Dataset Information

Quantum Mechanics/Fluctuating Charge Protocol to Compute Solvatochromic Shifts.

ABSTRACT: Despite the potentialities of the quantum mechanics (QM)/fluctuating charge (FQ) approach to model the spectral properties of solvated systems, its extensive use has been hampered by the lack of reliable parametrizations of solvents other than water. In this paper, we substantially extend the applicability of QM/FQ to solvating environments of different polarities and hydrogen-bonding capabilities. The reliability and robustness of the approach are demonstrated by challenging the model to simulate solvatochromic shifts of four organic chromophores, which display large shifts when dissolved in apolar, aprotic or polar, protic solvents.

SUBMITTER: Ambrosetti M

PROVIDER: S-EPMC8582258 | biostudies-literature | 2021 Nov

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Quantum Mechanics/Fluctuating Charge Protocol to Compute Solvatochromic Shifts.

Ambrosetti Matteo M Skoko Sulejman S Giovannini Tommaso T Cappelli Chiara C

Journal of chemical theory and computation 20211007 11

Despite the potentialities of the quantum mechanics (QM)/fluctuating charge (FQ) approach to model the spectral properties of solvated systems, its extensive use has been hampered by the lack of reliable parametrizations of solvents other than water. In this paper, we substantially extend the applicability of QM/FQ to solvating environments of different polarities and hydrogen-bonding capabilities. The reliability and robustness of the approach are demonstrated by challenging the model to simula ...[more]

PMID: 34619965

Similar Datasets

Project description:In quantum mechanics, the theory of quantum transitions is grounded on the convergence of a series of time-dependent perturbation theory. In nuclear and atomic physics, this series converges because the dynamics of quantum transitions (quantum jumps) are absent by definition. In molecular and chemical physics, on the contrary, the dynamics of "quantum" transitions, being determined by the joint motion of a light electron (or electrons) and very heavy nuclei, are present by definition, and the series of time-dependent perturbation theory becomes singular. An exception is the dynamic problem for stationary states in the Born-Oppenheimer adiabatic approximation, when the electronic subsystem turns out to be "off" from the general dynamic process and therefore is not dynamically full-fledged: it only forms an electric potential in which the nuclei oscillate. Removing the aforementioned singularity can be accomplished in two ways. The first method was consisted of introducing an additional postulate in the form of the Franck-Condon principle into molecular quantum mechanics, in which the adiabatic approximation is used. The second method was proposed by the author and consisted of damping the singular dynamics of the joint motion of an electron and nuclei in the intermediate (transient) state of molecular "quantum" transitions by introducing chaos. This chaos arises only during molecular quantum transitions and is called dozy chaos. Formally, the damping is carried out by replacing an infinitely small imaginary addition in the spectral representation of the complete Green's function of the system with its finite quantity. The damping chaos (dozy chaos) leads to the continuity of the energy spectrum in the molecular transient state, which is a sign of classical mechanics. Meanwhile, the initial and final states of the molecule obey quantum mechanics in the adiabatic approximation. Molecular quantum mechanics, which takes into account the chaotic dynamics of the transient state of molecular "quantum" transitions, can be called quantum-classical (dozy-chaos) mechanics. The efficacy of the damping for the aforementioned singularity was previously shown by dozy-chaos mechanics of elementary electron transfers in condensed matter, which is the simplest case of dozy-chaos mechanics, and its applications to a whole number of problems, especially to the optical spectra in polymethine dyes and their aggregates. This paper provides a regular exposition of this dozy-chaos (quantum-classical) mechanics of the elementary electron transfers. The main results of its applications presented in the introduction are also described.

Dataset Information

Quantum Mechanics/Fluctuating Charge Protocol to Compute Solvatochromic Shifts.

Publications

Quantum Mechanics/Fluctuating Charge Protocol to Compute Solvatochromic Shifts.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets