First-order hyperpolarizabilities of propellanes: elucidating structure-property relationships.

Following recent experimental work demonstrating strong nonlinear optical properties, namely second harmonic generation of light, in crystals composed of 16,20-dinitro-(3,4,8,9)-dibenzo-2,7-dioxa-5,10-diaza[4.4.4]propellane molecules [A. Miniewicz, S. Bartkiewicz, E. Wojaczynska, T. Galica, R. Zalesny and R. Jakubas, J. Mater. Chem. C, 2019, 7, 1255-1262] in this paper we aim to investigate "structure-property" relationships for a series of 16 propellanes presenting a wide palette of substituents with varying electron-accepting/donating capabilities. To that end, we use electronic- and vibrational-structure theories and a recently developed generalized few-state model combined with a range-separated CAM-B3LYP functional to analyze electronic and vibrational contributions to the first hyperpolarizability for the whole series of molecules. The variations in computed properties are large among the studied set of substituents and can reach an order of magnitude. It has been demonstrated that the maximum values of frequency-independent first hyperpolarizability are expected for strong electron-accepting NO2 substituents, but only at the preferred position with respect to the electronegative oxygen atom in the 1,4-oxazine moiety. This holds for electronic as well as vibrational counterparts.

Much of a Muchness: On the Origins of Two- and Three-Photon Absorption Activity of Dipolar Y-Shaped Chromophores.

The molecular origin of two- (2PA) and three-photon absorption (3PA) activity in three experimentally studied chromophores, prototypical dipolar systems, is investigated. To that end, a generalized few-state model (GFSM) formula is derived for the 3PA transition strength for nonhermitian theories and employed at the coupled-cluster level of theory. Using various computational techniques such as molecular dynamics, linear and quadratic response theories, and GFSM, an in-depth analysis of various optical channels involved in 2PA and 3PA processes is presented. It is found that the four-state model involving the second and third excited singlet states as intermediates is the smallest model among all considered few-state approximations that produces 2PA and 3PA transition strengths (for S0 → S1 transition) close to the reference results. By analyzing various optical channels appearing in these models and involved in studied multiphoton processes, we found that the 2PA and 3PA activities in all the three chromophores are dominated and hence controlled by the dipole moment of the final excited state. The similar origins of the 2PA and the 3PA in these prototypical dipolar chromophores suggest transferability of structure-property relations from the 2PA to the 3PA domain.

HeH+ under Spatial Confinement.

In the present study, the influence of spatial confinement on the bond length as well as dipole moment, polarizability and (hyper)polarizabilities of HeH+ ion was analyzed. The effect of spatial confinement was modelled by cylindrically symmetric harmonic oscillator potential, that can be used to mimic high pressure conditions. Based on the conducted research it was found that the spatial confinement significantly affects the investigated properties. Increasing the confinement strength leads to a substantial decrease of their values. This work may be of particular interest for astrochemistry as HeH+ is believed to be the first compound to form in the Universe.

Ab initio effective one-electron potential operators: Applications for charge-transfer energy in effective fragment potentials.

The concept of effective one-electron potentials (EOPs) has proven to be extremely useful in efficient description of electronic structure of chemical systems, especially extended molecular aggregates such as interacting molecules in condensed phases. Here, a general method for EOP-based elimination of electron repulsion integrals is presented, that is tuned toward the fragment-based calculation methodologies such as the second generation of the effective fragment potentials (EFP2) method. Two general types of the EOP operator matrix elements are distinguished and treated either via the distributed multipole expansion or the extended density fitting (DF) schemes developed in this work. The EOP technique is then applied to reduce the high computational costs of the effective fragment charge-transfer (CT) terms being the bottleneck of EFP2 potentials. The alternative EOP-based CT energy model is proposed, derived within the framework of intermolecular perturbation theory with Hartree-Fock noninteracting reference wavefunctions, compatible with the original EFP2 formulation. It is found that the computational cost of the EFP2 total interaction energy calculation can be reduced by up to 38 times when using the EOP-based formulation of CT energy, as compared to the original EFP2 scheme, without compromising the accuracy for a wide range of weakly interacting neutral and ionic molecular fragments. The proposed model can thus be used routinely within the EFP2 framework.

Vibrational nonlinear optical properties of spatially confined weakly bound complexes.

This study focuses on the theoretical description of the influence of spatial confinement on the electronic and vibrational contributions to (hyper)polarizabilities of two dimeric hydrogen bonded systems, namely HCNHCN and HCNHNC. A two-dimensional analytical potential is employed to render the confining environment (e.g. carbon nanotube). Based on the results of the state-of-the-art calculations, performed at the CCSD(T)/aug-cc-pVTZ level of theory, we established that: (i) the influence of spatial confinement increases with increasing order of the electrical properties, (ii) the effect of spatial confinement is much larger in the case of the electronic than vibrational contribution (this holds for each order of the electrical properties) and (iii) the decrease in the static nuclear relaxation first hyperpolarizability upon the increase of confinement strength is mainly due to changes in the harmonic term, however, in the case of nuclear relaxation second hyperpolarizability the anharmonic terms contribute more to the drop of this property.

Two-photon absorption of the spatially confined LiH molecule.

In the present contribution we study the influence of spatial restriction on the two-photon dipole transitions between the X1Σ+ and A1Σ+ states of lithium hydride. The bond-length dependence of the two-photon absorption strength is also analyzed for the first time in the literature. The highly accurate multiconfiguration self-consistent field (MCSCF) method and response theory are used to characterize the electronic structure of the studied molecule. In order to render the effect of orbital compression we apply a two-dimensional harmonic oscillator potential, mimicking the topology of cylindrical confining environments (e.g. carbon nanotubes, quantum wires). Among others, the obtained results provide evidence that at large internuclear distances the TPA response of lithium hydride may be significantly enhanced and this effect is much more pronounced upon embedding of the LiH molecule in an external confining potential. To understand the origin of the observed variation in the two-photon absorption response a two-level approximation is employed.

On the calculations of the static electronic dipole (hyper)polarizability for the free and spatially confined H.

The quality of the static electronic dipole (hyper)polarizabilities (α and γ) calculated using the coupled cluster with singles and doubles (CCSD) method and various basis sets for the isolated hydrogen anion (H-) was verified against highly accurate results obtained within the variation-perturbation scheme with the optimized explicitly correlated Gaussian functions. Moreover, the influence of spatial confinement on α and γ of H- was analyzed. The effect of confinement (orbital compression) was modeled by the spherically symmetric harmonic oscillator potential. Our results demonstrate that in order to obtain the value of α with a relative error less than 10% and correct order of magnitude of γ for the unconfined H- at the CCSD level of theory, at least triply augmented correlation consistent basis set (t-aug-cc-pVXZ, X = D,T,Q,5,6) has to be used. Furthermore, it was found that the spatial confinement significantly affects α and γ of H-.

Choosing Bad versus Worse: Predictions of Two-Photon-Absorption Strengths Based on Popular Density Functional Approximations.

We present a benchmark study of density functional approximation (DFA) performances in predicting the two-photon-absorption strengths in π-conjugated molecules containing electron-donating/-accepting moieties. A set of 48 organic molecules is chosen for this purpose, for which the two-photon-absorption (2PA) parameters are evaluated using different DFAs, including BLYP, PBE, B3LYP, PBE0, CAM-B3LYP, LC-BLYP, and optimally tuned LC-BLYP. Minnesota functionals and ωB97X-D are also used, applying the two-state approximation, for a subset of molecules. The efficient resolution-of-identity implementation of the coupled-cluster CC2 model (RI-CC2) is used as a reference for the assessment of the DFAs. Two-state models within the framework of both DFAs and RI-CC2 are used to gain a deeper insight into the performance of different DFAs. Our results give a clear picture of the performance of the density functionals in describing the two-photon activity in dipolar π-conjugated systems. The results show that global hybrids are best suited to reproduce the absolute values of 2PA strengths of donor-acceptor molecules. The range-separated functionals CAM-B3LYP and optimally tuned LC-BLYP, however, show the highest linear correlations with the reference RI-CC2 results. Hence, we recommend the latter DFAs for structure-property studies across large series of dipolar compounds.

Infrared Spectra of Hydrogen-Bonded Molecular Complexes Under Spatial Confinement.

Infrared (IR) spectroscopy is commonly used in chemical laboratories to study the geometrical structure of molecules and molecular complexes. The analysis of experimental IR spectra can nowadays be reliably supported by the results of quantum-chemical computations as vibrational frequencies and corresponding vibrational transition intensities are routinely calculated using harmonic approximation by virtually all quantum chemistry packages. In the present study we combine the methodology of computing vibrational spectra using high-level electron correlation treatments with an analytical potential-based approach to take into account spatial confinement effects. Using this approach, we perform a pioneering analysis of the impact of the spatial confinement caused by a cylindrical harmonic oscillator potential on the harmonic vibrational transition intensities and frequencies of two hydrogen-bonded complexes: HCN…HCN and HCN…HNC. The emphasis is put on the largest-intensity bands, which correspond to the stretching vibrations. The obtained results demonstrate that embedding the molecular complexes in an external confining potential causes significant changes of transition intensities and vibrational frequencies.

Fetal and Placental Weight in Pre-Gestational Maternal Obesity (PGMO) vs. Excessive Gestational Weight Gain (EGWG)-A Preliminary Approach to the Perinatal Outcomes in Diet-Controlled Gestational Diabetes Mellitus.

Both pre-gestational maternal obesity (PGMO) and excessive gestational weight gain (EGWG) increase the risk of gestational diabetes mellitus (GDM). Here, we conducted a retrospective study to comparatively examine the relation between fetal birth weight (FW) and placental weight (PW) in PGMO (n = 100) compared to EGWG (n = 100) with respect to perinatal outcomes in diet-controlled GDM. The control group was made up of 100 healthy pregnancies. The mean FW and the mean PW in EGWG were correlated with lowered fetal weight/placental weight ratio (FW/PW ratio). The percentage of births completed by cesarean section accounted for 47%, 32%, and 18% of all deliveries (EGWG, PGMO, and controls, respectively), with the predominance of FW-related indications for cesarean section. Extended postpartum hospital stays due to neonate were more frequent in EGWG, especially due to neonatal jaundice (p < 0.05). The results indicate the higher perinatal risk in mothers with EGWG compared to PGMO during GDM-complicated pregnancy. Further in-depth comparative studies involving larger patient pools are needed to validate these findings, the intent of which is to formulate guidelines for GDM patients in respect to management of PGMO and EGWG.