic parameters are determined from the ro-vibrational levels with Dunham expansion. The PECs are fitted into analytical potential energy functions using the Morse long-range potential function. The dipole moment functions of the states for KBe calculated with different FCOs are presented. The transition dipole moments for KBe between 1(2)Σ(+) and 2(2)Σ(+) states, 1(2)Π and 1(2)Σ(+) states, and 2(2)Π and 1(2)Σ(+) states are also obtained.

Insights into Photogenerated Carrier Dynamics and Overall Water Splitting of the CrS3/GeSe Heterostructure.

Based on the nonadiabatic molecular dynamics (NAMD) simulations and the first-principles calculations, we explore the overall water-splitting schemes and the photogenerated carrier dynamics for two configurations (CG and CyG) of the CrS3/GeSe van der Waals heterostructures. The photocatalytic direct Z-schemes and carrier migration pathways for hydrogen and oxygen evolution reactions (HER/OER) are constructed based on the electronic properties. The solar-to-hydrogen efficiency (η'STH values) of the schemes can reach 10.60% and 10.17% and further rise under tensile strain. The NAMD results demonstrate similar transfer times of the electron/hole for HER/OER and more rapid electron-hole recombination in CG enables it to be superior to CyG in photocatalytic performance. Moreover, the Gibbs free energy indicates that both the HERs and OERs turn to spontaneously proceed with CG and CyG at pH = 0-12.37 and pH = 2.55-11.01, respectively. These facts reveal that the CrS3/GeSe heterostructure is promising in photocatalytic overall water splitting.

The effect of the CPP size on the nonlinear optical properties of the new necklace-type molecules formed by carborane and [n]Cycloparaphenylenes(n = 8-11).

The new necklace-type molecules were formed by [8-13]CPP and carborane, which further manipulated the size of the macroring, revealing the effect of size on its luminescence behavior. In this work, the effects of ring size on the absorption spectrum, electron excitation and nonlinear optical properties of the compounds were investigated in detail, aiming to reveal an effective way to improve the optical properties of these necklace-type compounds. The absorption spectra of the compounds showed that the size of the CPP ring had little effect on the spectral shape and position, but the electron transition information showed that there were the significant charge transfer within the CPP ring and a gradual enhancement of interfragment charge transfer from the CPP ring to carborane. The increasing order of polarizability, first and second hyperpolarizability values of these compounds with the increase of CPP size indicated that increasing the size of the CPP ring was an effective way to increase the nonlinear optical properties of necklace-type molecules. Among the frequency dependent hyperpolarizability values, the γ(-ω;ω,0,0) value increased by a factor of 4 from complex 1 to 6 with the increase of CPP ring size, which indicated that increasing the size of the CPP ring was an effective way to increase the optical Kerr effect of necklace-type molecules. Therefore, these the new necklace-type nolecules formed by carborane and [n]Cycloparaphenylenes would be excellent nonlinear optical materials in the field of the all-optical switch.

2D XBiSe3(X = Ga, In, Tl) monolayers with high carrier mobility and enhanced visible-light absorption.

The geometrical configurations of the XBiSe3 (X = Ga, In, Tl) monolayers are identified by employing the first-principles density functional theory calculations, and the stabilities are confirmed by phonon dispersion, formation energy, and ab initio molecular dynamics simulation, respectively. The bandgap and band edges, the density of states, the optical absorption, mobility, and effect of strain engineering are evaluated to understand the photoelectronic properties of the monolayers. The results show that the XBiSe3 monolayers have the indirect bandgaps of 1.14-1.69 (1.20-1.84) eV by HSE06(GW), leading to the enhanced optical absorption from the visible to near-ultraviolet region. The large mobility of the electron and hole are also observed, which is helpful for the separation and transfer of the photogenerated carrier pair. The band edges and bandgaps, as well as the optical absorptions, can effectively be tuned by strain engineering. It should be noted that the band edges of the InBiSe3 monolayer could satisfy the condition of redox potential for the hydrogen evolution reaction under the compressive strain heavier than -3%, implicating this monolayer can also be used for photocatalytic water splitting to produce hydrogen. Therefore, these monolayers have potential applications in photocatalytic materials or photoelectronic devices such as energy harvesters and visible-light sensors.

Crystallization of alkane melts induced by carbon nanotubes and graphene nanosheets: a molecular dynamics simulation study.

The crystallization of alkane melts on carbon nanotubes (CNT) and the surface of graphene nanosheets (GNS) is investigated using molecular dynamics (MD) simulations. The crystallization process of the alkane melts is analyzed in terms of the bond-orientational order parameter, atomic radial distribution for the CNT/alkane, atomic longitudinal distribution for the GNS/alkane, and diffusion properties. The dimensional effects of the different carbon-based nanostructures on the crystallization of alkane melts are shown. It is found that one-dimensional CNT has a stronger ability to induce the crystallization of the polymer than that of two-dimensional GNS, which provides a support at molecular level for the experimental observation [Li et al., J. Am. Chem. Soc., 2006, 128, 1692 and Xu et al., Macromolecules, 2010, 43, 5000]. From the MD simulations, we also find that the crystallization of alkane molecules has been completed with the highly cooperative processes of adsorption and orientation.

Quasi-classical trajectory study of the Ne + H2(+) → NeH(+) + H reaction based on global potential energy surface.

Using the multireference configuration interaction method with a Davidson correction and a large orbital basis set (aug-cc-pVQZ), we obtain an energy grid that includes 32 038 points for the construction of a new analytical potential energy surface (APES) for the Ne + H(2)(+) → NeH(+) + H reaction. The APES is represented as a many-body expansion containing 142 parameters, which are fitted from 31 000 ab initio energies using an adaptive nonlinear least-squares algorithm. The geometric characteristics of the reported APES and the one presented here are also compared. On the basis of the APES we obtained, reaction cross sections are computed by means of quasi-classical trajectory (QCT) calculations and compared with the experimental and theoretical data in the literature.