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A close-coupling approximation is employed to theoretically investigate the excitation of the 3s3S0 and 3p3P states of atomic oxygen for electron impact energies ranging from 13.87-100 eV. The target states included in the expansion of the total wave function are modeled by accurate configuration-interaction wave functions. The results are consistent with recent experimental findings for the dipole-allowed 3P-3s3S0 transition.
HF, H2O, CN- and their hydrogen-bonded complexes were studied using state-of-the-art ab initio quantum mechanical methods. A large Gaussian one particle basis set consisting of triple zeta plus double polarization plus diffuse s and p functions (TZ2P + diffuse) was used. The theoretical methods employed include self consistent field, second order Moller-Plesset perturbation theory, singles and doubles configuration interaction theory and the singles and doubles coupled cluster approach. The FH-CN- and FH-NC- and H2O-CN-, H2O-NC- pairs of complexes are found to be essentially isoenergetic. The first pair of complexes are predicted to be bound by approx. 24 kcal/mole and the latter pair bound by approximately 15 kcal/mole. The ab initio binding energies are in good agreement with the experimental values. The two being shorter than the analogous C-N hydrogen bond. The infrared (IR) spectra of the two pairs of complexes are also very similar, though a severe perturbation of the potential energy surface by proton exchange means that the accurate prediction of the band center of the most intense IR mode requires a high level of electronic structure theory as well as a complete treatment of anharmonic effects. The bonding of anionic hydrogen-bonded complexes is discussed and contrasted with that of neutral hydrogen-bonded complexes.
It was recently proposed that the Euclidian norm of the t sub 1 vector of the coupled cluster wave function (normalized by the number of electrons included in the correlation procedure) could be used to determine whether a single-reference-based electron correlation procedure is appropriate. This diagnostic, T sub 1, is defined for use with self consistent field molecular orbitals and is invariant to the same orbital rotations as the coupled cluster energy. T sub 1 is investigated for several different chemical systems which exhibit a range of multireference behavior, and is shown to be an excellent measure of the importance of nondynamical electron correlation and is far superior to C sub 0 from a singles and doubles configuration interaction wave function. It is further suggested that when the aim is to recover a large fraction of the dynamical electron correlation energy, a large T sub 1 (i.e., greater than 0.02) probably indicates the need for a multireference electron correlation procedure.
It was recently proposed that the Euclidian norm of the t(sub 1) vector of the coupled cluster wave function (normalized by the number of electrons included in the correlation procedure) could be used to determine whether a single-reference-based electron correlation procedure is appopriate. This diagnostic, T(sub 1) is defined for use with self-consistent-field molecular orbitals and is invariant to the same orbital rotations as the coupled cluster energy. T(sub 1) is investigated for several different chemical systems which exhibit a range of multireference behavior, and is shown to be an excellent measure of the importance of non-dynamical electron correlation and is far superior to C(sub 0) from a singles and doubles configuration interaction wave function. It is further suggested that when the aim is to recover a large fraction of the dynamical electron correlation energy, a large T(sub 1) (i.e., greater than 0.02) probably indicates the need for a multireference electron correlation procedure.
A recently proposed scheme for using natural orbitals from atomic configuration interaction (CI) wave functions as a basis set for linear combination of atomic orbitals (LCAO) calculations is extended for the calculation of molecular properties. For one-electron properties like multipole moments, which are determined largely by the outermost regions of the molecular wave function, it is necessary to increase the flexibility of the basis in these regions. This is most easily done by uncontracting the outmost Gaussian primitives, and/or by adding diffuse primitives. A similar approach can be employed for the calculation of polarizabilities. Properties which are not dominated by the long-range part of the wave function, such as spectroscopic constants or electric field gradients at the nucleus, can generally be treated satisfactorily with the original atomic natural orbital (ANO) sets.
Researchers determined the equilibrium geometries and binding energies of Be and Mg trimers, tetramers and pentamers using single and double excitation coupled cluster (CCSD) and complete active space self-consistent-field (CASSCF) multireference configuration interaction (MRCI) wave functions in conjunction with extended atomic basis sets. Best estimates of the cluster binding energies are 24, 83 and 110 kcal/mole for Be3, Be4 and Be5; and 9, 31 and 41 kcal/mole for Mg3, Mg4 and Mg5, respectively. A comparison of the MRCI and CCSD results shows that even the best single-reference approach (limited to single and double excitations) is not capable of quantitative accuracy in determining the binding energies of Be and Mg clusters.
An important goal of quantum chemical calculations is to provide an understanding of chemical bonding and molecular electronic structure. A second goal, the prediction of energy differences to chemical accuracy, has been much harder to attain. First, the computational resources required to achieve such accuracy are very large, and second, it is not straightforward to demonstrate that an apparently accurate result, in terms of agreement with experiment, does not result from a cancellation of errors. Recent advances in electronic structure methodology, coupled with the power of vector supercomputers, have made it possible to solve a number of electronic structure problems exactly using the full configuration interaction (FCI) method within a subspace of the complete Hilbert space. These exact results can be used to benchmark approximate techniques that are applicable to a wider range of chemical and physical problems. The methodology of many-electron quantum chemistry is reviewed. Methods are considered in detail for performing FCI calculations. The application of FCI methods to several three-electron problems in molecular physics are discussed. A number of benchmark applications of FCI wave functions are described. Atomic basis sets and the development of improved methods for handling very large basis sets are discussed: these are then applied to a number of chemical and spectroscopic problems; to transition metals; and to problems involving potential energy surfaces. Although the experiences described give considerable grounds for optimism about the general ability to perform accurate calculations, there are several problems that have proved less tractable, at least with current computer resources, and these and possible solutions are discussed.
In a crossed-beam experiment the electron-impact-induced fluorescence spectrum of N2 in the extreme ultraviolet is studied at a spectral resolution of up to 0.03 nm. The optically thin experiment obtained the highest-resolution electron-impact emission spectrum of the Rydberg and valence states of N2. The spectral measurements provide the emission cross sections of each of the vibrational transitions of the Carroll-Yoshino and the Birge-Hopfield-II band systems. Laboratory vibrational-excitation cross sections arising from the mutual perturbation of the c4-prime 1Sigma(+)u and b-prime 1Sigma(+)u states by homogeneous configuration interactions are measured from 10 to 400 eV, and a modified Born approximation analytic model is given for them. The analysis leads to accurate band-system oscillator strengths. The relative emission and excitation cross sections each of the vibrational levels are compared. In addition, low-resolution measurements of the cross section of the atomic dissociation fragments (NI, NII, NIII) from 40 to 102 nm are made, and medium-resolution measurements are made of the emission cross section of the c4 1Pi(u), c5-prime 1Sigma(+)u, c5 1Pi(u), and c6-prime 1Sigma(+)u to X 1Sigma(+)g (0,0) transitions.
The state of the art in ab initio molecular structure calculations is reviewed with an emphasis on recent developments, such as full configuration-interaction benchmark calculations and atomic natural orbital basis sets. It is found that new developments in methodology, combined with improvements in computer hardware, are leading to unprecedented accuracy in solving problems in spectroscopy.
The state of the art in ab initio molecular structure calculations is reviewed, with an emphasis on recent developments such as full configuration-interaction benchmark calculations and atomic natural orbital basis sets. It is shown that new developments in methodology combined with improvements in computer hardware are leading to unprecedented accuracy in solving problems in spectroscopy.
The equilibrium geometries and binding energies of Be and Mg trimers, tetramers and pentamers have been determined using single and double excitation coupled cluster (CCSD) and complete active space self-consistent-field (CASSCF) multireference configuration interaction (MRCI) wave functions in conjunction with extended atomic basis sets. The best estimates of the cluster binding energies are 24, 83, and 110 kcal/mol for Be3, Be4, and Be5; and 9, 31, and 41 kcal/mol for Mg3, Mg4, and Mg5, respectively. A comparison of the MRCI and CCSD results shows that even the best single-reference approach (limited to single and double excitations) is not capable of quantitative accuracy in determining the binding energies of Be and Mg clusters.
A recently proposed scheme for using natural orbitals from atomic configuration interaction wave functions as a basis set for linear combination of atomic orbitals (LCAO) calculations is extended for the calculation of molecular properties. For one-electron properties like multipole moments, which are determined largely by the outermost regions of the molecular wave function, it is necessary to increase the flexibility of the basis in these regions. This is most easily done by uncontracting the outermost Gaussian primitives, and/or by adding diffuse primitives. A similar approach can be employed for the calculation of polarizabilities. Properties which are not dominated by the long-range part of the wave function, such as spectroscopic constants or electric field gradients at the nucleus, can generally be treated satisfactorily with the original atomic natural orbital sets.
HF, H2O, CN- and their hydrogen-bonded complexes were studied using state-of-the-art ab initio quantum mechanical methods. A large Gaussian one particle basis set consisting of triple zeta plus double polarization plus diffuse s and p functions (TZ2P + diffuse) was used. The theoretical methods employed include self consistent field, second order Moller-Plesset perturbation theory, singles and doubles configuration interaction theory and the singles and doubles coupled cluster approach. The FH-CN- and FH-NC- and H2O-CN-, H2O-NC- pairs of complexes are found to be essentially isoenergetic. The first pair of complexes are predicted to be bound by approx. 24 kcal/mole and the latter pair bound by approximately 15 kcal/mole. The ab initio binding energies are in good agreement with the experimental values. The two being shorter than the analogous C-N hydrogen bond. The infrared (IR) spectra of the two pairs of complexes are also very similar, though a severe perturbation of the potential energy surface by proton exchange means that the accurate prediction of the band center of the most intense IR mode requires a high level of electronic structure theory as well as a complete treatment of anharmonic effects. The bonding of anionic hydrogen-bonded complexes is discussed and contrasted with that of neutral hydrogen-bonded complexes.
The present study of the singlet and triplet states of Al2 below about 30,000/cm at the multireference configuration-interaction level attempts to identify and characterize the band systems in both the singlet and triplet manifolds. The spectroscopy of Al2 can be understood in terms of an X 3Pi(u) ground state. Calculations suggest that the assignments of the E and F systems recently noted in a jet-cooled beam are correct, although remaining differences between theoretical and experimental spectroscopic constants and radiative lifetimes preclude a definitive assignment.
The harmonic frequencies of Be3 and Be4, evaluated by multireference configuration-interaction (MRCI) and singles and doubles coupled-cluster (CCSD) methods, are reported, as are IR intensities evaluated by using the double harmonic approximation. A comparison of the results shows that the CCSD method augmented with a correction for connected triple excitations, CCSD(T), can be a viable alternative to MRCI for determining the ground-state properties of small Be clusters (other than the dimer). Results of normal mode analyses indicate that the anharmonic vibrational frequencies of Be3 and Be4 are reasonably consistent at the CCSD, CCSD(T), or MRCI levels of treatment.
The ground and lower excited states of methyl peroxy, CH3O2, radical have been investigated at the selected pseudofirst-order configuration interaction level by use of a double-zeta basis set. Selected singles and doubles calculations using a polarized double-zeta basis have been carried out on the two lowest states in the A-double prime symmetry. Dissociation energies with respect to CH3O2 yields CH3 + O2 and CH3O + O are computed to be 2.01 and 3.37 eV, respectively. Curve crossings between various states and photodissociation products are discussed and the dipole moment along various slices through the potential energy surface is evaluated.
A theoretical study of the A 3Sigma(-)-X 3Pi infrared transition in SiC is presented using atomic natural orbital Gaussian basis sets in conjuction with multireference configuration interaction calculations. Dipole moment functions have been computed for both states as well as the A-X electronic transition moment function. The calculations predict that T(00) is 3700 + or - 200/cm, so that the transition recently observed in emission near 4500/cm and assigned to the 0-0 band of the A 3Sigma(-)-X 3Pi system of SiC is actually the 1-0 band.
The electron impact induced fluorescence spectrum of N2 is measured in the 102-134 nm range at a 0.05 nm spectral resolution. The spectral measurements provide the emission cross sections of the transitions of the b 1Pi(u)-X 1Sigma(+)g Birge-Hopfield I-band system. The structure and vibrational population distribution of this system are strongly affected by a configuration interaction of the valence b 1Pi(u) and Rydberg c 1Pi(u) and o 1Pi(u) states. The excitation function (0-400 eV) for the b-X (1,2) transition is measured and a modified Born approximation analytic model is applied to calculate the oscillator strength for the b 1Pi(u)-X band system. With the exception of the v-prime = 1 level, vibrational levels of the b 1Pi(u) state predissociate with a branching ratio of between 0.95 and 1.00. Predissociation of the b 1Pi(u) state contributes approximately six percent of the total dissociation cross section of N2 by electron impact at 100 eV.