A5026738293- Spectroscopy and Quantum Chemical Studies
- DNA and Nucleic Acid Chemistry
- Photochemistry and Electron Transfer Studies
- Advanced Chemical Physics Studies
- Photoreceptor and optogenetics research
- Advanced biosensing and bioanalysis techniques
- Molecular Junctions and Nanostructures
- Molecular spectroscopy and chirality
- RNA and protein synthesis mechanisms
- Photochromic and Fluorescence Chemistry
- Machine Learning in Materials Science
- Atmospheric Ozone and Climate
- Electrochemical Analysis and Applications
- Chemical and Physical Studies
- Bacteriophages and microbial interactions
- Porphyrin and Phthalocyanine Chemistry
- bioluminescence and chemiluminescence research
- Radical Photochemical Reactions
- Light effects on plants
- Luminescence and Fluorescent Materials
- Quantum Computing Algorithms and Architecture
- Conducting polymers and applications
- Quantum Information and Cryptography
- Atmospheric chemistry and aerosols
- Atomic and Molecular Physics
Universitat de València
2012-2024
Parc Científic de la Universitat de València
2023
Imperial College London
2019-2021
Université Claude Bernard Lyon 1
2016-2020
École Normale Supérieure de Lyon
2015-2020
Centre National de la Recherche Scientifique
2016-2020
Transnational Press London
2019
Molecular Sciences Institute
2019
Laboratoire de Chimie
2015-2018
Lyon College
2018
In this report, we summarize and describe the recent unique updates additions to M olcas quantum chemistry program suite as contained in release version 8. These include natural spin orbitals for studies of magnetic properties, local linear scaling methods Douglas–Kroll–Hess transformation, generalized active space concept MCSCF methods, a combination multiconfigurational wave functions with density functional theory MC‐PDFT method, additional computation diabatization, analytical gradients...
MOLCAS/OpenMolcas is an ab initio electronic structure program providing a large set of computational methods from Hartree-Fock and density functional theory to various implementations multiconfigurational theory. This article provides comprehensive overview the main features code, specifically reviewing use code in previously reported chemical applications as well more recent including calculation magnetic properties optimized matrix renormalization group wave functions.
The developments of the open-source OpenMolcas chemistry software environment since spring 2020 are described, with a focus on novel functionalities accessible in stable branch package or via interfaces other packages. These span wide range topics computational and presented thematic sections: electronic structure theory, spectroscopy simulations, analytic gradients molecular optimizations, ab initio dynamics, new features. This report offers an overview chemical phenomena processes can...
We combine sub-20 fs transient absorption spectroscopy with state-of-the-art computations to study the ultrafast photoinduced dynamics of trans-azobenzene (AB). are able resolve lifetime ππ* state, whose decay within ca. 50 is correlated buildup nπ* population and emergence coherences in dynamics, date unobserved. Nonlinear simulations call for CNN in-plane bendings as active modes subps coherent out state. Radiative kinetic energy transfer into these drives system a high-energy planar...
The study concerns the relaxation of electronic excited states DNA nucleoside deoxycytidine (dCyd) and its methylated analogue 5-methyldeoxycytidine (5mdCyd), known to be involved in formation UV-induced lesions genetic code. Due existence four closely lying potentially coupled states, deactivation pathways these systems are particularly complex have not been assessed so far. Here, we provide a complete mechanistic picture state dCyd/5mdCyd three solvents-water, acetonitrile,...
For the first time, ultrafast deactivations of photoexcited water-solvated pyrimidine nucleosides are mapped employing hybrid QM(CASPT2)/MM(AMBER) optimizations that account for explicit solvation, sugar effects, and dynamically correlated potential energy surfaces. Low-energy S1/S0 ring-puckering ring-opening conical intersections (CIs) suggested to drive ballistic coherent subpicosecond (<200 fs) decays observed in each pyrimidine, energetics controlling this processes correlating with...
The most relevant 'dark' electronic excited states in DNA/RNA pyrimidine nucleosides are mapped water employing hybrid MS-CASPT2/MM optimisations with explicit solvation and including the sugar. Conical intersections (CIs) between initially accessed bright 1ππ* lowest energy dark 1nπ* states, involving lone pair localised on oxygen and/or nitrogen atoms characterised. They found vicinities of Franck-Condon (FC) region shown to facilitate non-adiabatic population transfer. state 1nOπ* state,...
The differences in the electroluminescence (EL) of red‐emitting free‐base ( H2TPP ) and Zn‐metalated ZnTPP archetypal porphyrins are rationalized light‐emitting electrochemical cells by means an electric‐field dependent effect, leading to whitish reddish devices, respectively. Although shows superior photophysical features compared , devices prepared with surprisingly stand out a deep‐red EL similar its photoluminescence (PL), while feature unexpected EL. Standard arguments such as...
The optical spectra of 5-methylcytidine in three different solvents (tetrahydrofuran, acetonitrile, and water) is measured, showing that both the absorption emission maximum water are significantly blue-shifted (0.08 eV). simulated based on CAM-B3LYP/TD-DFT calculations but including solvent effects with approaches: (i) a hybrid implicit/explicit full quantum mechanical approach, (ii) mixed QM/MM static (iii) method exploiting structures issuing from molecular dynamics classical simulations....
A new flavor of the frozen natural orbital complete active space second-order perturbation theory method (FNO-CASPT2, Aquilante et al., J. Chem. Phys. 131, 034113) is proposed herein. In this implementation, virtual in Cholesky decomposition-based CASPT2 computations (CD-CASPT2) truncated by excluding those orbitals that contribute least toward preserving a predefined value trace an approximate density matrix, as represents measure amount dynamic correlation retained model. way, included...
Pump-probe electronic spectroscopy using femtosecond laser pulses has evolved into a standard tool for tracking ultrafast excited state dynamics. Its two-dimensional (2D) counterpart is becoming an increasingly available and promising technique resolving many of the limitations pump-probe caused by spectral congestion. The ability to simulate 2D spectra from ab initio computations would allow one link mechanistic observables like molecular motions making/breaking chemical bonds experimental...
High-level quantum-chemical ab initio coupled-cluster and multiconfigurational perturbation methods have been used to compute the vertical adiabatic ionization potentials of several water clusters: dimer, trimer, tetramer, pentamer, hexamer book, ring, cage, prism. The present results establish reference values at a level not reported before for these systems, calibrating different computational strategies helping discard less reliable theoretical experimental data. systematic study with...
Abstract The decay channels of singlet excited adenine uracil monophosphate (ApU) in water are studied with CASPT2//CASSCF:MM potential energy calculations and simulation the 2D‐UV spectroscopic fingerprints aim elucidating role different electronic states stacked conformer state dynamics. 1 L a can without barrier to conical intersection ground state. In contrast, b S(U) have minima that separated from intersections by sizeable barriers. Depending on backbone conformation, CT undergo...
In this discussion we present a methodology to describe spectral lineshape from first principles, providing insight into the solvent-solute molecular interactions in terms of static and dynamic disorder how these shape signals recorded experimentally linear nonlinear optical spectroscopies, including two-dimensional electronic spectroscopy (2DES). Two different strategies for simulating are compared: both rely on same evaluation coupling between states intra-molecular vibrations, while they...
The photophysics and photochemistry of water-solvated guanine monophosphate (GMP) are here characterized by means a multireference quantum-chemical/molecular mechanics theoretical approach (CASPT2//CASSCF/AMBER) in order to elucidate the main photo-processes occurring upon UV-light irradiation. effect solvent phosphate group on energetics structural features this system evaluated for first time employing high-level ab initio methods thoroughly compared those vacuo previously reported...
The SOS//QM/MM [Rivalta et al., Int. J. Quant. Chem., 2014, 114, 85] method consists of an arsenal computational tools allowing accurate simulation one-dimensional (1D) and bi-dimensional (2D) electronic spectra monomeric dimeric systems with unprecedented details accuracy. Prominent features like doubly excited local excimer states, accessible in multi-photon processes, as well charge-transfer states arise naturally through the fully quantum-mechanical description aggregates. In this...
The present study provides new insights into the topography of potential energy hypersurfaces (PEHs) thymine nucleobase in order to rationalize its main ultrafast photochemical decay paths by employing two methodologies based on complete active space self-consistent field (CASSCF) and second-order perturbation theory (CASPT2) methods: (i) CASSCF optimized structures energies corrected with CASPT2 method at geometries (ii) energies. A direct comparison between these strategies is drawn,...
Here, analytical extended multi-state complete active space second-order perturbation method (XMS-CASPT2) gradients are used to rationalize the decreasing triplet quantum yield trend in 2-nitronaphthalene, 1-nitronaphthalene, and 2-methyl-1-nitronaphthalene, a series of nitro-substituted aromatic compounds. Comparison with XMS-CASPT2//CASSCF (where CASSCF stands for self-consistent field method) results highlights importance dynamic correlation geometry optimization challenges validity an...
In this article the recent developments of open-source OpenMolcas chemistry software environment, since spring 2020, are described, with main focus on novel functionalities that accessible in stable branch package and/or via interfaces other packages. These community span a wide range topics computational chemistry, and presented thematic sections associated electronic structure theory, spectroscopy simulations, analytic gradients molecular optimizations, ab initio dynamics, new features....
The photochemistry of the water dimer irradiated by UV light is studied means complete active space perturbation theory//complete self-consistent field (CASPT2//CASSCF) method and accurate computational approaches like as minimum energy paths. Both electronic structure computations ab initio molecular dynamics simulations are carried out. results obtained show small shifts relative to a single molecule on vertical excitation energies due hydrogen bond placed between donor (WD) acceptor (WA)....
Low-energy (0-3 eV) ballistic electrons originated during the irradiation of biological material can interact with DNA/RNA nucleobases yielding transient-anion species which undergo decompositions. Since discovery that these reactions eventually lead to strand breaking DNA chains, great efforts have been dedicated their study. The main fragmentation at 0-3 eV energy range is ejection a hydrogen atom from specific nitrogen positions. In present study, methodological approach introduced in...