The D′ → A′ transition in Br2

A vibrational and rotational analysis is presented for the D′ → A′ transition (2800–2950 Å) of Br₂. The analysis includes 11 rotationally analyzed bands for ⁷⁹Br₂ and 3 for ⁸¹Br₂, plus bandheads for 70 additional v′-v″ bands of ⁷⁹Br₂, ⁸¹Br₂, and ⁷⁹Br⁸¹Br. The latter include some violet-degraded and spikelike features at the long-wavelength end of the spectrum, which are interpreted and assigned with the aid of band profile simulations. The assigned features are fitted directly to 14 vibrational and rotational expansion parameters for the two electronic states, from which the following spectroscopic constants are obtained: ΔT_e = 35706 cm^?1, ω′_e = 150.86 cm^?1, ω″_e = 165.2 cm^?1, B′_e = 0.042515 cm^?1, B″_e = 0.05944 cm^?1, $\text{R′}{}_{\mathrm{e}}\text{= 3.170}\text{A}\text{?}$, $\text{R″}{}_{\mathrm{e}}\text{= 2.681}\text{A}\text{?}$. The spectroscopic parameters are used to calculate RKR potentials and Franck-Condon factors for the transition.     

Scaling of the “superstable” fraction of the 2D period-doubling interval

The scaling properties of a “superstable” parameter interval, $\text{C}$, where the eigenvalues about a period-2n orbit are complex, are derived for 2D period-doubling maps. The ratio of $\text{C}$ to the whole parameter interval, between the nth and the (n+1)st bifurcation, is shown to be a universal function of the effective jacobian, B_e, only (B_e≡B²ⁿ, B is thejacobian of th e map). Unlike the whole period-2ⁿ interval, $\text{C}$ has a convergence rate that behaves as $\text{4.6692016×B}{}^{\mathrm{<mtext>-1</mtext><mtext>4</mtext>}}{}_{\mathrm{e}}$ as B_e↓), wh ile its complement has a convergence rate 8.7210972/4 as B_e↑1.     

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, $\text{R′}{}_{\mathrm{e}}\text{= 3.53}\text{A}\text{?}$.     

Rotational analysis of the B3Π(0+) → X1Σ+ band systems of 35Cl35Cl and 35Cl37Cl in the chlorine afterglow emission spectrum

The B³Π(0⁺) → X¹Σ⁺ band system of Cl₂, excited by the recombination of ground state $\text{Cl}{}^2\text{P}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ atoms at total pressures near 2 Torr, has been rotationally analyzed in the range 6300–9900 Å. About 30 bands, with 0 ≤ v′ ≤ 6 and 5 ≤ v″ ≤ 14, were investigated, mostly for both ³⁵Cl³⁵Cl and ³⁵Cl³⁷Cl. The band origins and rotational constants for the B state were obtained with the help of the known constants for the ground state. The principal molecular constants (cm^?1) for the B³Π(0⁺) state of ³⁵Cl³⁵Cl are as follows: T_e′ = 17 817.67(3); ω_e′ = 255.38(3); ω_e′x_e′ = 4.59(1); ω_e′y_e′ = ?0.038(8); D_e′ = 3341.17(14); B_e′ = 0.16313(3); α_e′ = 2.42(3) × 10^?3; γ_e′ = ?5.7(7) × 10^?5. The equilibrium internuclear separation is 2.4311(2) Å. The results of Briggs and Norrish on a transient absorption spectrum of Cl₂ assigned as $\text{0}{}_{\mathrm{g}}{}^{\mathrm{+}}\text{← B}{}^3\text{Π}\text{(0}{}^{\mathrm{+}}\text{)}$ are reinterpreted with the present constants.     

An effective method of investigation of positive maps on the set of positive definite operators

Let $\text{A}$₁ be the algebra of linear operators on the n-dimensional Hilbert space $\text{H}$₁, and let $\text{A}$₂ be the algebra of linear operators of the m-dimensional Hilbert space $\text{H}$₂. Let $\text{L}$($\text{A}$₁, $\text{A}$₂) denote the complex space of linear maps from $\text{A}$₁ to $\text{A}$₂. By a positive map we mean an element of the space $\text{L}$($\text{A}$₁, $\text{A}$₂) (superoperator with respect to $\text{H}$₁) which maps positive definite operators in $\text{A}$₁ into positive definite operators in $\text{A}$₂. The aim of this paper is to present an effective method which allows to verify whether a given superoperator Λ∈$\text{L}$($\text{A}$₁, $\text{A}$₂) is a positive map. Besides that necessary and sufficient conditions for the positive definiteness of even-degree forms in many variables are given.     

The emission spectra of H35Cl+, H37Cl+, D35Cl+, and D37Cl+ in the region 2700–4100 Å

The $\text{A}{}^2\text{Σ}{}^{\mathrm{+}}\text{-X}{}^2\text{Π}$ emission spectrum of HCl⁺ has been measured and analyzed for four isotopic combinations. These analyses extend previous work and provide rotational constants for the v = 0–2 levels of the ground state and for the v = 0–9 levels of the excited state. RKR potentials have been determined for both states, although the upper state could not be fitted precisely to such a model. Calculated relative intensities based on these potentials demonstrated that the electronic transition moment must change rapidly with lower state vibrational quantum number. Although considerable caution should be exercised in applying the concept of equilibrium constants to the $\text{A}{}^2\text{Σ}{}^{\mathrm{+}}$ state, the following are the best estimates of these constants (in cm^?1) for the $\text{X}{}^2\text{Π}$ state of H³⁵Cl⁺: B_e = 9.9406, ω_e = 2673.7, A_e = ? 643.7, and $\text{r}{}_{\mathrm{e}}\text{= 1.315}\text{A}\text{?}$. For the $\text{A}{}^2\text{Σ}{}^{\mathrm{+}}$ state of H³⁵Cl: T_e = 28 628.08, B_e ～ 7.505, ω_e ～ 1606.5, and $\text{r}{}_{\mathrm{e}}\text{= 1.514}\text{A}\text{?}$.     

The 404.5-nm system of the ReO molecule

Observations on the emission spectrum of ReO in the region 375–870 nm are reported. Five bands of a $\text{ΔΩ}\text{= 0}$ system with (0, 0) band at 404.5 nm have been rotationally analyzed and the principal results for ¹⁸⁷ReO are (in cm^?1) ν₀ = 24 709.90, B′_e = 0.3819, B″_e = 0.4252, ω′_e = 874.8₂, and $\text{Δ}\text{G″(}\text{1}\text{2}\text{) = 979.1}{}_2$. Data on the minor isotopic species ¹⁸⁵ReO are also reported. It is suggested that broad rotational profiles found in bands near 842 nm may be due to nuclear hyperfine structure.     

The B2Σ+ → A2Πi system of silicon nitride,SiN

The 440-nm violet-degraded ${}^2\text{Σ →}{}^2\text{Π}$ bands of SiN, which were previously assigned to a $\text{“K” → A}$ system, have been reanalyzed. These bands are shown to be Δv = 0, ±1 sequence bands of the B²Σ⁺ → A²Π system of SiN. The first reliable value of T_e(A²Π) = 994.4(1) cm^?1 has been obtained, and this determines the location of the D²Π and L²Π states with respect to the ground state. The B²Σ⁺, v = 7 and D²Π, v = 3 levels are shown to be mutually perturbing. A detailed study has been made of the perturbed X²Σ⁺, v = 8 level. The 6–8 band of the B → X system has been photographed at high resolution. A deperturbation of this band confirms T_e(A²Π), and provides the first experimental verification of the inverted nature of the A state.     

Spectroscopic analysis of the d1Σ+→a1Σ+ and d1Σ+→b1Π green band systems of XeO

A comprehensive high resolution spectroscopic analysis has been made on the XeO green bands photographed in emission from an RF discharge source. Rotation-vibration constants derived from the analysis of the spectrum of the isotopically enriched species ¹²⁹Xe¹⁶O and ¹²⁹Xe¹⁸O were used to give RKR potential curves for the d¹Σ⁺ and b¹Π states. The bond distances and dissociation energies of the d¹Σ⁺ and b¹Π states were respectively found to be $\text{r}{}_{\mathrm{e}}\text{= 2.852 ± 0.002}\text{A}\text{?}$, D_e = 693 ± 10 cm^?1 and $\text{r}{}_{\mathrm{e}}\text{= 2.548 ± 0.002}\text{A}\text{?}$, D_e = 461 ± 10 cm^?1. For the a¹Σ⁺ state it was not possible to establish a unique vibrational numbering or to construct an RKR potential curve, since observed bands of the d¹Σ⁺→a¹Σ⁺ system involve only high vibrational levels of the a¹Σ⁺ state, which are severely predissociated. The observations are consistent with a fairly deep well, in agreement with the latest ab initio calculations which give a well depth of 0.7 eV.     

The D′ → A′ transition in I2

A detailed vibrational analysis is given for the D′(2g) → A′(2u³Π) transition (3300–3460 Å) in I₂. The assignments include ～ 150 v′-v″ bands in ¹²⁷I₂ and ～100 in ¹²⁹I₂, spanning v′ levels 0–15 and v″ levels 4–30. These bands are mainly red-degraded but include some violet-degraded and line-like features. The analysis is corroborated by Franck-Condon and band profile calculations. The least-squares fit yields the following constants (cm^?1); ΔT_c = 30 340.8, ω′_e = 103.95, ω_eχ′_e = 0.206, ω″_e = 106.1, ω_eχ″_e = 0.81. Anomalous behavior in the vibrational level structure above v″ = 23 makes the extrapolation to the A′ dissociation limit uncertain, so the absolute energies of both states remain ill-defined. However there is a possibility that the D′ state is the state labeled α by King et al. [Chem. Phys. 56, 145–156 (1981)], in which case the energies are known precisely. There is evidence of weak emission from at least two other electronic transitions in this spectral region, probably $\text{D(0}{}^{\mathrm{+}}\text{u) → X(}{}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}\text{)}$ ($\text{λ}\text{< 3300}\text{A}\text{?}$) and β → A(1u³Π) ($\text{λ}\text{> 3300}\text{A}\text{?}$).     

Cross section of ion excitation in ion-ion collision

The “effective Feynman diagram” technique introduced in a previous paper is used to express the cross section of ion excitation in ion-ion collisions $\text{(A + B → A}{}^1\text{+ B)}$ in terms of the corresponding photon resonance absorption $\text{(hv + A → A}{}^1\text{)}$ and Thomson-scattering (hv + B → hv + B) cross sections. The result is checked for the process He⁺ + H(1s) → He⁺ + H(2p) with experiment and very good agreement is obtained.     

Analysis of the B1Πu → X1Σg+ band system of 7Li2 molecule excited by the 4545- and 5287-Å visible lines of the argon ion laser

Two new fluorescence series have been excited by the two lines at the extreme ends of the range of visible Ar⁺ transitions, 4545 and 5287 Å. In each case the B¹Π_u electronic state of ⁷Li₂ is excited, to levels $\text{v′ = 12, J′ = 13 (4545}\text{A}\text{?}\text{)}$ and $\text{v′ = 2, J′ = 58 (5287}\text{A}\text{?}\text{)}$. Fluorescence to the ground state can be detected in the range 2 ≤ v″ ≤ 23 and 0 ≤ v″ ≤ 8, respectively. Measured relative intensities agree well with calculated radiative transition probabilities reported herein.     

A new electronic band system of PbO

The chemiluminescence spectrum of atomic Pb reacting with O₃ under single-collision conditions includes a series of 55 bands in the regions 450–850 nm. A vibrational analysis is obtained which shows emission is to the ground state of PbO from excited electronic states not previously analyzed. Forty-nine of the bands are assigned to the a(1)-X(0⁺) transition and the remaining six are tentatively identified as the forbidden b(0^?)-X(0⁺) transition. Both the a and b states are believed to be Hund's case (c) components of the ³Σ⁺ states arising from the configuration $\text{σ}{}^2\text{π}{}^3\text{π}{}^1$. The vibrational parameters of the a state are ν₄ = 16 029 ± 8, ω_e′ = 478.7 ± 1.9, and ω_ex_e′ = 2.292 ± 0.128 cm^?1, where the uncertainties represent two standard deviations of the least-squares fit. Emission is also observed from the PbO B state produced in the reaction of metastable Pb atoms with O₃. Using pulsed laser excitation, an attempt is made to determine radiative lifetimes. We find for the PbO A(0⁺) state τ = 3.74 ± 0.3 μsec, and for the PbO B(1) state τ = 2.58 ± 0.3 μsec, while for the a(1) state τ is estimated to be greater than 10 μsec. From the vibrational analysis, energy conservation arguments place a lower limits to the ground state dissociation energy of $\text{D}{}_0{}^0\text{(}\text{PbO}\text{) ≥ 3.74 ± 0.03}\text{eV}$ (86.2 ± 0.7 kcal/mole). For the Pb + O₃ reaction we find less than 1% of the products are PbO¹ molecules that emit in the visible. Correlations are made with the low-lying states of other Group IV chalconides based on the assignment of the PbO $\text{a}{}^3\text{Σ}{}^{\mathrm{+}}\text{(1)}$ state and the correspondence between the low-lying triplet states of PbO and CO.     

The A′(3Π2) state of ICl

Although $\text{A′(}{}^3\text{Π}{}_2\text{) ← X(}{}^1\text{Σ}{}^{\mathrm{+}}\text{)}$ is forbidden in near case c molecules the A′ ← X transition can be efficiently accomplished by the three-step sequence $\text{A′(}{}^3\text{Π}{}_2\text{) ← D′(2) ← A(}{}^3\text{Π}{}_1\text{) ← X(}{}^1\text{Σ}{}^{\mathrm{+}}\text{)}$. Transitions to a range of levels of A′, v_A′ = 2–38, have been recorded by this means, using J-selective polarization-labeling spectroscopy. Principal constants of the A′ state of I³⁵Cl are T_e = 12682.05, ω_e = 224.57, ω_eχ_e = 1.882, ω_ey_e = ?0.0107, B_e = 0.08653, and α_e = 0.000675 cm^?1. The A′ state is therefore similar in its physical characteristics to two other (relatively) deep states, $\text{A(}{}^3\text{Π}{}_1\text{)}$ and $\text{B(}{}^3\text{Π}{}_0\text{+)}$, of the 2431 configuration.     

Measurements of tau decay modes and a precise determination of the mass

The cross sections for e⁺e^? → e⁺(μ⁺ + non showering track + any photons have been measured for cm energies between 3.1 GeV and 5.2 GeV. We observe τ-pair production below the thresholdfor charm production and determine the τ mass to be 1.807 ± 0.020 GeV from a fit to the energy dependence of the cross section. The ration of the leptonic branching ratios B_μ/B_e = 0.92 ± 0.32 is consistent with eμ-universality. The following branching ratios are determined for a V-A coupling: $\text{B(τ → ν}{}_{\mathrm{\tau }}\text{e}\text{ν}\text{) = B(τ → ν}{}_{\mathrm{\tau }}\text{μ}\text{ν}\text{) = 0.182 + 0.028}$. B(τ → ν_τ + charged hadron + any photons) = 0.29 ± 0.11, B(τ → ν_τ + three or more charged hadrons + any photons) = 0.35 ± 0.11.     

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

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

,     

Spatial theory for algebras of unbounded operators

In this paper, the spatial theory of ¹-automorphisms is investigated in the context of algebras of unbounded operators. In particular, it is shown that ¹-automorphisms, satisfying some order relation, of the Op¹-algebra generated by the position and momentum operators q_j, p_j(j=1,...., n) on the Schwartz space $\text{I}\text{(}\text{R}{}^{\mathrm{n}}\text{)}$ are unitarily implemented.     

Vibration-rotation and deperturbation analysis of A2Π-X2Σ+ and B2Σ+-X2Σ+ systems of the CaI molecule

Doppler-limited laser excitation spectroscopy employing narrow-band fluorescence detection was used to obtain a rotational and vibrational analysis in the (0, 0) and (1, 1) bands of the A²Π-X²Σ⁺ system and the (4, 2) (3, 1), (0, 0), (0, 1), (1, 2), (2, 3), and (3, 4) bands of the B²Σ⁺-X²Σ⁺ system of CaI. The A and B states are deperturbed to obtain spectroscopic constants and Franck-Condon factors. Deperturbation was necessary because of the small separation of the A and B states relative to the A ～ B interaction strength and the A²Π spin-orbit splitting. The main deperturbed constants (in cm^?1) are

     

19.

Rotationally resolved spectra of two van der Waals states of I + Cl     

J.C.D Brand  A.R Hoy 《Journal of Molecular Spectroscopy》1985,114(1):219-227

Three-step optical resonance is used to execute state-selected transitions from the ground state of ICl to two van der Waals states, $\text{b(}\text{Ω}\text{= 1)}$ and $\text{b′(}\text{Ω}\text{= 2)}$, both of which correlate with the second dissociation limit, $\text{I}\text{(}{}^2\text{P}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{) +}\text{Cl}\text{(}{}^2\text{P}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{)}$, of ICl. Since the B(0⁺) state also belongs to this limit, three out of five states converging to I + Cl¹ are now accounted for. Principal constants of these states are: b′(2): T_e = 18275.84, ω_e = 31.093, ω_ex_e = 1.672, ω_ey_e = 0.0070, B_e = 0.034834, α_e = .001587, and D_e = 164.09 cm^?1; b(1): T_e = 18273.30, ω_e = 26.75, ω_ex_e = 0.882, B_e = 0.03579, q = 0.00084, and D_e = 166.63 cm^?1. In both states the equilibrium distance is near 4.2 Å, slightly greater than the sum of van der Waals contact radii, $\text{r}{}_{\mathrm{<mtext>I</mtext>}}\text{+ r}{}_{\mathrm{<mtext>Cl</mtext>}}\text{= 3.95}\text{A}\text{?}$. The large value of q in the b(1) state indicates that, in the basis set $\text{|j}{}_{\mathrm{a}}\text{j}{}_{\mathrm{b}}\text{j}\text{Ω}\text{〉}$ (a = I, b = Cl, j = j_a + j_b) the b(1) and b′(2) states belong to j = 1 and j = 2 “complexes,” respectively.     

20.

A spectrum of rhenium oxide     

Walter J Balfour  F.B Orth 《Journal of Molecular Spectroscopy》1980,84(2):424-430

The arc emission spectrum of the ReO molecule has been photographed in the region 590–860 nm and three bands of a single electronic transition have been rotationally analyzed. The separation of lines of the isotopic molecules ¹⁸⁵ReO and ¹⁸⁷ReO leads to the conclusion that the vibrational assignments for these bands are 1-0, 0-0, and 0–1. It is conceivable that an electronic isotope shift of ～0.08 cm^?1 exists. The following vibrational and rotational data (cm^?1) have been determined: ν₀(0-0) = 14 038.42, $\text{Δ}\text{G′(}\text{1}\text{2}\text{) = 867.85}$, $\text{Δ}\text{G″(}\text{1}\text{2}\text{) = 979.14}$; B′_e = 0.3889, α′_e = 0.0019, B″_e = 0.4257, α″_e = 0.0043. It is concluded that Λ′ ? Λ″ = +1 with Λ″ ≥ 2.     

	$\text{X}{}^2\text{Σ}{}^{\mathrm{+}}$	$\text{A}{}^2\text{Π}$	$\text{B}{}^2\text{Σ}{}^{\mathrm{+}}$
$\text{T}{}_{\mathrm{e}}$	0	15 624.67(5)	15 700.52(12)
$\text{ω}{}_{\mathrm{e}}$	238.7496(33)	241.19(7)	242.63(17)
$\text{ω}{}_{\mathrm{e}}\text{χ}{}_{\mathrm{e}}$	0.62789(64)	0.53(5) (Pekeris)	1.17(12) (Pekeris)
$\text{B}{}_{\mathrm{e}}$	0.0693254(84)	0.070460(14)	0.071572(22)
$\text{α}{}_{\mathrm{e}}\text{× 10}{}^4$	2.640(35)	2.15(10)	3.95(2)
$\text{A}{}_{\mathrm{e}}$	—	45.8968(52)	—
$\text{R}{}_{\mathrm{e}}\text{(}\text{A}\text{?}\text{)}$	2.8286(2)	2.8057(3)	2.7839(4)

Rotationally resolved spectra of two van der Waals states of I + Cl

Three-step optical resonance is used to execute state-selected transitions from the ground state of ICl to two van der Waals states, $\text{b(}\text{Ω}\text{= 1)}$ and $\text{b′(}\text{Ω}\text{= 2)}$, both of which correlate with the second dissociation limit, $\text{I}\text{(}{}^2\text{P}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{) +}\text{Cl}\text{(}{}^2\text{P}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{)}$, of ICl. Since the B(0⁺) state also belongs to this limit, three out of five states converging to I + Cl¹ are now accounted for. Principal constants of these states are: b′(2): T_e = 18275.84, ω_e = 31.093, ω_ex_e = 1.672, ω_ey_e = 0.0070, B_e = 0.034834, α_e = .001587, and D_e = 164.09 cm^?1; b(1): T_e = 18273.30, ω_e = 26.75, ω_ex_e = 0.882, B_e = 0.03579, q = 0.00084, and D_e = 166.63 cm^?1. In both states the equilibrium distance is near 4.2 Å, slightly greater than the sum of van der Waals contact radii, $\text{r}{}_{\mathrm{<mtext>I</mtext>}}\text{+ r}{}_{\mathrm{<mtext>Cl</mtext>}}\text{= 3.95}\text{A}\text{?}$. The large value of q in the b(1) state indicates that, in the basis set $\text{|j}{}_{\mathrm{a}}\text{j}{}_{\mathrm{b}}\text{j}\text{Ω}\text{〉}$ (a = I, b = Cl, j = j_a + j_b) the b(1) and b′(2) states belong to j = 1 and j = 2 “complexes,” respectively.     

A spectrum of rhenium oxide

The arc emission spectrum of the ReO molecule has been photographed in the region 590–860 nm and three bands of a single electronic transition have been rotationally analyzed. The separation of lines of the isotopic molecules ¹⁸⁵ReO and ¹⁸⁷ReO leads to the conclusion that the vibrational assignments for these bands are 1-0, 0-0, and 0–1. It is conceivable that an electronic isotope shift of ～0.08 cm^?1 exists. The following vibrational and rotational data (cm^?1) have been determined: ν₀(0-0) = 14 038.42, $\text{Δ}\text{G′(}\text{1}\text{2}\text{) = 867.85}$, $\text{Δ}\text{G″(}\text{1}\text{2}\text{) = 979.14}$; B′_e = 0.3889, α′_e = 0.0019, B″_e = 0.4257, α″_e = 0.0043. It is concluded that Λ′ ? Λ″ = +1 with Λ″ ≥ 2.