Coupling Real-Time Time-Dependent Density Functional Theory with Polarizable Force Field

Donati, Greta; Wildman, Andrew; Caprasecca, Stefano; Lingerfelt, David B.; Lipparini, Filippo; Mennucci, Benedetta; Li, Xiaosong

doi:10.1021/acs.jpclett.7b02320

Cited by 28 publications

(33 citation statements)

References 82 publications

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“…Hovewer, to recover a better and more physical description of the electrostatic interaction between the QM and MM portions, several polarizable QM/MM models, in which the MM atoms can be polarized by the QM density, have been developed. Such models can be based on distributed multipoles, [35][36][37][38] induced dipoles, [39][40][41][42] Drude oscillators, [43] or fluctuating charges (FQ). [44] The FQ model was first developed into a 3-layer fully polarizable approach with nonperiodic boundary conditions (QM/FQ/PCM).…”

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confidence: 99%

Simulating vertical excitation energies of solvated dyes: From continuum to polarizable discrete modeling

Giovannini

Macchiagodena

Ambrosetti

et al. 2018

Int J of Quantum Chemistry

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We present a computational study on the spectroscopic properties of UV-Vis absorbing dyes in water solution. We model the solvation environment by using both continuum and discrete models, with and without polarization, to establish how the physical and chemical properties of the solute-solvent interaction may affect the spectroscopic response of aqueous systems. Seven different compounds were chosen, representing different classes of organic molecules. The classical atomistic description of the solvent molecules was enriched with polarization effects treated by means of the fluctuating charges (FQ) model, propagated to the first-order response function of the quantum-mechanical (QM) solute to include its effects withing the modeling of the electronic excitations of the systems. Results obtained with the QM/FQ model were compared with those from continuum solvation models as well as nonpolarizable atomistic models, and then confronted with the experimental values to determine the accuracy that can be expected with each level of theory. Moreover, a thorough structural analysis using molecular dynamics simulations is provided for each system. K E Y W O R D S excitation energies, QM/FQ, QM/MM, QM/PCM, solvent effects, TD-DFT 1 | I N TR O DU C TI O N One-photon absorption spectroscopy within the UV-Visible range is often the most direct and inexpensive analytical tool that can be used to study the electronic properties of a system. Most commonly, such measurements are carried out on solvated samples, with water being a ubiquitous choice.With the gradual increase in the complexity of the systems under investigation, the correct interpretation of experimental data is increasingly reliant on their calculated ab initio counterparts. Many theoretical models based on quantum mechanics (QM), accompanied by their computational implementations, have been presented over the years offering different levels of compromise between the computational cost and the accuracy of the results. [1][2][3] At present, methods based on density functional theory (DFT) and its time-dependent counterpart (TD-DFT) have become the most popular choice for the simulation of absorption spectra of medium-large organic molecular systems thanks to their versatility stemming from the freedom of choice of density functional and basis set, as well as the favorable scaling with system size which allows their application to increasingly large systems. [1,[4][5][6] Many benchmarks studies have been presented elaborating on the merits and limitations of TD-DFT for the simulation of UV-Vis spectroscopy, as well as on the most appropriate choice of functional and basis set combination for different types of system. [6][7][8][9][10][11][12][13][14][15][16] And though many computational studies are carried out on isolated systems, solvent effects should not be neglected for the presence of the solvation environment can significantly alter the electronic absorption properties of a system, both qualitatively and quantitatively. [17][18][19][20][21][22][23][24][25][2...

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mentioning

confidence: 99%

Simulating vertical excitation energies of solvated dyes: From continuum to polarizable discrete modeling

Giovannini

Macchiagodena

Ambrosetti

et al. 2018

Int J of Quantum Chemistry

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“…Besides the fundamental aspect of taking into account both the dynamical response to charge density oscillating at the Bohr frequency (excitonic, dispersion‐like term) and the rearrangement of the electronic DoFs, there is still room for improvement in other respects, not explicitly treated in the present perspective. For instance, real‐time approaches, recently developed in the context of polarizable models, have not been treated in this scene, but represent a further important challenge in the modeling of nonequilibrium effects in ultrafast processes. Moreover, extensions of the continuum model to describe metal nanoparticles have also been developed and successfully implemented also in excitonic schemes .…”

Section: Discussionmentioning

confidence: 99%

On the description of the environment polarization response to electronic transitions

Guido

Caprasecca

2018

Int J of Quantum Chemistry

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This paper addresses the issue of accurately describing the structures and properties of electronically excited systems embedded in an environment, through multiscale approaches combining quantum-mechanical (QM) and polarizable classical representations of the system and environment, respectively. Such approaches represent an efficient strategy and allow to effectively study the excited states of molecular systems in the condensed phase, still maintaining the computational efficiency and the physical reliability of the ground-state calculations. The most important theoretical and computational aspects of the coupling between the QM system and the polarizable environment are presented and discussed. Even if these approaches already reached an evident degree of maturity, they can still be subject to further development, in order to achieve their full potential. This perspective presents an overview of the state of the art of these strategies, showing the fields of applicability and indicating the current limitations, which need to be overcome in future developments. K E Y W O R D S excited states, linear response, polarizable continuum model, polarizable molecular mechanics, state specific 1 | INTRODUCTIONThe efficient exploration of the excited state (ES) energy surfaces of (supra) molecular systems is fundamental for the understanding of many photochemical and photophysical processes of technological and biological interest. Geometries, energies and properties such as dipole moments and transition and state densities of electronic ESs are the key ingredients to simulate, among the others, linear and nonlinear spectroscopic signals, energy and electron transfer processes, photocatalysis, light emission, and optical information storage. Most of these phenomena occur in condensed phase, where the molecular environment may largely affect the electronic structure reorganization following an electronic transition [1,2] Multiscale approaches [3,4] are some of the most powerful computational strategies for interpreting and simulating molecular processes in the condensed phase: an effective microsystem (which can be a single molecule or an aggregate of supramolecular size, henceforth system, or Sys) is assumed to be responsible for the observed process, property or signal, as its nuclear and electronic degrees of freedom (DoFs) are directly involved in it. On the other hand, the embedding macrosystem (henceforth environment, or Env) does not take part in the process, but rather acts as a perturbation, thus affecting the result of the measurement. The two components can mutually interact but they typically keep their number of nuclei and electrons constant during the process investigated (although so-called adaptive QM/molecular mechanics (MM) models exist to simulate processes where a dynamical definition of the QM/MM boundary is introduced [5,6] ). By applying this simplified but effective picture, a quite accurate and complete interpretation is generally achieved for systems of increasing complexity.

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“…The coupling to polarizable and non-polarizable MM force fields has been described in Reference [24]. While interfacing with a non-polarizable force field is rather straightforward [76], the mutual polarization between the quantum and classical regions in the QM/MMpol framework makes propagation algorithms more involved [25,77,78]. We devised a stationary/non-stationary dual scheme [24] in which induced dipoles on MM atoms are fully relaxed at every electron propagation time steps.…”

Section: The In-demon2k Implementation Of Quantum Mechanical/molecmentioning

confidence: 99%

Molecular Simulations with in-deMon2k QM/MM, a Tutorial-Review

et al. 2019

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deMon2k is a readily available program specialized in Density Functional Theory (DFT) simulations within the framework of Auxiliary DFT. This article is intended as a tutorial-review of the capabilities of the program for molecular simulations involving ground and excited electronic states. The program implements an additive QM/MM (quantum mechanics/molecular mechanics) module relying either on non-polarizable or polarizable force fields. QM/MM methodologies available in deMon2k include ground-state geometry optimizations, ground-state Born–Oppenheimer molecular dynamics simulations, Ehrenfest non-adiabatic molecular dynamics simulations, and attosecond electron dynamics. In addition several electric and magnetic properties can be computed with QM/MM. We review the framework implemented in the program, including the most recently implemented options (link atoms, implicit continuum for remote environments, metadynamics, etc.), together with six applicative examples. The applications involve (i) a reactivity study of a cyclic organic molecule in water; (ii) the establishment of free-energy profiles for nucleophilic-substitution reactions by the umbrella sampling method; (iii) the construction of two-dimensional free energy maps by metadynamics simulations; (iv) the simulation of UV-visible absorption spectra of a solvated chromophore molecule; (v) the simulation of a free energy profile for an electron transfer reaction within Marcus theory; and (vi) the simulation of fragmentation of a peptide after collision with a high-energy proton.

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Coupling Real-Time Time-Dependent Density Functional Theory with Polarizable Force Field

Cited by 28 publications

References 82 publications

Simulating vertical excitation energies of solvated dyes: From continuum to polarizable discrete modeling

Simulating vertical excitation energies of solvated dyes: From continuum to polarizable discrete modeling

On the description of the environment polarization response to electronic transitions

Molecular Simulations with in-deMon2k QM/MM, a Tutorial-Review

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