FINE STRUCTURE OF THE SCHUMANN-RUNGE BANDS NEAR THE CONVERGENCE LIMIT AND THE DISSOCIATION ENERGY OF THE OXYGEN MOLECULE

1954 ◽  
Vol 32 (2) ◽  
pp. 110-135 ◽  
Author(s):  
P. Brix ◽  
G. Herzberg
Keyword(s):  
Dissociation Energy ◽  
Total Angular Momentum ◽  
Oxygen Molecule ◽  
Kcal Mole ◽  
Component Level ◽  
Absorption Bands ◽  
Precise Information ◽  
Near Ultraviolet ◽  
Triplet Splitting ◽  
The One

The Schumann-Runge absorption bands of O2[Formula: see text] have been photographed in the fourth order of a 3 m. vacuum spectrograph with a resolution of 160,000. Some spectra were taken with the O2 at liquid air temperature. A detailed line structure analysis has been carried out for all bands with ν′ > 11. In addition to the six main branches (with ΔJ = ΔN = ± 1), for low values of the quantum number N (total angular momentum apart from spin), several lines of the six satellite branches [Formula: see text] as well as of the two "forbidden" branches (with ΔN = ± 3, ΔJ = ± 1) have been identified. Values of the rotational constants and the vibrational quanta in the upper state have been derived up to ν′ = 21. The triplet splitting increases rapidly with N and with ν′; it cannot be described accurately by the known theoretical formulae.The origin of the 21–0 band is at 57115 cm−1. A very short extrapolation gives the convergence limit at 57128 ± 5 cm−1. This limit agrees excellently with the one derived from the near ultraviolet [Formula: see text] bands if it is assumed that at both limits those O atoms that are produced in the 3P state are in the lowest component level of this state, viz. 3P2. A discrepancy pointed out earlier by Herzberg is thus removed. The convergence limit just mentioned and certain other data derived from the spectrum lead to very precise information about the dissociation energy of O2. Without any extrapolation the dissociation energy into normal atoms can be given as 41260 ± 15 cm−1 (or 5.1148 ± 0.002 ev. or 117.96 ± 0.04 kcal./mole), which is 0.63% higher than the old value.

FORBIDDEN TRANSITIONS IN DIATOMIC MOLECULES: II. THE ABSORPTION BANDS OF THE OXYGEN MOLECULE

1952 ◽  
Vol 30 (3) ◽  
pp. 185-210 ◽  
Author(s):  
G. Herzberg
Keyword(s):  
Dissociation Energy ◽  
Band System ◽  
Opposite Sign ◽  
Dissociation Limit ◽  
Spin Orbit Coupling ◽  
Absorption Bands ◽  
Near Ultraviolet ◽  
Triplet Splitting ◽  
Forbidden Transition ◽  
Low Dispersion

The forbidden [Formula: see text] absorption bands of O2 in the near ultraviolet have been obtained under high resolution with absorbing paths up to 800 m. A detailed fine structure analysis has been carried out. It confirms the identification of the band system as a [Formula: see text] transition. Precise values of the rotational constants Bν and Dν as well as of the vibrational quanta [Formula: see text] in the upper state have been derived. Each of the "lines" of the Q branches observed under low dispersion is resolved into six components whose spacing yields the triplet splitting in the upper state. This splitting is more than twice as large as in the [Formula: see text] ground state and is of opposite sign. The splitting constants λ and γ have been determined and their variation with the vibrational quantum number observed. In addition to the Q-form branches weak O- and S-form branches have been found in agreement with the prediction of Present which is based on the assumption that spin–orbit coupling is the main cause for the occurrence of this forbidden transition. However, the relative intensities of the different branches deviate strongly from Present's prediction. The dissociation limit obtained from the convergence limit of the bands (without extrapolation) is at 41219 ± 40 cm.−1 This value is higher by about 220 cm.−1 than the value of the dissociation energy of O2 derived from the Schumann–Runge bands. It is possible that the limit of the Schumann–Runge bands, which is based on a short extrapolation, and therefore the value of the dissociation energy of O2 has to be slightly revised. The electron configurations and dissociation products of the various electronic states of O2 are briefly discussed.

The dissociation energy of gaseous diatomic sulfur

1969 ◽  
Vol 47 (21) ◽  
pp. 2423-2427 ◽  
Author(s):  
J. M. Ricks ◽  
R. F. Barrow
Keyword(s):  
Long Range ◽  
Dissociation Energy ◽  
The State ◽  
Rotational Analysis ◽  
Kcal Mole ◽  
Absorption Bands

Three limiting curves of predissociation for the F1, F2, and F3 components of the state B3Zu− of S2 have been obtained following a detailed rotational analysis of emission and absorption bands of 32S2, 34S2, and 32S34S. The three curves extrapolate to identical limits, at 35 999.0 ± 2.5 cm−1 above the minimum in X3Σg−. The predissociating state is thereby identified as a 1u state, and arguments based upon (i) the noncrossing rule for states of like Ω and (ii) a comparison of the observed shapes of the limiting curves with those calculated on the basis of long-range forces, indicate that the products at this limit are S(3P2) + S(3P1). D00 (32S2) is then 35 216.4 ± 2.5 cm−1, or 100.69 ±.01 kcal mole−1.

The C—Br bond dissociation energy in halogenated bromomethanes

1951 ◽  
Vol 209 (1096) ◽  
pp. 110-131 ◽  
Keyword(s):  
Bond Dissociation Energy ◽  
Dissociation Energy ◽  
Methyl Bromide ◽  
Frequency Factor ◽  
Unimolecular Dissociation ◽  
Bond Dissociation Energies ◽  
Kcal Mole ◽  
Fast Reaction ◽  
Bond Dissociation ◽  
Dissociation Energies

The pyrolyses of methyl bromide and of the halogenated bromomethanes, CH 2 CI. Br, CH 2 Br 2 , CHCl 2 .Br, CHBr 3 , CF 3 Br, CCI 3 . Br and CBr 4 , have been investigated by the ‘toluene-carrier' technique. It has been shown that all these decompositions were initiated by the unimolecular process R Br → R + Br. (1) Since all these decompositions were carried out in the presence of an excess of toluene, the bromine atoms produced in process (1) were readily removed by the fast reaction C 6 H 5 .CH 3 + Br → C 6 H 5 . CH 2 • + HBr. Hence, the rate of the unimolecular process (1) has been measured by the rate of formation of HBr. The C—Br bond dissociation energies were assumed to be equal to the activation energies of the relevant unimolecular dissociation processes. These were calculated by using the expression k ═ 2 x 10 13 exp (- D/RT ). The reason for choosing this particular value of 2 x 10 13 sec. -1 for the frequency factor of these reactions is discussed. The values obtained for the C—Br bond dissociation energies in the investigated bromomethanes are: D (C—Br) D (C—Br) compound (kcal./mole) compound (kcal./mole) CH 3 Br (67.5) CHBr 3 55.5 CH 2 CIBr 61.0 CF 3 Br 64.5 CH 2 Br 2 62.5 CCI 3 Br 49.0 CHCl 2 Br 53.5 CBr 4 49.0 The possible factors responsible for the variation of the C—Br bond dissociation energy in these compounds have been pointed out.

REDUCTIVE CLEAVAGE WITH METAL IN LIQUID AMMONIA: I. THE SELECTIVE CLEAVAGE OF THE BENZYLTHIO C—S BOND VERSUS THE BENZYLIDENEDIOXY C—O BOND IN METHYL S-BENZYL-4,6-O-BENZYLIDENE-2-THIO-α-D-ALTROPYRANOSIDES; THE INFLUENCE OF THE COSOLVENT 1,2-DIMETHOXYETHANE ON THE COURSE OF THE REACTION

1966 ◽  
Vol 44 (5) ◽  
pp. 591-602 ◽  
Author(s):  
U. G. Nayak ◽  
R. K. Brown
Keyword(s):  
Infrared Absorption ◽  
Liquid Ammonia ◽  
Reductive Cleavage ◽  
The Other ◽  
Metallic Sodium ◽  
Absorption Bands ◽  
Strong Band ◽  
The One ◽  
Infrared Absorption Bands ◽  
Phenyl Moiety

The improved solubility of methyl S-benzyl-4,6-O-benzylidene-2-thio-α-D-altropyranoside (1) in liquid ammonia diluted with 1,2-dimethoxyethane has permitted the selective cleavage by metallic sodium or lithium of the C—S bond to give methyl 4,6-O-benzylidene-2-thio-α-D-altropyranoside in 70–75% yield. On the other hand, the slight solubility of I in liquid ammonia alone results only in the completely hydrogenolyzed material, methyl 2-thio-α-D-altropyranoside, along with unchanged I.Generally, in liquid ammonia alone, reductive cleavage is rapid (15–20 min) and the benzylidene and benzyl groups are converted largely into toluene accompanied by a small amount of bibenzyl. In liquid ammonia – 1,2-dimethoxyethane mixtures the reaction is much slower (≥ 1.5 h); under these conditions the benzylidene and benzyl groups are converted to a larger extent into bibenzyl, the rest becoming toluene.The two strong infrared absorption bands (in Nujol) in the region of 766 to 778 cm−1 and 706 to 718 cm−1 have been assigned to the phenyl moiety of the benzylidene group, and the one strong band in the region of 702 cm−1 to the phenyl moiety of the S-benzyl group.

A new photoluminescent coordination polymer constructed with an N-donor ligand having extended coordination capabilities derived from quinoline and pyridine

2020 ◽  
Vol 76 (5) ◽  
pp. 500-506
Author(s):  
Kamil Twaróg ◽  
Małgorzata Hołyńska ◽  
Andrzej Kochel
Keyword(s):  
Coordination Polymer ◽  
Pyridyl Ring ◽  
Ligand Molecule ◽  
Hydrothermal Conditions ◽  
Absorption Bands ◽  
Donor Ligand ◽  
One Dimensional ◽  
The One ◽  
Chloride Monohydrate ◽  
Carboxylic Acid Ligand

Employment of the organic 2-(pyridin-4-yl)quinoline-4-carboxylic acid ligand with extended coordination capabilities leads to the formation of the one-dimensional copper(II) coordination polymer catena-poly[[diaquacopper(II)]-bis[μ-2-(pyridin-4-yl)quinoline-4-carboxylato]-κ2 N 2:O;κ2 O:N], {[Cu(C15H9N2O2)2(H2O)2]·2H2O} n , under hydrothermal conditions. The ligand, isolated as its hydrochloride salt, namely, 4-(4-carboxyquinolin-2-yl)pyridinium chloride monohydrate, C15H11N2O2 +·Cl−·H2O, reveals a pseudosymmetry element (translation a/2) in its crystal structure. The additional pyridyl N atom, in comparison with the previously reported analogues with an arene ring instead of the pyridyl ring in the present ligand molecule, promotes the formation of a one-dimensional coordination polymer, rather than discrete molecules. This polymer shows photoluminescent properties with bathochromic/hypsochromic shifts of the ligand absorption bands, leading to a single band at 479 nm. The CuII ions are involved in weak antiferromagnetic interactions within dimeric units, as evidenced by SQUID magnetometry.

THE INFRARED SPECTRUM AND THERMAL DECOMPOSITION OF HYDRAZINE PERCHLORATE HEMIHYDRATE

1966 ◽  
Vol 44 (20) ◽  
pp. 2435-2443 ◽  
Author(s):  
P. W. M. Jacobs ◽  
A. Russell-Jones
Keyword(s):  
Infrared Spectrum ◽  
Reaction Mechanisms ◽  
Low Temperatures ◽  
Room Temperature ◽  
Kcal Mole ◽  
Absorption Bands ◽  
Kinetics Of Decomposition ◽  
Salt Melts ◽  
Chemical Equation ◽  
Kinetics Of

The infrared spectrum of hydrazine perchlorate hemihydrate (HPH) has been determined and an assignment of the absorption bands made. Invacuo, HPH will partially dehydrate even at room temperature; when heated the remainder of the half-mole of water is lost at 61 °C. The dehydrated salt melts at 138 °C and decomposition ensues. The kinetics of decomposition may be followed in the temperature range 180–280 °C. The activation energy is 36.3 kcal/mole. At low temperatures the decomposition is represented by the chemical equation[Formula: see text]but when the temperature is high enough the rate of decomposition of the ammonium perchlorate formed becomes appreciable also. Possible reaction mechanisms are discussed.

THE THERMAL DECOMPOSITION OF PERACETIC ACID IN THE VAPOR PHASE

1963 ◽  
Vol 41 (7) ◽  
pp. 1819-1825 ◽  
Author(s):  
C. Schmidt ◽  
A. H. Sehon
Keyword(s):  
Thermal Decomposition ◽  
Vapor Phase ◽  
Dissociation Energy ◽  
Peracetic Acid ◽  
Kcal Mole ◽  
Temperature Range ◽  
Primary Reactions

The thermal decomposition of peracetic acid in a stream of toluene was studied over the temperature range 127–360 °C. The main products of the reaction were CO2, CH3COOH, C2H6, CH4, HCHO, O2, and traces of CO. Dibenzyl was also formed.The overall decomposition of peracetic acid was partly heterogeneous and was represented by the two parallel primary reactions[Formula: see text] [Formula: see text]The dissociation energy of the O—O bond in peracetic acid was estimated to be 30–34 kcal/mole.

Determination of the heat of formation of trimethylindium and calculation of the mean In—CH3 bond dissociation energy

1968 ◽  
Vol 46 (10) ◽  
pp. 1633-1634 ◽  
Author(s):  
W. D. Clark ◽  
S. J. W. Price
Keyword(s):  
Bond Dissociation Energy ◽  
Dissociation Energy ◽  
Chloroform Solution ◽  
Kinetic Studies ◽  
Heat Of Formation ◽  
Enthalpy Of Reaction ◽  
Kcal Mole ◽  
Bond Dissociation ◽  
The Mean

The enthalpy of reaction of In(CH3)3,c with a chloroform solution of bromine is −162.5 kcal mole−1. With this value ΔHf0298[In(CH3)3,c] = 29.5 kcal mole−1 and ΔHf0298[In(CH3)3,g] = 41.1 kcal mole−1. Combining the latter with ΔHf0298[CH3,g] = 33.2 kcal mole−1 and ΔHf0298[In,g] = 58.2 kcal mole−1 then gives E(In—CH3) = 38.9 kcal mole−1. From previous kinetic studies D[(CH3)2In—CH3] + D[In—CH3] = 87.9 kcal mole−1. Hence D[CH3In—CH3] = 28.8 kcal mole−1.

Spectroelectrochemical Study of some μ3-Oxo-μ-acetato Trinuclear Rhodium(III) and Iridium(III) Complexes

1995 ◽  
Vol 50 (4) ◽  
pp. 551-557 ◽  
Author(s):  
Kenta Takahashi ◽  
Keisuke Umakoshi ◽  
Akihiro Kikuchi ◽  
Yoichi Sasaki ◽  
Masato Tominaga ◽  
...  
Keyword(s):  
Absorption Spectrum ◽  
Electronic Absorption Spectrum ◽  
Absorption Spectra ◽  
Electronic Absorption ◽  
Electronic Absorption Spectra ◽  
Visible Region ◽  
Absorption Bands ◽  
Visible Absorption ◽  
The One ◽  
Species Being

New trinuclear rhodium(III) complexes, [Rh3(μ3-O)(μ-CH3COO)6(L)3]+ (L = imidazole (Him), 1-methylimidazole (Meim), and 4-methylpyridine (Mepy)) have been prepared. The Him, Meim, and Mepy complexes show reversible one-electron oxidation waves at E1/2 = +1.12, +1.12, and +1.28 V vs Ag/AgCl, respectively, in acetonitrile. Electronic absorption spectra of the one electron oxidized species of these complexes and [Rh3(μ3-O)(μ-CH3COO)6(py)3]+ (py = pyridine) (E1/2 = +1.32 V ) were obtained by spectroelectrochemical techniques. While the Rh3(III,III,III) states show no strong visible absorption, the Rh3(III,III,IV ) species give a band at ca. 700 nm (ε = 3390-5540 mol dm-3 cm-1). [Ir3(μ3-O)(μ-CH3COO)6(py)3]+ with no strong absorption in the visible region, shows two reversible one-electron oxidation waves at +0.68 and +1.86 V in acetonitrile. The electronic absorption spectrum of the one-electron oxidized species (Ir3(III,III,IV )) also shows some absorption bands (688 nm (ε, 5119), 1093 (2325) and 1400 (ca. 1800)). It is suggested that the oxidation removes an electron from the fully occupied anti-bonding orbital based on metal-dπ-μ3-O-pπ interactions, the absorption bands of the (III,III,IV ) species being assigned to transitions to the anti-bonding orbital.

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