Geometric Structure, Electronic, and Spectral Properties of Metal-free Phthalocyanine under the External Electric Fields

[Image: see text] Here, the ground-state structures, electronic structures, polarizability, and spectral properties of metal-free phthalocyanine (H(2)Pc) under different external electric fields (EEFs) are investigated. The results show that EEF has an ultrastrong regulation effect on various aspects of H(2)Pc; the geometric structures, electronic properties, polarizability, and spectral properties are strongly sensitive to the EEF. In particular, an EEF of 0.025 a.u. is an important control point: an EEF of 0.025 a.u. will bend the benzene ring subunits to the positive and negative x directions of the planar molecule. Flipping the EEF from positive (0.025 a.u.) to negative (−0.025 a.u.) flips also the bending direction of benzene ring subunits. The H(2)Pc shows different dipole moments projecting an opposite direction along the x direction (−84 and 84 Debye for EEFs of −0.025 and 0.025 a.u., respectively) under negative and positive EEF, revealing a significant dipole moment transformation. Furthermore, when the EEF is removed, the molecule can be restored to the planar structure. The transformation of the H(2)Pc structure can be induced by the EEF, which has potential applications in the molecular devices such as molecular switches or molecular forceps. EEF lowers total energy and reduces highest occupied molecular orbital–lowest unoccupied molecular orbital (HOMO–LUMO) gap; especially, an EEF of 0.025 a.u. can reduce the HOMO–LUMO gap from 2.1 eV (in the absence of EEF) to 0.37 eV, and thus, it can enhance the molecular conductivity. The first hyperpolarizability of H(2)Pc is 0 in the absence of EEF; remarkably, an EEF of 0.025 a.u. can enhance the first hyperpolarizability up to 15,578 a.u. Therefore, H(2)Pc under the EEF could be introduced as a promising innovative nonlinear optical (NLO) nanomaterial such as NLO switches. The strong EEF (0.025 a.u.) causes a large number of new absorption peaks in IR and Raman spectra and causes the redshift of electronic absorption spectra. The changes of EEF can be used to regulate the structure transformation and properties of H(2)Pc, which can promote the application of H(2)Pc in nanometer fields such as molecular devices.