Application of the iterative difference-dedicated configuration interaction method to the determination of excitation energies in some benchmark systems: Be, CH+, BH and CH2

The iterative difference-dedicated CI method (IDDCI) has been applied to determine excitation energies in small systems for which benchmark FCI and other high-level calculations exist. Transitions to excited singlet and triplet states in Be and vertical transitions in CH⁺, BH and CH₂ are reported. The deviations from FCI results are lower than 0.1 eV and compare advantageously with SDCI including size-consistency corrections, (SC)²SDCI, and with coupled cluster calculations including the effect of triples, especially for the states which have a predominant double excitation character. The IDDCI procedure has been speeded up by using smaller subspaces for optimizing the molecular orbitals. Received: 17 January 1997 / Accepted: 31 July 1997     

A parallel implementation of the COLUMBUS multireference configuration interaction program

Summary In this work a parallel implementation of the COLUMBUS MRSDCI program system is presented. A coarse grain parallelization approach using message passing via the portable toolkit TCGMSG is used. The program is very well portable and runs on shared memory machines like the Cray Y-MP, Alliant FX/2800 or Convex C2 and on distributed memory machines like the iPSC/860. Further implementations on a network of workstations and on the Intel Touchstone Delta are in progress. Overall, results are quite satisfactory considering the complexity and the prodigious requirements, especially the I/O bandwidth, of MRCI programs in general. For our largest test case we obtain a speedup of a factor of 7.2 on an eight processor Cray Y-MP for that section of the program (hamiltonian matrix times trial vector product) which has been parallelized. The speedup for one complete diagonalization iteration amounts to 5.9. An absolute speed close to 1 GFLOPS is found. Results for the iPSC/860 show that ordinary disk I/O is certainly not sufficient in order to guarantee a satisfactory performance. As a solution for that problem, the implementation of a fully asynchronous distributed-memory model for certain data files is in preparation. On leave from: Bereich Informatik, Universität Leipzig, Augustusplatz 10/11, O-7010 Leipzig, Germany     

The unrestricted natural orbital-restricted active space method: methodology and implementation

The full configuration interaction method in the space of fractionally occupied unrestricted natural orbitals (UNO-CAS method) is extended to excited states as well as to strongly correlated and reactive systems with large active spaces. This is accomplished by␣using restricted active space (RAS) wave functions introduced by Olsen et al. [(1988) J Chem Phys 89: 2185] and using the UNOs without the expensive orbital optimization step. In RAS, the space of active orbitals is subdivided into three groups: a group with essentially doubly occupied orbitals (RAS1), the usual CAS space (RAS2), and a space with weakly occupied active orbitals (RAS3). We select these spaces on the basis of the occupation numbers of the UNOs. All possible electron distributions are allowed in the usual CAS space, but the number of vacancies is limited in RAS1 and the number of electrons is limited in RAS3. We discuss an efficient algorithm for generating a RAS wave function. This is based on the Handy-Knowles determinantal expansion with an addressing scheme adopted for the restricted expansion. Results for both ground and excited states of azulene and free base porphyrin are presented. Received: 16 July 1998 / Accepted: 7 August 1998 / Published online: 19 October 1998     

Semiempirical PM5 molecular orbital study on chlorophylls and bacteriochlorophylls: comparison of semiempirical, ab initio, and density functional results

The semiempirical PM5 method has been used to calculate fully optimized structures of magnesium-bacteriochlorin, magnesium-chlorin, magnesium-porphin, mesochlorophyll a, chlorophylls a, b, c(1), c(2), c(3), and d, and bacteriochlorophylls a, b, c, d, e, f, g, and h with all homologous structures. Hartree-Fock/6-31G* ab initio and density functional B3LYP/6-31G* methods were used to optimize structures of methyl chlorophyllide a, chlorophyll c(1), and methyl bacteriochlorophyllides a and c for comparison. Spectroscopic transition energies of the chromophores and their 1:1 or 1:2 solvent complexes were calculated with the Zindo/S CIS method. The self-consistent reaction field model was used to estimate solvent shifts. The PM5 calculations predict planar structure of the porphyrin ring and central position of the four coordinated magnesium atoms in all pigments studied, in accord with the experimental, ab initio, and density functional results, a significant improvement as compared to the older semiempirical PM3 approach. Only small differences in PM5 and B3LYP/6-31G* or Hartree-Fock/6-31G* minimum energy geometries of the reference molecules were observed. Calculations show that in 1:1 solvent complexes, where the magnesium atom is five coordinated, the magnesium atom is shifted out of the plane of the porphyrin ring towards the solvent molecule, while the hexa coordinated 1:2 complexes are again planar. The PM5 method gives atomic charges that are comparable with those obtained from the Hartree-Fock/6-31G* and B3LYP/6-31G* calculations. The single point ZINDO/S CIS calculations with PM5 minimum energy structure gave excellent correlations between calculated and experimental transition energies of the chlorophylls and bacteriochlorophylls studied. Such correlations may be used for prediction of transition energies of the chromophores in protein binding sites. Calculations also predict existence of dark electronic states below the main Soret absorption band in all chromophores studied. The results suggest that the semiempirical PM5 method is a fairly reliable and computationally efficient method in predicting molecular parameters of porphyrin-like molecules.     

GRECP/5e‐MRD‐CI calculation of the electronic structure of PbH

The correlation calculation of the electronic structure of PbH is carried out with the generalized relativistic effective core potential (GRECP) and multireference single‐ and double‐excitation configuration interaction (MRD‐CI) methods. The 22‐electron GRECP for Pb is used and the outer core 5s, 5p, and 5d pseudospinors are frozen using the level‐shift technique, so only five external electrons of PbH are correlated. A new configuration selection scheme with respect to the relativistic multireference states is employed in the framework of the MRD‐CI method. The [6, 4, 3, 2] correlation spin–orbit basis set is optimized in the coupled cluster calculations on the Pb atom using a recently proposed procedure, in which functions in the spin–orbital basis set are generated from calculations of different ionic states of the Pb atom and those functions are considered optimal that provide the stationary point for some energy functional. Spectroscopic constants for the two lowest‐lying electronic states of PbH (²Π_1/2, ²Π_3/2) are found to be in good agreement with the experimental data. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002     

Identification and characterization of impurities in an insecticide,bifenthrin technical

The HPLC‐DAD and GC/MS methods were successfully used for the identification and characterization of the impurities in an agrochemical insecticide, bifenthrin technical. Three impurities ranging from 0.175%–0.541% were detected by the HPLC‐DAD method. The LC/MS technique with ESI or APCI source failed to detect the impurities detected by HPLC‐DAD, due to lack of ionization in ESI or APCI. The three impurities were enriched by prep‐HPLC, and then their structures were elucidated based on the GC/EIMS and CIMS data. The EI mass spectra of bifenthrin and its impurities displayed molecular ion and provided structure indicative fragment ions; the CIMS data further confirmed their molecular weight. The identity of the impurity 1 was further confirmed by the synthesis of the authentic sample followed by NMR and GC/MS data.     

Theoretical Studies on Electronic Spectra and Second-order Nonlinear Optical Properties of Barbituric Acid Derivatives Substituted with Schiff Base

Barbituric acid (BA) is a very important kind of compound in biological chemistry and medicine. It can be applied in abirritative medicine and antioxidants.1 It is an important sort of raw material for organic synthe-sis.2 It predicts the important reactive mechanism for organic synthesis.3 Some investigations for NLO prop-erties of a series of BA derivatives have been reported by Feng and coworkers in the view of theory.4,5 The Schiff base has extensive application in the fields of organi…     

Theoretical study of the <Superscript>1,3</Superscript>Σ<Superscript>+</Superscript> states of the NaH molecule in the adiabatic and diabatic representations

Adiabatic and diabatic study for all the states dissociating below the ionic limit [i.e., Na (3s, 3p, 4s, 3d, 4p, 5s, 4d, and 4f) + H (1s)] in ¹Σ⁺ and ³Σ⁺ symmetries are presented. Adiabatic results are also reported for ^1,3Π and ^1,3Δ symmetries. Pseudo-potential, operatorial core-valence correlation, and full valence CI approaches combined with an efficient diabatization procedure are used in these ab initio calculations. Our vibrational-level spacings and spectroscopic constants are in good agreement with the available experimental data for the low-lying states. Diabatic potentials and dipole moments are analyzed, revealing the strong imprint of the ionic state in the ¹Σ⁺ adiabatic states. The hydrogen electron affinity correction was taken into account by the use of the efficient diabatization method. This leads to a better agreement with the available experimental data. Experimental suggestions are also given for the higher excited states based on their unusual behavior.     

A CASSCF-CI study of the coordination of ethylene with iron

Summary Complete active space SCF, CASSCF, and contracted CI calculations have been performed on the -bonded complex between ethylene and an iron atom. An extended basis set of the ANO type was used, which included polarization functions on all centers. The results indicate an attractive interaction between Fe ⁵ F(d⁷s) and ethylene, with an estimated binding energy of 14 kcal/mol. The low spin complex arising from Fe ³ F(d⁷s) was found to be bound with 18 kcal/mol. Both these potential minima are, however, above the ground state of the iron atom. It is concluded that the interaction between atomic ground state iron and ethylene is not of the normal -bonded type, but is dominated by dispersion forces. A preliminary study showed this interaction to be almost isotropic, with no preferred site for the iron atom.     

Use of very long-distance NOEs in a fully deuterated protein: an approach for rapid protein fold determination

The high sensitivity of modern NMR instrumentation, in combination with full deuteration, enabled the measurement of long-range NOEs between amide protons in a fully deuterated protein corresponding to distances up to 8A. These are beyond the limit normally observed in protonated samples. Such long-distance NOEs could be observed using long mixing times, which became possible due to reduced spin diffusion and T1 relaxation of the amide protons in the fully deuterated sample. This information was used in combination with secondary structure restraints derived from secondary chemical shifts for structure calculations. With these backbone amide proton NOEs only, a unique fold could be obtained with positional root mean square deviations from the average of 1.30 and 2.25 A for backbone and heavy atoms, respectively. Despite the low density of restraints, no mirror image problems were observed. Addition of sidechain NOE information increased the precision of the ensemble and in particular of the core packing. The structures obtained in this way were close to the published crystal structure. NOE completeness analysis revealed that the cumulative completeness is still more than 80% for an 8.0 A cut-off distance.