Search results for "Orbital"
showing 10 items of 679 documents
Ab Initio Methods for Excited States
2005
This chapter focuses mainly on the performance of ab initio methods for the description of spectroscopic molecular properties of compounds. Most of the quantum-chemical methods developed up to date are based on the concept of the one-electron wave function. The electronic states of a system with N electrons are described by a double expansion. Molecular orbitals (MOs) are one-electron wave functions expressed as linear combinations of a known one-electron basis set (K) and the N electron wave function is formulated in a many-electron basis set formed by determinants (or linear combination of them to form spin-adapted wave functions), built as normalized antisymmetric products of MOs. Accord…
Ab initio molecular orbital study of SenS4−nN4 (n = 0−4)
1995
Abstract We report an ab initio study of Se n S 4− n N 4 ( n = 0−4). The full geometry optimization for each molecule was performed at the Hartree-Fock level of theory involving the MIDI-4 ∗ basis sets for atomic orbitals. The correction for electron correlation was carried out for optimized geometries by utilizing the second-order Moller-Plesset (MP2) perturbation theory. The fundamental vibrations calculated for all molecular species verified that all molecules lie at the local minima. All molecules showed cage structures similar to those observed experimentally for S 4 N 4 and Se 4 N 4 . The calculated bond parameters of S 4 N 4 and Se 4 N 4 were in good agreement with the experimental v…
Quantitative prediction of gas-phase F19 nuclear magnetic shielding constants
2008
Benchmark calculations of (19)F nuclear magnetic shielding constants are presented for a set of 28 molecules. Near-quantitative accuracy (ca. 2 ppm deviation from experiment) is achieved if (1) electron correlation is adequately treated by employing the coupled-cluster singles and doubles (CCSD) model augmented by a perturbative correction for triple excitations [CCSD(T)], (2) large (uncontracted) basis sets are used, (3) gauge-including atomic orbitals are used to ensure gauge-origin independence, (4) calculations are performed at accurate equilibrium geometries [obtained from CCSD(T)/cc-pVTZ calculations correlating all electrons], and (5) vibrational averaging and temperature corrections…
A two-scale approach to electron correlation in multiconfigurational perturbation theory.
2014
We present a new approach for the calculation of dynamic electron correlation effects in large molecular systems using multiconfigurational second-order perturbation theory (CASPT2). The method is restricted to cases where partitioning of the molecular system into an active site and an environment is meaningful. Only dynamic correlation effects derived from orbitals extending over the active site are included at the CASPT2 level of theory, whereas the correlation effects of the environment are retrieved at lower computational costs. For sufficiently large systems, the small errors introduced by this approximation are contrasted by the substantial savings in both storage and computational de…
First Principles Calculations of Atomic and Electronic Structure of Ti3+Al- and Ti2+Al-Doped YAlO3
2021
M.G.B. appreciates support from the Chongqing Recruitment Program for 100 Overseas Innovative Talents (grant no. 2015013), the Program for the Foreign Experts (grant no. W2017011), Wenfeng High-end Talents Project (grant no. W2016-01) offered by the Chongqing University of Posts and Telecommunications (CQUPT), Estonian Research Council grant PUT PRG111, European Regional Development Fund (TK141), and NCN project 2018/31/B/ST4/00924. This study was supported by a grant from Latvian Research Council No. LZP-2018/1-0214 (for AIP). Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2020 Framework Program H202…
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…
Quantum chemistry calculations on the effect of electron confinement upon the frontier molecular orbitals of ethylene and benzene in sodalite. Implic…
1997
Abstract Quantum chemistry calculations using HF / STO-3G, CEP-41G, and 3-21G basis sets have been carried out in order to study the effect of the electron confinement of ethylene and benzene in the microporous environment existing in a sodalite cage. The electron confinement produces an increase of 1.06 and 1.31 eV at the 3-21G level in the energy of the HOMO of ethylene and benzene, respectively, when placed in the centre of the cavity with respect to the HOMO energy in the gas phase. There is an increase in the energy of the HOMO when the molecules approach the walls of the zeolite.
Young, active radio stars in the AB Doradus moving group
2017
Context. Precise determination of stellar masses is necessary to test the validity of pre-main-sequence (PMS) stellar evolutionary models, whose predictions are in disagreement with measurements for masses below 1.2 M. To improve such a test, and based on our previous studies, we selected the AB Doradus moving group (AB Dor-MG) as the best-suited association on which to apply radio-based high-precision astrometric techniques to study binary systems. Aims. We seek to determine precise estimates of the masses of a set of stars belonging to the AB Dor-MG using radio and infrared observations. Methods. We observed in phase-reference mode with the Very Large Array (VLA) at 5 GHz and with the Eur…
Osmium and lithium isotope evidence for weathering feedbacks linked to orbitally paced organic carbon burial and Silurian glaciations
2022
Abstract The Ordovician (∼487 to 443 Ma) ended with the formation of extensive Southern Hemisphere ice sheets, known as the Hirnantian glaciation, and the second largest mass extinction in Earth History. It was followed by the Silurian (∼443 to 419 Ma), one of the most climatically unstable periods of the Phanerozoic as evidenced by several large scale ( > 5 ‰ ) carbon isotope (δ13C) perturbations associated with further extinction events. Despite several decades of research, the cause of these environmental instabilities remains enigmatic. Here, we provide osmium (187Os/188Os) and lithium (δ7Li) isotope measurements of marine sedimentary rocks that cover four Silurian δ13C excursions. Osmi…
Counter anion binding in the phenoxyimine, salan and metallocene olefin polymerization catalysts activated with perfluorophenylborate
2012
Abstract Ion pair separation is a process that may influence the activity of homogeneous catalysts of olefin polymerization. We have studied the energy of separation for selected titanium and zirconium metallocene and post-metallocene catalytic ion pairs by means of DFT, dispersion-corrected DFT and Paired Interacting Orbitals method (PIO). Unusually weak cation–anion interactions in the bis(phenoxyimine) systems were attributed to strong electron-donating properties of the phenoxyimine ligands. Energy decomposition analysis (EDA) revealed that almost 70% of the counter ion binding energy results from electrostatic interactions. The PIO method made it possible to analyze the nature of the c…