Unraveling the Electric Field-Induced Second Harmonic Generation Responses of Stilbazolium Ion Pairs Complexes in Solution Using a Multiscale Simulation Method

Author(s)

Ramos, Tarcius N. ^{[1, 2]} ; Canuto, Sylvio ^[1] ; Champagne, Benoit ^[2]

Affiliation

^[1] Univ Sao Paulo, Inst Fis, BR-05508090 Sao Paulo, SP - Brazil

^[2] Univ Namur, Theoret Chem Lab, Unit Theoret & Struct Phys Chem, Namur Inst Struct Matter, B-5000 Namur - Belgium

• Document type: Journal article
• Source: JOURNAL OF CHEMICAL INFORMATION AND MODELING; v. 60, n. 10, p. 4817-4826, OCT 26 2020.
• Web of Science Citations: 0

Abstract

The electric field-induced second harmonic generation (EFISHG) response has been largely used to describe the first beta and the second gamma hyperpolarizabilities in solution. Although the EFISHG technique cannot be applied to charged compounds (due to the external static electric field), it can be used to describe ion pairs as neutral complexes. A multiscale computational approach is required to generate representative geometrical configurations of such kinds of complexes (using classical force fields), to compute the electronic structure of each configuration (using quantum mechanics methods), and to perform statistical analyses describing the behavior of the nonlinear optical properties. In this work, we target solvated neutral ion pairs complexes, of which the cation is an organic chromophore, and we estimate their EFISHG and hyper-Rayleigh scattering responses. It is shown that the anion-cation relative spatial distribution determines the permanent dipole moment of the complexes, and therefore the relative distance controls the EFISHG response. On the other hand, the beta tensor is independent of the dipole moment and it shows a weak linear correlation with the p-electron conjugation length of the cations. The gamma contributions in the global EFISHG response range from 5% to 15%, which is mostly due to the variations of amplitude of the mu beta(parallel to) contribution, which results from differences in the mu and beta vectors' orientations. The applied multiscale approach provides reasonable results compared with experimental ones, although additional efforts are still required to improve such comparison mainly to consider the possible dissociation effects. (AU)

• FAPESP's process: 15/14189-3 - Two-Photon Absorption Spectroscopy in Organic Molecules Including Solvent Effects
• Grantee: Tárcius Nascimento Ramos
• Support Opportunities: Scholarships in Brazil - Doctorate
• FAPESP's process: 18/17453-1 - QM/MM investigation of the electric field-induced second harmonic generation (EFISHG) response of ion pairs in solution
• Grantee: Tárcius Nascimento Ramos
• Support Opportunities: Scholarships abroad - Research Internship - Doctorate