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Carbonyl-functionalized quaterthiophenes: a study of the vibrational Raman and electronic absorption/emission properties guided by theoretical calcul…
2011
This work investigates the evolution of the molecular, vibrational, and optical properties within a family of carbonyl-functionalized quaterthiophenes: 5,5'''-diheptanoyl-2,2':5',2'':5'',2'''-quaterthiophene (1), 5,5'''-diperfluorohexylcarbonyl-2,2':5',2'':5'',2'''-quaterthiophene (2), and 2,7-[bis(5-perfluorohexylcarbonylthien-2-yl)]-4H-cyclopenta[2,1-b:3,4-b']-dithiophene-4-one (3). The analysis is performed by Raman and UV/Vis absorption/excitation/fluorescence spectroscopy in combination with density functional calculations. Theoretical calculations show that substitution with carbonyl groups and perfluorohexyl chains induces progressive quinoidization of the π-conjugated backbone in co…
Theoretical investigation of the potential energy surface of the van der Waals complex CH4-N-2
2009
International audience; The interaction potential energy surface of the van der Waals CH4-N-2 complex has been calculated for a broad range of intermolecular separations and configurations in the approximation of rigid interacting molecules at the CCSD(T) and MP2 levels of theory using the correlation consistent aug-cc-pVTZ basis set. The BSSE correction was taken into account for all the calculations. The most stable configurations of the complex were found. Binding energies were calculated in the CBS limit with accounting for the molecular deformations. The harmonic and anharmonic fundamental vibrational frequencies and rotational constants for the ground and first excited vibrational sta…
Multiple vibrational resonances in the Raman spectra of liquid ethanes
1990
The Raman spectra of liquid ethane, ethane-d3 and ethane-d6 were recorded and analysed. The CH3 and CD3 stretching regions were computer resolved using Cauchy-Gaussian and Voigt functions to account for asymmetric band shapes. Multiple vibrational resonances were investigated using the wavenumbers and observed intensities in these regions. The developed basis functions show strong mixing of the levels in these regions. In general the resonances appear to be less strong in the liquid phase than reported in previous studies of the gaseous state. Some new assignments in the liquid-state spectra of ethanes could be suggested.
Communication: multireference equation of motion coupled cluster: a transform and diagonalize approach to electronic structure.
2014
The novel multireference equation-of-motion coupled-cluster (MREOM-CC) approaches provide versatile and accurate access to a large number of electronic states. The methods proceed by a sequence of many-body similarity transformations and a subsequent diagonalization of the transformed Hamiltonian over a compact subspace. The transformed Hamiltonian is a connected entity and preserves spin- and spatial symmetry properties of the original Hamiltonian, but is no longer Hermitean. The final diagonalization spaces are defined in terms of a complete active space (CAS) and limited excitations (1h, 1p, 2h, …) out of the CAS. The methods are invariant to rotations of orbitals within their respective…
Quasi-RRHO approximation and DFT study for understanding the mechanism and kinetics of nitration reaction of benzonitrile with nitronium ion
2021
Abstract The nitration reaction of benzonitrile with nitronium cation, NO2+, has been studied within the Molecular Electron Density Theory at the MN15-L/aug-cc-pVTZ level of theory. For this electrophilic aromatic substitution (EAS) reaction, three regioisomeric reaction paths have been studied. Quasi-RRHO approximation was applied to consider the vibrational contribution to entropy and correct the Gibbs free energy profile of the reaction in the solvent phase. Benzonitrile is less nucleophilically activated than benzene due to the presence of the electron-withdrawing CN group the meta position is the more favorable reaction path of this EAS reaction. The analysis of ELF and AIM demonstrate…
A quantum dynamics study of the benzopyran ring opening guided by laser pulses
2014
Abstract The ring-opening photoisomerization of benzopyran, which occurs via a photochemical route involving a conical intersection, has been studied with quantum dynamics calculations using the multi-configuration time-dependent Hartree method (MCTDH). We introduce a mechanistic strategy to control the conversion of benzopyran to merocyanine with laser pulses. We use a six-dimensional model developed in a previous work for the potential energy surfaces (PES) based on an extension of the vibronic-coupling Hamiltonian model (diabatization method by ansatz), which depends on the most active degrees of freedom. The main objective of these quantum dynamics simulations is to provide a set of str…
Full-dimensional control of the radiationless decay in pyrazine using the dynamic Stark effect
2014
We present a full quantum-mechanical study of the laser control of the radiationless decay between the B3u(nπ(*)) and B2u(ππ(*)) states of pyrazine using the dynamic Stark effect. In contrast to our previous study [Sala et al., J. Chem. Phys. 140, 194309 (2014)], where a four-dimensional model was used, all the 24 degrees of freedom are now included in order to test the robustness of the strategy of control. Using a vibronic coupling Hamiltonian model in a diabatic representation, the multi-layer version of the multi-configuration time-dependent Hartree method is exploited to propagate the corresponding wave packets. We still observe a trapping of the wavepacket on the B2u(ππ(*)) potential …
Introducing Memory in Coarse-Grained Molecular Simulations
2021
[Image: see text] Preserving the correct dynamics at the coarse-grained (CG) level is a pressing problem in the development of systematic CG models in soft matter simulation. Starting from the seminal idea of simple time-scale mapping, there have been many efforts over the years toward establishing a meticulous connection between the CG and fine-grained (FG) dynamics based on fundamental statistical mechanics approaches. One of the most successful attempts in this context has been the development of CG models based on the Mori–Zwanzig (MZ) theory, where the resulting equation of motion has the form of a generalized Langevin equation (GLE) and closely preserves the underlying FG dynamics. In…
Spin-orbit ZORA and four-component Dirac-Coulomb estimation of relativistic corrections to isotropic nuclear shieldings and chemical shifts of noble …
2015
Hartree-Fock and density functional theory with the hybrid B3LYP and general gradient KT2 exchange-correlation functionals were used for nonrelativistic and relativistic nuclear magnetic shielding calculations of helium, neon, argon, krypton, and xenon dimers and free atoms. Relativistic corrections were calculated with the scalar and spin-orbit zeroth-order regular approximation Hamiltonian in combination with the large Slater-type basis set QZ4P as well as with the four-component Dirac-Coulomb Hamiltonian using Dyall's acv4z basis sets. The relativistic corrections to the nuclear magnetic shieldings and chemical shifts are combined with nonrelativistic coupled cluster singles and doubles …
Nonlinear response theory for Markov processes II: Fifth-order response functions
2017
The nonlinear response of stochastic models obeying a master equation is calculated up to fifth-order in the external field thus extending the third-order results obtained earlier (G. Diezemann, Phys. Rev. E{\bf 85}, 051502 (2012)). For sinusoidal fields the $5\om$-component of the susceptibility is computed for the model of dipole reorientations in an asymmetric double well potential and for a trap model with a Gaussian density of states. For most realizations of the models a hump is found in the higher-order susceptibilities. In particular, for the asymmetric double well potential model there are two characteristic temperature regimes showing the occurence of such a hump as compared to a …