Dataset Information

Density Functional Theory Applied to Excited State Intramolecular Proton Transfer in Imidazole-, Oxazole-, and Thiazole-Based Systems.

ABSTRACT: Excited state intramolecular proton transfer (ESIPT) is a photoinduced process strongly associated to hydrogen bonding within a molecular framework. In this manuscript, we computed potential energy data using Time Dependent Density Functional Theory (TDDFT) for triphenyl-substituted heterocycles, which evidenced an energetically favorable proton transfer on the excited state (i.e., ESIPT) but not on the ground state. Moreover, we describe how changes on heterocyclic functionalities, based on imidazole, oxazole, and thiazole systems, affect the ESIPT process that converts an enolic species to a ketonic one through photon-induced proton transfer. Structural and photophysical data were obtained theoretically by means of density functional theory (DFT) calculations and contrasted for the three heterocyclics. Different functionals were used, but B3LYP was the one that adequately predicted absorption data. It was observed that the intramolecular hydrogen bond is strengthened in the excited state, supporting the occurrence of ESIPT. Finally, it was observed that, with the formation of the excited state, there is a decrease in electronic density at the oxygen atom that acts as proton donor, while there is a substantial increase in the corresponding density at the nitrogen atom that serves as proton acceptor, thus, indicating that proton transfer is indeed favored after photon absorption.

SUBMITTER: de Carvalho F

PROVIDER: S-EPMC6100175 | biostudies-other | 2018 May

REPOSITORIES: biostudies-other

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Density Functional Theory Applied to Excited State Intramolecular Proton Transfer in Imidazole-, Oxazole-, and Thiazole-Based Systems.

de Carvalho Fabricio F Coutinho Neto Maurício D MD Bartoloni Fernando H FH Homem-de-Mello Paula P

Molecules (Basel, Switzerland) 20180521 5

Excited state intramolecular proton transfer (ESIPT) is a photoinduced process strongly associated to hydrogen bonding within a molecular framework. In this manuscript, we computed potential energy data using Time Dependent Density Functional Theory (TDDFT) for triphenyl-substituted heterocycles, which evidenced an energetically favorable proton transfer on the excited state (i.e., ESIPT) but not on the ground state. Moreover, we describe how changes on heterocyclic functionalities, based on imi ...[more]

PMID: 29883373

Similar Datasets

Project description:Excimers are supramolecular systems whose binding strength is influenced by many factors that are ongoing challenges for computational methods, such as charge transfer, exciton coupling, and London dispersion interactions. Treating the various intricacies of excimer binding at an adequate level is expected to be particularly challenging for time-dependent Density Functional Theory (TD-DFT) methods. In addition to well-known limitations for some TD-DFT methods in the description of charge transfer or exciton coupling, the inherent London dispersion problem from ground-state DFT translates to TD-DFT. While techniques to appropriately treat dispersion in DFT are well-developed for electronic ground states, these dispersion corrections remain largely untested for excited states. Herein, we aim to shed light on current TD-DFT methods, including some of the newest developments. The binding of four model excimers is studied across nine density functionals with and without the application of additive dispersion corrections against a wave function reference of SCS-CC2/CBS(3,4) quality, which approximates select CCSDR(3)/CBS data adequately. To our knowledge, this is the first study that presents single-reference wave function dissociation curves at the complete basis set level for the assessed model systems. It is also the first time range-separated double-hybrid density functionals are applied to excimers. In fact, those functionals turn out to be the most promising for the description of excimer binding followed by global double hybrids. Range-separated and global hybrids-particularly with large fractions of Fock exchange-are outperformed by double hybrids and yield worse dissociation energies and inter-molecular equilibrium distances. The deviation between each assessed functional and reference increases with system size, most likely due to missing dispersion interactions. Additive dispersion corrections of the DFT-D3(BJ) and DFT-D4 types reduce the average errors for TD-DFT methods but do so inconsistently and therefore do not offer a black-box solution in their ground-state parametrised form. The lack of appropriate description of dispersion effects for TD-DFT methods is likely hindering the practical application of the herein identified more efficient methods. Dispersion corrections parametrised for excited states appear to be an important next step to improve the applicability of TD-DFT methods and we hope that our work assists with the future development of such corrections.

Project description:Excimers are supramolecular systems whose binding strength is influenced by many factors that are ongoing challenges for computational methods, such as charge transfer, exciton coupling, and London dispersion interactions. Treating the various intricacies of excimer binding at an adequate level is expected to be particularly challenging for Time-Dependent Density Functional Theory (TD-DFT) methods. In addition to well-known limitations for some TD-DFT methods in the description of charge transfer or exciton coupling, the inherent London dispersion problem from ground-state DFT translates to TD-DFT. While techniques to appropriately treat dispersion in DFT are well-developed for electronic ground states, these dispersion corrections remain largely untested for excited states. Herein, we aim to shed light on current TD-DFT methods, including some of the newest developments. The binding of four model excimers is studied across nine density functionals with and without the application of additive dispersion corrections against a wave function reference of SCS-CC2/CBS(3,4) quality, which approximates select CCSDR(3)/CBS data adequately. To our knowledge, this is the first study that presents single-reference wave function dissociation curves at the complete basis set level for the assessed model systems. It is also the first time range-separated double-hybrid density functionals are applied to excimers. In fact, those functionals turn out to be the most promising for the description of excimer binding followed by global double hybrids. Range-separated and global hybrids-particularly with large fractions of Fock exchange-are outperformed by double hybrids and yield worse dissociation energies and inter-molecular equilibrium distances. The deviation between each assessed functional and reference increases with system size, most likely due to missing dispersion interactions. Additive dispersion corrections of the DFT-D3(BJ) and DFT-D4 types reduce the average errors for TD-DFT methods but do so inconsistently and therefore do not offer a black-box solution in their ground-state parametrised form. The lack of appropriate description of dispersion effects for TD-DFT methods is likely hindering the practical application of the herein identified more efficient methods. Dispersion corrections parametrised for excited states appear to be an important next step to improve the applicability of TD-DFT methods and we hope that our work assists with the future development of such corrections.

Dataset Information

Density Functional Theory Applied to Excited State Intramolecular Proton Transfer in Imidazole-, Oxazole-, and Thiazole-Based Systems.

Publications

Density Functional Theory Applied to Excited State Intramolecular Proton Transfer in Imidazole-, Oxazole-, and Thiazole-Based Systems.

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