scholarly journals Application of DFT and EMS to the Study of Strained Organic Molecules

1998 ◽  
Vol 51 (4) ◽  
pp. 707 ◽  
Author(s):  
W. Adcock ◽  
M. J. Brunger ◽  
M. T. Michalewicz ◽  
D. A. Winkler
Keyword(s):  
Wave Function ◽  
Density Functional ◽  
Impulse Approximation ◽  
Basis Sets ◽  
Functional Theory ◽  
Electron Momentum ◽  
Plane Wave Impulse Approximation ◽  
Electron Momentum Spectroscopy ◽  
Momentum Distributions ◽  
Self Consistent Field

Electron momentum spectroscopy (EMS) studies of the valence shells of [1.1.1]propellane, 1,3-butadiene, ethylene oxide and cubane are reviewed. Binding energy spectra were measured in the energy regime of 3·5–46·5 eV over a range of different target electron momenta, so that momentum distributions (MDs) could be determined for each ion state. Each experimental electron momentum distribution is compared with those calculated in the plane wave impulse approximation (PWIA) using both a triple-? plus polarisation level self-consistent field (SCF) wave function and a further range of basis sets as calculated using density functional theory (DFT). A critical comparison between the experimental and theoretical momentum distributions allows us to determine the ‘optimum’ wave function for each molecule from the basis sets we studied. This ‘optimum’ wave function then allows us to investigate chemically or biologically significant molecular properties of these molecules. EMS-DFT also shows promise in elucidating the character of molecular orbitals and the hybridisation state of atoms.

On the dissociation energy of Ti(OH2)+. An MCSCF, CCSD(T), and DFT study

1996 ◽  
Vol 74 (10) ◽  
pp. 1824-1829 ◽  
Author(s):  
A. Irigoras ◽  
J.M. Ugalde ◽  
X. Lopez ◽  
C. Sarasola
Keyword(s):  
Dissociation Energy ◽  
Density Functional ◽  
Basis Sets ◽  
Coupled Cluster ◽  
Functional Theory ◽  
Consistent Field ◽  
Self Consistent ◽  
Self Consistent Field ◽  
Self Consistent Field Theory ◽  
Effective Core Potentials

The dissociation energy of the Ti(OH2)+ ion–molecule complex was calculated by the multiconfigurational self-consistent field theory, coupled cluster theory, and two density functional theory based methods, using both all-electron basis sets and effective core potentials. The calculations show that approximate density functional theory gives results in better agreement with experiment than either the multiconfigurational self-consistent field theory or the coupled cluster theory, with both all-electron basis sets and effective core potentials. Nevertheless, the optimized geometries and harmonic vibration frequencies are very similar, irrespective of the level of theory used. The interconfigurational energy ordering of the two valence electronic configurations dn−1s and dn−2s2 of the 4F electronic state of the titanium cation were also calculated and are discussed. Key words: ab initio, dissociation energy, ion–molecule complex, effective core potentials, transition metals.

EMS studies of larger molecules of chemical and biochemical interest

1996 ◽  
Vol 74 (11-12) ◽  
pp. 773-781 ◽  
Author(s):  
J. J. Neville ◽  
Y. Zheng ◽  
B. P. Hollebone ◽  
N. M. Cann ◽  
C. E. Brion ◽  
...  
Keyword(s):  
Density Functional ◽  
Polyatomic Molecules ◽  
Target Compound ◽  
Frontier Orbitals ◽  
Functional Theory ◽  
Electron Momentum ◽  
Hartree Fock ◽  
Electron Momentum Spectroscopy ◽  
Key Factor ◽  
Increased Sensitivity

The challenges involved in extending electron momentum spectroscopy (EMS) studies beyond small polyatomic molecules to more complicated systems are discussed. EMS results for the highest occupied (frontier) molecular orbitals of glycine (NH2CH2COOH) and dimethoxymethane ((CH3O)2CH2) demonstrate possible approaches to overcoming such challenges as closely spaced valence orbitals, low volatility, and the conformational mobility of the target compound. The increased sensitivity available from recently developed multichannel electron momentum spectrometers is a key factor in overcoming these challenges and making such EMS studies feasible. The utility of Kohn–Sham density functional theory (DFT) for EMS calculations on larger molecules such as glycine and dimethoxymethane using the recently formulated target Kohn–Sham approximation is also investigated as experimental momentum profiles are compared with theoretical momentum profiles generated via Kohn–Sham DFT and a range of Hartree–Fock calculations. The Kohn–Sham DFT calculations provide better agreement with experiment for the frontier orbitals of glycine and dimethoxymethane than even the near Hartree–Fock limit results.

scholarly journals A Valence-Bond-Based Multiconfigurational Density Functional Theory: The λ-DFVB Method Revisited

Molecules ◽  
2021 ◽  
Vol 26 (3) ◽  
pp. 521
Author(s):  
Peikun Zheng ◽  
Chenru Ji ◽  
Fuming Ying ◽  
Peifeng Su ◽  
Wei Wu
Keyword(s):  
Density Functional Theory ◽  
Wave Function ◽  
Density Functional ◽  
Valence Bond ◽  
Field Calculation ◽  
Excitation Energies ◽  
Functional Theory ◽  
Consistent Field ◽  
Self Consistent ◽  
Self Consistent Field

A recently developed valence-bond-based multireference density functional theory, named λ-DFVB, is revisited in this paper. λ-DFVB remedies the double-counting error of electron correlation by decomposing the electron–electron interactions into the wave function term and density functional term with a variable parameter λ. The λ value is defined as a function of the free valence index in our previous scheme, denoted as λ-DFVB(K) in this paper. Here we revisit the λ-DFVB method and present a new scheme based on natural orbital occupation numbers (NOONs) for parameter λ, named λ-DFVB(IS), to simplify the process of λ-DFVB calculation. In λ-DFVB(IS), the parameter λ is defined as a function of NOONs, which are straightforwardly determined from the many-electron wave function of the molecule. Furthermore, λ-DFVB(IS) does not involve further self-consistent field calculation after performing the valence bond self-consistent field (VBSCF) calculation, and thus, the computational effort in λ-DFVB(IS) is approximately the same as the VBSCF method, greatly reduced from λ-DFVB(K). The performance of λ-DFVB(IS) was investigated on a broader range of molecular properties, including equilibrium bond lengths and dissociation energies, atomization energies, atomic excitation energies, and chemical reaction barriers. The computational results show that λ-DFVB(IS) is more robust without losing accuracy and comparable in accuracy to high-level multireference wave function methods, such as CASPT2.

scholarly journals Satellite Intensities in Photoelectron Spectroscopy and Electron Momentum Spectroscopy-Synchrotron Radiation Studies of Argon 3s and Xenon 5s Photoionisation (hv - 60?130 eV)

1986 ◽  
Vol 39 (5) ◽  
pp. 565 ◽  
Author(s):  
CE Brion ◽  
KH Tan
Keyword(s):  
Synchrotron Radiation ◽  
Photon Energy ◽  
Photoelectron Spectroscopy ◽  
Impulse Approximation ◽  
Main Line ◽  
Magic Angle ◽  
Electron Momentum ◽  
X Ray ◽  
Plane Wave Impulse Approximation ◽  
Electron Momentum Spectroscopy

Binding energy spectra for the main line, satellite lines and associated double ionization continuum for argon 3s and xenon 5s photoionisation have been measured in the photon energy range 60-130 eV using monochromatised synchrotron radiation and magic angle photoelectron spectroscopy. In particular the ratio of satellite to main line intensities has been investigated and compared with the results of earlier experiments using X-ray and ultraviolet photoelectron spectroscopy as well as with recent measurements by electron momentum [i.e. binary (e,2e)] spectroscopy. The results of the presently reported photoelectron measurements show that the satellite intensity relative to that of the main ns -1 line increases with increasing photon energy and approaches the value given by electron momentum spectroscopy. These findings are contrary to predictions based on recent calculations of photoelectron intensities. The present work lends support to the direct interpretation of satellite intensities (pole strengths or spectroscopic factors) in binary� (e, 2e) spectroscopy using the plane wave impulse approximation. The need for improved calculations of photoionisation intensities as well as further photoelectron measurements in the X-ray region is stressed.

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