Issue 18, 2001

The electronic spectra of symmetric cyanine dyes: A CASPT2 study

Abstract

Ab initio quantum mechanical calculations were performed to study the electronic spectra of symmetric all-E configurated streptocyanine dyes, [R2N–(CH–CH)n–CH–NR2]+, R = H and CH3, from n = 0 (monomethine) to n = 4 (nonamethine). Ground state geometries were optimized based on density functional theory. Excitation energies were calculated using multi-configurational second-order perturbation theory (CASPT2). CASPT2 corrected vertical excitation energies for the long wavelength absorptions were within 0.08 eV of the experiment. Also, these calculations reproduced the 100 nm vinylene shift which is characteristic for these dyes. The agreement between calculated and experimental oscillator strengths was satisfactory. The results were compared with calculations based on a single determinant ab initio approach and on density functional linear response theory. These methods systematically overestimated experimental transition energies.

Article information

Article type
Paper
Submitted
17 Apr 2001
Accepted
06 Jul 2001
First published
22 Aug 2001

Phys. Chem. Chem. Phys., 2001,3, 3906-3912

The electronic spectra of symmetric cyanine dyes: A CASPT2 study

M. Schreiber, V. Buß and M. P. Fülscher, Phys. Chem. Chem. Phys., 2001, 3, 3906 DOI: 10.1039/B103417K

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements