Search results for "QUANTUM MECHANICS"
showing 10 items of 2468 documents
Analytic first derivatives for a spin-adapted open-shell coupled cluster theory: Evaluation of first-order electrical properties
2014
An analytic scheme is presented for the evaluation of first derivatives of the energy for a unitary group based spin-adapted coupled cluster (CC) theory, namely, the combinatoric open-shell CC (COSCC) approach within the singles and doubles approximation. The widely used Lagrange multiplier approach is employed for the derivation of an analytical expression for the first derivative of the energy, which in combination with the well-established density-matrix formulation, is used for the computation of first-order electrical properties. Derivations of the spin-adapted lambda equations for determining the Lagrange multipliers and the expressions for the spin-free effective density matrices for…
Magnetic exchange interaction in clusters of orbitally degenerate ions. I. Effective Hamiltonian
2001
Abstract A new effective Hamiltonian is reported for the kinetic exchange between two arbitrary terms 2S A +1 Λ A and 2S B +1 Λ B that can be ground or excited in octahedrally coordinated transition metal ions. This Hamiltonian is applicable to both homo- and heterometallic clusters. For the homonuclear cluster the resonance part of the effective Hamiltonian is also presented for the case when one of the ions is excited. The operator part of the exchange Hamiltonian contains symmetry adapted products of the cubic irreducible tensors acting in orbital spaces ΛA and ΛB and scalar product of site spin operators. The parameters of the Hamiltonian are defined by the relevant intercenter transfer…
On a topological interpretation of electronic and vibrational molecular energies
1998
Abstract A relationship between Randic's connectivity index and various quantum mechanical parameters derived from the Huckel Molecular Orbital (HMO) approach is demonstrated. When applied to conjugated hydrocarbons, this index represents the measure of the global π electron molecular energy and, therefore, of the resonance energy. Moreover, the development of the procedure, allows the introduction of a new definition of the bond order which, in turn, makes possible a better prediction not only for bond lengths of naphtalene but also for the resonance integral and conjugation energy for butadiene. Also, a corrected value for the Randic index is deduced, which allows for the reduction of the…
Does glycosyl transfer involve an oxacarbenium intermediate? Computational simulation of the lifetime of the methoxymethyl cation in water
2011
2D free-energy surfaces for transfer of the methoxymethyl cation between two water molecules are constructed from molecular dynamics (MD) simulations in which these atoms are treated quantum-mechanically within a box of 1030 classical solvent water molecules at 300 K. This provides a simple model for glycosyl transfer in water. The AM1/TIP3P surfaces with 2D-spline corrections at either MPWB1K/6-31+G(d,p) or MP2/6-31+G(d,p) contain a shallow free-energy well corresponding to an oxacarbenium ion intermediate in a DN*AN mechanism. MD analysis at three temperatures leads to a classical estimate of the lifetime of the methoxymethyl cation in water; when quantum corrections for vibrational zero-…
Magnetic Excitations in Polyoxometalate Clusters Observed by Inelastic Neutron Scattering: Evidence for Anisotropic Ferromagnetic Exchange Interacti…
1999
The ground-state properties of the tetranuclear Co2+ cluster [Co4(H2O)2(PW9O34)2]10- were investigated by combining specific heat, magnetic susceptibility, and magnetization measurements with a detailed inelastic neutron scattering (INS) study on a fully deuterated sample of K10[Co4(H2O)2(PW9O34)2]·22H2O. As a result of the single ion anisotropy of the octahedral Co2+, the appropriate exchange Hamiltonian of the Co4 spin cluster is anisotropic. INS turns out to be essential for the determination of energy splittings in the ground state resulting from the coupling. Besides the energy pattern, INS provides information about the wave functions of the split ground-state components of the spin c…
The equilibrium structure of trans-glyoxal from experimental rotational constants and calculated vibration–rotation interaction constants
2003
A total of six high-resolution FT-IR spectra for trans-glyoxal-d2, trans-glyoxal-d1 and trans-glyoxal-13C2 were recorded with a resolution ranging from 0.003 to 0.004 cm−1. By means of a simultaneous ground state combination difference analysis for each of these isotopologues using the Watson Hamiltonian in A-reduction and Ir-representation the ground state rotational constants are obtained. An empirical equilibrium structure is determined for trans-glyoxal using these experimental ground state rotational constants and vibration–rotation interaction constants calculated at the CCSD(T)/cc-pVTZ level of theory. The least-squares fit yields the following structural parameters for trans-glyoxal…
Multireference equation-of-motion coupled cluster theory.
2012
A generalization of the equation-of-motion coupled cluster theory is proposed, which is built upon a multireference parent state. This method is suitable for a number of electronic states of a system that can be described by similar active spaces, i.e., different linear combinations of the same set of active space determinants. One of the suitable states is chosen as the parent state and the dominant dynamical correlation is optimized for this state using an internally contracted multireference coupled cluster ansatz. The remaining correlation and orbital relaxation effects are obtained via an uncontracted diagonalization of the transformed Hamiltonian, Ĥ = e(-T) Ĥe(T), in a compact multire…
ChemInform Abstract: Getting Discriminant Functions of Antibacterial Activity from Physicochemical and Topological Parameters.
2010
Linear discriminant analysis has been demonstrated to be a very useful tool in the selection and design of new drugs. Up to now we have used it through the search of a topological pattern of activity. In this work our goal is to calculate a complete set of physicochemical parameters using semiempirical (quantum chemical) calculations as well as topological indices (TIs) and try to find out any discriminant function for antibacterial activity through the combined use of both types of descriptors. The physicochemical parameters, such as heat of formation, HOMO, LUMO, dipole moment, polarizability, hyperpolarizability, PM3 generated IR vibrational frequencies, etc., were calculated using PM3 H…
The infrared spectrum of CH 3 D between 900 and 3200 cm −1 : extended assignment and modeling
2000
Abstract The high resolution infrared spectrum of CH 3 D in the region from 900 to 3200 cm −1 has been analyzed on the basis of Fourier transform spectra recorded at Kitt Peak and at Giessen. A theoretical model for an effective hamiltonian in terms of irreducible tensor operators recently adapted to symmetric top molecules has been used in order to consider simultaneously all available transitions between the lowest three polyads of the molecule: the Ground State (G.S.), the Triad (three interacting fundamental bands in the 8 μm region) and the Nonad (nine interacting bands in the 4 μm region). A preliminary simultaneous fit of 3467 Triad–G.S., 5208 Nonad–G.S., and 2487 Nonad–Triad (hot ba…
The Nature of Transannular Interactions in E4N4 and E82+ (E = S, Se)
2015
The electronic structures of tetrachalcogen tetranitrides, E4N4, and octachalcogen dications, E8(2+), and the nature of their intramolecular E···E interactions (E = S, Se) was studied with high-level theoretical methods. The results reveal that the singlet ground states of both systems have a surprisingly large correlation contribution which functions to weaken and therefore lengthen the cross-ring E-E bond. The observed correlation effects are primarily static in E4N4, whereas in E8(2+) the dynamic part largely governs the total correlation contribution. The presented description of bonding is the first that gives an all-inclusive picture of the origin of cross-ring interactions in E4N4 an…