Rydberg states of SiBr

New uv absorption spectra have been observed for SiBr. Five Rydberg states are identified to the states $\text{(4sσ)}{}^2\text{Σ}{}^{\mathrm{+}}$, $\text{(5sσ)}{}^2\text{Σ}{}^{\mathrm{+}}$, $\text{(4pπ)}{}^2\text{Π}$, $\text{(3dπ)}{}^2\text{Π}$, and $\text{(3dδ)}{}^2\text{Δ}$ by comparison with SiF and SiCl. The ionization potentials of SiCl and SiBr have been determined for the first time, and were 6.82 and 6.67 eV, respectively.     

Rydberg states of carbon dioxide and carbon disulfide

The electronic absorption spectra of carbon dioxide and carbon disulfide have been reexamined. Model potential calculations have been used to calculate the energies of excited states in Rydberg approximation, and (npσ) and (npπ) Rydberg series have been assigned. For both molecules, the lowest excited ¹Π_g and ¹Π_u states are identified as Rydberg states. The lowest ${}^1\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ state is mainly Rydberg for CO₂, but contains some valence character for CS₂, There is no evidence for transitions to additional valence states of these symmetries.It is shown that $\text{LCAO}\text{MO}$ predictions about excited states can be misleading because of near-linear dependencies which arise in multicenter expansions. A consideration of the united atom orbitals for CO₂ and CS₂ predicts that there should be only the number of low-energy excited states which are found from the spectral analysis.     

Absorption spectrum of CO in the Hopfield helium continuum region: Rydberg bands converging to the X2Σ+ state of CO+ in the region 960–1080 Å

The high resolution absorption spectrum of CO has been reinvestigated in the Hopfield helium continuum region, particularly from 960 to 1080 Å. The Rydberg state 3pπE¹Π was extended to v = 2, and other Rydberg states, $\text{3dσ}{}^3\text{Σ}{}^{\mathrm{+}}$ and F¹Σ⁺, $\text{3dπ}{}^1\text{Π}$, and $\text{4sσ}{}^3\text{Σ}{}^{\mathrm{+}}$ and ¹Σ⁺, which are converging to the X²Σ⁺ ground state of CO⁺, have been identified. The rotational structures of only five bands among the observed ten Rydberg bands have been analyzed.     

Theoretical prediction of the vertical electronic spectrum of the C2H radical

The vertical transition energies and oscillator strengths from the $\text{X}\text{?}{}^2\text{Σ}{}^{\mathrm{+}}$ ground and $\text{A}\text{?}{}^2\text{Π}$ excited states of the ethynyl radical C₂H to all higher-lying states resulting from excitation out of π and σ into $\text{π}{}^1$ and $\text{σ}{}^1$ valence-shell MO's, respectively, as well as into 3s and 3p Rydberg species, are calculated by large-scale CI techniques. It is found that the first excited states all result from $\text{π → π}{}^1$ excitations (the lowest three with quartet character), and not from the 4σ → 5σ counterparts favored in the case of isoelectronic CN. This distinction can be explained on the basis of orbital stability differences caused by the effects of hydrogen mixing. The first six states of the C₂H⁺ ion are also treated, and the correspondence with the various associated Rydberg series is discussed. Dipole moments for the $\text{X}\text{?}{}^2\text{Σ}{}^{\mathrm{+}}$ and $\text{A}\text{?}{}^2\text{Π}$ states are also calculated.     

Rydberg series in the photoionization spectrum of Pd I

We present the first experimental investigation of the photoionization in Pd I using the synchroton radiation facility of the 800 MeV electron storage ring in Berlin (BESSY) and atomic beam technique. The experiments have been concentrated on the study of the Rydberg series of autoionizing levels $\text{4}\text{d}{}^9\text{(}{}^2\text{D}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{)n}\text{p}$ and nf which lie between the two 4d thresholds.     

New valence and Rydberg states of the P18O molecule

The absorption spectrum of the P¹⁸O molecule has been studied in the region 1650–1800 Å. The upper levels of the transitions are shown to be levels of new ²Π valence, ²Π Rydberg and ²Δ Rydberg states of the PO molecule. Most of the levels are perturbed; some of them are predissociated. The new valence state P²Π corresponds to a regular state of the electronic configuration $\text{σ}{}^2\text{π}{}^3\text{π}{}^{12}$ and the ²Π and ²Δ Rydberg states belong to the 5p, 3d, 4d complex series. Perturbations of the P²Π state are shown to arise from Rydberg ～ Non Rydberg interactions with states of same or different symmetry. The complexity of the interactions does not allow to carry out a deperturbation but a comparison with the data of the P¹⁶O molecule allows to give a vibrational assignment to the levels of the P²Π state.     

Absorption spectrum of naphthalene in rare-gas matrices

The absorption spectrum of naphthalene has been studied in rare-gas matrices (RGM). Molar extinction coefficients have been determined and oscillator strengths of various $\text{π}{}^1\text{-π}$ transitions deduced. Bands in the 6.5 to 7.1 eV region, some of which were previously observed and interpreted as members of an impurity exciton (Rydberg) series, have been assigned to a $\text{π}{}^1\text{-π}$ transition. The results are compared with the theoretical prediction.     

Energies and orbital sizes for some Rydberg and valence states of the nitrogen molecule

Accurate SCF computations are reported on the Rydberg states of N₂ of electron configurations $\text{---1π}{}_{\mathrm{u}}{}^3\text{2π}{}_{\mathrm{u}}$, $\text{---1π}{}_{\mathrm{u}}{}^3\text{3σ}{}_{\mathrm{u}}$, and ---3σ_g2π_g, also on the valence states of the configuration $\text{---1π}{}_{\mathrm{u}}{}^3\text{1π}{}_{\mathrm{g}}$. The Rydberg state calculations supplement those of Lefebvre-Brion and Moser. A comparison is made between the $\text{---1π}{}_{\mathrm{u}}{}^3\text{2π}{}_{\mathrm{u}}$ states and the parallel set of states of the $\text{1π}{}_{\mathrm{u}}{}^3\text{1π}{}_{\mathrm{g}}$ configuration. This comparison shows a sharp difference in the ¹Σ⁺ states of the two configurations, the ¹Σ⁺ state being very high in the latter but relatively low in the former configuration. Recknagel coefficients are given for the several states of the two configurations; as expected, these are much smaller for the $\text{1π}{}_{\mathrm{u}}{}^3\text{2π}{}_{\mathrm{u}}$ configuration. Also, the ¹Δ state is relatively lower for the latter configuration.     

The five-nucleon system above the three-particle threshold

Compound nucleus states in ${}^5\text{Li}$ and ${}^5\text{He}$ have been investigated with the ${}^3\text{He(d,p)pt}$ and ${}^3\text{H(d,n)pt}$ three-particle reactions. The observed $\text{J}{}^{\mathrm{\pi }}\text{=}\text{3}\text{2}{}^{\mathrm{?}}$ states (E_X≈20 MeV) can be understood, in analogy to the ground states of the A=5 system, by coupling a $\text{p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ nucleon to the first 0⁺ excited state of ${}^4\text{He}$.     

Molecular Rydberg transitions: Cyanogen chloride

The electronic absorption spectrum of cyanogen chloride has been investigated in the range 2200-1250 Å. The first s-Rydberg transitions, $\text{X}\text{?}{}^1\text{Σ}{}^{\mathrm{+}}\text{→}{}^3\text{Π}{}_1$ and $\text{X}\text{?}{}^1\text{Σ}{}^{\mathrm{+}}\text{→}{}^1\text{Π}{}_1$ have been assigned, and analyzed to yield exchange and spin-orbit coupling parameters. The relative intensities of these two transitions have been shown to accord with an intermediate coupling situation. The $\text{π → π}{}^1$ intravalence excitations, leading to ^1.3(Σ^?, Δ and Σ⁺) states, have been discussed. It has been shown that one or both of the ¹Σ^? and ¹Δ states have bent geometries and that the ¹Σ⁺ state is located (tentatively) at 79 755 cm^?1. Two $\text{σ → π}{}^1\text{π → σ}{}^1$ states have been assigned, one at 56 340 cm^?1, the other at 74 450 cm^?1. The latter assignment is tentative, being largely based on observed vibronic interferences between the $\text{X}\text{?}{}^1\text{Σ}{}^{\mathrm{+}}\text{→}{}^1\text{Π}{}_1$ transition and the 74 450 cm^?1 transition. A considerable amount of vibrational oscillator strength and quantum defect data is presented.     

Stereoelectronic properties of photosynthetic and related systems: Ab initio configuration interaction calculations on the ground and lower excited singlet and triplet states of magnesium chlorin and chlorin

Ab initio configuration interaction wavefunctions and energies are reported for the ground state and many low-lying singlet and triplet states of magnesium chlorin and chlorin, and are employed in an analysis of the electronic absorption spectra of these systems.In chlorin, the calculated visible spectrum consists of two ${}^1\text{(π, π}{}^1\text{)}$ states, the lower energy, y-polarized state exhibiting moderate absorption intensity in contrast to the very weak absorption of the higher energy x-polarized state. The configurational composition of both states is well described by the four-orbital model. Five ${}^1\text{(π, π}{}^1\text{)}$ states are responsible for the Soret band envelope. A moderately intense y-state lies under the low energy edge of the band envelope, while two x-polarized states of moderate and strong intensity, respectively, are responsible for the band maximum. The final two ${}^1\text{(π, π}{}^1\text{)}$ states lie at the high energy edge of the Soret band and introduce a measure of asymmetry into the band envelope. Two ${}^1\text{(n, π}{}^1\text{)}$ states of very weak oscillator strength are also found in this region of the spectrum. All the Soret states are of complex configurational composition, and several of the higher lying states contain contributions from doubly excited configurations.The calculated visible spectrum of magnesium chlorin also consists of two ${}^1\text{(π, π}{}^1\text{)}$ states, with the weakly absorbing x-polarized state lying approximately 200 cm^?1 lower in energy than the moderately intense y-polarized state. The configurational composition of both states is well described by the four-orbital model. Four ${}^1\text{(π, π}{}^1\text{)}$ states constitute the bulk of the intensity in the Soret band envelope. In distinction to chlorin, the moderately intense ${}^1\text{(π, π}{}^1\text{)}$ state at the low energy edge of the band envelope is x-polarized. Two intense ${}^1\text{(π, π}{}^1\text{)}$ states of y- and x-polarization, respectively, constitute the band maximum region, and a single x-polarized state of moderately strong intensity can be assigned to the high energy shoulder of the band envelope. Two other weakly absorbing ${}^1\text{(π, π}{}^1\text{)}$ states are also found in this region, along with another weakly absorbing state of mixed in-plane and out-of-plane polarization. No clearly defined ${}^1\text{(n, π}{}^1\text{)}$ states are observed. As was the case for chlorin, all the Soret states are of complex configurational composition, and some of the higher energy states contain significant contributions from doubly excited configurations.Chlorin and magnesium chlorin both possess three ${}^3\text{(π, π}{}^1\text{)}$ states which lie below S₁ and a single ${}^3\text{(π, π}{}^1\text{)}$ which lies slightly above S₂. All four of the low-lying ${}^3\text{(π, π}{}^1\text{)}$ states in each molecule are well described by the four-orbital model, with T₁ being essentially a single configuration in each case. The remainder of the ${}^3\text{(π, π}{}^1\text{)}$ states are clustered in the same energetic region as the comparable ${}^1\text{(π, π}{}^1\text{)}$ Soret states, with comparably complex configurational compositions.Dipole moments and charge distributions for low-lying singlet and triplet states are also reported, and are used to rationalize chemical reactivity characteristics.     

The 6Li-induced three-nucleon transfer reaction on 40Ca

Analog (fp)³ states preferentially excited in the ${}^{40}\text{Ca}\text{(}{}^6\text{Li,t}\text{)}{}^{43}\text{Ti}$ and the ${}^{40}\text{Ca}\text{(}{}^6\text{Li}\text{, τ)}{}^{43}\text{Sc}$ reactions have been identified in the mass 43 mirror nuclei. A simple zero-range DWBA calculation made with a cluster form factor gives good agreement with the measured angular distributions, but spectroscopic strengths deduced for mirror levels do not agree. The 3p-0h states are excited with a rather uniform cross section not strongly correlated with spins.     

Rotational bands in 195, 197Tl

High-spin states in ^{195, 197}Tl have been populated with (α, xn) reactions and studied by means of in-beam γ-ray and e^? spectroscopic methods. Complementary studies of the decay of ^{195, 197}Pb to ^{195, 197}Tl have been carried out. Several new features have been observed in these nuclei. The $\text{9}\text{2}{}^{\mathrm{?}}$ bands of ^{195, 197}T1. extended to $\text{27}\text{2}{}^{\mathrm{(?)}}$ and $\text{29}\text{2}{}^{\mathrm{(?)}}$, respectively, show a quenching of energy spacings between the $\text{23}\text{2}{}^{\mathrm{?}}$, $\text{25}\text{2}{}^{\mathrm{?}}$, $\text{27}\text{2}{}^{\mathrm{(?}}$ and $\text{29}\text{2}{}^{\mathrm{(?}}$ states. This has been interpreted as resulting from the coupling of a $\text{h}{}_{\mathrm{<mtext>9</mtext><mtext>2</mtext>}}$ proton to the ($\text{π}\text{h}{}^{\mathrm{?2}}{}_{\mathrm{<mtext>11</mtext><mtext>2</mtext>}}\text{)}{}_{\mathrm{8+,\; 10+}}$ configurations in the core nuclei ^{194, 196}Hg. Furthermore, positive-parity bands based on $\text{15}\text{2}{}^{\mathrm{+}}$ states were established up to the $\text{35}\text{2}{}^{\mathrm{(+)}}$ and $\text{29}\text{2}{}^{\mathrm{(+)}}$ states in ^{195, 197}Tl respectively. Probably these bands originate from the coupling of a h${}_{\mathrm{<mtext>9</mtext><mtext>2</mtext>}}$ proton to a broken neutron pair. This pair consists of a rotation-aligned $\text{i}{}_{\mathrm{<mtext>13</mtext><mtext>2</mtext>}}$ neutron and a low-j neutron in the $\text{P}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$, $\text{P}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ or $\text{f}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}$ shell. It is known to constitute the 5^? bands in ^{194, 196}Hg.     

Predissociation and Λ-doubling in the even-parity Rydberg states of the nitrogen molecule

Predissociations in the y¹Π_g and $\text{x}{}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{?}}$ Rydberg states of N₂ (configurations $\text{1π}{}_{\mathrm{u}}{}^{\mathrm{?1}}\text{4pσ}$ and $\text{1π}{}_{\mathrm{u}}{}^{\mathrm{?1}}\text{3pπ}$, respectively) and their likely causes, are discussed. Peaking of rotational intensity at unusually low J values, without sharp breaking off, is interpreted as due to case c^? or case cⁱ predissociation. Λ doubling in the y state, attributed to interactions with the $\text{x}{}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{?}}$ state and with another, ¹Σ⁺, state of the same electron configuration as x, is analyzed. From this analysis the location of the (unobserved) ${}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$ state, here labeled x′, is obtained. It is concluded that the predissociation in the Π⁺ levels of the y state is an indirect one mediated by the interaction with x′ coupled with predissociation of x′ by a ${}^3\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{?}}$ state dissociating to ${}^4\text{S +}{}^2\text{P}$ atoms: combined, however, with perturbation of the y state by the k¹Π_g Rydberg state (configuration $\text{3σ}{}_{\mathrm{g}}{}^{\mathrm{?1}}\text{4dπ}$), whose Π⁺ levels are completely predissociated.     

Lifetimes of the Si I 3p4s 1P1 and 3p3d 1P1 states

A beam of metastable silicon atoms was produced by collisional dissociation of silicon molecules and selectively excited by a pulsed dye laser. The lifetimes of the excited Si I states were directly determined from the fluorescence decay curve: $\text{τ(3p4s}{}^1\text{P}{}_1\text{) = 4.1 (4) ns}$, $\text{τ(3p4s}{}^3\text{P}{}_2\text{) = 4.4 (4) ns}$, $\text{τ(3p3d}{}^1\text{P}{}_1\text{) = 8.1(5) ns}$.     

Analyzing power in two-neutron stripping reactions

Analyzing powers have been measured for six states from the ${}^{208}\text{Pb(}\text{t}\text{, p)}{}^{210}\text{Pb}$ reaction and seven states from the ${}^{90}\text{Zr(}\text{t}\text{, p)}{}^{92}\text{Zr}$ reaction. These studies were performed with a beam from a new polarized triton source, and the reaction protons were detected in a Q3D spectrometer. The analyzing powers and differential cross sections are adequately described by DWBA calculations for both the medium and heavy targets up through L-transfers of 4. Above this value, some disagreement is seen.     

Luminescence and biexcitons in nitrogen crystals

We have studied vacuum ultraviolet luminescence spectra of nitrogen crystals at different excitation densities. Forbidden transitions from three singlet states $\text{a}{}^1\text{Π}{}_{\mathrm{g}}\text{, a'}{}^1\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{?}}\text{,}\text{and}\text{w}{}^1\text{Δ}{}_{\mathrm{u}}$, have been observed. A non-linear dependence of luminecence of the excitation intensity has been found. A characteristic feature of the singlet transitions observed is a fine structure of vibronic bands. The luminescence spectra of pure crystalline nitrogen is compared with those of impurity luminescence of solid solutions N₂—Ar. The nature of singlet luminescence of nitrogen crystals is discussed proceeding from the two-particle radiation mechanism.     

Observation of Dicke superradiance at 1.30 μm in atomic Tl vapor

Dicke superradiance in the 1.30-μm $\text{7}{}^2\text{P}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{→ 7}{}^2\text{S}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ transition in Tl vapor has been induced by a 379.1-nm pulsed dye laser. Superradiant delays of up to 12 nsec have been observed.     

Spin measurements and reaction mechanism in the inelastic scattering of 18O on 12C

The alpha-decay of states in ¹⁸O have been studied in the inelastic scattering reaction ${}^{12}\text{C}\text{(}{}^{18}\text{O}\text{,}{}^{18}\text{O}{}^1\text{→}{}^{14}\text{C}\text{-α)}$ at 82 MeV. The double differential cross sections have been analysed with a strong absorption model. A systematic dependence of emission angle on spin is observed, allowing the determination of the transferred angular momentum.