Search results for "basis"
showing 10 items of 760 documents
Multistate active spaces from local CAS-SCF molecular orbitals: the photodissociation of HFCO as an example.
2005
A recently developed algorithm to generate localized molecular orbitals (LMO) is applied to the study of excited states along a photodissociation process. The LMOs allow for the selection of a consistent complete active space (CAS) for the simultaneous description of all the electronic states involved in a multistate process on the basis of simple chemical criteria. The local nature of the orbitals is used to label them in a unique way that does not depend on the molecular geometry. The selection of the electronic configurations of interest for the set of target states on only the basis of the dominant excitations required by the simplest configuration interaction (CI) descriptions for both…
Basis set and correlation effects in the calculation of accurate gas phase dimerization energies of two M+2 to give M2+4 (M = S, Se)
2000
The dimerization energies of two M2+ to give M42+ (M = S, Se) were calcd. They depend strongly on the size of the basis set and the correlation method used (ranging from 217 to 522 kJ/mol, M = S) and, therefore, a systematic study of basis set and correlation effects was performed [MP2, MP3, MP4(SDQ), CCSD, CCSD(T)]. The introduction of a second set of polarizing d-functions caused a significant redn. of the dimerization energies, but neither of the above limits is reached by the MPn (n = 2, 3, 4) theory, even with the largest basis sets [cc-pVQZ]. However, convergence was achieved by CCSD(T), compd. methods or hybrid HF/DFT calcns. employing flexible basis sets [e.g., CCSD(T)/cc-pV5Z, CBS-…
Vertical spectrum of the C2H 2+ system. An open shell (SC)2-CAS-SDCI study
2003
The open shell (SC)(2)-CAS-SDCI method along with a basis set of atomic natural orbitals (ANO) has been applied for calculating the main ionization potentials of acetylene, as well as the manifold of excited states of the different symmetries up to 32 eV. In this method, the single and double excitations of a CAS space are generated and the corresponding CI matrix is corrected by means of the (SC)(2) procedure that cancels the size-extensivity error and adds some high order contributions. The mean absolute error for the outer-valence X (2)Pi(u)(1pi(u) (-1)), A (2)Sigma(g) (+)(3sigma(g) (-1)), and B (2)Sigma(u) (+)(2sigma(u) (-1)) states, and the inner-valence C (2)Sigma(g) (+)(2sigma(g) (-1…
State-specific multireference coupled-cluster theory
2012
The multireference problem is considered one of the great challenges in coupled-cluster (CC) theory. Most recent developments are based on state-specific approaches, which focus on a single state and avoid some of the numerical problems of more general approaches. We review various state-of-the-art methods, including Mukherjee's state-specific multireference coupled-cluster (Mk-MRCC) theory, multireference Brillouin–Wigner coupled-cluster (MR-BWCC) theory, the MRexpT method, and internally contracted multireference coupled-cluster (ic-MRCC) theory. Related methods such as extended single-reference schemes [e.g., the complete active space coupled-cluster (CASCC) theory] and canonical transfo…
CCSD-CTOCD static dipole shielding polarizability for quantification of the chiral NMR effects in oxaziridine derivatives
2014
Chiral discrimination by nuclear magnetic resonance (NMR) spectroscopy might be achieved through the pseudo-scalar derived from the dipole shielding polarizability tensor. Coupled Cluster Singles and Doubles-Quadratic Response (CCSD-QR) calculations inside the continuous translation of the origin of the current density formalism have been carried out to determine the effects of basis set, electron correlation, and gauge translation on the determination of this magnitude in oxaziridine derivatives. Inclusion of electronic correlation is needed for adequately describing the pseudo-scalar for the heavier nuclei, making CCSD a rigorous and affordable method to compute these high order propertie…
Stability and -gain controller design for positive switched systems with mixed time-varying delays
2013
This paper investigates the problems of stability and L"1-gain controller design for positive switched systems with mixed time-varying delays. The mixed time-varying delays are presented in the forms of discrete delay and distributed delay. The purpose of this paper is to design a class of switching signals and a state feedback controller for the considered system such that the resulting closed-loop system is exponentially stable with L"1-gain performance. By constructing an appropriate co-positive type Lyapunov-Krasovskii functional and using the average dwell time approach, we propose a sufficient condition to ensure the exponential stability with weighted L"1-gain performance for the sys…
The molecular structure of N-hydroxyurea
1996
Ab initio calculations were performed on the tautomers and conformers of N-hydroxyurea using a 6-31G** basis set. The minimum-energy structures have been found and the importance of the intramolecular hydrogen bond as the stabilizing factor was pointed out. © 1996 John Wiley & Sons, Inc.
Space-Frequency Quantization using Directionlets
2007
In our previous work we proposed a construction of critically sampled perfect reconstruction transforms with directional vanishing moments (DVMs) imposed in the corresponding basis functions along different directions, called directionlets. Here, we combine the directionlets with the space-frequency quantization (SFQ) image compression method, originally based on the standard two-dimensional (2-D) wavelet transform (WT). We show that our new compression method outperforms the standard SFQ as well as the state-of-the-art compression methods, like SPIHT and JPEG-2000, in terms of the quality of compressed images, especially in a low-rate compression regime. We also show that the order of comp…
BELM: Bayesian Extreme Learning Machine
2011
The theory of extreme learning machine (ELM) has become very popular on the last few years. ELM is a new approach for learning the parameters of the hidden layers of a multilayer neural network (as the multilayer perceptron or the radial basis function neural network). Its main advantage is the lower computational cost, which is especially relevant when dealing with many patterns defined in a high-dimensional space. This brief proposes a bayesian approach to ELM, which presents some advantages over other approaches: it allows the introduction of a priori knowledge; obtains the confidence intervals (CIs) without the need of applying methods that are computationally intensive, e.g., bootstrap…
MultivariateApart: Generalized partial fractions
2021
We present a package to perform partial fraction decompositions of multivariate rational functions. The algorithm allows to systematically avoid spurious denominator factors and is capable of producing unique results also when being applied to terms of a sum separately. The package is designed to work in Mathematica, but also provides interfaces to the Form and Singular computer algebra systems.