Search results for "SCF"
showing 10 items of 40 documents
Towards an accurate molecular orbital theory for excited states : Ethene, butadiene, and hexatriene
1993
A newly proposed quantum chemical approach for ab initio calculations of electronic spectra of molecular systems is applied to the molecules ethene, trans‐1,3‐butadiene, and trans‐trans‐1,3,5‐hexatriene. The method has the aim of being accurate to better than 0.5 eV for excitation energies and is expected to provide structural and physical data for the excited states with good reliability. The approach is based on the complete active space (CAS) SCF method, which gives a proper description of the major features in the electronic structure of the excited state, independent of its complexity, accounts for all near degeneracy effects, and includes full orbital relaxation. Remaining dynamic ele…
Excited states of the water molecule: Analysis of the valence and Rydberg character
2008
The excited states of the water molecule have been analyzed by using the extended quantum-chemical multistate CASPT2 method, namely, MS-CASPT2, in conjunction with large one-electron basis sets of atomic natural orbital type. The study includes 13 singlet and triplet excited states, both valence and 3s-, 3p-, and 3d-members of the Rydberg series converging to the lowest ionization potential and the 3s- and 3p-Rydberg members converging to the second low-lying state of the cation, 1 math. The research has been focused on the analysis of the valence or Rydberg character of the low-lying states. The computation of the 1 math state of water at different geometries indicates that it has a predom…
On the non-malacostracan crustaceans (Crustacea: Branchiopoda, Copepoda, Ostracoda) from the inland waters of Fthiotida (Greece)
2019
In the frame of the activities of the LIFE11 NAT/GR/1014 ForOpenForests, some water bodies occurring in the "Ethnikos Drymos Oitis" (GR2440004) and "Oros Kallidromo" (GR2440006) (Sterea Ellada) were investigated with the aim of providing a first census of the composition and diversity of their crustacean fauna. Overall, the sampling of 15 water bodies (7 of them listed as "Mediterranean temporary ponds" sensu EU "Habitats Directive") led to the finding of 13 branchiopod, 11 copepod, and 7 ostracod taxa, including 4 species new for mainland Greece, i.e. the copepods Arctodiaptomus alpinus (Imhoff, 1885) and Diaptomus cf. serbicus, and the branchiopods Leptestheria dahalacensis (Rüppel, 1837)…
Modelling Photoionisations in Tautomeric DNA Nucleobase Derivatives 7H-Adenine and 7H-Guanine: Ultrafast Decay and Photostability
2021
The study of radiation effects in DNA is a multidisciplinary endeavour, connecting the physical, chemical and biological sciences. Despite being mostly filtered by the ozone layer, sunlight radiation is still expected to (photo)ionise DNA in sizeable yields, triggering an electron removal process and the formation of potentially reactive cationic species. In this manuscript, photoionisation decay channels of important DNA tautomeric derivatives, 7H-adenine and 7H-guanine, are characterised with accurate CASSCF/XMS-CASPT2 theoretical methods. These simulation techniques place the onset of ionisation for 7H-adenine and 7H-guanine on average at 8.98 and 8.43 eV, in line with recorded experimen…
Elementary presentation of self‐consistent intermediate Hamiltonians and proposal of two totally dressed singles and doubles configuration interactio…
1994
Intermediate Hamiltonians are effective Hamiltonians which are defined on an N‐dimensional model space but which only provide n<N exact eigenvalues and the projections of the corresponding eigenvectors onto the model space. For a single root research, the intermediate Hamiltonian may be obtained from the restriction of the Hamiltonian to the model space by an appropriate, uniquely defined dressing of the diagonal energies or of the first column. Approximate self‐consistent dressings may be proposed. The simplest perturbative form gives the same result as the original 2nd order intermediate Hamiltonian or the ‘‘shifted Bk’’ technique but it is of easier implementation. Self‐consistent inclus…
A Multiconfigurational Theoretical Study of the Octamethyldimetalates of Cr(II), Mo(II), and Re(III): Revisiting the Correlation Between M-M Bond Len…
2005
Four compounds containing metal-metal quadruple bonds, the [M 2(CH3)8]n- ions (M = Cr, Mo, W, Re and n = 4, 4, 4, 2, respectively), have been studied theoretically using multiconfigurational quantum-chemical methods. The molecular structure of the ground state of these compounds has been determined and the energy of the δ → δ* transition has been calculated and compared with previous experimental measurements. The high negative charges on the Cr, Mo, and W complexes lead to difficulties in the successful modeling of the ground-state structures, a problem that has been addressed by the explicit inclusion of four Li+ ions in these calculations. The ground-state geometries of the complexes and…
Strontium and iron-doped barium cobaltite prepared by solution combustion synthesis: exploring a mixed-fuel approach for tailored intermediate temper…
2013
Ba0.5Sr0.5Co0.8Fe0.2O3-? (BSCF) powders were prepared by solution combustion synthesis using single and double fuels. The effect of the fuel mixture on the main properties of this well-known solid oxide fuel cell cathode material with high oxygen ion and electronic conduction was investigated in detail. Results showed that the fuel mixture significantly affected the area-specific resistance of the BSCF cathode materials, by controlling the oxygen deficiency and stabilizing the Co2+ oxidation state. It was demonstrated that high fuel-to-metal cations molar ratios and high reducing power of the combustion fuel mixture are mainly responsible for the decreasing of the area-specific resistance o…
Ab initio molecular dynamics simulations of negative thermal expansion in ScF3: the effect of the supercell size
2020
The authors sincerely thank S. Ali, A. Kalinko, and F. Rocca for providing experimental EXAFS data, as well as M. Isupova, V. Kashcheyevs, and A. I. Popov for stimulating discussions. Financial support provided by project No. 1.1.1.2/VIAA/l/16/147 (1.1.1.2/16/I/001) under the activity “Post-doctoral research aid” realized at the Institute of Solid State Physics, University of Latvia is greatly acknowledged by D.B. A.K and J.P. would like to thank the support of the Latvian Council of Science project No. lzp-2018/2–0353.
Modelling Photoionisation in Isocytosine: Potential Formation of Longer‐Lived Excited State Cations in its Keto Form
2021
Abstract Studying the effects of UV and VUV radiation on non‐canonical DNA/RNA nucleobases allows us to compare how they release excess energy following absorption with respect to their canonical counterparts. This has attracted much research attention in recent years because of its likely influence on the origin of our genetic lexicon in prebiotic times. Here we present a CASSCF and XMS‐CASPT2 theoretical study of the photoionisation of non‐canonical pyrimidine nucleobase isocytosine in both its keto and enol tautomeric forms. We analyse their lowest energy cationic excited states including 2π+ , 2nO+ and 2nN+ and compare these to the corresponding electronic states in cytosine. Investigat…
Photoinduced Formation Mechanism of the Thymine−Thymine (6−4) Adduct
2013
The photoinduced mechanism leading to the formation of the thymine-thymine (6-4) photolesion has been studied by using the CASPT2//CASSCF approach over a dinucleotide model in vacuo. Following light absorption, localization of the excitation on a single thymine leads to fast singlet-triplet crossing that populates the triplet (3)(nπ*) state of thymine. This state, displaying an elongated C(4)═O bond, triggers (6-4) dimer formation by reaction with the C(5)═C(6) double bond of the adjacent thymine, followed by a second intersystem crossing, which acts as a gate between the excited state of the reactant and the ground state of the photoproduct. The requirement of localized excitation on just …