Ab initio and DFT study of the dipole (hyper) polarizabilities of p-nitrophenylphosphine molecule

Issue title: III Congress of Theoretical and Computational Physical Chemistry, 2–4 December 2010, Altos de Pipe, Caracas, Venezuela

Guest editors: Humberto Soscunxy, Fernando Ruettez and Anibal Sierraltaz

Article type: Research Article

Authors: Urdaneta, Johan^{a; *} | Bermúdez, Yaneth^a | Bracho, Ricardo^a | Moreno, Roxana^a | Soscún, Humberto^{a; b; *}

Affiliations: [a] Laboratorio de Química Inorgánica Teórica LQIT, Departamento de Química, Facultad Experimental de Ciencias, La Universidad del Zulia, Maracaibo, Venezuela | [b] Centro de Quimica, IVIC, Caracas, Venezuela | [x] Centro Tecnológico, Instituto Venezolano de Investigaciones Científicas, IVIC, Caracas, Venezuela | [y] Departamento de Química, Facultad Experimental de Ciencias, La Universidad del Zulia LUZ, Maracaibo, Venezuela | [z] Centro de Química, Instituto Venezolano de Investigaciones Científicas, IVIC, Caracas, Venezuela

Correspondence: [*] Corresponding authors: Johan Urdaneta, Laboratorio de Química Inorgánica Teórica LQIT, Departamento de Química, Facultad Experimental de Ciencias, La Universidad del Zulia, Apdo 526, Maracaibo, Venezuela. E-mail: johansub@gmail.com; Humberto Soscún, Laboratorio de Química Inorgánica Teórica LQIT, Departamento de Química, Facultad Experimental de Ciencias, La Universidad del Zulia, Apdo 526, Maracaibo, Venezuela. E-mail: hsoscun@luz.edu.ve; hsoscun@gmail.com

Abstract: The static dipole (hyper) polarizabilities (α,β and γ) of p-nitrophenylphospine (PNPhP), a hypothetical Push-Pull organic molecule, were calculated using ab initio (HF, MP2, MP4) and density functional theory DFT (B3LYP, CAM-B3LYP, WB97X-D) hybrid approaches, in conjunction with the standard 6-31+G(d,p) and 6-311++G(3d,3p) basis sets. Similar (hyper) polarizability calculations were additionally carried out for p-Nitroaniline PNA molecule for comparison purposes. These response properties were evaluated within the Finite Field methodology based in the Kurtz equations, where the effects of replacing the -NH2 donor group of PNA by the -PH2 group originating the p-nitrophenylphospine PNPhP molecule are analyzed. The results of α, β and γ properties evaluated at different levels of theory show that PNPhP molecule is much more (hyper)polarizable than PNA one. Electron correlation effects, evaluated at MP2, MP4, DFT/B3LYP, CAM-B3LYP and WB97X-D levels of theory, show that αave increases between 7 to 16% with respect to the HF values. Likewise, the largest responses are obtained with the most extended basis sets such as 6-311++G(3d,3p), where polarizability increase between 4 to 9% with respect to 6-31+G(d,p) one. The tendencies for β and γ NLO values follow the electron density delocalization of the molecular system, that is more extended in PNPhP than PNA one. Electron correlation effects increase β and γ properties in the order of two or three times with respect to the HF values. Finally, the impact of dynamic and solvent effects on the first hyperpolarizability of PNA molecule were also taken into account, which are discussed in terms of recent literature. The analysis of results, allow us to conclude that PNPhP is an interesting hypothetic molecule that can be useful as building block for the design and creation of new materials with enhanced nonlinear optic applications.

Keywords: Optical properties, Push-Pull molecules, finite field, p-nitrophenylphosphine, p-nitroaniline

DOI: 10.3233/JCM-120430

Journal: Journal of Computational Methods in Sciences and Engineering, vol. 12, no. 4-6, pp. 407-421, 2012