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.     

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.     

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.     

Neutron-proton shell model multiplets in 88Y and 90Y from a study of the (α, nγ) reaction

The non-selective nature of the (α, nγ) reaction has been used to complement information from charged-particle reactions on the level structure of ⁸⁸Y and ⁹⁰Y. The γ-ray spectra were recorded with a 25 cm³ Ge(Li) detector at 90° to the beam using primarily targets of ⁸⁵Rb₂CO₃ and ⁸⁷Rb₂CO₃ and α-particle energies of 11.8, 12.2 and 13.0 MeV. The resulting transitions were accommodated in level schemes that involved primarily the following shell model configurations: $\text{(π}\text{p}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{)}{}^1\text{(ν}\text{g}{}_{\mathrm{<mtext>9</mtext><mtext>2</mtext>}}\text{)}{}^{\mathrm{?1}}$, $\text{(π}\text{g}{}_{\mathrm{<mtext>9</mtext><mtext>2</mtext>}}\text{)}{}^{\mathrm{?1}}\text{(ν}\text{g}{}_{\mathrm{<mtext>9</mtext><mtext>2</mtext>}}\text{)}{}^1$, $\text{(π}\text{p}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{)}{}^1\text{(ν}\text{p}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{)}{}^{\mathrm{?1}}$, $\text{(π}\text{f}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{)}{}^{\mathrm{?1}}\text{(ν}\text{g}{}_{\mathrm{<mtext>9</mtext><mtext>2</mtext>}}\text{)}{}^{\mathrm{?1}}$ in ⁸⁸Y and $\text{(π}\text{p}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{)}{}^1\text{(ν}\text{d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{)}{}^1$, $\text{π}\text{g}\text{(}{}_{\mathrm{<mtext>9</mtext><mtext>2</mtext>}}\text{)}{}^1\text{(ν}\text{d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{)}{}^1$,$\text{(π}\text{p}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{)}{}^1\text{(ν}\text{s}{}_{\mathrm{<mtext>1</mtext><mtext>2)</mtext>}}\text{)}{}^1$ in ⁹⁰Y.     

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.     

Analysis of the Raman spectrum of SF6

The Raman active fundamentals ν₁(A1g), ν₂(Eg), ν₅(F2g), and the overtone 2ν₆ of SF₆ have been investigated with a higher resolution and the band origins were estimated to be: ν₁ = 774.53 cm^?1, ν₂ = 643.35 cm^?1, ν₅ = 523.5 cm^?1, and 2ν₆ = 693.8 cm^?1. Raman and infrared data have been combined for estimation of several anharmonicity constants. The ν₆ fundamental frequency is calculated as 347.0 cm^?1. From the analysis of the ν₂ Raman band, the following rotational constants of both the ground and upper states have been calculated:

$\text{B}{}_0\text{= 0.09111 ± 0.00005}\text{cm}{}^{\mathrm{?1}}\text{; D}{}_0\text{= (0.16±0.08)10}{}^{\mathrm{?7}}\text{cm}{}^{\mathrm{?1}}$

;

$\text{B}{}_2\text{= 0.09116 ± 0.00005}\text{cm}{}^{\mathrm{?1}}\text{; D}{}_2\text{= (0.18±0.04)10}{}^{\mathrm{?7}}\text{cm}{}^{\mathrm{?1}}$

.     

Why are formaldehyde and (possibly) propynal nonplanar in their S1(π1, n) electronic states?

Abnormally low frequencies observed for the out-of-plane vibration (b₁) of the $\text{A}\text{?}{}^1\text{A}{}_2$ electronic state of formaldehyde (H₂CO) and for the analogous carbonyl hydrogen vibration (a″) of $\text{A}\text{?}{}^1\text{A″}$ propynal (HCCCHO) are modeled by means of two-state calculations of vibronic coupling with higher singlet states, ¹B₂ and ¹A′, respectively. In each case, the active vibration is the out-of-plane hydrogen motion. The same vibronic calculations reproduce also the large positive anharmonicities of the active vibrations in the $\text{A}\text{?}\text{(π}{}^1\text{, n)}$ states; for H₂CO the calculated vibrational spacing alternates as observed, consistent with the known nonplanar structure, while in propynal the calculated spacing increases regularly, thus predicting an effectively planar structure. The nonplanarity of H₂CO is caused mainly by a vibronic coupling constant nearly twice that of propynal. The H₂CO coupling constant is near the value estimated independently by means of the intensity “borrowed” by the S₁-S₀ transition from the much stronger S₂-S₀ transition. Brief consideration is given to analogous vibrational levels of the ¹A₂ state of H₂CS and of the ³A₂ state of D₂CO in the vibronic context of this paper.     

Acetylene fluorescence

Previously unobserved acetylene ${}^1\text{A}{}_{\mathrm{u}}\text{(}{}^1\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{?}}\text{) →}{}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$ fluorescence occurs following 1933-Å ArF laser excitation of C₂H₂ or C₂H₄ and their deuterated analogs in solid Ne and Ar hosts at 4.2 K. Acetylene is a photolysis product of matrix-isolated ethylene. Ground-state vibrational levels as high as ν″₃ = 30 of the degenerate ν₃ bending vibration are observed for C₂D₂. Only ν₃ is appreciably active in the fluorescence. The negative ν₃ anharmonicity, previously observed in the gas phase, also occurs in Ne host. Consideration of rotational selection rules indicates that the Ne host strongly hinders free rotation about the low-moment-of-inertia $\text{a}\text{?}$ axis in the excited state.     

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.     

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.     

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.     

The lowest singlet and triplet excited states of pyrazine

The phosphoresence, fluorescence and absorption spectra of pyrazine-h₄ and -d₄ have been obtained at 4°K in a benzene matrix. For comparison, those of the isotopically mixed crystal pyrazine-h₄ in d₄ were also taken. All these spectra show extremely sharp and well-resolved lines and reveal detailed vibronic structure.The coincidence of origins of absorption and emission shows that the lowest singlet state is an allowed transition, properly designated as ${}^1\text{B}{}_{\mathrm{3u}}\text{←}{}^1\text{A}{}_{\mathrm{1g}}$. The forbidden component ¹B_2g, predicted by both “exciton” and MO theories to be below the allowed component, must lie higher. Its exact location still remains uncertain.The phosphorescence spectrum, when compared with the singlet-triplet excitation spectrum, indicates that the lowest triplet state is also symmetry allowed, showing a strong 0-0 band and the coincidence of origins of absorption and emission. In accordance with previous work, the triplet state is designated as ³B_3u.The vibronic structure of the phosphorescence spectrum is very complicated. The first work on the analysis of this spectrum concluded that a simple progression of ν_6a exists. Under the high resolution attainable in the present experiments, the supposed ν_6a progression proves to have a composite structure, starting from the second member of the progression. Not only is the ν_9a hydrogen-bending mode present as shown by the appearance of the CD bending mode in the d₄ spectrum, but a band assigned as 2ν_6b was also identified. The latter's anomalous intensity in the phosphorescence spectrum is interpreted as due to the Fermi resonance with 2ν_6a and ν_9a bands. To help resolve the present controversy over the origin of the phosphoresence spectrum observed in crystalline pyrazine, detailed vibrational analyses of the emission spectra were made. The fluorescence spectrum has essentially the same vibronic structure as the phosphorescence spectrum.     

Nuclear magnetic moment of the 9.7 h 12− isomer 196mAu

The magnetic hyperfine splitting v_M=|gμ_NB_HF/h| of ^196mAu (j^π=12^?; configuration ¦(π$\text{11}\text{2}$($\text{v}\text{13}\text{2}{}^{\mathrm{+}}\text{)〉}{}_{12}{}^{\mathrm{?}}$; $\text{T}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{= 9.7}\text{h}\text{)}$ as dilute impurity in Ni has been determined with nuclear magnetic resonance on oriented nuclei as 96.0(2) MHz. With the known hyperfine field B_HF = ?264.4(3.9) kG corrected for hyperfine anomalies the g-factor and magnetic moment of ^196mAu are deduced to be |g| = 0.476(7) and |μ| = 5.72(8) μ_N. Taking into account the known magnetic properties of $\text{π}\text{1}\text{2}{}^{\mathrm{?}}$ and $\text{v}\text{13}\text{2}{}^{\mathrm{+}}$ isomeric states in the neighbouring odd Pt, Au and Hg nuclei the structure of the 12^? state is discussed.     

The 352 nm emission spectrum of difluorodiazirine

Difluorodiazirine fluoresces strongly in the vapor phase showing an extensive band system from about 352 to 451 nm and with no background continuum. The fluorescence is assigned as $\text{A}\text{?}{}^1\text{B}{}_1\text{(nπ}{}^1\text{)-}\text{X}\text{?}{}^1\text{A}{}_1$ and corresponds to the 352 nm absorption system previously studied.The band system is dominated by a progression in ν₁″, the a₁N = N stretching vibration, with ν₄″, the a₁ CF₂ symmetrical deformation vibration, showing a shorter progression.The 0₀⁰ and most others show type B rotational contours but type C bands, involving ν₅″ (a₂), and probably type A bands, involving ν₇″ (b₁) and perhaps ν₆″ (b₁) are also observed.The extremely low intensity of bands involving ν₃″ (a₁) is surprising but there seems to be no reason to doubt the assignment from infrared and Raman data.There is a strong vibrational perturbation affecting some quite strong bands in a region within about 275 cm^?1 of bands 1_n⁰4₀⁰, where n = 0 – 3. The cause of the perturbation is not known.There is no evidence for the emission spectrum consisting of more than one band system.     

The ã3A2 ← X̃1A1 absorption spectrum of thioformaldehyde: A vibrational and rotational analysis

The results of a vibrational and rotational analysis of the banded $\text{a}\text{?}{}^3\text{A}{}_2\text{←}\text{X}\text{?}{}^1\text{A}{}_1$ transition in $\text{CH}{}_2\text{S}\text{CD}{}_2\text{S}$ are presented. Only three of the six vibrational modes are active in the spectrum with $\text{ν′}{}_2\text{=}\text{1320}\text{1012}$, $\text{ν′}{}_3\text{=}\text{859}\text{798}$, and $\text{2ν′}{}_4\text{=}\text{711}\text{516}\text{cm}{}^{\mathrm{?1}}$. The spin forbidden transition gains intensity primarily by a mixing of the ${}^1\text{A}{}_1\text{(π}{}^1\text{,π)}$ and ${}^3\text{A}{}_2\text{(π}{}^1\text{,n)}$ states. This is confirmed by a rotational analysis of the 0₀⁰ band of both isotopes. The rotational analysis shows that the coupling in the $\text{a}\text{?}{}^3\text{A}{}_2$ state is near Hund's case b and that the spin constants are nearly 10 times greater than those observed for CH₂O. A $\text{CNDO}\text{2}$ calculation shows that this difference is due to the greater spin orbit coupling of S in CH₂S and to the smaller energy differences between the $\text{B}\text{?}{}^1\text{A}{}_1\text{(π}{}^1\text{,π)}$, $\text{b}\text{?}{}^3\text{A}{}_1\text{(π}{}^1\text{,π)}$, $\text{X}\text{?}{}^1\text{A}{}_1$, and the $\text{a}\text{?}{}^3\text{A}{}_2\text{(π}{}^1\text{,n)}$ states. The r₀ structure calculated from the rotational constants is $\text{r}{}_{\mathrm{<mtext>CS</mtext>}}\text{= 1.683}\text{A}\text{?}$, $\text{r}{}_{\mathrm{<mtext>CH</mtext>}}\text{= 1.082}\text{A}\text{?}$, β_HCH = 119.6°, and α (out of plane) = 16.0°. A simultaneous fit of the vibrational levels in ν′₄ of CH₂S and CD₂S to a double minimum potential function yielded a barrier to molecular inversion of 13 cm^?1 and an equilibrium out-of-plane angle of 15°.     

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.     

Dimethyl-s-tetrazine vapor: Visible absorption,laser-excited fluorescence,and photophysics

Except for broader bands, hot bands, and a 500-cm^?1 shift of the 0-0 band to higher frequencies, dimethyl-s-tetrazine as a vapor is found to exhibit the same visible absorption and excited-state zero-level emission spectra that it does when dissolved in p-xylene at 4.2 K and below. Vibrational frequencies in both $\text{A}\text{?}{}^1\text{B}{}_{\mathrm{3u}}$ and $\text{X}\text{?}{}^1\text{A}{}_{\mathrm{g}}$ states show almost no solvent effects. Even an unusual “negative” anharmonicity of the principal progression-forming mode ν_6a in the ground state is the same in both phases. Franck-Condon activity also is independent of phase; in fact, for ν_6a it is the same as for s-tetrazine in the vapor phase. Single vibronic level excitations into the 0-0, 6a₀¹, 1₀¹, and 6a₀² bands show that vibrational relaxation is appreciable for pressures of a Torr and greater. Mode-to-mode flow does not follow the propensity rules exhibited by the S₁ state of benzene. Rotational relaxation and competition of collisional relaxations with predissociation are revealed when foreign gas is added.     

Study of the 91Zr(d, 3He)90Y reaction

The ⁹¹Zr(d, ³He) reaction was studied at a deuteron energy of 28 MeV. Angular distributions were measured from 13° to 47°; l_p values were extracted for the prominent lines of ⁹⁰Y. The l_p values and transition strengths were determined by DWBA analysis. The angular distributions for the $\text{(π}\text{p}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{)(ν}\text{d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{)}$ doublet (g.s. and 0.20 MeV state) exhibit the characteristic l = 1 shape. States at 1.42, 1.57, 1.64 and 1.81 MeV were also populated strongly in the (d, ³He) reaction; the 1.42, 1.57 and 1.81 MeV levels contain l= 1 transition strength and are most likely members of the $\text{(π}\text{p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}{}^{\mathrm{?1}}\text{)(ν}\text{d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{)}$ multiplet. The 2.03 MeV state has a characteristic l = 3 angular distribution and is suggested to be the only member of the $\text{(π}\text{f}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}{}^{\mathrm{?1}}\text{)(ν}\text{d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{)}$ sextet to be unambiguously observed in this study, most probably the 5^? or 4^? member. The members of the $\text{(π}\text{g}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{)(ν}\text{d}{}_{\mathrm{<mtext>9</mtext><mtext>2</mtext>}}\text{)}$ sextet were populated weakly (less than 100 μb/sr) in this reaction.     

The 370-nm electronic spectrum of tropolone: Evidence from single vibronic level fluorescence spectra regarding the assignment of some vibrational fundamentals in the X̃ and à states

Single vibronic level fluorescence (SVLF) spectra of tropolone from vibronic levels in the $\text{A}\text{?}{}^1\text{B}{}_2$ electronic state, in combination with recently reported supersonic jet spectra, have enabled the assigning of many absorption bands in the region of 0₀⁰ which had previously been impossible. Some of the complexity in these bands has been shown to be due to a large Duschinsky effect involving the two lowest b₁ vibrations, ν₂₅ and ν₂₆. It has been shown that these vibrations have wavenumbers of 176 and 110 cm^?1, respectively, in the $\text{X}\text{?}$ state, and 172 and 39 cm^?1 in the $\text{A}\text{?}$ state. This last value shows how unresistent the molecule is in the $\text{A}\text{?}$ state to out-of-plane bending in the region of the five-membered ring. Other aspects of the vibrational complexity are due to the effect of ν′₂₆ in increasing the barrier to tunnelling of the hydrogen-bonding proton in the $\text{A}\text{?}$ state contrasting with very little effect of ν″₂₆ in the $\text{X}\text{?}$ state.