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.     

On the presence of the S4z-term in Fe(HCOO)2 · 2H2O

The magnetic specific heat of ferrous formate dihydrate is analysed on the basis of a model, $\text{S}{}_{\mathrm{A}}\text{=}\text{1}\text{2}$ and S_B = 2. The experimental result turns out to be well explained by the introduction of a large S⁴_z-term for B site ions.     

Temperature dependence of the ESR spectra of Mn2+ in iron pyrite (FeS2)

The first observation of the ESR spectra of Mn²⁺, entering substitutionally for Fe²⁺ in the Van Vleck paramagnet FeS₂ (polycrystals), is reported. The data from 5 to 295 K fits the spin-Hamiltonian $\text{h}{}_{\mathrm{s}}\text{= gβ}\text{H}\text{·}\text{S}$ + $\text{[S}{}^{\mathrm{<mtext>2</mtext>}}{}_{\mathrm{z}}\text{?}\text{1}\text{3}\text{S(S + 1)] + A}\text{S}\text{·}\text{I}$, with g = 2.000 ± 0.001, A/β = ?95.0 ± 0.5 Oe and D/β varying from 50 Oe (5K) to 59 Oe (295 K). The temperature dependence of D can be described in terms of a single phonon-mode with frequency ? 145 cm^?1.     

Average polarization of 12B in 12C(μ, ν)12B(g.s.) reaction: Helicity of the π-decay muon and nature of the weak coupling

The helicity, h^?, of μ^? in π-decay has been determined as positive (h^??+0.90) from the average polarization, P_av≡〈J_B·s_μ〉, of ¹²B produced in the $\text{μ}{}^{\mathrm{?}}\text{+}{}^{12}\text{C}\text{→ν}{}_{\mathrm{\mu }}\text{+}{}^{12}\text{B}$ reaction. We obtain also dynamical information on μ-capture: (i) the weak magnetism form factor, μ=4.5±1.1, and (ii) the sum of the induced pseudoscalar (g_p) and the 2nd class induced tensor (g_T) couplings versus g_A, ($\text{g}{}_{\mathrm{<mtext>P</mtext>}}\text{+g}{}_{\mathrm{<mtext>T</mtext>}}\text{)}\text{g}{}_{\mathrm{<mtext>A</mtext>}}\text{=7.1±2.7}$. The latter result, adopting the “canonical” value of $\text{g}{}_{\mathrm{<mtext>P</mtext>}}\text{g}{}_{\mathrm{<mtext>A</mtext>}}$, leads to $\text{g}{}_{\mathrm{<mtext>T</mtext>}}\text{g}{}_{\mathrm{<mtext>A</mtext>}}\text{=+1±2.7}$ which is compatible with zero and in strong contradiction with the value ?—6 recently advocated by Kubodera, Delorme and Rho.     

nπ1 Transitions in tetramethyl-1,3-cyclobutanedithione-h12 and -d12

The polarized low-temperature crystal absorption spectra of tetramethyl-1,3-cyclobutanedithione-h₁₂ and -d₁₂ have been measured in the visible region, and $\text{nπ}{}^1$ excited states identified as follows: ³A_u with origin ($\text{h}{}_{12}\text{d}{}_{12}$) at $\text{16 829}\text{16 836}\text{cm}{}^{\mathrm{?1}}$; ¹A_u and ¹B₁₀ with nearly degenerate origins near 18 000 cm^?1; and probably ¹A_u and ¹B_1g near 19 500 cm^?1. The singlet excited states lie close together and perturb each other strongly. As in the corresponding dione, $\text{CH}\text{CD}$ stretching vibrations of the substituent methyl groups are active in intensity borrowing, and the effects of excitation are delocalized over the entire molecule.     

Two emission systems of BS

Two new systems of emission bands near 2100 and 3100 Å have been produced by a microwave discharge in B₂S₃ vapor. From the known X²Σ⁺ and A²Π_i states of BS, these systems have been assigned as E²Σ⁺ → X²Σ⁺ and E²Σ⁺ → A²Π_i. Constants in cm^?1 for the new state are

$\text{E}{}^2\text{∑}{}^{\mathrm{\pm }}\text{: T}{}_{\mathrm{e}}\text{= 47 929.3, B}{}_{\mathrm{e}}\text{= 0.671 (λ}{}_{\mathrm{e}}\text{= 1.752 A), α}{}_{\mathrm{e}}\text{= 0.008}$

,     

“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 $\text{α}{}_{\mathrm{e}}\text{(}{}^{\mathrm{o}}\text{) = 93.32}{}_8\text{± 0.02}$.     

Non affinity of Fe2+ for B sites in iron thiochromites and compared band structures of oxides and sulfides spinels

Departure from stoichiometry in vapor grown FeCr₂S₄ was studied using Mössbauer spectroscopy. The paramagnetic Mössbauer spectra give evidence of two singlets and two doublets which correspond respectively to A site Fe²⁺ ? Fe³⁺, Fe^II in T_d symmetry and in symmetry lower than T_d. The following ionic distribution has been deduced:

$\text{(Fe}{}^{\mathrm{2+}}{}_{\mathrm{1?y}}\text{Fe}{}^{\mathrm{3+}}{}_{\mathrm{y}}\text{)|Cr}{}^{\mathrm{3+}}{}_{\mathrm{2?x}}\text{□}{}_{\mathrm{x}}\text{|S}{}_{\mathrm{4?z}}\text{□}{}_{\mathrm{z}}$

Compounds in the system Fe_1+xCr_2?xS₄ have been studied for 0 ? x ? 0.1. The spectra are solved assuming Fe^II in A site with T_d symmetry, A site Fe^II with lower symmetry and B site Fe³⁺. No Fe²⁺ appears in B site. These features are discussed in terms of schematic band structures implying single electron narrow bands. The non-affinity of Fe²⁺ for B sites of iron thiochromites is discussed in relation with B site Cr²⁺ level.     

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°.     

Molecular structure of phosgene as studied by gas electron diffraction and microwave spectroscopy: The rz structure and isotope effect

The r_z structure of phosgene has been determined by a joint analysis of the electron diffraction intensity and the rotational constants as follows: $\text{r}{}_{\mathrm{z}}\text{(}\text{CO}\text{) = 1.1785 ± 0.0026}\text{A}\text{?}$, $\text{r}{}_{\mathrm{z}}\text{(}\text{CCl}\text{) = 1.7424 ± 0.0013}\text{A}\text{?}$, ∠_z;ClCCl = 111.83 ± 0.11°, where uncertainties represent estimated limits of experimental error. The effective constants representing bond-stretching anharmonicity have been obtained from an analysis of the isotopic differences in the r_z structure: $\text{a}{}_3\text{(}\text{CO}\text{) = 2.9 ± 0.9}\text{A}\text{?}{}^{\mathrm{?1}}$, $\text{a}{}_3\text{(}\text{CCl}\text{) = 1.6 ± 0.4}\text{A}\text{?}{}^{\mathrm{?1}}$. The equilibrium bond distances have been estimated from the r_z structure for the normal species and from the anharmonic constants to be $\text{r}{}_{\mathrm{e}}\text{(}\text{CO}\text{) = 1.1756 ± 0.0032}\text{A}\text{?}$, $\text{r}{}_{\mathrm{e}}\text{(}\text{CCl}\text{) = 1.7381 ± 0.0019}\text{A}\text{?}$.     

Polarization spectroscopy of the E0g+-B0u+ band system of Br2

The E-B (0_g⁺-0_u⁺) band system of Br₂ has been investigated at Doppler-limited resolution using polarization labeling spectroscopy. Merged E state data for the three naturally occurring isotopes in the range v_E = 0–16, expressed in terms of the constants for ⁷⁹Br₂, are (in cm^?1) Y_0,0 = 49 777.962(54), Y_1,0 = 150.834(22), Y_2,0 = ?0.4182(28), Y_3,0 = 6.6(11) × 10^?4, Y_0,1 = 4.1876(28) × 10^?2, Y_1,1 = ?1.607(16) × 10^?4, and Y_0,2 = 1.39(39) × 10^?8. The bond distance is $\text{r}{}_{\mathrm{<mtext>e</mtext>}}\text{= 3.194}\text{A}\text{?}$, and the diabatic dissociation energy to $\text{Br}{}^{\mathrm{+}}\text{(}{}^3\text{P}{}_2\text{) +}\text{Br}{}^{\mathrm{?}}\text{(}{}^1\text{S}{}_0\text{)}\text{is 34 700 cm}{}^{\mathrm{?1}}$.     

Three-nucleon results for separable potentials modelled on the Reid soft-core potential

Using a solution to the inverse scattering problem we have generated phase-equivalent separable potentials in the ${}^1\text{S}{}_0$ and ${}^3\text{S}{}_1\text{?}{}^3\text{D}{}_1$ states, which have nearly the same singlet UPA form factors and deuteron parameters (E_D, P_D, Q_D, A_S and $\text{A}{}_{\mathrm{D}}\text{A}{}_{\mathrm{S}}$) as the Reid soft-core potential. We compare our results for the binding energy of the triton and the neutron-deuteron doublet scattering length with the corresponding values for the Reid soft-core potential.     

Dissociation activation barrier and heat of chemisorption: A morse-type analytical approach

The activation barrier ΔE¹_ABfor dissociation AB → A + B on transition-metal surfaces is analyzed within an additive Morse-type approach based on the bond-order conservation. It is shown that $\text{Δ}\text{E}{}^1{}_{\mathrm{AB}}\text{=}\text{D}{}_{\mathrm{AB}}\text{?(}\text{Q}{}_{\mathrm{A}}\text{+}\text{Q}{}_{\mathrm{B}}\text{+}\text{Q}{}_{\mathrm{A}}\text{Q}{}_{\mathrm{B}}\text{/(}\text{Q}{}_{\mathrm{A}}\text{+}\text{Q}{}_{\mathrm{B}}\text{)}$ where D_AB is the gas-phase dissociation energy and Q_A(Q_B) is the heat of atomic chemisorption. Estimates of $\text{Δ}\text{E}{}^1\text{for H}{}_2\text{, N}{}_2\text{, O}{}_2$, and NO are shown to be in reasonable agreement with experiment. The two-dimensional potential diagram of the metal-AB interactions is defined analytically and discussed in some detail.     

Hartree-fock wave functions and oscillator strengths for the helium isoelectronic sequence

Oscillator strengths for 1¹S?n¹P transitions for some members of the helium isoelectronic sequence have been calculated by utilizing the dipole length, velocity and acceleration forms of the transition matrix element with coupled H.F. wave functions. Good agreement has been obtained between the values of the oscillator strengths. The quantities $\text{(?}{}_{\mathrm{A}}\text{??}{}_{\mathrm{L}}\text{)}$ and $\text{(?}{}_{\mathrm{A}}\text{??}{}_{\mathrm{V}}\text{)}$ decrease slowly with nuclear charge Z, whereas $\text{(?}{}_{\mathrm{L}}\text{-?}{}_{\mathrm{V}}\text{)}$ first increase to a maximum value and then decreases slowly.     

Polarization and polarization transfer in the 2H(d,n)3He reaction at 10 MeV

Angular distributions of six polarization transfer coefficients $\text{K}{}_{\mathrm{x}}{}^{\mathrm{x\prime }}\text{(θ), k}{}_{\mathrm{x}}{}^{\mathrm{z\prime }}\text{(θ), K}{}_{\mathrm{z}}{}^{\mathrm{<mtext>x</mtext><mtext>?</mtext>}}\text{(θ), K}{}_{\mathrm{z}}{}^{\mathrm{<mtext>z</mtext><mtext>?</mtext>}}\text{(θ),}\text{and}\text{K}{}_{\mathrm{yy}}{}^{\mathrm{<mtext>y</mtext><mtext>?</mtext>}}\text{(θ)}$; of the four analyzing powers A_y(θ), A_xx(θ), A_yy(θ), and A_zz(θ); and of the polarization function P^ý(θ), have been measured atE_d = 10.00 MeV for the reaction ²H(d, n)³He. Measurements were made for neutron lab angles between 0° and 80° in 10° steps. Additionally the y-axis associated quantities were measured at θ_1ab = 99°. Most of the measured coefficients are large at some angles and all show considerable variation with angle.     

Long-lived non-equilibrium population of Fe3+ electronic states after the K-capture of 57Co

Mössbauer emission spectra of a frozen aqueous solution of ⁵⁷CoCl₂ show contributions from the $\text{S}{}_{\mathrm{z}}\text{= +}\text{5}\text{2}$ and the $\text{S}{}_{\mathrm{z}}\text{= +}\text{3}\text{2}$ Zeeman levels of Fe³⁺ ions at T = 4.2 K in H ? 30 kG. The K-capture results in a non-equilibrium state of relaxation time comparable to the lifetime of the nuclear excited state (～ 10^?7 s).     

Nuclear incompressibility: From finite nuclei to nuclear matter

The recent increase of experimental data concerning the giant monopole resonance energy E_M gives information on the incompressibility modulus of nuclear matter, provided one can extrapolate the incompressibility of a nucleus K_A, defined by $\text{E}{}_{\mathrm{<mtext>M</mtext>}}\text{=[}\text{h}\text{?}{}^2\text{K}{}_{\mathrm{<mtext>A</mtext>}}\text{/m〈r}{}^2\text{〉]}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$, to the infinite medium. We discuss the theoretical interpretation of the coefficients of an $\text{A}{}^{\mathrm{<mtext>?1</mtext><mtext>3</mtext>}}$ expansion of K_A by studying the asymptotic behaviour of two RPA sum rules (corresponding to the scaling and the constrained model), evaluated using self-consistent Thomas-Fermi calculations. We show that the scaling model is the most suitable one as it leads to a rapidly converging $\text{A}{}^{\mathrm{<mtext>?1</mtext><mtext>3</mtext>}}$ expansion of the corresponding incompressibility K_A^s, whereas this is not the case with the constrained model. Some semi-empirical relations between the coefficients of the expansion of K_A^s are established, which reduce to one the number of free parameters in a best-fit analysis of the experimental data. This reduction is essential due to the still limited number and accuracy of experimental data. We then show the compatibility of the data given by the various experimental groups with this parametrization and obtain a value of K_n.m. = 220 ± 20 MeV, in good agreement with more microscopic analyses.     

The electronic isotope shift in the A2Π-X2Σ+ bands of BeH,BeD and BeT

The 0-0, 1-1, 2-2, and 3-3 bands of the A²Π-X²Σ⁺ transition of the tritiated beryllium monohydride molecule have been observed at 5000 Å in emission using a beryllium hollow-cathode discharge in a He + T₂ mixture. The rotational analysis of these bands yields the following principal molecular constants.

$\text{A}{}^2\text{Π:}\text{B}{}_{\mathrm{e}}\text{= 4.192}\text{cm}{}^{\mathrm{?1}}\text{; r}{}_{\mathrm{e}}\text{= 1.333}\text{A}\text{?}$

$\text{X}{}^2\text{Σ:}\text{B}{}_{\mathrm{e}}\text{= 4.142}\text{cm}{}^{\mathrm{?1}}\text{; r}{}_{\mathrm{e}}\text{= 1.341}\text{A}\text{?}$

$\text{ω}{}_{\mathrm{e}}\text{′ ? ω}{}_{\mathrm{e}}\text{″ = 16.36}\text{cm}{}^{\mathrm{?1}}\text{; ω}{}_{\mathrm{e}}\text{′X}{}_{\mathrm{e}}\text{′ ? ω}{}_{\mathrm{e}}\text{″X}{}_{\mathrm{e}}\text{″ = 0.84}\text{cm}{}^{\mathrm{?1}}$

From the pure electronic energy difference (E_Π - E_Σ)_BeT = 20 037.91 ± 1.5 cm^?1 and the corresponding previously known values for BeH and BeD, the following electronic isotope shifts are derived

$\text{ΔE}{}_{\mathrm{e}}{}^{\mathrm{i}}\text{(}\text{BeH}\text{?}\text{BeT}\text{) = ?4.7 ≠ 1.5}\text{cm}{}^1\text{, ΔE}{}_{\mathrm{e}}{}^{\mathrm{i}}\text{(}\text{BeH}\text{?}\text{BeT}\text{) = ?1.8 ≠ 1.5}\text{cm}{}^1$

and related to the theoretical approach given by Bunker to the problem of the breakdown of the Born-Oppenheimer approximation.     

Microwave spectra of deuterated ethylenes: Dipole moment and rz structure

The pure rotational spectra of three deuterated ethylenes, CH₂CD₂, CH₂CHD, and cis-CHDCHD, were observed by microwave spectroscopy, and the rotational and centrifugal distortion constants were determined precisely. The dipole moment of CH₂CD₂ was calculated from the Stark effects to be 0.0091 ± 0.0004 D. From the observed rotational constants the average structure was calculated to be $\text{r}{}_{\mathrm{z}}\text{(CC)}\text{= 1.3391 ± 0.0013}\text{A}\text{?}$, $\text{r}{}_{\mathrm{z}}\text{(CH)}\text{= 1.0869 ± 0.0013}\text{A}\text{?}$, θ_z(CCH) = 121.28 ± 0.10°, and $\text{r}{}_{\mathrm{z}}\text{(CH)}\text{- r}{}_{\mathrm{z}}\text{(CD)}\text{= 0.00137 ± 0.00037}\text{A}\text{?}$, where the errors include one standard deviation in the fitting and errors due to an uncertainty (±0.03°) in θ_z(CCH) - θ_z(CCD).     

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.