The electronic spectra of symmetric cyanine dyes: A CASPT2 study

Literature Information

Publication Date 2001-08-22
DOI 10.1039/B103417K
Impact Factor 3.676
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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.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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