Dynamic effects on the nonlinear optical properties of donor acceptor stenhouse adducts: insights from combined MD + QM simulations.

The second-order nonlinear optical (NLO) responses of a donor-acceptor stenhouse adduct (DASA) are investigated by using a computational approach combining molecular dynamics simulations and density functional theory (DFT) calculations. Specific force fields for the open and closed photoswitching forms are first parameterized and validated according to the Joyce protocol, in order to finely reproduce the geometrical features and potential energy surfaces of both isomers in chloroform solution. Then, DFT calculations are performed on structural snapshots extracted at regular time steps of the MD trajectories to address the influence of the thermalized conformational dynamics on the NLO responses related to hyper-Rayleigh scattering (HRS) experiments. We show that accounting for the structural dynamics largely enhances the HRS hyperpolarizability (ßHRS) compared to DFT calculations considering solely equilibrium geometries, and greatly improves the agreement with experimental measurements. Furthermore, we show that the NLO responses of the NLO-active open form are correlated with the bond order alternation along the triene bridge connecting the donor and acceptor moieties, which is rationalized using simple essential state models.

Electric-field induced second harmonic generation responses of push-pull polyenic dyes: experimental and theoretical characterizations.

The second-order nonlinear optical properties of four series of amphiphilic cationic chromophores involving different push-pull extremities and increasingly large polyenic bridges have been investigated both experimentally, by means of electric field induced second harmonic (EFISH) generation, and theoretically, using a computational approach combining classical molecular dynamics (MD) and quantum chemical (QM) calculations. This theoretical methodology allows to describe the effects of structural fluctuations on the EFISH properties of the complexes formed by the dye and its iodine counterion, and provides a rationale to EFISH measurements. The good agreement between experimental and theoretical results proves that this MD + QM scheme constitutes a useful tool for a rational, computer-aided, design of SHG dyes.

Impact of van der Waals interactions on the structural and nonlinear optical properties of azobenzene switches.

The geometrical structures, relative Z-E energies, and second-order nonlinear responses of a collection of azobenzene molecules symmetrically substituted in the meta-position with functional groups of different bulkiness are investigated using various ab initio and density functional approximations. We show that RI-MP2 and RI-CC2 approximations provide very similar geometries and relative energies and evidence that London dispersion interactions existing between bulky meta-substituents stabilize the Z conformer. The ωB97X-D exchange-correlation functional provides an accurate description of these effects and gives a good account of the nonlinear optical response of the molecules. We show that density functional approximations should include no less than 50% of Hartree-Fock exchange to provide accurate hyperpolarizabilities. A property-structure analysis of the azobenzene derivatives reveals that the main contribution to the first hyperpolarizability comes from the azo bond, but phenyl meso-substituents can enhance it.

Two-Photon Absorption Strengths of Small Molecules: Reference CC3 Values and Benchmarks.

We present a large dataset of highly accurate two-photon transition strengths (δTPA) determined for standard small molecules. Our reference values have been calculated using the quadratic response implementation of the third-order coupled cluster method including iterative triples (Q-CC3). The aug-cc-pVTZ atomic basis set is used for molecules with up to five non-hydrogen atoms, while larger molecules are assessed with aug-cc-pVDZ; the differences due to the basis sets are discussed. This dataset, encompassing 82 singlet transitions of various characters (Rydberg, valence, and double excitations), enables a comprehensive benchmark of smaller basis sets and alternative wavefunction methods when Q-CC3 calculations become beyond reach as well as time-dependent density functional theory (TD-DFT) approaches. The evaluated wavefunction methods include quadratic response and equation-of-motion CCSD approximations, Q-CC2, and second-order algebraic diagrammatic construction in its intermediate state representation (I-ADC2). In the TD-DFT framework, a set of five commonly used exchange-correlation functionals are evaluted. This extensive analysis provides a quantitative assessment of these methods, revealing how different system sizes, response intensities, and types of transitions affect their performances.

Are Accelerated and Enhanced Wave Function Methods Accurate to Compute Static Linear and Nonlinear Optical Properties?

Key components of organic-based electro-optic devices are challenging to design or optimize because they exhibit nonlinear optical responses, which are difficult to model or rationalize. Computational chemistry furnishes the tools to investigate extensive collections of molecules in the quest for target compounds. Among the electronic structure methods that provide static nonlinear optical properties (SNLOPs), density functional approximations (DFAs) are often preferred because of their low cost/accuracy ratio. However, the accuracy of the SNLOPs critically depends on the amount of exact exchange and electron correlation included in the DFA, precluding the reliable calculation of many molecular systems. In this scenario, wave function methods such as MP2, CCSD, and CCSD(T) constitute a reliable alternative to compute SNLOPs. Unfortunately, the computational cost of these methods significantly restricts the size of molecules to study, a limitation that hampers the identification of molecules with significant nonlinear optical responses. This paper analyzes various flavors and alternatives to MP2, CCSD, and CCSD(T) methods that either drastically reduce the computational cost or improve their performance but were scarcely and unsystematically employed to compute SNLOPs. In particular, we have tested RI-MP2, RIJK-MP2, RIJCOSX-MP2 (with GridX2 and GridX4 setups), LMP2, SCS-MP2, SOS-MP2, DLPNO-MP2, LNO-CCSD, LNO-CCSD(T), DLPNO-CCSD, DLPNO-CCSD(T0), and DLPNO-CCSD(T1). Our results indicate that all these methods can be safely employed to calculate the dipole moment and the polarizability with average relative errors below 5% with respect to CCSD(T). On the other hand, the calculation of higher-order properties represents a challenge for LNO and DLPNO methods, which present severe numerical instabilities in computing the single-point field-dependent energies. RI-MP2, RIJK-MP2, or RIJCOSX-MP2 are cost-effective methods to compute first and second hyperpolarizabilities with a marginal average error with respect to canonical MP2 (up to 5% for ß and up to 11% for γ). More accurate hyperpolarizabilities can be obtained with DLPNO-CCSD(T1); however, this method cannot be employed to obtain reliable second hyperpolarizabilities. These results open the way to obtain accurate nonlinear optical properties at a computational cost that can compete with current DFAs.