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Active Space (active + space)

Distribution by Scientific Domains

Chemistry	83%

Terms modified by Active Space

active space self-consistent field

Selected Abstracts

Efficient generation of Heisenberg Hamiltonian matrices for VB calculations of potential energy surfaces

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 3 2009
A. M. Tokmachev
Abstract The spin-Hamiltonian valence bond theory relies upon covalent configurations formed by singly occupied orbitals differing by their spin counterparts. This theory has been proven to be successful in studying potential energy surfaces of the ground and lowest excited states in organic molecules when used as a part of the hybrid molecular mechanics,valence bond method. The method allows one to consider systems with large active spaces formed by n electrons in n orbitals and relies upon a specially proposed graphical unitary group approach. At the same time, the restriction of the equality of the numbers of electrons and orbitals in the active space is too severe: it excludes from the consideration a lot of interesting applications. We can mention here carbocations and systems with heteroatoms. Moreover, the structure of the method makes it difficult to study charge-transfer excited states because they are formed by ionic configurations. In the present work we tackle these problems by significant extension of the spin-Hamiltonian approach. We consider (i) more general active space formed by n ± m electrons in n orbitals and (ii) states with the charge transfer. The main problem addressed is the generation of Hamiltonian matrices for these general cases. We propose a scheme combining operators of electron exchange and hopping, generating all nonzero matrix elements step-by-step. This scheme provides a very efficient way to generate the Hamiltonians, thus extending the applicability of spin-Hamiltonian valence bond theory. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 [source]

Equivalent orbitals for multiconfigurational spin-tensor electron propagator method (MCSTEP): The vertical ionization potentials of B, NO, CF, and OF

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 6 2008
Dongxia Ma
Abstract The multiconfigurational spin tensor electron propagator method (MCSTEP) was developed as an implementation of electron propagator/single particle Green's function methods for ionization potentials (IPs) and electron affinities (EAs). MCSTEP was specifically designed for open shell and highly correlated (nondynamically correlated) initial states. For computational efficiency the initial state used in MCSTEP is typically a small complete active space (CAS) multiconfigurational self-consistent field (MCSCF) state. If in a molecule there are some degenerate orbitals which are not fully or half occupied, usual MCSCF calculations will make these orbitals inequivalent, i.e., the occupied ones will be different from the nonoccupied ones, so that the degeneracy is broken. In this article, we use a state averaged MCSCF method to get equivalent orbitals for the initial state and import the integrals into the subsequent MCSTEP calculations. This gives, in general, more reliable MCSTEP vertical IPs. © 2008 Wiley Periodicals, Inc., 2008 [source]

A combined freeze-and-cut strategy for the description of large molecular systems using a localized orbitals approach

JOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 10 2005
Stefano Borini
Abstract A technique to reduce the computational effort in calculating ab initio energies using a localized orbitals approach is presented. By exploiting freeze strategy at the self-consistent field (SCF) level and a cut of the unneeded atomic orbitals, it is possible to perform a localized complete active space (CAS-SCF) calculation on a reduced system. This will open the possibility to perform ab initio treatments on very large molecular systems, provided that the chemically important phenomena happen in a localized zone of the molecule. Two test cases are discussed, to illustrate the performance of the method: the cis,trans interconversion curves for the (7Z)-13 ammoniotridec-7-enoate, which demonstrates the ability of the method to reproduce the interactions between charged groups; and the cisoid,transoid energy barrier for the aldehydic group in the C13 polyenal molecule. © 2005 Wiley Periodicals, Inc. J Comput Chem 26: 1042,1051, 2005 [source]

Effects of environmental variables on fish feeding ecology: implications for the performance of baited fishing gear and stock assessment

JOURNAL OF FISH BIOLOGY, Issue 6 2004
A. W. Stoner
The effectiveness of baited fishing gear ultimately depends upon behaviour of the target species , activity rhythms, feeding motivation, and sensory and locomotory abilities. While any environmental parameter that mediates feeding or locomotion can have an important influence on the active space presented by the bait and fish catchability, few biologists have considered how such variation in behaviour might affect catch per unit effort (CPUE) and the resultant stock abundance estimates or population parameters. This review reveals that environment-related variation in feeding behaviour can act through four different mechanisms: metabolic processes, sensory limitations, social interactions and direct impacts. Water temperature, light level, current velocity and ambient prey density are likely to have largest effects on fish catchability, potentially affecting variation in CPUE by a factor of ten. Feeding behaviour is also density-dependent, with both positive and negative effects. Over time and geographic space a target species can occupy wide ranges of environmental conditions, and in certain cases, spatial and temporal variation in feeding biology could have a larger impact on CPUE than patterns of abundance. Temperature, light and current can be measured with relative facility and corrections to stock assessment models are feasible. Making corrections for biological variables such as prey density and bait competitors will be more difficult because the measurements are often not practical and relationships to feeding catchability are more complex and poorly understood. There is a critical need for greater understanding of how environmental variables affect feeding-related performance of baited fishing gear. A combination of field observations and laboratory experiments will be necessary to parameterize stock assessment models that are improved to accommodate variation in fish behaviour. Otherwise, survey data could reveal more about variation in behaviour than abundance trends. [source]