Daniel L. Silva

The role of molecular conformation and polarizable embedding for one- and two-photon absorption of disperse orange 3 in solution.

Solvent effects on the one- and two-photon absorption (1PA and 2PA) of disperse orange 3 (DO3) in dimethyl sulfoxide (DMSO) are studied using a discrete polarizable embedding (PE) response theory. The scheme comprises a quantum region containing the chromophore and an atomically granulated classical region for the solvent accounting for full interactions within and between the two regions. Either classical molecular dynamics (MD) or hybrid Car-Parrinello (CP) quantum/classical (QM/MM) molecular dynamics simulations are employed to describe the solvation of DO3 in DMSO, allowing for an analysis of the effect of the intermolecular short-range repulsion, long-range attraction, and electrostatic interactions on the conformational changes of the chromophore and also the effect of the solute-solvent polarization. PE linear response calculations are performed to verify the character, solvatochromic shift, and overlap of the two lowest energy transitions responsible for the linear absorption spectrum of DO3 in DMSO in the visible spectral region. Results of the PE linear and quadratic response calculations, performed using uncorrelated solute-solvent configurations sampled from either the classical or hybrid CP QM/MM MD simulations, are used to estimate the width of the line shape function of the two electronic lowest energy excited states, which allow a prediction of the 2PA cross-sections without the use of empirical parameters. Appropriate exchange-correlation functionals have been employed in order to describe the charge-transfer process following the electronic transitions of the chromophore in solution.

Molecular Structure – Optical Property Relationships for a Series of Non-Centrosymmetric Two-photon Absorbing Push-Pull Triarylamine Molecules

This article reports on a comprehensive study of the two-photon absorption (2PA) properties of six novel push-pull octupolar triarylamine compounds as a function of the nature of the electron-withdrawing groups. These compounds present an octupolar structure consisting of a triarylamine core bearing two 3,3′-bis(trifluoromethyl)phenyl arms and a third group with varying electron-withdrawing strength (H < CN < CHO < NO2 < Cyet < Vin). The 2PA cross-sections, measured by using the femtosecond open-aperture Z-scan technique, showed significant enhancement from 45 up to 125 GM for the lowest energy band and from 95 up to 270 GM for the highest energy band. The results were elucidated based on the large changes in the transition and permanent dipole moments and in terms of (i) EWG strength, (ii) degree of donor-acceptor charge transfer and (iii) electronic coupling between the arms. The 2PA results were eventually supported and confronted with theoretical DFT calculations of the two-photon transition oscillator strengths.

Broadband three-photon absorption spectra of platinum acetylide complexes

We investigate the three-photon absorption spectra of four platinum acetylides complexes employing femtosecond pulses. We observed strong three-photon absorption cross-section in the near-infrared region (from 850 nm to 1200 nm). The three-photon absorption (3PA) spectra present resonance enhancement effect as two photons of the excitation wavelength approach the lower two-photon allowed states of the molecules as well as a 3PA allowed band around 1180 nm. The 3PA cross-section spectra were interpreted using the sum-over-essential-states approach, considering a three-energy-level diagram.

Two-photon absorption spectra of carotenoids compounds

Carotenoids are biosynthetic organic pigments that constitute an important class of one-dimensional π-conjugated organic molecules with enormous potential for application in biophotonic devices. In this context, we studied the degenerate two-photon absorption (2PA) cross-section spectra of two carotenoid compounds (β-carotene and β-apo-8′-carotenal) employing the conventional and white-light-continuum Z-scan techniques and quantum chemistry calculations. Because carotenoids coexist at room temperature as a mixture of isomers, the 2PA spectra reported here are due to samples containing a distribution of isomers, presenting distinct conjugation length and conformation. We show that these compounds present a defined structure on the 2PA spectra, that peaks at 650 nm with an absorption cross-section of approximately 5000 GM, for both compounds. In addition, we observed a 2PA band at 990 nm for β-apo-8′-carotenal, which was attributed to a overlapping of 11Bu+-like and 21Ag–-like states, which are strongly one...

Large changes of static electric properties induced by hydrogen bonding: an ab initio study of linear HCN oligomers.

We report the partitioning of the interaction-induced static electronic dipole (hyper)polarizabilities for linear hydrogen cyanide complexes into contributions arising from various interaction energy terms. We analyzed the nonadditivities of the studied properties and used these data to predict the electric properties of an infinite chain. The interaction-induced static electric dipole properties and their nonadditivities were analyzed using an approach based on numerical differentiation of the interaction energy components estimated in an external electric field. These were obtained using the hybrid variational-perturbational interaction energy decomposition scheme, augmented with coupled-cluster calculations, with singles, doubles, and noniterative triples. Our results indicate that the interaction-induced dipole moments and polarizabilities are primarily electrostatic in nature; however, the composition of the interaction hyperpolarizabilities is much more complex. The overlap effects substantially quench the contributions due to electrostatic interactions, and therefore, the major components are due to the induction and exchange-induction terms, as well as the intramolecular electron-correlation corrections. A particularly intriguing observation is that the interaction first hyperpolarizability in the studied systems not only is much larger than the corresponding sum of monomer properties, but also has the opposite sign. We show that this effect can be viewed as a direct consequence of hydrogen-bonding interactions that lead to a decrease of the hyperpolarizability of the proton acceptor and an increase of the hyperpolarizability of the proton donor. In the case of the first hyperpolarizability, we also observed the largest nonadditivity of interaction properties (nearly 17%) which further enhances the effects of pairwise interactions.

Experimental and Theoretical Study on the One- and Two-Photon Absorption Properties of Novel Organic Molecules Based on Phenylacetylene and Azoaromatic Moieties

This Article reports a combined experimental and theoretical analysis on the one and two-photon absorption properties of a novel class of organic molecules with a π-conjugated backbone based on phenylacetylene (JCM874, FD43, and FD48) and azoaromatic (YB3p25) moieties. Linear optical properties show that the phenylacetylene-based compounds exhibit strong molar absorptivity in the UV and high fluorescence quantum yield with lifetimes of approximately 2.0 ns, while the azoaromatic-compound has a strong absorption in the visible region with very low fluorescence quantum yield. The two-photon absorption was investigated employing nonlinear optical techniques and quantum chemical calculations based on the response functions formalism within the density functional theory framework. The experimental data revealed well-defined 2PA spectra with reasonable cross-section values in the visible and IR. Along the nonlinear spectra we observed two 2PA allowed bands, as well as the resonance enhancement effect due to the presence of one intermediate one-photon allowed state. Quantum chemical calculations revealed that the 2PA allowed bands correspond to transitions to states that are also one-photon allowed, indicating the relaxation of the electric-dipole selection rules. Moreover, using the theoretical results, we were able to interpret the experimental trends of the 2PA spectra. Finally, using a few-energy-level diagram, within the sum-over-essential states approach, we observed strong qualitative and quantitative correlation between experimental and theoretical results.

Experimental and theoretical investigation of the first-order hyperpolarizability of a class of triarylamine derivatives.

This paper reports on the static and dynamic first-order hyperpolarizabilities of a class of push-pull octupolar triarylamine derivatives dissolved in toluene. We have combined hyper-Rayleigh scattering experiment and the coupled perturbed Hartree-Fock method implemented at the Density Functional Theory (DFT) level of theory to determine the static and dynamic (at 1064 nm) first-order hyperpolarizability (βHRS) of nine triarylamine derivatives with distinct electron-withdrawing groups. In four of these derivatives, an azoaromatic unit is inserted and a pronounceable increase of the first-order hyperpolarizability is reported. Based on the theoretical results, the dipolar/octupolar character of the derivatives is determined. By using a polarizable continuum model in combination with the DFT calculations, it was found that although solvated in an aprotic and low dielectric constant solvent, due to solvent-induced polarization and the frequency dispersion effect, the environment substantially affects the first-order hyperpolarizability of all derivatives investigated. This statement is supported due to the solvent effects to be essential for the better agreement between theoretical results and experimental data concerning the dynamic first-order hyperpolarizability of the derivatives. The first-order hyperpolarizability of the derivatives was also modeled using the two- and three-level models, where the relationship between static and dynamic first hyperpolarizabilities is given by a frequency dispersion model. Using this approach, it was verified that the dynamic first hyperpolarizability of the derivatives is satisfactorily reproduced by the two-level model and that, in the case of the derivatives with an azoaromatic unit, the use of a damped few-level model is essential for, considering also the molecular size of such derivatives, a good quantitative agreement between theoretical results and experimental data to be observed.

Revealing the Electronic and Molecular Structure of Randomly Oriented Molecules by Polarized Two-Photon Spectroscopy.

In this Letter, we explored the use of polarized two-photon absorption (2PA) spectroscopy, which brings additional information when compared to methods that do not use polarization control, to investigate the electronic and molecular structure of two chromophores (FD43 and FD48) based on phenylacetylene moieties. The results were analyzed using quantum chemical calculations of the two-photon transition strengths for circularly and linearly polarized light, provided by the response function formalism. On the basis of these data, it was possible to distinguish and identify the excited electronic states responsible for the lowest-energy 2PA-allowed band in both chromophores. By modeling the 2PA circular-linear dichroism, within the sum-over-essential states approach, we obtained the relative orientation between the dipole moments that are associated with the molecular structure of the chromophores in solution. This result allowed to correlate the V-shape structure of the FD48 chromophore and the quantum-interference-modulated 2PA strength.

Self-Aggregation and Optical Absorption of Stilbazolium Merocyanine in Chloroform

Dipolar aggregation is in many cases detrimental for the functioning of optical materials. In this study we investigate self-aggregation and optical absorption of stilbazolium merocyanine (SM) in chloroform solution by performing classical Molecular Dynamics (MD) simulations under ambient conditions. The reversal solvatochromic shift, the large bathochromic shift, and the structured absorption band presented by SM in chloroform solution are all aspects of its optical absorption behavior for which the existence of self-aggregation is yet not completely understood. Moreover, the spectroscopic properties of SM oligomers and their occurrence in solvent of low polarity remain a relevant topic that deserves to be investigated. Our analysis of the aggregation behavior of SM in chloroform verified that the majority of the chromophores are involved in the formation of oligomers in solution, where the whole dimer and part of the trimer populations present a stable π-stacking structure. The optical properties of the monomers and oligomers in solution were evaluated by means of a discrete polarizable embedding quantum mechanical/molecular mechanical (PE-QM/MM) response scheme where the quantum part is described at the level of density functional theory. The visible absorption spectrum of SM in chloroform is simulated using time average values obtained for the monomeric and oligomeric forms of SM from the PE-QM/MM calculations performed on uncorrelated configurations extracted from the classical MD simulations. This study shows that the self-aggregation of SM in chloroform may exist, but it is not essential for reproducing the reversal solvatochromic shift in chloroform and that the process does not contribute to enhance the bathochromic shift nor explain the structure observed in its absorption band. Moreover, it is verified that since the electronic transitions of the monomer and oligomers are close together, changes in the interplane separation between the monomeric units of the stacked oligomers substantially affect the spectral resolution of their contribution to the optical absorption spectrum.

Electronic spectroscopy of biomolecules in solution: fluorescein dianion in water

A combined and sequential Monte Carlo–quantum mechanics methodology is used to describe the electronic absorption spectrum of the fluorescein dianion in water. Different sets of 100 statistically relevant configurations composed of the solute and several solvent molecules are sampled from the Monte Carlo simulation for a posteriori quantum mechanical calculations of the spectra. In the largest case the configurations are composed of fluorescein and 90 explicit water molecules embedded in the electrostatic field of all remaining water molecules within a distance of 11.3 Å. These configurations include 305 atoms and 842 valence electrons, justifying the use of a semi-empirical approach. The electronic spectrum is then calculated using the INDO/CIS method. The solvatochromic shift of fluorescein in water, compared with in isolation, is calculated using the discrete and explicit solvent models. The use of electrostatically embedded explicit water molecules, in INDO/CIS calculations, gives a good description of the spectral shift of the fluorescein dianion in aqueous environment. The results are verified to converge both statistically and with respect to the number of explicit solvent molecules used.