Laser-excited phosphorescence spectrum of C3S2 in an Ar matrix

The phosphorescence spectrum of C₃S₂ was observed in a low-temperature Ar matrix with excitation of an Ar⁺ laser. The spectrum consists of a very strong 0-0 band at 18 287 cm^?1 and well-resolved progressions in the ν₂, ν₅, ν₆, and ν₇ vibrations. Side bands were found on the high-energy sides of some transitions. The separation between the main and side bands is 23 cm^?1. Polarization analysis suggests that C₃S₂ is linear symmetric in the Phosphorescent state as in the ground electronic state. On the basis of symmetry considerations and a qualitative evaluation of spin-orbit coupling, the phosphorescent state is assigned to ³Σ_u^? with Σ_u⁺ and Π_u components split by spin-spin interaction. The Σ_u⁺ level is lower than the Π_u one by 23 cm^?1 and the main and side band emissions start from the Σ_u⁺ and Π_u levels, respectively. The Σ_u⁺ component seems to acquire allowed character from a ¹Σ_u⁺ state by spin-orbit coupling and from bent ${}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{?}}\text{(}{}^1\text{B}{}_2\text{)}$ and ${}^1\text{Δ}{}_{\mathrm{g}}\text{(}{}^1\text{A}{}_1\text{+}{}^1\text{B}{}_2\text{)}$ states by ν₅ vibronic coupling. Mixing of the Σ_u⁺ and Π_u components through ν₅ is responsible for most of the side bands. The ν₅ frequency is estimated to be 160 ± 20 cm^?1 in the ³Σ_u^? state from the intensities of ν₅ progression bands and from the ground-state frequency, 411 cm^?1.     

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.     

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.     

Model calculation of the electronic structure and spectroscopy of Hg2

Energy curves and transition moments of the excited valence states of Hg₂ were obtained in a model calculation based on calculated Mg₂ energy levels and the assumption that the asymptotic spin-orbit matrix elements for the Hg atom are applicable to the molecular states. The spin-orbit and orbital-rotational interaction of the excited states of Hg₂ is analyzed in both a Hund's case (c) and (a) representation. The intermediate (a) → (c) transition moments are obtained as a function of the internuclear distance. The effect of the orbital-rotational interaction which introduces Hund's case (b) and (e) couplings is found to be small for transitions among excited states under the conditions normally encountered for populating excimer states.Using the energy level positions and transition moments, the observed spectra and predicted spectra are compared for both radiative transitions including the ground state and among the excited states. The lifetime of the $\text{1}{}_{\mathrm{u}}\text{(}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{)}$ excimer state is calculated to be 1.4 μsec with the 335 nm band assigned to the $\text{1}{}_{\mathrm{u}}\text{→ X}{}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$ transition. The 485 nm bands cannot be assigned to any Hg₂ transitions. Strong bound-continuum absorptions are predicted for the 485 nm bands. On the other hand, the 335 nm emission is predicted to be absorbed by bound-bound transitions only.     

Microwave optical double resonance and continuous wave dye laser excitation spectroscopy of NO2: Rotational assignment of the K = 0−4 subbands of the 593 nm band

A rotational assignment of approximately 80 lines with K_a′ = 0, 1, 2, 3, and 4 has been made of the 593 nm ${}^2\text{A}{}_1\text{→}{}^2\text{B}{}_2$ band of NO₂ using cw dye laser excitation and microwave optical double-resonance spectroscopy. Rotational constants for the ²B₂ state were obtained as A = 8.52 cm^?1, B = 0.458 cm^?1, and C = 0.388 cm^?1. Spin splittings for the K_a′ = 0 excited state levels fit a simple symmetric top formula and give $\text{(?}{}_{\mathrm{bb}}\text{+ ?}{}_{\mathrm{cc}}\text{)}\text{2}\text{= ?0.0483}\text{cm}{}^{\mathrm{?1}}$. Spin splittings for K_a′ = 1 (N′ even) are irregular and are shown to change sign between N′ = 6 and 8. Assuming that the large inertial defect of 4.66 amu Ų arises solely from A, a structure for the ²B₂ state is obtained which gives $\text{r}\text{(NO) = 1.35}\text{A}\text{?}$ and an ONO angle of 105°. Alternatively, weighting the three rotational constants equally gives $\text{r = 1.29}\text{A}\text{?}$ and θ = 118°.     

Spectrum and structure of the He2 molecule: Characterization of the singlet and triplet states associated with the UAO's 4s, 4dσ, 4dπ, and 4dδ

The emission spectrum of the He₂ molecule has been rephotographed in the ～4000–～5700 Å region and the $\text{4d(}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{,}{}^3\text{Π}{}_{\mathrm{u}}\text{,}{}^3\text{Δ}{}_{\mathrm{u}}\text{) → 2pπ}{}^3\text{Π}{}_{\mathrm{g}}$, $\text{4d(}{}^1\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{,}{}^1\text{Π}{}_{\mathrm{u}}\text{,}{}^1\text{Δ}{}_{\mathrm{u}}\text{) → 2pπ}{}^1\text{Π}{}_{\mathrm{g}}$, $\text{4s}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{→ 2pπ}{}^3\text{Π}{}_{\mathrm{g}}$ and $\text{4s}{}^1\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{→ 2pπ}{}^1\text{Π}{}_{\mathrm{g}}$ transitions analyzed. The 4dδj³Δ_u, 4dπj³Π_u, $\text{4dσj}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ and $\text{4sh}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ states have been characterized through v = 2 and the 4dδJ¹Δ_u, 4dπJ¹Π_u, $\text{4dσJ}{}^1\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$, and $\text{4sH}{}^1\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ states for v = 0. The term levels for these perturbed and l-uncoupled states have been confirmed (a) by analyses of bands with common levels from Δv = 0, ±1 sequences and (b) by analyses of the transitions between the above states from 4d and 4s and the $\text{c}{}^3\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$ and $\text{C}{}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$ states associated with 3pσ. Molecular constants are reported which have been partially corrected for the effects of l-uncoupling and the homogeneous perturbations between the state pairs J, H and j, h.     

Electron-vibration splitting of the vibronic levels of the 1T2g state of MgO:Ni2+

Magnetic circular dichroism (MCD) and magnetic linear dichroism (MLD) measurements of the ${}^3\text{A}{}_{\mathrm{2g}}\text{→}{}^1\text{T}{}_{\mathrm{2g}}$ absorption band in MgO:Ni²⁺ are reported. It is shown that for the lowest energy vibrational peak there is considerable evidence of splitting of the T_2g × T_1u vibronic levels by the electron-vibration interaction.     

Thioformaldehyde: Vibrational analysis of the Ã1A2-X̃1A1 visible absorption system

The electronic absorption spectra of thioformaldehyde and thioformaldehyde-d₂ have been obtained. A vibrational analysis of the discrete band system in the 6100-4400-Å region is reported. The type A origin bands are at $\text{16 394}\text{16 484}\text{cm}{}^{\mathrm{?1}}$ for $\text{CH}{}_2\text{S}\text{CD}{}_2\text{S}$, and are magnetic dipole allowed. The electronic transition is $\text{A}\text{?}{}^1\text{A}{}_2\text{-}\text{X}\text{?}{}^1\text{A}{}_1$ under the C_2v point group. Most of the intensity of the system is in type B bands, and is due to vibronic mixing with higher ¹B₂ states when the inversion mode ν₄ is excited. The molecule in the excited ¹A₂ state is “floppy-planar,” having a broad potential function with a barrier of the order of 20 cm^?1 to the inversion motion.     

Energy levels of low lying triplet states of N2 from infrared emission studies

A theoretical model used to describe the $\text{B′}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{?}}$ and B³Π_g states of N₂ is presented. Using recently acquired high resolution spectra of the $\text{B′}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{?}}\text{→ B}{}^3\text{Π}{}_{\mathrm{g}}$ (0-0) band, rotational energy levels of the v = 0 vibrational levels of these two states are generated with this model. These levels are in excellent agreement with those obtained using a combination differences technique. The precision of the model generated levels is 0.01 cm^?1. The previously unpublished rotational levels of Dieke and Heath for the $\text{A}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$, B³Π_g and C³Π_u states are referenced to the $\text{N}{}_2\text{X}{}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$ (v = 0, J = 0) ground level and tabulated here. Estimates of the precision of their work are made.     

Reorientational motion of the OH− ion in cubic sodium hydroxide

The rotational motion of the OH^? ion was studied in cubic NaOH at 575 K with quasielastic incoherent neutron scattering. The data are compared to two simple models yielding values for the radius of rotation R, the translational mean square displacement 〈u²〉_H, the rotational jump rate τ^?1 and the rotational diffusion coefficient D_R. The following parameter values are obtained: (a) rotational jump model: $\text{R = 0.95}\text{A}\text{?}$, $\text{〈u}{}^2\text{〉}{}_{\mathrm{H}}\text{= 0.052}\text{A}\text{?}{}^2\text{, τ}{}^{\mathrm{?1}}\text{= 2}\text{meV}$, (b) rotational diffusion model: $\text{R = 0.99}\text{A}\text{?}\text{, 〈u}{}^2\text{〉}{}_{\mathrm{H}}\text{= 0.046}\text{A}\text{?}{}^2\text{, D}{}_{\mathrm{R}}\text{= 0.72}\text{meV}$.     

Analysis of the 2770-Å emission system in I2

A weak emission spectrum of I₂ near 2770 Å is reanalyzed and found to to minate on the A(1u³Π) state. The assigned bands span v″ levels 5–19 and v′ levels 0–8. The new assignment is corroborated by isotope shifts, band profile simulations, and Franck-Condon calculations. The excited state is an ion-pair state, probably the 1g state which tends toward $\text{I}{}^{\mathrm{?}}\text{(}{}^1\text{S) +}\text{I}{}^{\mathrm{+}}\text{(}{}^3\text{P}{}_1\text{)}$. In combination with other results for the A state, the analysis yields the following spectroscopic constants: T″_e = 10 907 cm^?1, $\text{D}$″_e = 1640 cm^?1, ω″_e = 95 cm^?1, $\text{R″}{}_{\mathrm{e}}\text{= 3.06}\text{A}\text{?}$; T′_e = 47 559.1 cm^?1, ω′_e = 106.60 cm^?1, $\text{R′}{}_{\mathrm{e}}\text{= 3.53}\text{A}\text{?}$.     

New S1 vibronic level assignments for s-tetrazine vapor: Polarization and lifetime measurements

New fluorescence excitation and dispersed SVL fluorescence spectra of s-tetrazine vapor in supersonic expansions of helium and argon are reported. A forbidden in-plane-polarized component of the $\text{A}\text{?}{}^1\text{B}{}_{\mathrm{3u}}\text{-}\text{X}\text{?}{}^1\text{A}{}_{\mathrm{g}}$ transition is discovered at (0, 0) + 578 cm^?1 with a type-B band contour in rotationally resolved excitation spectra obtained with a single-frequency cw ring dye laser. Linewidth measurements of single rovibronic transitions provide data to calculate lifetimes of low-lying S₁ vibronic states of the isolated molecule. Depending on the vibrational mode involved, the lifetime varies from 0.05 to greater than 1 nsec. The number of cold-band assignments in the absorption spectrum of s-tetrazine vapor now confirmed by analysis of SVL fluorescence spectra increases from three to ten.     

Near-uv spectra with fully resolved rotational structure of naphthalene and perdeuterated naphthalene

The combination of a single-frequency, tunable uv source with a well-collimated supersonic molecular beam and sensitive fluorescence detection has been used to obtain spectra with rovibronic resolution for some large organic molecules. The results of analysis of the 0₀⁰ and $\text{8}$₀¹ vibronic bands of the ${}^1\text{B}{}_{\mathrm{3u}}\text{←}{}^1\text{A}{}_{\mathrm{g}}$ electronic transition for naphthalene and naphthalene-d_g are presented. The obtained spectra are assigned using a rigid asymmetric rotor Hamiltonian and the structure in both the ground and electronically excited states is determined. The rotational temperature of the molecules cooled in the beam has been determined. The influence of the nuclear spin statistics on the line intensities is observed and discussed.     

Quark masses

In quark gluon theory with very small bare masses, -$\text{ψ}$$\text{M}$ψ, spontaneous breakdown of chiral symmetry generates sizable masses M_u, M_d, M_s, … We find ($\text{M}{}_{\mathrm{<mtext>u</mtext>}}\text{+ M}{}_{\mathrm{<mtext>d</mtext>}}\text{) /2 ≈ m}\text{p}\text{/ √6 ≈ 312}\text{MeV}\text{,}\text{and}\text{M}{}_{\mathrm{<mtext>s</mtext>}}\text{≈ 432}\text{MeV}$. Scalar densities have well determined non-zero vaccum expectations $\text{〈0|u}{}^{\mathrm{a}}\text{|0〉 ≡ 〈0|ψ(x) (λ}{}^{\mathrm{a}}\text{/2)ψ(x)/0〉 ≈ ?}{}_{\mathrm{\pi }}{}^2\text{M}{}^{\mathrm{a}}\text{,}\text{i.e}\text{〈0? u}{}^{\mathrm{o}}\text{/vb0〉 ≈ 8 × 10}{}^{\mathrm{?3}}\text{(}\text{GeV}\text{)}{}^3$ at an SU(3) breaking of the vacuum c′ ≡ 〈0|u⁸|〉/〈0|u^o|0〉 ≈ ? 16%     

V.U.V. Excitation of benzene: C6H6 fluorescence and phosphorescence in rare gas and nitrogen matrices

Benzene isolated in rare gas or nitrogen matrix at about 5 K has been irradiated with photons of 4, 6, 8.4, and 10 eV energy. The phosphorescence $\text{a}\text{?}{}^3\text{B}{}_{\mathrm{1u}}\text{→}\text{X}\text{?}{}^1\text{A}{}_{\mathrm{1g}}$ and the fluorescence $\text{A}\text{?}{}^1\text{B}{}_{\mathrm{2u}}\text{→}\text{X}\text{?}{}^1\text{A}{}_{\mathrm{1g}}$ are observed amost in every case, from the vibrationally relaxed states. For both emissions, shifts are observed from one matrix to another. They depend upon the vibronic bands in the fluorescence case. Some features of spectra are interpreted as phonon-induced, specially the 0-0 bands electronically forbidden for both transitions. The phosphorescence versus fluorescence ratio increases when passing from a nitrogen matrix to a xenon matrix and as the photon energy increases. To account for these observations, we are led to believe that the $\text{a}\text{?}{}^3\text{B}{}_{\mathrm{1u}}$ state is not only populated from the $\text{A}\text{?}{}^1\text{B}{}_{\mathrm{2u}}$ state, but through upper singlet and (or) triplet states.     

Vibronic coupling as a major cause of the anharmonicity of antisymmetric stretching in the ground state of NO2

Approximate experimental and theoretical information about vibronic coupling of the $\text{X}\text{?}{}^2\text{A}{}_1$ (ground) and $\text{A}\text{?}{}^2\text{B}{}_2$ electronic states of NO₂—by its antisymmetric vibration ν₃(b₂)—is tested in model calculations of the accurately known ground-state levels ν₃ = 0, 1, 2, 3. The test is positive and it is estimated that 64% of the very large observed anharmonic constant χ₃₃ has its origin in vibronic coupling. In this model, ν₃ in the à state is predicted at about 1200 cm^?1.     

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.     

Rotational analysis of the 8000–9000 Å bands of nitrogen dioxide

The rotational structure of bands of NO₂ vapor in the region 8300–9000 Å has been partially analyzed and the absorption assigned to the (000)-(000) and (000)-(010) vibronic bands of the $\text{A}\text{?}{}^2\text{B}{}_2\text{←}\text{X}\text{?}{}^2\text{A}{}_1$ electronic transition. Irregular weak perturbations in the N-structure of the upper-state manifold are accompanied by larger resonance-type crossings in the K-structure. The larger perturbation is attributed to vibronic coupling between the à state and excited vibrational levels of the ground state, characterized by a low density of ground state levels and a large vibronic coupling matrix element between the à and X? states. The reconstituted, deperturbed bands have blue-degraded N-structure and strongly red-degraded K-structure, indicating that the bond angle decreases sharply in the excited state. The physical structure of the ²B₂ state is uncertain but some suggestions are made. The electronic energy of the ²B₂ state is T₀ = 11 962.9 cm^?1.     

The determination of the electric dipole moment of H2CS in the Ã1A2 excited state using dye-laser electric field spectroscopy

An electric field spectrum of thioformaldehyde has been measured for the 4₀¹ vibronic band of the $\text{A}\text{?}{}^1\text{A}{}_2\text{-}\text{X}\text{?}{}^1\text{A}{}_1$ electronic transition, using a tunable dye laser as the radiation source. Measurements of the Stark splittings of a number of lines in electric fields up to 8.7 kV/cm lead to a value of 0.79 ± 0.04 D for the excited state dipole moment. The decrease of dipole moment on excitation is compared with the equivalent change in formaldehyde and with predictions from ab initio calculations.     

Two-photon excitation of the C̃1B2 state of sulfur dioxide

The two-photon excitation (TPE) spectrum of sulfur dioxide is reported in the region of the $\text{C}\text{?}{}^1\text{B}{}_2\text{←}\text{X}\text{?}{}^1\text{A}{}_1\text{[2b}{}_1\text{(π}{}^1\text{) ← 1a}{}_2\text{(π)]}$ transition. The spectrum shows considerable rovibronic structure; the band contours are identified as arising from ΔK_?1 = ± 1 transitions and rotational features are assigned by comparison with synthetic spectra generated from known rotational constants. The vibronic structure observed in TPE is quite similar to that observed in the one-photon spectrum: no zero-rank tensor transitions to levels with odd v₃ are identified, though they are allowed in the presence of vibronic coupling. The vibronic intensity distribution in the TPE spectrum below the dissociation limit is similar to that in one-photon absorption. However, near the dissociation threshold (5.63–5.67 eV), marked intensity redistribution occurs, from which it is concluded that the lowest energy photo-dissociation process proceeds through asymmetric stretching of the SO bonds.