Title

Two-Photon Circular-Linear Dichroism of Perylene in Solution: A Theoretical-Experimental Study

Authors

Authors

M. G. Vivas; C. Diaz; L. Echevarria; C. R. Mendonca; F. E. Hernandez;L. De Boni

Comments

Authors: contact us about adding a copy of your work at STARS@ucf.edu

Abbreviated Journal Title

J. Phys. Chem. B

Keywords

EXCITED-STATE SYMMETRY; OPTICAL NONLINEARITIES; ABSORPTION PROPERTIES; ORGANIC-MOLECULES; POLYMETHINE DYES; ONE-PHOTON; POLARIZATION; CHROMOPHORES; DENSITY; SPECTROSCOPY; Chemistry, Physical

Abstract

Herein, we report on the theoretical-experimental analysis of the two-photon absorption (TPA) and two-photon circular-linear dichroism (TPCLD) spectra of a highly conjugated, rigid, and centrosymmetric molecule in solution, that is, perylene/CH2Cl2. We show how a three-energy-level diagram, under the sum-over-essential states approach, assists in the determination of the magnitude of transition electric dipole moments and the angle between them for the main TPA transitions. We demonstrate the potential of TPCLD to reveal the symmetry of excited states and the angles between their transition electric dipole moments and that of the ground state. By means of TPCLD, we explain how the overwhelming contribution of certain TPA transitions can mask important spectral features in regions where the transition electric dipole moments are perpendicular. TPCLD is expected to enhance the understanding of the photophysical properties of materials that are not accessible using conventional linear and two-photon spectroscopy. TPA and TPCLD measurements were performed employing the open-aperture Z-scan technique using an amplified femtoseconcl system. Time-dependent density functional theory (TD-DFT) calculations were carried out using response theory at the B3LYP level with the aug-cc-pVDZ basis set. Solvent effects were included through the polarizable continuum model (PCM).

Journal Title

Journal of Physical Chemistry B

Volume

117

Issue/Number

9

Publication Date

1-1-2013

Document Type

Article

Language

English

First Page

2742

Last Page

2747

WOS Identifier

WOS:000315979600015

ISSN

1520-6106

Share

COinS