HEИндивидуална стипендия2024–2027

NEOSC · Post Born-Oppenheimer Approximation for Semiclassical Spectroscopy Investigation of Proton-Coupled Electron Transfer Processes

„Хоризонт Европа“ — Действия „Мария Склодовска-Кюри“

Период: 2024-01-01 → 2027-01-31
Финансиране от ЕС: 288 859 €
Участници: 2
Схема: HORIZON-TMA-MSCA-PF-GF

Линиите свързват координатора с партньорите.

Накратко на български

Процесите на едновременен трансфер на електрони и протони се анализират чрез нов софтуер за молекулярна динамика. Това помага за по-точното тълкуване на спектроскопични данни и разбирането на структурните промени в химията и биологията.

Този кратък обзор е генериран от изкуствен интелект

Кратко обяснение, генерирано от езиков модел по текста на CORDIS. Оригиналът е по-долу.

Резултати накратко

Post Born-Oppenheimer Approximation for Semiclassical Spectroscopy Investigation of Proton-Coupled Electron Transfer Processes

The Born-Oppenheimer Approximation (BOA) has determined how chemists describe molecules since 1927. BOA separates electronic and nuclear degrees of freedom, considering that the electron timescale is much shorter than the nuclear one. This project develops an accurate molecular dynamics method implemented as open-source software with two fundamental features. First, a proper treatment of proton-electron coupling to describe chemical processes that break down the Born-Oppenheimer approximation, which is usually taken for granted in chemistry simulations; Second, going beyond the common classical dynamics assumption for the non-hydrogen nuclei. Quantum effects are not confined to H but have also been experimentally observed for C, N, O. The new approach will unify two cutting-edge methods, the Nuclear Electronic Orbital (NEO), which treats selected nuclei (usually hydrogens) beyond the BOA, and the Divide-and-Conquer Semiclassical Initial Value Representation (DC-SCIVR) which accounts for anharmonicity and effectively approximates quantum effects in molecules. A ubiquitous process in chemistry and biology, involving the quantum-mechanical coupled motion of electrons and protons, is the Proton-Coupled Electron Transfer (PCET) mechanism. The couplings between the transferring protons and the other nuclei' motions are so crucial that the proton transfer does not spontaneously occur without molecular structural relaxation. PECT is usually investigated experimentally using Time-Resolved InfraRed spectroscopy (TRIR), which follows molecular vibrations in real time. With the new dynamical framework developed in this project, TRIR can be simulated beyond the state of the art, aiding the spectra interpretation and revealing the structural dynamics complementing the proton transfer after photoinduced PCET. Remarkably, biological photosynthesis catalyzes water splitting through PCET. Therefore, a precise theoretical understanding and accurate simulation of PCET could, in the long term, help make water splitting less energy-intensive and more cost-effective in solar energy devices. PCET is also critical in many fields, such as fuel cells, catalysis, antioxidant reactivity, and chemical synthesis The new non-BO theory will be implemented in an open-source code, ensuring it will reach the scientific community at large. In fact, TRIR spectroscopy is a widely employed tool, ranging from medical research on DNA damage induced by UV radiation to biological studies of vision-related molecular reactions to the engineering of molecular catalysts for converting solar light into chemical energy.

Текст от CORDIS, на английски · Данни: CORDIS, © Европейски съюз

Цел на проекта

The Born-Oppenheimer Approximation (BOA) has determined how chemists describe molecules since 1927. BOA separates electronic and nuclear degrees of freedom, considering that the electron timescale is much shorter than the nuclear one. This assumption does not hold in Proton Coupled Electron Transfer (PCET) processes. PCET is the key to efficiency in biological photosynthesis. Time-Resolved Infrared spectroscopy (TRIR) assists PCET investigations but it is usually interpreted with harmonic frequency calculations or classical nuclear dynamics simulations on a BO potential energy surface. To gain further physical insights into PCET it is necessary to revise the theoretical framework for spectroscopy, going beyond the BOA and including a quantum treatment for all nuclei. To reach this goal, this project unifies two cutting-edge methods. One is the Nuclear Electronic Orbital (NEO) approach that goes beyond the BOA by including into the electronic structure calculations the PCET transferred proton. The other is the Semiclassical Initial Value Representation technique that simulates IR spectra by accounting for quantum effects, such as the zero-point energy, overtones, or tunneling, for all nuclei, even in large molecular systems. The project will introduce a new post-BOA conceptual picture for vibrational spectroscopy. Specifically, semiclassical nuclear density calculations will be used to tailor new basis sets to efficiently simulate large molecular systems, gradually including many protons and other nuclei in the NEO wavefunction. In this way, a new spectroscopy theory will be developed for the simulation of TRIR spectra at semiclassical accuracy on NEO post-BOA PESs. These advances will be implemented in an open-source code that we employ to study prototypical PCET systems and gain accurate mechanistic information. This new knowledge will foster applied research by exploiting a deeper understanding of the PCET processes.

Оригинален текст от CORDIS (на английски).

Участници

UNIVERSITA DEGLI STUDI DI MILANO · MilanoКоординаторИталия
TRUSTEES OF PRINCETON UNIVERSITY · Princeton, NjСъединени щати