99 research outputs found
Unveiling the photophysics of thiourea from CASPT2/CASSCF potential energy surfaces and singlet/triplet excited state molecular dynamics simulations
This work describes the decay mechanism of photoexcited thiourea, both in gas
phase and in solution, from the information inferred from the topography of the
excited and ground state potential energy surfaces and mixed singlet/triplet
quantum classical molecular dynamics simulations. Our gas phase results reveal
T1/S0 intersystem crossing as the dominant (49%) intrinsic decay channel to the
ground state, which reaches a population of 0.28 at the final time of our
simulations (10 ps). Population of the T1, would occur after internal
conversion to the S1 from the spectroscopic S2 electronic state, followed by
S1->T2 intersystem crossing and T2->T1 internal conversion processes. Minor
decay channels occurring exclusively along the singlet manifold, i.e. S2->S0
(33%) and S1->S0 (18%), were also observed to play a role in the relaxation of
photoexcited thiourea in the gas phase. The explicit incorporation of
water-thiourea interactions in our simulations was found to provoke a very
significant delay in the decay to the ground state of the system, with no
transitions to the S0 being registered during the first 10 ps of our
simulations. Intermolecular vibrational energy redistribution and explicit
hydrogen bond interaction established between water molecules and the NH2 group
of thiourea were found to structurally or energetically hamper the access to
the intersystem crossing or internal conversion funnels with the ground state
Probing Vibrationally Mediated Ultrafast Excited-state Reaction Dynamics With Multireference (caspt2) Trajectories
Excited-state trajectories computed at the complete active space second-order perturbation theory (CASPT2) reveal how vibrational excitation controls the molecular approach to the intersection space that drives the photodissociation of a prototypical halogenated methyl radical, namely CF2I. Translating the Franck-Condon structure along the ground-state CASPT2 vibrational modes in this system followed by propagating the displaced structures in the first excited doublet state simulates specific vibrational excitations and vibrationally mediated dynamics, respectively. Three distinct situations are encountered: the trajectories (i) converge to an energetically flat segment of the intersection space, (ii) locate a segment of the intersection space, and (iii) access a region where the intersection space degeneracy is lifted to form a ridge of avoided crossings. The computational protocol documented herein can be used as a tool to design control strategies based on selective excitation of vibrational modes, including adaptive feedback schemes using coherent light sources
A Jeziorski-Monkhorst fully uncontracted Multi-Reference perturbative treatment I: principles, second-order versions and tests on ground state potential energy curves
The present paper introduces a new multi-reference perturbation approach
developed at second order, based on a Jeziorsky-Mokhorst expansion using
individual Slater determinants as perturbers. Thanks to this choice of
perturbers, an effective Hamiltonian may be built, allowing for the dressing of
the Hamiltonian matrix within the reference space, assumed here to be a CAS-CI.
Such a formulation accounts then for the coupling between the static and
dynamic correlation effects. With our new definition of zeroth-order energies,
these two approaches are strictly size-extensive provided that local orbitals
are used, as numerically illustrated here and formally demonstrated in the
appendix. Also, the present formalism allows for the factorization of all
double excitation operators, just as in internally contracted approaches,
strongly reducing the computational cost of these two approaches with respect
to other determinant-based perturbation theories. The accuracy of these methods
has been investigated on ground-state potential curves up to full dissociation
limits for a set of six molecules involving single, double and triple bond
breaking. The spectroscopic constants obtained with the present methods are
found to be in very good agreement with the full configuration interaction
(FCI) results. As the present formalism does not use any parameter or
numerically unstable operation, the curves obtained with the two methods are
smooth all along the dissociation path.Comment: 4 figures, 18 page
Ultrafast electron diffraction imaging of bond breaking in di-ionized acetylene
Visualizing chemical reactions as they occur requires atomic spatial and femtosecond temporal resolution. Here, we report imaging of the molecular structure of acetylene (C2H2) 9 femtoseconds after ionization. Using mid-infrared laser–induced electron diffraction (LIED), we obtained snapshots as a proton departs the [C2H2]2+ ion. By introducing an additional laser field, we also demonstrate control over the ultrafast dissociation process and resolve different bond dynamics for molecules oriented parallel versus perpendicular to the LIED field. These measurements are in excellent agreement with a quantum chemical description of field-dressed molecular dynamicsPostprint (author's final draft
Luscus: molecular viewer and editor for MOLCAS
The novel program for graphical display and editing of molecular systems, luscus, is described. The program allows fast and easy building and/or editing different molecular structures, up to several thousands of atoms large. Luscus is able to visualise dipole moments, normal modes, molecular orbitals, electron densities and electrostatic potentials. In addition, simple geometrical objects can be rendered in order to reveal a geometrical feature or a physical quantity. The program is developed as a graphical interface for the MOLCAS program package, however its adaptive nature makes possible to use luscus with other computational program packages and chemical formats. All data files are opened via simple plug-ins which makes easy to implement a new file format in luscus. The easiness of editing molecular geometries makes luscus suitable for teaching students chemical concepts and molecular modelling
Mapping the scientific research on maize or corn: a bibliometric analysis of top papers during 2008–2018
Based on the Essential Science Indicators (ESI) database, this study analyzed 966 top papers of maize and corn research from 2008 to 2018, which include 964 highly cited papers and 15 hot papers in the field. Results showed that all papers written in English, were from 4,353 authors, 1,287 organizations and 84 countries/territories, listed in 290 core journals. Top 5 core journals with higher impact factor ranked as Plant Physiology, PNAS, Plant Cell, Food Chemistry and Bioresource Technology. Top six countries and regions were USA, Peoples R China, Germany, France, Australia, England. Top 5 organizations were Cornell Univ, Chinese Acad Sci, Univ Minnesota, Iowa State Univ, Univ Wisconsin. Based on the analysis of network map of VOSviewer, was highlighted cooperation for authors, organizations and countries or regions. The analysis of all keywords showed that maize or corn research was separated six clusters. In addition, this study demonstrates that there are more top papers come from journals with the higher IF and higher rank in WoS Category. So, authors can choose their ideal journal with a high impact factor or Q1 in Category to publish their papers in the English language related to their research field
Chiral Hydrogen Bond Environment Providing Unidirectional Rotation in Photoactive Molecular Motors
Generation of a chiral hydrogen bond environment in efficient molecular photoswitches is proposed as a novel strategy for the design of photoactive molecular motors. Here, the following strategy is used to design a retinal-based motor presenting singular properties: (i) a single excitation wavelength is needed to complete the unidirectional rotation process (360°); (ii) the absence of any thermal step permits the process to take place at low temperatures; and (iii) the ultrafast process permits high rotational frequencies.Ministerio de EconomĂa y CompetitividadMinisterio de Ciencia e InnovaciĂłnUniversidad de Alcal
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