A configuration interaction study of the valence shell photoelectron spectrum of argon

The detailed satellite structure of the photoelectron spectrum of the valence shell of Ar is investigated theoretically with correlated wavefunctions calculated by a configuration interaction technique using near Hartree-Fock numerical orbitals as a basis set. It is shown that, while the 3s²3p⁴ns,d ²S satellites gain intensity principally from mixing with the 3s3p⁶²S state, the 3s²3p⁴np²p^o satellites gain intensity principally from relaxation. The remaining structure can largely be explained in terms of the 3s²3p⁴ns,d ²D states, which gain intensity by initial state configuration interaction.     

The electronic spectrum of the SiC radical: A theoretical study

Electronic structure and spectroscopic properties of the low-lying electronic states of the SiC radical have been determined from the ab initio based configuration interaction calculations. Potential energy curves of 32 Λ-S states of singlet, triplet, and quintet spin multiplicities have been constructed. Spectroscopic constants (r_e, T_e, and ω_e) of 23 states within 6 eV are reported and compared with the existing data. The dipole moments (μ_e) of most of these states at their respective equilibrium bond lengths have been computed. Effects of the spin-orbit coupling on the spectroscopic properties of SiC have been studied. The E³Π state is found to be an important one which has not been studied before. A transition of the type E³Π-X³Π is predicted to take place in the range 25 000-26 000 cm⁻¹. The partial radiative lifetimes for several electric dipole allowed transitions such as A³Σ⁺-X³Π, B³Σ⁺-X³Π, C³Π-X³Π, D³Δ-X³Π, E³Π-X³Π etc. have been reported.     

Pressure induced configuration demixing in the electronic spectrum of NO

Previous low resolution studies indicated that, in the absorption spectrum, transitions to Rydberg states are far more sensitive to pressure than transitions to valence states in accordance with the complete vanishing of Rydberg bands and the deperturbation of the valence bands in the spectrum of NO trapped in a solid rare gas matrix. The present study of NO is the first extensive investigation of medium and high resolution molecular electronic spectra subjected to pressure of foreign gases. It is observed that, at the highest pressure attained (～1000 bar), almost all of the Rydberg bands have vanished whereas the remaining valence bands stay relatively sharp. While high pressure medium resolution spectra give information about the deperturbation of intensities and of vibrational spacings of the valence bands, inspection of low pressure high resolution spectra reveals that the rotational lines react to pressure in a way reflecting closely the degree of configuration mixing between Rydberg and valence states.     

Multireference configuration interaction study on spectroscopic properties of low-lying electronic states of As2 molecule

The potential energy curves (PECs) of four electronic states (X1Σ+g , e3△u , a 3 Σ-u , and d 3Πg ) of an As 2 molecule are investigated employing the complete active space self-consistent field (CASSCF) method followed by the valence internally contracted multireference configuration interaction (MRCI) approach in conjunction with the correlation-consistent aug-cc-pV5Z basis set. The effect on PECs by the relativistic correction is taken into account. The way to consider the relativistic correction is to employ the second-order Douglas-Kroll Hamiltonian approximation. The correction is made at the level of a cc-pV5Z basis set. The PECs of the electronic states involved are extrapolated to the complete basis set limit. With the PECs, the spectroscopic parameters (Te , Re , ωe , ωexe , ωeye , αe , βe , γe , and Be ) of these electronic states are determined and compared in detail with those reported in the literature. Excellent agreement is found between the present results and the experimental data. The first 40 vibrational states are studied for each electronic state when the rotational quantum number J equals zero. In addition, the vibrational levels, inertial rotation and centrifugal distortion constants of d 3Πg electronic state are reported which are in excellent agreement with the available measurements. Comparison with the experimental data shows that the present results are both reliable and accurate.     

The electronic spectrum of benzvalene

A detailed investigation of the electronic spectrum of benzvalene [tricyclo (3.1.0.0^2,6)hex-3-ene] in the vapor phase is reported. The spectrum appears to consist of two overlapping electronic transitions above 200 nm. The lower energy transition is broad and structureless, has an onset near 285 nm, and is assigned as ${}^1\text{B}{}_2\text{←}{}^1\text{A}{}_1$. The second transition, showing forbidden vibronic structure based on two false origins near 226 nm, is assigned ${}^1\text{A}{}_2\text{←}{}^1\text{A}{}_1$. The ¹A₂ state presumably arises from a $\text{σπ}{}^1$ configuration, which indicates significant ring strain and/or σ-π interaction. A one-state assignment of the spectrum is also possible.     

A further study on the electronic structure and spectrum of ethylene

Calculations on the lower electronic states, ionization potential and electron affinity of ethylene are carried out by a semi-empirical ASMO method including configuration interaction. The carbon-carbon sigma bonding electrons are explicitly included. One-centre quantities for ethylene, ethylene negative ion and ethylene positive ion are evaluated from atomic valence-state energies, taking account of changes in effective nuclear charges of the corresponding states. Two-centre electronic repulsion integrals are determined by interpolation between theoretical values for distant nuclear separations and one-centre repulsion integrals obtained; two-centre core integrals are computed purely theoretically. Good agreement between calculated and observed values is obtained. Although preferential stabilization of the ion cannot be expected from sigma-pi configuration interaction, it is shown that the reorganization of the electronic sub-structure of the atom upon ionization plays a significant role.     

The effect of spatial quantization of the electronic spectrum on the exchange interaction in multilayers

A strong influence of the quantization of the electronic spectrum of nonmagnetic spacers in multilayers is discovered on the dependence of the exchange interaction on the thickness of the spacer. It is shown that the antiferromagnetic dip is observed experimentally in Fe/Cr multilayers, as small thicknesses can be interpreted in terms of the simple RKKY approximation.     

The electronic spectrum of Dewar benzene

The electronic spectrum of Dewar benzene [bicyclo (2.2.0) hexa-2,5-diene] consists of two transitions above 185 nm. The lower energy transition is structureless and broad with a maximum at 205 nm. The other system begins around 200 nm and shows initially well-defined vibronic structure on a background of increasing continuous absorption, but becomes structureless by 185 nm. Arguments are presented that the two excited states involved in the spectrum are ¹A₂ arising from a $\text{π-π}{}^1$ excitation, and ¹B₁ from a $\text{σ-π}{}^1$ excitation involving the strained σ-bridge bond in Dewar benzene. The interrelationships both photochemical and photophysical of the (CH)₆ potential surface are discussed.     

The electronic spectrum of gaseous SnS

Observations of the spectrum of SnS excited in chemiluminescence have led to the characterization of two low-lying excited states of SnS, $\text{a}\text{Ω}\text{1(}{}^3\text{Σ}{}^{\mathrm{+}}\text{)}$, with T_e = 18 143.9 cm^?1, and $\text{A0}{}^{\mathrm{+}}\text{(}{}^3\text{Π}\text{)}$, with T_e = 22 021.3 cm^?1. Extended rotational analyses of the perturbed bands observed in the absorption spectrum enable assignments to be suggested for the components $\text{Ω}\text{0}{}^{\mathrm{+}}$ and 1 of ³Σ^? and $\text{Ω}\text{1}$ of ³Π.     

The electronic emission spectrum of SiB

The gas phase spectrum of the silicon boride radical has been observed for the first time. Two electronic transitions were observed in emission from a corona excited supersonic expansion source. The D⁴Σ⁻-X⁴Σ⁻ system consists of emission from v′ = 0 to v″ = 0-3, while the A⁴Π-X⁴Σ⁻ system consists of numerous bands with v′ = 0-5 and v″ = 0-11, although only the strong 0-0 and 0-1 bands have been analyzed so far.     

The electronic spectrum of silicon monotelluride radical

In the electronic spectrum of silicon monotelluride which has been produced in microwave discharges through sealed tubes, a large number of new bands belonging to theA ¹Π-X ¹Σ⁺ system (3100–3900 Å) and theE ¹Σ⁺-X ¹Σ⁺ system (2800–3100 Å) of Si¹³⁰Te has been observed. The vibrational structure analyses of these band systems have resulted in the determination of improved vibrational constants in all the three electronic states involved in these transitions. An error in the previous determination of the vibrational constants of theE ¹Σ⁺ state has been corrected. An upper limit for the dissociation energy of the silicon monotelluride has been determined to be 40,000 cm^?1.     

The electronic spectrum of a three-dimensional quasicrystal

The electronic spectrum of an icosahedral quasicrystal with a central-atom decoration of the Amman-Mackay network is investigated in the tight-binding approximation. The quasicrystal is described as a structural limit of the optimal cubic approximants with increasing period. The electronic spectra for the first four optimal cubic approximants do not contain the hierarchical gap structure which is typical for the Cantor set of the spectrum of a one-dimensional quasicrystal. At the same time, as the order of the approximant increases, the spectrum becomes singular throughout the entire energy scale. Pis’ma Zh. éksp. Teor. Fiz. 67, No. 8, 557–562 (25 April 1998) Published in English in the original Russian journal. Edited by Steve Torstveit.     

A study of the electronic excitation of he from grazing incidence ion-surface interaction

The neutralization of He⁺ at grazing incidence from a Ni(111) surface leads to excited states. The light emission from the 3d ³ D and 3d ¹ D states is studied as a function of the beam energy and angular parameters. The observed circular polarization dependence on the crystallographic surface directions is interpreted in terms of the Brillouin zone of the solid.     

A study of coplanar methylene dimerization by complete neglect of differential overlap with configuration interaction

Doubly degenerate configurations are incorporated to calculate the planar dimerization of methylenes; configuration interaction eliminates the singularities on the potential-energy curve, and the wave function for the lowest state in the presence of methylene interaction indicates that the reaction is allowed if the methylenes are in the³B₁ state.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 72–75, July, 1974.     

The electronic Raman spectrum of cobalt doped MgO

The energies of the ⁴T_1g states of Co²⁺ as a dilute substitutional impurity in MgO relative to the ground Λ_6g doublet have been found by low temperature Raman spectroscopy to be two Λ_8g states at 305 ± 3 cm^?1 and 930 ± 3 cm^?1; the remaining Λ_7g energy is predicted to be in the 980–1010 cm^?1 range the corresponding Λ_6g → Λ_7g Raman transition being weak and buried in the extensive two-phonon background. A second-order perturbation calculation which couples the spin-orbit states to both E_g and T_2g modes of vibration gives a weak but important Jahn-Teller stabilization energy for the Λ_8g states.     

The electronic spectrum of tantalum hydride and deuteride

The diatomic molecule tantalum hydride (TaH) and its isotopologue tantalum deuteride (TaD) have been detected for the first time by laser excitation spectroscopy. The gas-phase molecules were produced in a hollow cathode discharge. Two red-degraded bands, one arising from TaH at 636 nm and the other from TaD at 635 nm, have been recorded at sub-Doppler resolution by intermodulated fluorescence spectroscopy. A rotational analysis shows that both bands are Ω = 2←2 in character, with well-resolved Ω-doubling in the upper state of TaH. Analysis of the ¹⁸¹Ta magnetic dipole and electric quadrupole hyperfine structure reveals that the lower X³Φ₂ electronic state of the two transitions arises from a σ²πδ electronic configuration, in agreement with previous theoretical calculations. The bond length in the TaH X³Φ₂ (v = 0) level is found to be 1.756960(4) Å.     

Ab initio SCF CI study of the electronic spectrum of s-tetrazine

Configuration interaction (CI) studies of ground, n→ π* and π→ π* electronically excited states are reported for s-tetrazine. The first n→ π* singlet excited state (¹ B _3u ), which is responsible for the purple-red colour of the molecule, is calculated at 2·80 eV, compared to the experimental transition energy of 2·22–2·70 eV. The singlet-triplet split of the first n→ π* states (¹ B _3u and ³ B _3u states) is calculated to be 0·76 eV.

The interaction of nitrogen lone pair orbitals (n-orbitals) is studied in terms of the ordering of the n π* excited states and found that the SCF orbital ordering is qualitatively in accord with the ordering of the n π* excited states in the CI level.

The first π→ π* excited state (¹ B _2u ) is calculated at 5·99 eV, slightly above the observed range of absorption. Numerous other high-lying singlet states as well as the triplet states have been calculated and they are used to verify several proposals relating to the excited state dynamics in the photo-physical studies of s-tetrazine.