Nonlinear Molecules Research Articles

Nonlinear optical properties and optimization strategies of D-π-A type phenylamine derivatives in the near-infrared region

Modifying simple molecular structures to significantly improve nonlinear optical (NLO) performance is a primary prerequisite for scientific research. Based on the four phenylamine derivatives reported in previous studies, we designed four organic nonlinear molecules by changing the acceptor group and π-linker. (Time-dependent) density functional theory (DFT/TD-DFT) was performed on molecular geometry optimization, the contribution of π electrons to the bond order, linear and two-photon absorption (TPA) spectra, the intra-molecular charge transfer matrix (CTM), and NLO coefficients. These aspects were considered to analyze in detail how the structural modification of acceptors and π-linkers affects NLO characteristics. The three modification methods were: adding a carbonyl group at the junction of the π-linker and the acceptor group, adding a carbonyl group and a nitrogen atom to the acceptor group, and replacing the quinolinone with a pyrenyl group as the π-linker. The latter two methods can significantly reduce the excitation energy and enhance the intensity of intra-molecular charge transfer during the two-photon transition. The maximum TPA cross-sections and wavelengths of the designed molecules are DPPM (84722.6 GM, 815.7 nm) and DDPM (21600.6 GM, 781.3 nm). These two molecules have large TPA cross-sections in the near-infrared region, which renders them as possible NLO materials with broad application prospects.

Designing Special Nonmetallic Superalkalis Based on a Cage-like Adamanzane Complexant.

In this study, to examine the possibility of using cage-like complexants to design nonmetallic superalkalis, a series of X@36adz (X = H, B, C, N, O, F, and Si) complexes have been constructed and investigated by embedding nonmetallic atoms into the 36adamanzane (36adz) complexant. Although X atoms possess very high ionization energies, these resulting X@36adz complexes possess low adiabatic ionization energies (AIEs) of 0.78–5.28 eV. In particular, the adiabatic ionization energies (AIEs) of X@36adz (X = H, B, C, N, and Si) are even lower than the ionization energy (3.89 eV) of Cs atoms, and thus, can be classified as novel nonmetallic superalkalis. Moreover, due to the existence of diffuse excess electrons in B@36adz, this complex not only possesses pretty low AIE of 2.16 eV but also exhibits a remarkably large first hyperpolarizability (β 0) of 1.35 × 106 au, indicating that it can also be considered as a new kind of nonlinear optical molecule. As a result, this study provides an effective approach to achieve new metal-free species with an excellent reducing capability by utilizing the cage-like organic complexants as building blocks.

Dancing with Azulene

It seems interesting to adopt the idea of dance in the context of the arrangement of molecular blocks in the building of molecular systems. Just as various dances can create various feelings, the nature and arrangement of molecular blocks in the generated molecular system can induce different properties. We consider obtaining such “dancing” systems in which the still little-known azulene moieties are involved. The dark blue nonbenzenoid aromatic azulene has one less axis of symmetry relative to the two axes of its isomer, i.e., the fully benzenoid naphthalene, acquiring valuable properties as a result that can be used successfully in technical applications. In a dancing system, the azulene moieties can be connected directly, or a more or less complex spacer can be inserted between them. Several azulene moieties can form a linear oligomer or a polymer and the involvement of azulene moieties in nonlinear molecules, such as crown ethers, calixarenes, azuliporphyrins, or azulenophane, is a relatively new and intensely studied topic. Some aspects are covered in this review, which are mainly related to obtaining the mentioned azulene compounds and less to their characterization or physico-chemical properties.

First theoretical probe for alkynyl bridged thiophene modified coumarin nonlinear optical materials with D-π-A and A-π-D-π-A structures

First-principles exploration is very important to molecular design. In this study, geometric structure, intramolecular charge transfer (ICT), energy levels, polar moment, and ultraviolet–visible (UV–Vis) spectroscopy of eight novel and different alkynyl bridged thiophene modified coumarin nonlinear optical molecules with [Formula: see text]-[Formula: see text]-[Formula: see text] and [Formula: see text]-[Formula: see text]-[Formula: see text]-[Formula: see text]-[Formula: see text] structures had been studied by density-functional theory (DFT) calculations within B3LYP hybrid functional using 6-31 [Formula: see text], [Formula: see text] Gaussian type molecular-orbital basis set. This has guiding significance for the design of nonlinear optical molecules and the development of coumarin-based photoelectric molecules.

All Structures Great and Small: Nanoscale Modulations in Nematic Liquid Crystals.

The nature of the nanoscale structural organization in modulated nematic phases formed by molecules having a nonlinear molecular architecture is a central issue in contemporary liquid crystal research. Nevertheless, the elucidation of the molecular organization is incomplete and poorly understood. One attempt to explain nanoscale phenomena merely “shrinks down” established macroscopic continuum elasticity modeling. That explanation initially (and mistakenly) identified the low temperature nematic phase (NX), first observed in symmetric mesogenic dimers of the CB-n-CB series with an odd number of methylene spacers (n), as a twist–bend nematic (NTB). We show that the NX is unrelated to any of the elastic deformations (bend, splay, twist) stipulated by the continuum elasticity theory of nematics. Results from molecular theory and computer simulations are used to illuminate the local symmetry and physical origins of the nanoscale modulations in the NX phase, a spontaneously chiral and locally polar nematic. We emphasize and contrast the differences between the NX and theoretically conceivable nematics exhibiting spontaneous modulations of the elastic modes by presenting a coherent formulation of one-dimensionally modulated nematics based on the Frank–Oseen elasticity theory. The conditions for the appearance of nematic phases presenting true elastic modulations of the twist–bend, splay–bend, etc., combinations are discussed and shown to clearly exclude identifications with the nanoscale-modulated nematics observed experimentally, e.g., the NX phase. The latter modulation derives from packing constraints associated with nonlinear molecules—a chiral, locally-polar structural organization indicative of a new type of nematic phase.

On the dynamics of DNA molecules with an-harmonics potential in the normal and damaged states

DNA damage is due to any change that introduces a deviation from the usual double-helical structure. At this state, the study of the motion of DNA molecules requires novel dynamical models. We propose a discrete model to describe the nonlinear dynamics DNA molecule with inharmonic potential. We consider two physical situations, the ideal or homogeneous state, and the inhomogeneous or damage state. The problem of the homogeneous (normal) case with ANHP was considered in the literature, but the dynamics of DNA molecules were not inspected. Here, our objective is to distinguish between the dynamics of DNA in the normal and damaged states. The novelty of the present work stems from a conjuncture that the DNA state can be depicted from the dynamics of the molecules. The unified and extended unified methods are used to find the exact solutions of the systems in both cases, respectively. Numerically, it is found that, in the ideal case, the motion of DNA molecules is periodic and stable. Considering the inhomogeneous case due to damage, the small or moderate values of the backbone rigidity make the motion of the molecule periodic and stable, but for high values, the motion becomes aperiodic and unstable. But for small or moderate values of the backbone rigidity, the motion becomes periodic and stable. These results are of interest in vulgarizing the physical properties of DNA molecules.

Three-dimensional tomographic imaging of CO molecular orbitals reveals multi-electron effects

According to the asymmetric molecular orbital reconstruction algorithm, which divides orbital into gerade and ungerade components and which does not depend on the unidirectional recollisional condition, we obtain the two-dimensional highest occupied molecular orbital (HOMO) of CO based on the directly calculated transition dipole moment and the harmonic spectra calculated by the Lewenstein model, respectively, which is the three-dimensional (3D) HOMO projected onto the plane perpendicular to the laser propagation direction. In order to retrieve the full orbital function, a 3D molecular orbital tomography (MOT) method is developed and is successfully applied to the reconstructions of the HOMO of CO, which simplifies the 3D imaging process of orbitals of linear molecules, and is expected to be extended to reconstruct the 3D orbitals of nonlinear molecules. In addition, the time-dependent density functional theory is employed to acquire the harmonic spectra of CO in a 800 nm and 1500 nm wavelength laser, respectively. The comparison of these two reconstruction results helps identify the multi-electron effects for asymmetric MOT, which requires further study. This work advances the development of MOT and is expected to reveal multi-electron effects in orbital imaging of complex polyatomic molecules.

Towards molecular frame photoelectron angular distributions in polyatomic molecules from lab frame coherent rotational wavepacket evolution

A theory and method for a matrix-based reconstruction of molecular frame (MF) photoelectron angular distributions (MFPADs) from laboratory frame (LF) measurements (LFPADs) is developed and basic applications are explored. As with prior studies of MF reconstruction, the experimental side of this protocol is based upon time-resolved LF measurements in which a rotational wavepacket is prepared and probed as a function of time via photoionization, followed by a numerical reconstruction routine. In contrast to other methodologies, the protocol presented here does not require determination of the photoionization matrix elements, and consequently takes the relatively simple numerical form of a matrix equation. Significantly, this simplicity allows the successful reconstruction of MFPADs for nonlinear polyatomic molecules with D nh point group symmetry. We numerically demonstrate this scheme for two realistic molecular photoionization cases: N2 and C2H4. This new technique is expected to be generally applicable to a broad range of MF reconstruction problems involving photoionization of polyatomic molecules.

Absolute NMR shielding scales in methyl halides obtained from experimental and calculated nuclear spin-rotation constants

The nonrelativistic ``Ramsey-Flygare relationship'' is the most used procedure to obtain semiexperimental nuclear magnetic resonance (NMR) absolute shieldings by a correspondence between NMR shieldings ($\mathbit{\ensuremath{\sigma}}$) and nuclear spin-rotation constants ($\mathbit{M}$). One of its generalizations to the relativistic framework is known as the M-V model, which was proposed few year ago by some of the authors of the present work and right now is only applied to linear molecules. This model includes terms that do not have nonrelativistic counterparts and also include the paramagnetic contribution to the NMR shielding of nuclei in free atoms. All this ensures that its results fit quite well with those of four-component (4c) calculations. The first application of the M-V model to nonlinear molecules, like methyl halides or ${\mathrm{CH}}_{3}X$ molecules ($X=\mathrm{F}$, Cl, Br, and I), is given here. The analysis of each electronic mechanism of $\mathbit{\ensuremath{\sigma}}$ shows that most of their electron correlation effects are strongly related with the same effects in $\mathbit{M}$. By including experimental data of $M$ in the M-V model most of the correlation effects are accurately taken into account for the absolute values of $\mathbit{\ensuremath{\sigma}}$. Calculations of ${\mathbit{M}}_{Y}$ and ${\mathbit{\ensuremath{\sigma}}}_{Y}$ ($Y=\mathrm{H}$, C, and $X$) were carried out within the linear response formalism at the random-phase level of approach and density functional theory in both 4c and nonrelativistic frameworks. The best fits between calculations of $\mathbit{M}$ and experimental data are obtained from calculations at 4c-PBE0 level of theory in all cases, but not for ${M}_{\ensuremath{\parallel},\mathrm{Cl}}$, which suggests that a revision of the available experimental data may be necessary. There is an additional advantage of using the M-V model: one can indirectly calculate shieldings of open-shell free atoms, which cannot be obtained at the moment by applying 4c methods.

Role of Virally Encoded Circular RNAs in the Pathogenicity of Human Oncogenic Viruses.

Human oncogenic viruses are a group of important pathogens that etiologically contribute to at least 12% of total cancer cases in the world. As an emerging class of non-linear regulatory RNA molecules, circular RNAs (circRNAs) have gained increasing attention as a crucial player in the regulation of signaling pathways involved in viral infection and oncogenesis. With the assistance of current circRNA enrichment and detection technologies, numerous novel virally-encoded circRNAs (vcircRNAs) have been identified in the human oncogenic viruses, initiating an exciting new era of vcircRNA research. In this review, we discuss the current understanding of the roles of vcircRNAs in the respective viral infection cycles and in virus-associated pathogenesis.

Laser cooling of symmetric top molecule

Ultracold Physics Experimental progress over the past few decades has led to the mastery of ultracold atomic gases. A major thrust of current research is to extend this success to ultracold molecules, which would open qualitatively new perspectives for quantum information science, precision measurement, quantum chemistry, and other fields. The internal degrees of freedom in molecules preclude immediate implementation of conventional methods. Using a specific combination of rovibronic optical transitions, Mitra et al. report direct Sisyphus laser cooling of the symmetric top molecule CaOCH3 to temperatures below 1 millikelvin (see the Perspective by Hudson). The proposed scheme for cooling is potentially applicable to a wide range of nonlinear polyatomic molecules. Science , this issue p. [1366][1]; see also p. [1304][2] [1]: /lookup/doi/10.1126/science.abc5357 [2]: /lookup/doi/10.1126/science.abd1657

Laser cooling of larger quantum objects.

A nonlinear polyatomic molecule, CaOCH 3 , has been laser-cooled to below 1 millikelvin

Molecular Asymmetry and Optical Cycling: Laser Cooling Asymmetric Top Molecules

We present a practical roadmap to achieve optical cycling and laser cooling of asymmetric top molecules (ATMs). Our theoretical analysis describes how reduced molecular symmetry, as compared to diatomic and symmetric non-linear molecules, plays a role in photon scattering. We present methods to circumvent limitations on rapid photon cycling in these systems. We calculate vibrational branching ratios for a diverse set of asymmetric top molecules and find that many species within a broad class of molecules can be effectively cooled with a manageable number of lasers. We also describe methods to achieve rotationally closed optical cycles in ATMs. Despite significant structural complexity, laser cooling can be made effective using extensions of the current techniques used for linear molecules. Potential scientific impacts of laser-cooled ATMs span frontiers in controlled chemistry, quantum simulation, and searches for physics beyond the Standard Model.

Long-Lasting Molecular Orientation Induced by a Single Terahertz Pulse.

We present a novel, previously unreported phenomenon appearing in a thermal gas of nonlinear polar molecules excited by a single THz pulse. We find that the induced orientation lasts long after the excitation pulse is over. In the case of symmetric-top molecules, the time-averaged orientation remains indefinitely constant, whereas in the case of asymmetric-top molecules the orientation persists for a long time after the end of the pulse. We discuss the underlying mechanism, study its nonmonotonous temperature and amplitude dependencies, and show that there exist optimal parameters for maximal residual orientation. The persistent orientation implies a long-lasting macroscopic dipole moment, which may be probed by even harmonic generation and may enable deflection by inhomogeneous electrostatic fields.

Using correlation diagrams to study the vibrational spectrum of highly nonlinear floppy molecules: The K-CN case

The correlation diagrams of vibrational energy levels considering the Planck constant as a variable parameter have proven as a very useful tool to study vibrational molecular states, and more specifically in relation to the quantum manifestations of chaos in such dynamical systems. In this paper, we consider the highly nonlinear K-CN molecule, showing how the regular classical structures, i.e., Kolmogorov-Arnold-Moser tori, existing in the mixed classical phase space appear in the quantum levels correlation diagram as emerging diabatic states, something that remains hidden when only the actual value of the Planck constant is considered. Additionally, a quantum transition from order to chaos is unveiled with the aid of these correlation diagrams, where it appears as a frontier of scarred functions.

Empirical normal intensity distribution for overtone vibrational spectra of triatomic molecules

Theoretical calculations are contributing a significantly higher proportion of data to contemporary spectroscopic databases, which have traditionally relied on experimental observations and semi-empirical models. It is now a common procedure to extend calculated line lists to include ro-vibrational transitions between all bound states of the ground electronic state up to the dissociation limit. Advanced ab initio methods are utilized to calculate the potential energy and dipole moment surfaces (PESs and DMSs), and semi-empirical PESs are then obtained by combining ab initio and experimental data. The objective is to reach high accuracy in the calculated transition intensities for all parts of spectrum, i.e. to increase the predictive power of the model. We show that in order to perform this task, one needs, in addition to the standard improvements of the PES and DMS in the spectroscopically accessible regions, to extend the ab initio calculations of the PES towards the united-atom limit along the stretching coordinates. The argument is based on the correlation between the intensities of high-overtone transitions and the repulsive potential wall that has previously been theoretically established for diatomic molecules and is empirically extended here to linear and nonlinear triatomic molecules. We generate partial line lists for water and ozone, and together with an already available line list for carbon dioxide, we derive the normal intensity distribution, which is a direct consequence of this correlation. The normal distribution is not an instrument to compute highly accurate intensities, rather it is a means to analyse the intensities computed by the traditional methods.

Nonreciprocity via Nonlinearity and Synthetic Magnetism

We propose how to realize nonreciprocity for a weak input optical field via nonlinearity and synthetic magnetism. We show that the photons transmitting from a linear cavity to a nonlinear cavity (i.e., an asymmetric nonlinear optical molecule) exhibit nonreciprocal photon blockade but no clear nonreciprocal transmission. Both nonreciprocal transmission and nonreciprocal photon blockade can be observed, when one or two auxiliary modes are coupled to the asymmetric nonlinear optical molecule to generate an artificial magnetic field. Similar method can be used to create and manipulate nonreciprocal transmission and nonreciprocal photon blockade for photons bi-directionally transport in a symmetric nonlinear optical molecule. Additionally, a photon circulator with nonreciprocal photon blockade is designed based on nonlinearity and synthetic magnetism. The combination of nonlinearity and synthetic magnetism provides us an effective way towards the realization of quantum nonreciprocal devices, e.g., nonreciprocal single-photon sources and single-photon diodes.

IYPt is a highly polar, nonlinear triatomic molecule

A quantum chemical study of the triatomic molecule IYPt, its isomers and dimer, its unimolecular decomposition and interaction with dioxygen, and its group 17 congeners is carried out. The results indicate that IYPt is a ground-state singlet with a bent geometry and a large electric dipole moment of magnitude 4.8 D. The IPtY isomer also is bent but 33.5 kcal mol−1 higher in energy whereas the isomer with the central iodine atom is unstable.

Structure and performance optimization of phenol polyphosphazene grafted by 2,4-dinitroaniline containing small nonlinear optical molecules

Abstract Electro-optic (EO) polymers, possessing high EO coefficient and low dielectric constant, are considered to be a new generation of nonlinear optical materials that have great application prospect in photo-communication, information storage, and data processing. The host-guest structure of EO polymers is the most typical one in this field. However, the phase separation during polarization between the host polymer and the guest nonlinear optical molecule (NLO) limits potential applications of the material. To solve the problem, a new synthetic method was designed in this paper. First, 2,4-dinitroaniline was grafted to phenol polyphosphazene by chemical method for polar improvement of the main chain. Then, another small NLO molecule was mixed into the polymer by physical method for further improvement of EO coefficient. The preparation process was studied and the structure of the product was characterized. The effects of different NLO mixing proportions and different polarizing temperatures on EO coefficient were investigated in details. Orientation stability of the sample was tested. Experimental results show that our products possess not only high EO coefficient but also good phase stability, which makes them good candidates for the application in information technology.

Recent advances with electro-optic polymers

In recent years the electro-optic polymers emerged as an important branch of material science. This growth and interest is fundamentally motivated by practical application of these materials in second-order nonlinear optics and in waveguiding configuration. Indeed, these materials marry excellent optical quality of amorphous σ bonded polymers with enhanced first hyperpolarizability of imbedded organic nonlinear optical molecules. Although a big progress was achieved with them, concerning particularly the science, understanding and applications, some problems remain still incompletely solved, particularly the stability of induced polar order by the application of external electric field and the molecule aggregation. In this review paper we recall techniques of thin film fabrication, poling, characterization of NLO properties and discuss more precisely problems of molecule aggregation as well as the temporal decay of polar order. A novel 3D second-order NLO chromophores, namely the [2] paracyclophanes, which may help to limit the aggregation, are proposed. We show, in particular, that this molecule can be poled in doped PMMA thin films. Practical applications of electro-optic polymers are also reviewed and discussed.