First Principles Treatment of Configuration Optimizations, Excited-State Properties, and Dynamic Third-Order Polarizabilities of Chloro-Metal Phthalocyanines MPcCl (M = Al, Ga, In)

Abstract

We report optimized geometrical structures at the RHF/6-31G* and 3-21G levels, the properties of excited states using time-dependent density functional theory based on the B3LYP/3-21G* level, and the frequency dependence of third-order nonlinear optical polarizabilities γ in different optical processes of THG, EFISHG, and DFWM by using B3LYP coupled with the sum over states methods (SOS//TDDFT-B3LYP/3-21G*) for the MPcCl (M = Al, Ga, In) molecules. The calculated results show that both the distance of the central atom from the Pc plane and the γ value increase in the order of AlPcCl < GaPcCl < InPcCl. The dispersion behaviors of the three different optical processes are discussed, and the calculated susceptibilities of χ(3)(−ω; ω, ω, −ω) match the measured values and correspond to the varied trends in the measurements of AlPcCl < GaPcCl < InPcCl films. It is found that a large ionic radius of M makes a large distortion away from C 4 v symmetry and that a larger d-electron transfer results in a red shift in the absorption spectrum and a large third-order nonlinear optical susceptibility among the MPcCl (M = Al, Ga, In) materials.

Orientational Ordering of Nonplanar Phthalocyanines on Cu(111): Strength and Orientation of the Electric Dipole Moment

“…An experimentally and theoretically challenging model system of non-planar organic molecules with a significant dipole moment, for which these effects can be directly studied, is chlorogallium phthalocyanine (GaClPc, Fig. 1) [14].In this letter, we present a detailed study on the bonding and orientational ordering of GaClPc on Cu(111) surfaces using the X-ray standing wave (XSW) technique [15], ultra-violet photoelectron spectroscopy (UPS) and density functional theory (DFT) based calculations. While XSW data are taken to determine exact the atomic positions along the surface normal and, thereby, also the orientation of the molecules, the UPS measurements reveal how the adsorbate affects the electronic energy levels.…”

“…An experimentally and theoretically challenging model system of non-planar organic molecules with a significant dipole moment, for which these effects can be directly studied, is chlorogallium phthalocyanine (GaClPc, Fig. 1) [14].…”

Effect of Cage Charges on Multiphoton Absorptions: First-Principles Study on Metallofullerenes Sc2C2@C68 and Sc3N@C68

“…The 2PA cross section δ can be related to the imaginary part of the third-order polarizability γ(−ω;ω,ω,−ω) at degenerate four-wave mixing process as , δ false( normalω false) = 8 π 2 ℏ ω 2 n 2 c 2 L 4 Im γ false( − ω ; ω , ω , − ω false) where ℏ is Planck’s constant divided by 2π, ω denotes the frequency of the perturbating radiation field, n is the refractive index, c is the speed of light in vacuum, and L is the local field factor (equal to 1 for vacuum). The frequency-dependent polarizability γ can be calculated by the SOS method as follows − γ i j k l false( − normalω pol ; normalω 1 , normalω 2 , normalω 3 false) = newline ( 2 π / h ) K 3 false( − normalω pol ; normalω 1 …”

Theoretical Study of Two-Photon Absorption in Donor−Acceptor Chromophores Tetraalkylammonium Halide/Carbon Tetrabromide

“…The treatment of electron−electron interactions (EEI) is included in a natural way in the TDDFT calculations . The validity that the TDDFT/B3LYP method is employed to compute excitation energy and frequency-dependent response functions of γ was described in refs and .…”