TY - JOUR
A1 - Peric, M.
A1 - Engels, Bernd
T1 - Ab initio calculation of the vibronically averaged hyperfine coupling constants in the 1\(^2\)Π\(_u\) electronic state of CH\(_2 ^+\)
N2 - The results of pure ab initio calculations of the hyperfine coupling constants for the 1 \(^2 \pi _u\) electronic state for various isotopomers of CHi in the energy range between 0 and 20 000 cm\(^{-1}\) are presented. Effects of vibronic and spin-orbit coupling are discussed.
KW - Organische Chemie
Y1 - 1992
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58951
ER -
TY - JOUR
A1 - Bündgen, P.
A1 - Engels, Bernd
A1 - Peyerimhoff, S.D.
T1 - An MRD-CI study of low-lying electronic states in CaF
N2 - Dipole moments and various spectroscopic constants of some low-lying electronic states of the CaF molecule have been calculated using the multireference single· and double-excitation configuration-interaction (MRD-CI) method. The electronic structure of the highly ionic molecule in various excited states can be explained in tenns of different polarisations of the mainly Cacentered valence electron in the field of the F\(^-\) anion. Plots of natural orbitals occupied by the valence electron in the different states give a qualitative picture of the charge distribution and provide a visualisation of the different polarisations of the valence electron in the various states. Comparisons with the electrostatic polarisation model ofTörring, Ernstand Kändler (TEK model) are made. The unknown A' \(^2 \Delta\) state is predicted to lie about 21200 cm\(^{-1}\) above the ground state.
KW - Organische Chemie
Y1 - 1991
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58880
ER -
TY - JOUR
A1 - Engels, Bernd
T1 - Estimation of the influence of the configurations neglected within truncated MR-CI wavefunctions on molecular properties
N2 - Reliable prediction of the isotropic hyperfine coupling constant, a\(_{iso}\), is still a difficult task for ab initio calculations. Strong dependence on the method used for its calculation is found. Within a truncated multi-referencc ansatz a\(_{iso}\) is strongly affected by the size ofthe reference space and the nurober of terms in the truncated Cl expansion. In the present paperdifferent effects of the neglected Cl space are discussed. Modified B\(_K\) and A\(_K\) methods are used to estimate the contributions ofthe neglected configurations. lt can be shown that a combination of both methods is able to recover about 90-9 S% of the total error in a\(_{iso}\)· Furthermore, it was found that to obtain about 90% of the B\(_K\) correction only about I 0-20% ofthe configurations within H0 have to be corrected.
KW - Organische Chemie
Y1 - 1991
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58890
ER -
TY - JOUR
A1 - Peric, M.
A1 - Engels, Bernd
A1 - Peyerimhoff, S.D.
T1 - Ab initio investigation of the vibronic structure of the C\(_2\)H spectrum Calculation of the hyperfine coupling constants for the three lowest lying electronic states
N2 - The hyperfine coupling constants (isotropic hfcc and four Cartesian components of the ani~ tropic tensor) are calculated for all three atoms of C\(_2\)H in its three lowest-lying electronic states at various molecu)ar geometries by means of the ab initio configuration interaction ( MRO.CI) method. The off-diagonal electronic matrix elements involving the two species ofthe A' symmetry are also computed. A diabatic transforrnation is perforrned Jeading to simple geometrical depen· dences of the hyperline coupling constants.
KW - Organische Chemie
Y1 - 1991
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58901
ER -
TY - JOUR
A1 - Peric, M.
A1 - Engels, Bernd
A1 - Peyerimhoff, S.D.
T1 - Ab initio investigation of the vibronic structure of the C\(_2\)H spectrum Computation of the vibronically-averaged values for the Hyperfine Coupling Constants
N2 - The vibronically averaged values for tbe hyperfine coupling constants in the X\(^2 \sum\)-A\(^2 \Pi\) system of the ethynyl radical are computed by means of tbe ab initio metbod calculations. The results point at tbe importance of taking into account the coupling of a1l tbree electronic states in question ( I\(^2\)A', 2\(^2\)A', and 1\(^2\)A") for a reliable explanation of the available experimental findings. The mean values of the hfcc's for K = 0 and 1 levels in \(^{13}\)C\(_2\)H and \(^{13}\)C\(_2\)D in the energy range up to 6000 cm\(^{-1}\) are predicted.
KW - Organische Chemie
Y1 - 1991
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58915
ER -
TY - JOUR
A1 - Engels, Bernd
A1 - Peyerimhoff, S.D.
A1 - Skell, P.S.
T1 - Theoretical study of the potential energy surface governing the stereochemistry in ClC\(_2\)H\(_4\) reactions
N2 - Large-scale multireference configuration interaction calculations in a double·t·type AO basis including polarization functions are carried out for the potential surface of the ClC\(_2\)H\(_4\9 system. The charge distribution for various extreme points of the surface is discussed. The absolute minimum is found for an asymmetric ClC2H4 structure. The symmetrical bridged nuclear conformation is also found to be stable with respect to dissociation into Cl + C\(_2\)H\(_4\)• The activation energy for rotation about the C-C axis is calculated tobe around 18 kJ/mol, which is comparable tothat for the 1,2 migration {around 26 kJ/mol). The stereochemistry is governed by the fact that addition of CI to C\(_2\)H\(_4\) (or dissociation) is a two-step reaction proceeding through a symmetrica1 intermediate. The direct addition pathway possesses a small barrier of about 8 kJ jmol.
KW - Organische Chemie
Y1 - 1990
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58851
ER -
TY - JOUR
A1 - Karna, S.P.
A1 - Grein, F.
A1 - Engels, Bernd
A1 - Peyerimhoff, S.D.
T1 - Ab initio configuration-interaction studies of the ground state potential energy and hyperfine coupling constants of \(^{35}\)Cl\(_2^-\)
N2 - Potential energy and spectroscopic constants for the X\(^2 \sum^+ _\mu\) ground state of a;, were calculated by configuration-interaction (Cl) methods, using large basis sets with polarization and diffuse functions. From these CI wavefunctions, the isotropic (a\(_{iso}\)) and dipolar (A\(_{dip}\)) components of the hyperfine coupling constant were obtained. The effects of various s, p basis sets, polarization and diffuse functions, as well as the influence of reference configurations and configuration selection thresholds were investigated. The best values obtained are 35·31 G for a\(_{iso}\) and 29·440 for A\(_{dip}\)• tobe compared with experimental values of 37 ± 1 G and 32 ± 1 G, respectively. It is shown that the contributions to a1so of the K and L shells are opposite in sign, differing by about 4 G. Upon vibrational averaging, both a\(_{iso}\) and A\(_{dip}\) move towards smaller values as v increases. An adiabatic electron affinity of 2·46eV was obtained for CL\(_2\) , and a vertical electron detachment energy of 3·71 eV for Cl;.
KW - Organische Chemie
Y1 - 1990
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58869
ER -
TY - JOUR
A1 - Funken, K.
A1 - Engels, Bernd
A1 - Peyerimhoff, S.D.
A1 - Grein, F.
T1 - Study of the hyperfine coupling constants of the moleculs NH2, NHD and ND2
N2 - In the present paper we c:alculate tbe magnetic hyperfine couplina constants (hfcc) ai.ID and A11 of the ground states of the isotopes NH2, NHD and ND2 using truncated MR..CI methods. Differences from other theoretical methocls and shortoominp of the truncated Cl approach in calculating tlj10 are studied. Polarization effects wbich detennirae ailo. as weU as a simple model to describe the dipolar hfcc's, are discussed. All results are in. excellent aareement with experimental data. lt is shown that ab initio methods are able to obtain reliable values for otf-diaaonal values of A41 which are difficult to measure experimentaDy.
KW - Organische Chemie
Y1 - 1990
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58875
ER -
TY - JOUR
A1 - Engels, Bernd
A1 - Peyerimhoff, S.D.
T1 - Theoretical study of FC\(_2\)H\(_4\)
N2 - Large-scale multireference configuration interaction (MRD-CI) calculations in a quite flexible AO basis are employed to study the energy hypersurface for the reaction intermediate FC\(_2\)H\(_4\) • The reaction F + C\(_2\)H\(_4\) -> FC\(_2\)H\(_4\) as weil as the 1,2 migration of the fluorine atom in FC\(_2\)H\(_4\) is investigated. In addition the rotation around the CC bond in the optimum conformation is studied. The absolute minimum in the potential energy is found for the asymmetric structure but the symmetric structure is also found to be stable with respect to the dissociation, so that a shuttling of the fluorine atom is in principle possible but highly unlikely because ( l) the activation energy is high ( II 5-130 kJ fmol) and the saddle point lies only 4(}-50 kJ jmol below the dissociation Iimit of F + C\(_2\)H\(_4\) and (2) the competitive motion, i.e., rotation around the CC axis, is nearly free (I 1-17 kJ/mol).
KW - Organische Chemie
Y1 - 1989
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58824
ER -
TY - JOUR
A1 - Engels, Bernd
A1 - Peyerimhoff, S.D.
T1 - The hyperfine coupling constants of the X\(^3\)Σ\(^-\) state of NH : Influence of polarization functions and configuration space on the description of spin polarization
N2 - The hyperfine coupling constants for the \(^3\)Σ\(-\) ground state of the NH molecule are determined by configuration interaction calculations whereby the infl.uence of polarization functions as weil as of the configuration space on the spin polarization mechanism is analysed. The dipolar part Au(N) and Au(H) can be obtained very reliably without much computational effort (A .. (N) == -45·3 MHz and A"(H) = -62·3 MHz). The value for the isotropic contribution a1.., in the best AO basis and MRD-CI treatment is - 64·5 MHz for H and 16·6 MHz for nitrogen compared to the corresponding experimental quantities of -66 MHz and 19 MHz respectively. Their determination depends on a subtle balance of the lu, 2u and 3u shell correlation description, whereby the dominant contribution to a1..,(H) results from the 2u shell. It is shown that the often good agreement of a110 values with experiment in a small basis singledouble configuration interaction treatment results from a cancellation of two errors.
KW - Organische Chemie
Y1 - 1989
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58832
ER -