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Reddy VS, Camacho C, Xia J, et al. Quantum Dynamics Simulations Reveal Vibronic Effects on the Optical Properties of [n]Cycloparaphenylenes. J Chem Theory Comput. 2014;10(9):4025-36doi: 10.1021/ct500524y.
Reddy, V. S., Camacho, C., Xia, J., Jasti, R., & Irle, S. (2014). Quantum Dynamics Simulations Reveal Vibronic Effects on the Optical Properties of [n]Cycloparaphenylenes. Journal of chemical theory and computation, 10(9), 4025-36. https://doi.org/10.1021/ct500524y
Reddy, V Sivaranjana, et al. "Quantum Dynamics Simulations Reveal Vibronic Effects on the Optical Properties of [n]Cycloparaphenylenes." Journal of chemical theory and computation vol. 10,9 (2014): 4025-36. doi: https://doi.org/10.1021/ct500524y
Reddy VS, Camacho C, Xia J, Jasti R, Irle S. Quantum Dynamics Simulations Reveal Vibronic Effects on the Optical Properties of [n]Cycloparaphenylenes. J Chem Theory Comput. 2014 Sep 09;10(9):4025-36. doi: 10.1021/ct500524y. PMID: 26588546.
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J Chem Theory Comput. 2014 Sep 09;10(9):4025-36. doi: 10.1021/ct500524y.

Quantum Dynamics Simulations Reveal Vibronic Effects on the Optical Properties of [n]Cycloparaphenylenes.

Journal of chemical theory and computation

V Sivaranjana Reddy, Cristopher Camacho, Jianlong Xia, Ramesh Jasti, Stephan Irle

Affiliations

  1. School of Chemistry, University of Costa Rica , San Pedro de Montes de Oca, San José 11501-2060, Costa Rica.
  2. Department of Chemistry, Boston University , Boston, Massachusetts 02215, United States.

PMID: 26588546 DOI: 10.1021/ct500524y

Abstract

The size-dependent ultraviolet/visible photophysical property trends of [n]cycloparaphenylenes ([n]CPPs, n = 6, 8, and 10) are theoretically investigated using quantum dynamics simulations. For geometry optimizations on the ground- and excited-state Born-Oppenheimer potential energy surfaces (PESs), we employ density functional theory (DFT) and time-dependent DFT calculations. Harmonic normal-mode analyses are carried out for the electronic ground state at Franck-Condon geometries. A diabatic Hamiltonian, comprising four low-lying singlet excited electronic states and 26 vibrational degrees of freedom of CPP, is constructed within the linear vibronic coupling (VC) model to elucidate the absorption spectral features in the range of 300-500 nm. Quantum nuclear dynamics is simulated within the multiconfiguration time-dependent Hartree approach to calculate the vibronic structure of the excited electronic states. The symmetry-forbidden S0 → S1 transition appears in the longer wavelength region of the spectrum with weak intensity due to VC. It is found that the Jahn-Teller and pseudo-Jahn-Teller effects in the doubly degenerate S2 and S3 electronic states are essential in the quantitative interpretation of the experimental observation of a broad absorption peak around 340 nm. The vibronic mixing of the S1 state with higher electronic states is responsible for the efficient photoluminescence from the S1 state. The fluorescence properties are characterized on the basis of the stationary points of the excited-state PESs. The findings reveal that vibronic effects become important in determining the photophysical properties of CPPs with increased ring size.

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