An ab initio study of the hyperfine structure in the X2 Pi electronic state of CCCH

The results of an ab initio study of the magnetic hyperfine structure in the X (2)Pi electronic state of CCCH are reported. The potential surfaces for two components of the X (2)Pi electronic state were computed by means of an extensive configuration interaction approach. The electronically averaged hyperfine coupling constants of H and (13)C for (12)C (12)C (12)CH, (13)C (12)C (12)CH, (12)C (13)C (12)CH, and (12)C (12)C (13)CH are obtained as functions of two bending vibrational modes by the density functional theory method. The vibronic wave functions are calculated with the help of a variational approach which takes into account the Renner-Teller effect and spin-orbit coupling. The model Hamiltonian is expressed in terms of the normal bending coordinates. It is found that, due to the generally strong geometry dependence of the hyperfine coupling constants, it is necessary to carry out the vibronic averaging of the corresponding functions in order to obtain the values which can be compared to the results of the measurements. The results of the present study help to reliably interpret the experimental data previously published. They also predict the yet unobserved hyperfine structure in excited vibronic states.     

An ab initio study of the vibronic, spin-orbit, and magnetic hyperfine structure in the X2Pi electronic state of NCO

In the present study we give the results of the ab initio calculations on the vibronic, spin-orbit, and magnetic hyperfine structure in the X (2)Pi electronic state of the NCO radical. The calculations of the potential surfaces and the electronic mean values of the hyperfine coupling constants are carried out by means of the density functional theory approach (B3LYP functional combined with an atomic orbital basis set suitable for calculations of the hyperfine structure). The vibronic levels, spin-orbit splitting, and the vibronic mean values of the components of the hyperfine tensor in the vibronic species are calculated using a variational method. The results of the calculations are in good agreement with the available experimental data.     

The hyperfine coupling constants of 19F: An ab initio MRD-CI basis set study

The isotropic (a_iso) and dipolar (A_dip) hyperfine coupling constants of ¹⁹F were obtained from MRD -CI wave functions using a variety of basis sets. In series I, increasing numbers of d functions were added to a 5s4p contracted Huzinaga/Dunning basis. In series II, the 5s3p basis set was uncontracted in several steps until 9s5p was reached, to which were added from one to three d-polarization functions. CI parameters (selection thresholds and the number of reference configurations) were also varied. A study of the R dependence of a_iso and A_dip was performed. The best values obtained at R_e are 260 G for a_iso and 308 G for A_dip, compared with experimental values of about 280 G for a_iso and 320 G for A_dip.     

An ab initio calculation of 14n quadrupole coupling constants

Ab initio SCF-MO calculations of ¹⁴N quadrupole coupling constants are reported for HCN, HNC, CH₃CN, CH₃NC, NH₃, NH₂NH₂, FCN, N₂O, (CN)₂, BrCN, pyridine and pyrazine. There is excellent correlation between calculation and experiment yielding Q = 1.503 ± 0.159 × 10^?26 cm² for the ¹⁴N nuclear quadrupole moment. Dunning sp basis sets are more than adequate for such calculations, STO/4G basis sets yielding almost identical results for pyridine and pyrazine. Unsuccessful attempts were made to correlate coupling constants with electronic population analysis indices.     

An ab initio study of the low-lying electronic states of S3

Accurate calculations of the low-lying singlet and triplet electronic states of thiozone, S(3), have been carried out using large multireference configuration interaction wave functions. Cuts of the full potential energy surfaces along the stretching and bending coordinates have been presented, together with the vertical excitation spectra. The strong experimentally observed absorption around 395 nm is assigned to the 1 (1)B(2) state, which correlates to ground state products. Absorption at wavelengths shorter than 260 nm is predicted to lead to singlet excited state products, S(2) (a (1)Delta(g))+S((1)D). The spectroscopic properties of the X (3)Sigma(g) (-), a (1)Delta(g), and b (1)Sigma(g) (+) electronic states of the S(2) radical have also been accurately characterized in this work. The investigations of the low-lying electronic states were accompanied by accurate ground state coupled cluster calculations of the thermochemistry of both S(2) and S(3) using large correlation consistent basis sets with corrections for core-valence correlation, scalar relativity, and atomic spin-orbit effects. Resulting values for D(0)(S(2)+S) and SigmaD(0) for S(3) are predicted to be 61.3 and 162.7 kcal/mol, respectively, with conservative uncertainties of +/-1 kcal/mol. Analogous calculations predict the C(2v)-D(3h) (open-cyclic) isomerization energy of S(3) to be 4.4+/-0.5 kcal/mol.     

An ab initio study of the vibronic structure in the a1Delta g electronic state of C2H2++

The results of an ab initio study of the vibronic structure in the a1Deltag electronic state of C2H2++ and its deuterated species (C2D2++) are presented. They are generated employing a simple model that incorporates the minimal number of terms contributing to the Renner-Teller effect. The trans- and cis-bending potential curves at planar nuclear arrangements are obtained by means of large-scale configuration interaction calculations. The corresponding harmonic vibrational frequencies are 717 and 650 cm-1 for C2H2++, and 549 and 477 cm-1 in the case of C2D2++. It is found that the splitting of the potential surfaces is moderate at trans-distortions of linearity, while it is extremely small at cis-bending vibrations. The eigenvalues and eigenfunctions of the model Hamiltonian employed are obtained by means of a perturbative and a variational approach.     

An ab initio study on the ground and low-lying doublet electronic states of SbO2

Geometry optimization and harmonic vibrational frequency calculations have been carried out on the low-lying doublet electronic states of antimony dioxide (SbO(2)) employing a variety of ab initio methods, including the complete active space self-consistent field/multireference configuration interaction and the RCCSD(T) methods. Both large and small core relativistic effective core potentials were used for Sb in these calculations, together with valence basis sets of up to aug-cc-pV5Z quality. Contributions from outer core correlation and off-diagonal spin-orbit interaction to relative electronic energies have been calculated. The ground electronic state of SbO(2) is determined to be the X (2)A(1) state, as is the case for dioxides of other lighter group 15 p-block (or group VA) elements. However, the A (2)B(2) and B (2)A(2) states are estimated to be only 4.1 and 10.7 kcalmole above the X (2)A(1) state, respectively, at the complete basis set limit. Reliable vertical excitation energies from the X (2)A(1) state to low-lying excited states of SbO(2) have been computed with a view to assist future spectral assignments of the absorption and/or laser-induced fluorescence spectra of SbO(2), when they become available.     

An ab initio investigation of the geometry,bonding and coupling constants of BF2

Comparative calculations, using five different basis sets of contracted Gaussian functions, of the geometry, bonding and hyperfine coupling constants of BF₂ are reported. The best calculation, using a near Hartree-Fock atomic basis, predicts a bond angle of 120° and a bond length of 2.50 a.u. (=1.32 Å) for the X ² A ₁ ground state. The geometries of three low-lying excited states are also presented.     

An ab initio study of the nuclear spin-spin coupling constants in the second-row hydrides

Ab initio SCF perturbation theory calculations have been performed for the contact, orbital and dipolar contributions to the nuclear spin—spin coupling constants in A1H₃, SiH₄ PH₃, H₂S and HCl, using large, stable gaussian basis sets. The results for J(XH) are in reasonably good agreement with experiment, those for. J(HH) are rather less good.     

An ab initio multireference doubles excitation configuration interaction study of low-lying electronic states of Cd2 using Slater-type orbitals

Potential-energy curves for the ground state and lower excited states of the Cd₂ dimer have been calculated. They are obtained using a multireference doubles excitation configuration interaction procedure and employing Slater basis sets, previously optimized at the self-consistent-field level for excited states of the Cd atom. The spectroscopic constants and excitation energies for the bound states of Cd₂ have been compared with experimental as well as other theoretical results. The ground state of Cd₂ is essentially repulsive and presents a shallow van der Waals minimum. The computed adiabatic electronic transitions are in good agreement with the experimental ones. Received: 16 September 1999 / Accepted: 3 February 2000 / Published online: 2 May 2000     

Theoretical investigation of the vibronic spectrum in the X(2)Pi(u) electronic state of C(6)(+)

In this study we employ the recently developed model for handling the Renner-Teller effect in Pi electronic states of six-atomic molecules with linear equilibrium geometry to calculate the vibronic spectrum in the X(2)Pi(u) electronic state of the C(6)(+) ion. The applied model Hamiltonian excludes the stretching vibrations and end-over-end rotations. On the other hand, it considers the interplay between the vibronic and spin-orbit couplings. The parameters determining the shape of the bending potential energy surfaces are computed by means of a Density functional theory, and the spin-orbit coupling constant by the Multireference CI program using state-averaged complete active space self-consistent field (SA-CASSCF) wavefunctions. The results of the present study are expected to motivate and help future experimental investigations on C(6)(+).     

The low-lying electronic states of H2CN+: a preliminary ab initio study

Ab initio molecular-orbital calculations have been carried out on the low-lying triplet and singlet electronic states of the H₂CN⁺ cation, at the SCF and Møller-Plesset levels of theory. Both triplet ³A₂ and ³B₂ electronic states have similar energies. The barriers to isomerization to the ³A″ and ³A' electronic states of HCNH⁺ are estimated. It appears that ³A₂ and ³B₂ states are stable towards both isomerization and dissociation. The results of mass spectroscopic experiments involving H₂CN⁺ are discussed.     

An ab initio MO calculation of the electronic structure and geometry of protonated methanol

Protonated methanol, CH₃ OH₂⁺, has been studied using the LCAO—MO—SCF method with a 7, 3 and 9, 5, 1 Gaussian orbital basis set on the heavy atoms and 4s on hydrogen. It is found that the ground state is non-planar around oxygen, in contrast with previous calculations, with an inversion barrier of 3 kcal mol^?1. The changes in electron distribution in the reacting systemCH₃⁺ + H₂O → CF₃OH₂⁺is also examined.     

Ab initio calculations of isotropic hyperfine coupling constants in β-ketoenolyl radicals

Ab initio unrestricted Hartree–Fock (UHF ), unrestricted second-order Møller–Plesset (UMP 2) perturbation, unrestricted coupled cluster (UCCD ), and unrestricted quadratic configuration interaction (UQCISD ) calculations have been performed on the organic radicals CH₃, CH₃CH₂, CH₂CHCH₂, CH₃CHCOO^?, HCOCHCOH, CH₃COCHCOH, CH₃COCHCOCH₃, and CH₃COC(CH₃)COCH₃, using double-zeta and split-valence-plus-polarization basis sets. These radicals are derived from common organic ligands and have been observed in recent experimental work on tris(β-ketoenolato)cobalt(III) complexes. Their geometry has been optimized at the UHF level using the two mentioned basis sets. From these calcuations, values for the isotropic hyperfine coupling constants at the hydrogen atoms are predicted and compared with the experimental results. The usefulness of semiempirical extrapolations based on limited basis sets and treatment of electron correlation effects is carefully analyzed in the examples considered. © 1994 John Wiley & Sons, Inc.     

Comprehensive ab initio calculation and simulation on the low-lying electronic states of TlX (X = F, Cl, Br, I, and At)

The low-lying electronic states of TlX (X=F, Cl, Br, I, and At) are investigated using the configuration interaction based complete active space third-order perturbation theory [CASPT3(CI)] with spin-orbit coupling accounted for. The potential energy curves and the corresponding spectroscopic constants are reported. The results are grossly in good agreement with the available experimental data. The absorption spectra are simulated as well to reassign the experimental bands. The present results are also useful for guiding future experimental measurements.     

An ab initio study of the electronic spectrum of dichlorocarbene CCl2

The lower-lying electronic states of dichlorocarbene have been studied by ab initio methods at different levels of accuracy. For the ¹B₁ ← ¹A₁ transition, the calculated transition energy (1.95 eV) is in good agreement with the gas-phase value (2.10 eV) of Predmore, Murray and Harmony. The discrepancy with the previous CI study by Ha. Gremlich and Bühler is commented on. The vibrational frequencies of CCl₂ in both ¹A₁ and ¹B₁ states were calculated and compared with experiment. The first four triplet and four cationic states have also been examined.     

An ab initio model calculation of the π and σ electronic structure of the ethylene molecule

The ab initio SCF-MO-LCAO calculation of the ethylene molecule considering explicitly all valence electrons and using a minimum basis set of Slater orbitals as well as the Mulliken approximation of integrals is presented. Further, a CI calculation including all mono-excited and some di-excited configurations has been carried out. The implications of this study with respect to the validity of the — separability conditions are discussed.

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Zusammenfassung Es wird eine ab initio SCF-MO-LCAO Berechnung des Äthylenmoleküls vorgelegt, in der alle Valenzelektronen in Betracht gezogen sind. Als Funktionenansatz wurde ein aus Slater-Atomeigenfunktionen bestehendes System benützt, die Atomintegrale wurden nach der Mullikenschen Näherung berechnet. Weiter wurde eine CI-Rechnung mit Berücksichtigung aller einfach angeregten und einiger doppelt angeregten Zustände angeschlossen und die Folgerungen in Bezug auf die — -Separation diskutiert.

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Résumé Dans cette communication on présente les résultats d'un calcul ab initio par la méthode SCF-MO-LCAO, dans lequel on tient compte explicitement de tous les éléctrons de valence en utilisant une base minimum des orbitales de Slater et l'approximation des intégrals par Mulliken. On a aussi performé le calcul par la méthode de l'interaction des configurations avec toutes les configurations monoexcitées et quelques diexcitées. On discute les implications de cette étude en relation avec la validité des conditions de la f séparabilité.

     

Ab initio calculation of vibronic levels in the 2πu state of ph2

The results of an ab initio treatment of the Renner effect in the ²π_u state of PH₂ are reported The Born-Oppenheimer potential surfaces calculated by means of the MRD CI method are used A variational method, based on polynomial expansions of the molecular potentials and the kinetic-energy operator, is employed for calculation of vibronic levels.