1,721,102 research outputs found
Use of molecular symmetry in the computation of solvation energies and their analytical derivatives by the polarizable continuum model
No full textRadical cations of DNA bases: some insights on structure and fragmentation patterns by density functional methods
No full textAb-initio study of the gas-phase structure and electronic properties of M-CH3 (M=Li,Na) and M-CCH (M=Li,Na,K): A combined post Hartree-Fock and density functional study
No full textRadical cations of DNA bases: some insights on structure and fragmentation patterns by density functional methods
No full textQuantum mechanical prediction of the magnetic titration curve of a nitroxide 'spin probe'
No full textUse of molecular symmetry in the computation of solvation energies and their analytical derivatives by the polarizable continuum model
No full textAb-initio study of the gas-phase structure and electronic properties of M-CH3 (M=Li,Na) and M-CCH (M=Li,Na,K): A combined post Hartree-Fock and density functional study
No full textQuantum mechanical prediction of the magnetic titration curve of a nitroxide 'spin probe'
No full textExcited state gradients for a state-specific continuum solvation approach: The vertical excitation model within a Lagrangian TDDFT formulation
No full textThe accurate modeling of the environment response is a fundamental challenge for accurately describing the photophysics and photochemistry of molecules both in solution and in more complex embeddings. When large rearrangements of the electron density occur after an electronic transition, state-specific formulations, such as the vertical excitation model, are necessary to achieve a proper modeling of the processes. Such a state-specific model is fundamental not only to obtain accurate energies, but also to follow the geometrical relaxation accompanying the evolution of the excitedstates. This study presents the analytical expression of the gradients of the vertical excitation model approach by a Lagrangian formulation in the time dependent density functional theory framework. Representative organic chromophores in solution are used to test the reliability of the implementation and provide comparisons with the linear response description. Published by AIP Publishing
Excited State Dipole Moments in Solution: Comparison between State-Specific and Linear-Response TD-DFT Values
No full textWe compare different response schemes for coupling continuum solvation models to time-dependent density functional theory (TD-DFT) for the determination of solvent effects on the excited state dipole moments of solvated molecules. In particular, linear-response (LR) and state-specific (SS) formalisms are compared. Using 20 low-lying electronic excitations, displaying both localized and charge-transfer character, this study highlights the importance of applying a SS model not only for the calculation of energies, as previously reported (J. Chem. Theory Comput., 2015, 11, 5782, DOI: 10.1021/acs.jctc.5b00679), but also for the prediction of excited state properties. Generally, when a range-separated exchange-correlation functional is used, both LR and SS schemes provide very similar dipole moments for local transitions, whereas differences of a few Debye units with respect to LR values are observed for CT transitions. The delicate interplay between the response scheme and the exchange-correlation functional is discussed as well, and we show that using an inadequate functional in a SS framework can yield to dramatic overestimations of the dipole moments
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