Electronic spectrum of 1,5-naphthyridine: Crystal spectra

Polarized spectra (4 K) of the following systems are recorded in the region 26 000 – 29 000 cm^?1 ($\text{π}{}^1\text{← n}$ transition): 1,5-naphthyridine-d₀ in durene, p-xylene, neat crystal and naphthalene; 1,5-naphthyridine-d₆ in durene and in naphthalene. The spectra in naphthalene differ radically from the others, which resemble the vapor spectrum in being built principally upon two main origins interpreted as the true origin 0 and a vibronic origin (6a_u)₀¹ near 0 + 183 cm^?1 (0 + 163 cm^?1, -d₆). The favored interpretation of the naphthalene spectrum, which is polarized in the molecular plane, invokes an origin (L-polarized), but (6a_u)₀¹ is missing, and there are then three further vibronic origins, each with distinctive polarization at 0 + 309, 0 + 362, 0 + 516 cm^?1 (-d₀), 0 + 312, 0 + 384, 0 + 492 cm^?1 (-d₆). The changed appearance of the spectrum in naphthalene is attributed to a diminution, because of an increased spacing between the interacting states, of the strong vibronic coupling which is considered to exist between the n, $\text{π}{}^1$ state and two higher π, $\text{π}{}^1$ states.     

Electronic spectra of azanaphthalenes: Solid state spectra of cinnoline and quinazoline

The first electronic absorption region ($\text{π}{}^1\text{← n}$) of cinnoline has been measured in durene and naphthalene as host crystals at 4 K and of quinazoline likewise in durene, naphthalene, and the pure crystal. The $\text{π}{}^1\text{← n}$ region is analyzed as a single transition in both cases in agreement with prior vapor studies, but all the spectra are complicated by the presence of at least two inequivalent sites with site splittings as large as 450 cm^?1. In one instance (quinazoline in naphthalene) polarization ratios permit the conclusion that the two observed site spectra correspond to the two alternative placements of the guest molecule in a vacancy in the host lattice. Site and host dependent effects are documented on phonon activity, vibrational frequencies, polarization ratios, and the incidence of vibronic (Herzberg-Teller) activity.The salient properties of the first $\text{π}{}^1\text{← π}$ absorptions of both molecules and of the $\text{π}{}^1\text{→ π}$ phosphorescence of quinazoline are briefly noted.     

Electronic spectrum of 1,5-naphthyridine: Vapor spectra

Analyses of the vapor spectra of 1,5-naphthyridine-d₀ and -d₆ are presented. The spectra are characterized by two principal origins, one the true electronic origin, magnetic dipole allowed, ${}^1\text{B}{}_{\mathrm{g}}\text{←}{}^1\text{A}{}_{\mathrm{g}}$, 27 598.5 cm^?1 (-d₆ 27 676.9), and the other a vibronic origin, electricd-dipole allowed, corresponding to the activity of a low-frequency vibration 6a_u, 183 cm^?1 (-d₆ 163). Extensive sequence structure is evident and the relative intensities of the sequence bands associated with the two origins provide the strongest argument for their assignments. The absence of 6a_u as a major source of intensity in the hot bands is in agreement with vibronic coupling calculations which propose that in absorption intensity “flows” to the lower-frequency vibrations.     

Kerr-effect and dielectric tensor elements of magnetite (Fe3O4) between 0.5 and 4.3 eV

The complex polar Kerr effect (rotation and ellipticity) of magnetite single crystals has been measured at room temperature between 0.5 and 4.3 eV. From the magneto-optical data and the optical constants, the off-diagonal elements (?_xy) of the dielectric tensor has been derived. Three well separated magneto-optical transitions have been indentified. At about 0.75 eV one strong magneto-optical structure with a diamagnetic line shape is assigned to a $\text{3d}{}^6\text{→3d}{}^5\text{(}{}^6\text{A}{}_{\mathrm{1g}}\text{) 4s}$ transition from Fe²⁺ in octahedral sites. Two other structures with paramagnetic line shapes near 1.85 and 2.90 eV are assigned to the orbital promotion processes $\text{3d}{}^6\text{(Fe}{}^{\mathrm{2+}}{}_{\mathrm{oct}}\text{)→3d}{}^5\text{(}{}^4\text{T}{}_{\mathrm{1g}}\text{) 4s}$ and $\text{3d}{}^5\text{(Fe}{}^{\mathrm{3+}}{}_{\mathrm{tet}}\text{)→3d}{}^4\text{(}{}^5\text{T}{}_2\text{) 4s}$, respectively, which take into account Fe 3d^n?1 final state effects.     

Forbidden pure rotational Raman spectra of C3v and Td molecules

Some of the pure rotational Raman transitions of polyatomic molecules that are forbidden according to rigid rotor selection rules may acquire intensity by a centrifugal distortion mechanism. These are analogous to forbidden rotational electric dipole transitions which recently have been studied extensively (1–6). A simple technique to obtain the intensity factors leading to the line strengths of such Raman transitions is presented. The intensity factors $\text{b}{}_{\mathrm{J\prime k\prime }}{}^{\mathrm{Jk}}$ and $\text{b}{}_{\mathrm{J\prime }}{}^{\mathrm{J}}$ of the Q, R, and S branches of molecules with C_3v and T_d symmetry are obtained. For C_3v molecules, in addition to the usual selection rules for J, those for k are found to be Δk = ±3 and ±6. There is a modification of intensity of the normally allowed Δk = 0 transitions. T_d molecules, which normally do not have pure rotational spectra, now give rise to weak Raman transitions due to centrifugal distortion.     

Absolute vacuum ultraviolet absorption spectra of some gaseous azabenzenes

Absolute extinction coefficient and oscillator strength of pyridine, pyrimidine, pyrazine, and s-triazine were recorded with moderate resolution in the region of 3.5–9.5 eV. Analogous to ${}^1\text{A}{}_{\mathrm{<mtext>1</mtext><mtext>g</mtext>}}\text{→}{}^1\text{B}{}_{\mathrm{<mtext>2</mtext><mtext>u</mtext>}}$, ¹B_1u, ${}^1\text{E}{}_{\mathrm{<mtext>1</mtext><mtext>u</mtext>}}\text{π → π}{}^1$ transitions of benzene, several $\text{n → π}{}^1$ and Rydberg transitions are presented and discussed.     

Excited vibrational state microwave spectra,structure, and force-field of trifluorosilane

The J = 2?1 microwave spectrum of six isotopic species of HSiF₃ has been observed and assigned in excited states of five of the six fundamental vibrations. The assignment is based on relative intensities, double resonance experiments, and trial anharmonic force constant calculations. Analysis of the spectra leads to experimental values for five of the $\text{α}{}_{\mathrm{r}}{}^{\mathrm{B}}$ constants, all three l-doubling constants q_t, one Fermi resonance constant φ₂₃₃, and one zeta constant $\text{ζ}{}_{\mathrm{6,\; 6}}{}^{\mathrm{(z)}}$.The harmonic force field has been refined to all the available data on vibration wavenumbers, centrifugal distortion constants, and zeta constants. The cubic anharmonic force field has been refined to the data on $\text{α}{}_{\mathrm{r}}{}^{\mathrm{B}}$ and q_t constants, using two models: a valence force model with two cubic force constants for SiH and SiF stretching, and a more sophisticated model. With the help of these calculations, the following equilibrium structure has been determined: $\text{r}{}_{\mathrm{e}}\text{(}\text{SiH}\text{) = 1.4468(±5)}\text{A}\text{?}$, $\text{r}{}_{\mathrm{e}}\text{(}\text{SiF}\text{) = 1.5624(±1)}\text{A}\text{?}$, ∠HSiF = 110.64(±3)°,     

The A-dependence of J/ψ-particle inclusive distributions

The differential cross sections $\text{d}\text{σ}\text{d}\text{x}$ and $\text{d}\text{σ}\text{d}\text{p}{}_{\mathrm{t}}{}^2$ of inclusive J/ψ production by 43 GeV/c π^? off Be, Cu and W nuclei have been measured. Fitting $\text{d}\text{σ}\text{d}\text{p}{}_{\mathrm{t}}{}^2\text{～ A}{}^{\mathrm{\alpha }}\text{(p}{}_{\mathrm{t}}{}^2\text{)}$ we observed the increase of α with p_t².     

Interpretation of electronic spectra by configuration analysis: Absorption spectra of monosubstituted naphthalenes

The electronic absorption spectra of four monosubstituted naphthalenes, α-, β-naphthols, and α-, β-naphthylamines have been investigated by means of configuration analysis with particular attention to the dependence of spectra on the position of substitution and on the electron-donating power of the substituent. The results of molecular orbital calculations based on the Pariser-Parr-Pople method are analyzed in terms of locally excited states and intramolecular charge-transfer configurations. The characteristic changes in location and polarization of the L_b, L_a, and B_b bands caused by substitution at the α- or β-position are adequately explained by the analysis. Two strong absorption bands of α-substituted naphthalenes, which appear in place of the B_b band of naphthalene, are shown to result from a mixing of the $\text{B}{}_{\mathrm{3u}}{}^{\mathrm{+}}\text{(B}{}_{\mathrm{b}}\text{)}$ and $\text{A}{}_{\mathrm{g}}{}^{\mathrm{?}}$ states. The amino group exerts a great influence on the electronic structure of the parent molecule, so that the B_b band cannot be identified in the spectrum of β-naphthylamine.     

Laser excitation spectra of He2

Metastable $\text{a(2sσ)}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ He₂ molecules are produced by a dc discharge in a flowing He stream. Laser excitation downstream of the discharge produces excitation spectra for a number of He₂ states. LIF spectra are observed for the $\text{(npπ)}{}^3\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$ series for n = 4–9, excepting 5 and the $\text{(npπ)}{}^3\text{Π}{}_{\mathrm{g}}$ series for n = 5–15.     

“Forbidden” rotational spectra of symmetric-top molecules: PH3 and PD3

A millimeter-wave spectrometer having a sensitivity of 4 × 10^?10 cm^?1 in the 2-mm region has been constructed for observation of extremely weak millimeter-wave spectra of gases. It has been used to measure J → J, K = 0 ← 3 transitions in PH₃ and J → J, K = 0 ← 3 as well as K = ±1 ← ±4 transitions in PD₃. The B₀ and C₀ spectral constants (in MHz) are: for PH₃, B₀ = 133 480.15 ± 0.12 and C₀ = 117 488.85 ± 0.16; for PD₃, B₀ = 69 471.10 ± 0.03 and C₀ = 58 974.37 ± 0.05. The effective ground-state values obtained for the bond angle and bond length are: for PH₃, $\text{r}{}_0\text{(}\text{A}\text{?}\text{) = 1.420}{}_0$ and $\text{α}{}_0\text{(}{}^{\mathrm{o}}\text{) = 93.34}{}_5$; for PD₃, $\text{r}{}_0\text{(}\text{A}\text{?}\text{) = 1.417}{}_6$ and $\text{α}{}_0\text{(}{}^{\mathrm{o}}\text{) = 93.35}{}_9$. The corresponding zero-point-average values were calculated to be: for PH₃, $\text{r}{}_{\mathrm{z}}\text{(}\text{A}\text{?}\text{) = 1.4269}{}_9\text{± 0.0002}$ and $\text{α}{}_{\mathrm{z}}\text{(}{}^{\mathrm{o}}\text{) = 93.228}{}_7$; for PD₃, $\text{r}{}_{\mathrm{z}}\text{(}\text{A}\text{?}\text{) = 1.4226}{}_5\text{± 0.0001}$ and $\text{α}{}_{\mathrm{z}}\text{(}{}^{\mathrm{o}}\text{) = 93.256}{}_7\text{± 0.004}$. For both species, the equilibrium values are $\text{r}{}_{\mathrm{e}}\text{(}\text{A}\text{?}\text{) = 1.4115}{}_9\text{± 0.0006}$ and $\text{α}{}_{\mathrm{e}}\text{(}{}^{\mathrm{o}}\text{) = 93.32}{}_8\text{± 0.02}$.     

The reactions K−p → K1− + nucleon at 3.13 and 3.3 GeV/c

Results are presented of a 12 event/μb bubble-chamber experiment; the reactions discussed in detail are $\text{K}{}^{\mathrm{?}}\text{p}\text{→}\text{K}{}^1\text{(890)}{}^{\mathrm{?}}\text{p, K}{}^1\text{(1420)}{}^{\mathrm{?}}\text{p and K}{}^1\text{(890)}{}^{\mathrm{?}}\text{Δ}{}^{\mathrm{+}}$.The K¹ (890)^?p channel is dominated by the forward peak. The suggestion of flattering at cos θ = 1 is more pronounced in $\text{(?}{}_{11}\text{+ ?}{}_{\mathrm{1?1}}\text{)}\text{d}\text{σ}\text{d}\text{t}$; which is mainly natural-parity exchange. Pseudoscalar exchange contributes to $\text{?}{}_{00}{}^{\mathrm{J}}\text{d}\text{σ}\text{d}\text{t}$; this is more sharply peaked in t. The value of $\text{(?}{}_{11}\text{? ?}{}_{\mathrm{1?1}}\text{)}\text{d}\text{σ}\text{d}\text{t}$ is somewhat larger than the upper limit from the dominant natural-parity exchange. There is significant structure in $\text{?}{}_{00}{}^{\mathrm{H}}\text{d}\text{σ}\text{d}\text{t}\text{at}\text{t ≈ ?0.6 (}\text{GeV}\text{/c)}{}^2$.The K¹ (1420)^?p channel is much more pronounced at 3.3 GeV/c than at 3.13 GeV/c, but is not markedly peripheral. The width of the K¹ (1420) in the 3.3 GeV/c data is 42 ± 12 MeV/c².The cross section for $\text{K}{}^{\mathrm{1?}}\text{Δ}{}^{\mathrm{+}}$ agrees with that expected from $\text{K}{}^{\mathrm{+}}\text{p}\text{→}\text{K}{}^1\text{Δ}$, assuming a single t-channel exchange. Our measured density matrix elements are consistent with a strong pseudoscalar exchange.     

Magnetic circular dichroism of transition metal ions in solids—II K2NaGaF6: Cr3+

The absorption and MCD spectra of the ${}^4\text{A}{}_{\mathrm{2g}}\text{→}{}^4\text{T}{}_{\mathrm{2g}}$, ${}^4\text{A}{}_{\mathrm{2g}}$, ${}^4\text{A}{}_{\mathrm{2g}}\text{→}{}^4\text{T}{}_{\mathrm{1g}}{}^{\mathrm{a}}$ and ${}^4\text{A}{}_{\mathrm{2g}}\text{→}{}^4\text{T}{}_{\mathrm{1g}}{}^{\mathrm{b}}$ spin-allowed transitions of Cr³⁺ in K₂NaGaF₆ are reported. It is shown that transitions to the ${}^4\text{T}{}_{\mathrm{1g}}$. states are induced by T_1u vibratio the other spin-allowed transition, ${}^4\text{A}{}_{\mathrm{2g}}\text{→}{}^4\text{T}{}_{\mathrm{2g}}$, there are three competing intensity mechanisms: electric dipole induced by T_1u vibrations, electric dipole induced by T_2u vibrations and magnetic dipole, and an estimate is made of the relative importance of these. The magnetic dipole ${}^4\text{A}{}_{\mathrm{2g}}\text{→}{}^2\text{E}{}_{\mathrm{g}}$ zero-phonon line is observed to be accompanied by a vibrational sideband for which the coupling is predominantly with T_2u vibrations. Other weak transitions are observed in MCD spectra and their origin briefly discussed.     

Laser magnetic resonance spectrum of BrO (2Π12 ← 2Π32)

Magnetic dipole transitions between the ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ components of the ground electronic state of BrO have been detected using the technique of laser magnetic resonance on three CO₂ laser lines between 964 and 970 cm^?1. This is the first direct observation of the ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ state in BrO. The spin-orbit splitting parameter, A, is determined to be ?967.9831(2) cm^?1 for ⁷⁹Br¹⁶O and ?967.9981(2) cm^?1 for ⁸¹Br¹⁶O. Accurate values for the rotational constant $\text{B}{}^{\mathrm{<mtext>eff</mtext>}}\text{(}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{)}$, the hyperfine parameters ($\text{b}{}_{\mathrm{F}}\text{+}\text{2c}\text{3}$) and d, the Λ-doubling parameter p, and the Zeeman parameter g| are also determined from an analysis of the measured spectra.     

Noncoplanar correlation spectra from the 2H(p, 2p)n reaction at Einc = 44.9 MeV

The differential cross section $\text{d}{}^3\text{σ/}\text{d}\text{Ω}{}_3\text{d}\text{Ω}{}_4\text{d}\text{E}{}_3$ for the ²H(p, 2p)n reaction at E_inc = 44.9 MeV is measured in noncoplanar geometry. The Amado model in general gives a good fit to the absolute cross section. The dependence of the cross section on the momentum of the undetected particle Q₅, on the scattering angle θ₃₄, as well as on the angle of the undetected particle is investigated.     

The microwave spectrum of MnO3F

The microwave spectrum of MnO₃F has been remeasured and several corrections and new results have been obtained: B₀ = 4129.141 MHz, D_J = 1.12 kHz, D_JK = 1.87 kHz; $\text{α}{}_3{}^{\mathrm{B}}\text{= 8.622}$, $\text{α}{}_5{}^{\mathrm{B}}\text{= ? 11.994}$, $\text{α}{}_6{}^{\mathrm{B}}\text{= 6.042}$, |q₅| = 16.005, and |q₆| = 8.456 MHz.     

Vibrational spectra and force constants of symmetric tops: High resolution spectra of monoisotopic H3SiCl in the 2200-cm−1 region and rovibrational analysis of the ν1 and ν4 fundamentals

The gas phase infrared spectra of monoisotopic H₃Si³⁵Cl and H₃Si³⁷Cl have been studied in the $\text{ν}{}_1\text{ν}{}_4$ region near 2200 cm^?1 with a resolution of 0.012 and 0.04 cm^?1, respectively, and rotational fine structure for ΔJ = ±1 branches has been resolved. In addition, some information on ν₃ + ν₄ of H₃Si³⁵Cl near 2750 cm^?1 has been obtained. ν₁ and ν₄ are weakly coupled by Coriolis x, y resonance, $\text{B}\text{Ω}{}_{14}\text{ζ}{}_{14}\text{～ 2 × 10}{}^{\mathrm{?3}}\text{cm}{}^{\mathrm{?1}}$, only the upper states K′ = 2, l = 0 and K′ = 1, l = ?1 being substantially affected. Local perturbation due to rotational l(±1, ±1)-type resonance with ν₃ + ν₅⁺¹ + ν₆⁺¹ and ν₃ + ν₅⁺¹ + ν₆^?1 is revealed in the ΔK = +1 and ?1 branches, respectively. From a fit of the experimental line positions, standard deviations of 1.4 and 3.8 × 10^?3 cm^?1, respectively, to a model with five interacting levels conventional excited state parameters and interaction constants have been obtained. In $\text{H}{}_3\text{Si}{}^{35}\text{Cl}\text{H}{}_3\text{Si}{}^{37}\text{Cl}$ the fundamentals are ν₁, $\text{2201.94380(15)}\text{2201.9345(7)}$ and ν₄, $\text{2209.63862(8)}\text{2209.6254(2)}\text{cm}{}^{\mathrm{?1}}$, respectively. Q branches of the “hot” band (ν₃ + ν₄) ? ν₃ and of ν₄ of the ²⁹Si and ³⁰Si species have been detected.     

Electronic spectra of azanaphthalenes. Mixed crystal spectra of 1,6-naphthyridine-d6, cinnoline-d6, and quinoline-d7

The electronic spectra of 1,6-naphthyridine-d₆, cinnoline-d₆, and quinoline-d₇ have been recorded. For each molecule only one $\text{n,π}{}^1$ singlet state is identified and the spectral analyses proposed are in close correspondence to those reported for the fully protonated species. Features of particular interest are the reduced prominence of sites and the many instances of crystal induced coupling of vibronic bands.     

Some effects of spin-orbit interaction on rotational levels and rotational line intensities in vibrationally unexcited 2A, 2E, and 2F electronic states of open-shell XY4 molecules

Rotational energy levels in vibronic ground states of ²A, ²E, and ²F electronic states of open-shell XY₄ molecules, as well as rotational line intensities for allowed transitions between such states, are discussed, including the effects of spin-orbit interaction and tetrahedral splittings. Jahn-Teller effects are assumed to be small, and are only taken into account implicitly, through their contributions to various parameters in the effective Hamiltonian. Qualitative information is obtained by considering several limiting-case coupling schemes among the electron spin angular momentum S, the electron orbital angular momentum L, and the pure rotational angular momentum R. These limiting cases are similar in spirit to Hund's coupling cases in diatomic molecules, but differ sufficiently from the latter to make detailed correspondences unhelpful. Quantitative information on rotational energy levels and line intensities is obtained numerically by diagonalizing a Hamiltonian matrix set up in a basis set characterized by uncoupled moleculefixed projections of S, L, and the total angular momentum J, and symmetrized so that all basis set functions belong to a definite species in the subgroup D_2d of the true point group T_d. Hamiltonian matrix elements are determined by ladder operator techniques. Three sample calculated spectra, corresponding to $\text{p(}{}^2\text{F}{}_2\text{)-s(}{}^2\text{A}{}_1\text{)}$, $\text{d(}{}^2\text{E)-p(}{}^2\text{F}{}_2\text{)}$, and $\text{d(}{}^2\text{F}{}_2\text{)-p(}{}^2\text{F}{}_2\text{)}$ are presented. As one might expect, when the spin-orbit constant A is set equal to zero, then both qualitative and quantitative aspects of the rotational-electronic problem in open-shell XY₄ molecules can be mapped easily onto discussions of the rotation-vibration problem from the CH₄ literature.