Title

Electronic Hyperpolarizabilities For Donor-Acceptor Molecules With Long Conjugated Bridges: Calculations Versus Experiment

Abstract

We investigate the molecular first hyperpolarizability (β) for donor/acceptor (D/A) substituted π-conjugated organic molecules with different D/A groups and π-systems (including up to eight π-bonds). The results of the MP2 and density functional theory (PBE0, BMK, M05, M05-2X) calculations are compared to those obtained from experimental data. The goal of this study is to select a protocol with optimal quality/cost ratio to be used for systematic prediction of molecular nonlinear optical (NLO) properties. This goal is closely related to the way in which theoretical βs are compared to experimental ones and to the accuracy and consistency of experimental hyperpolarizabilities used to test theoretical predictions. We found that two DFT functional with the larger fraction of Hartree-Fock exchange (BMK and especially M05-2X) provide the best agreement to the experiment, comparable to that of the MP2 method. Due to high computational cost of MP2 method, we recommend to use the M05-2X functional as a tool for systematic prediction of molecular hyperpolarizabilities. © 2009 American Chemical Society.

Publication Date

10-15-2009

Publication Title

Journal of Physical Chemistry A

Volume

113

Issue

41

Number of Pages

10994-11001

Document Type

Article

Personal Identifier

scopus

DOI Link

https://doi.org/10.1021/jp902293q

Socpus ID

70349915665 (Scopus)

Source API URL

https://api.elsevier.com/content/abstract/scopus_id/70349915665

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