The relative aromaticity of benzenoid rings in the linear polyacenes is investigated using two novel aromaticity approaches. According to the first, the aromaticity of individual benzene rings was gauged by the values of six-center bond indices (SCI) calculated within the so-called Generalized Population Analysis (GPA). In the second approach, the same goal is addressed using the theory of Molecular Quantum Similarity (MQS). Both independent approaches are found to correlate very well, and both point toward decreasing aromaticity in any linear polyacenes upon going from the outer to inner rings.
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http://dx.doi.org/10.1002/jcc.20491 | DOI Listing |
J Chem Phys
December 2023
MOE Key Laboratory of Environmental Theoretical Chemistry, South China Normal University, Guangzhou 510006, China.
Singlet fission (SF) is a very significant photophysical phenomenon and possesses potential applications. In this work, we try to give a rather detailed theoretical investigation of the SF process in the stacked polyacene dimer by combining the high-level quantum chemistry calculations and the quantum dynamics simulations based on the tensor network method. Starting with the construction of the linear vibronic coupling model, we explore the pure electronic dynamics and the vibronic dynamics in the SF processes.
View Article and Find Full Text PDFJ Phys Chem Lett
December 2022
School of Chemical Sciences, Indian Association for the Cultivation of Science, Jadavpur, Kolkata700032, India.
The singlet triplet (ST) gap of linear polyacenes decays exponentially with the system size as a result of extended conjugation and reducing highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gaps. These low ST gaps can ideally be leveraged toward energy applications but are hindered by the decreasing stability of the systems. Thus, there is the need to understand the ST gap of nonlinear polyacenes, which are markedly more stable than their linear counterparts.
View Article and Find Full Text PDFJ Phys Chem A
May 2021
Department of Chemistry, American University, Washington, District of Columbia 20016, United States.
Molecular symmetry is vital to the selection rule of vibrationally resolved electronic transition, particularly when the nuclear dependence of electronic wave function is explicitly treated by including Franck-Condon (FC) factor, Franck-Condon/Herzberg-Teller (FC/HT) interference, and Herzberg-Teller (HT) coupling. Our present study investigated the light absorption spectra of highly symmetric tetracene, pentacene, and hexacene molecules of point-group , as well as their monobrominated derivatives with a lower symmetry. It was found that the symmetry-breaking monobromination allows more vibrational normal modes and their pairs to contribute to FC/HT interference and HT coupling, respectively.
View Article and Find Full Text PDFJ Chem Theory Comput
May 2021
Department of Chemistry, Virginia Tech, Blacksburg, Virginia 24061, United States.
We present a practical approach to treat static and dynamical correlation accurately in large multiconfigurational systems. The static correlation is taken into account by using the spin-flip approach, which is well-known for capturing static correlation accurately at low-computational expense. Unlike previous approaches to add dynamical correlation to spin-flip models which use perturbation theory or coupled-cluster theory, we explore the ability to use the on-top pair-density functional theory approaches recently developed by Gagliardi and co-workers (, , , 3669).
View Article and Find Full Text PDFJ Mol Graph Model
September 2020
Chemistry Department, College of Sciences, Shiraz University, Shiraz, 71454, Iran. Electronic address:
In the present work, the total non-Lewis structure (TNLS) is introduced for describing the stability and reactivity of linear and angular polyacenes. TNLS of a molecule is derived from the natural bond orbital theory representing the antibonding orbitals and/or electron delocalization of π orbitals. To verify this application, we obtained the TNLS values of thirteen linear and angular polyacenes and evaluated with other quantitative aromaticity probes based on reactivities, energetics, geometrics, and magnetic properties.
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