A re-examination of the I.R. spectrum of dinitrogen trioxide

Assuming a planar geometry of C _s symmetry and using a Urey-Bradley potential field, the force constants of dinitrogen trioxide have been re-determined within the formalism of Wilson's G-F matrix method. The outcome of the present investigation suggests a new set of force constants some of which are drastically (～ 50 per cent) different than those previously reported. Furthermore, since the i.r. frequencies used in the present investigation were obtained both in the solid state and at low temperatures, the mean amplitudes of thermal vibrations of both ¹⁴N₂O₃ and ¹⁵N₂O₃ are given at 77°k. Finally, it is suggested that more isotopic i.r. data is necessary to ascertain unequivocably the geometry of dinitrogen trioxide.     

Environmental perturbations on foreign atoms and molecules in solid argon,krypton and xenon

Perturbations which are responsible for the shifts of electronic and vibrational spectra of species trapped in a solid are considered in terms of the intermolecular potential which describes interactions between these species and neighbouring atoms. It is shown that in certain instances London's theory can give an adequate approximation to the dispersion energy between an electronically excited species and a rare gas atom. The experimental shifts in the electronic absorption spectra of Hg, NH and C₂ at lattice sites in rare gas crystals at 4·2°k are explained quantitatively on the basis of a Lennard-Jones (6-12) or (6-8-12) potential between the trapped species and the rare gas atoms. The theory does not adequately explain the shifts in those cases where strong angular dependent forces differing appreciably in the two electronic states are present, data on trapped NH₂ free radicals being presented as a case in point. The interaction of sodium atoms with argon at 4·2°k is very complex, the data being consistent with multiple trapping sites for the atoms, a large repulsive interaction between the excited state of sodium and the rare gas, and apparent removal of the three-fold orbital degeneracy in the excited state by the environmental perturbation. The three-fold orbital degeneracy in the ³P₁ state of mercury was found also to be removed. The blue shift of 1281 cm^-1 for the ³P₁ ← ¹S₀ transition of mercury in solid argon at 4·2°k corresponds almost exactly with the position of one of the two prominent features in the spectrum of mercury in argon gas at comparable densities and illustrates the similarity of structure in the two physical states. The interesting perturbations on the vibrational states of NH and C₂ suggest a close similarity to the effect which causes environmental variations of coupling constants for hyperfine interactions in trapped hydrogen atoms.     

An attempt to find a connection between the atomic distribution in liquid and solid metals

The distance of nearest neighbours r ₁, as well as the ‘reduced’ densities extrapolated to 0°k of liquid and solid metals are compared. Some liquids are close-packed at 0°k. With increasing temperature the degree of atomic misfit increases while r ₁ stays constant or even decreases, contrary to the behaviour in the solid phase.     

Assignment of a perturbation in the FT-ICLAS spectrum of 12C2H2 around 12 709.5 cm−1

The vibrational state perturbing the J = 17 and 18 rotational states of the zero-order v ₁ + 3v ₃ state of ¹²C₂H₂ is assigned to the state with vibrational energy predicted at G _ν = 12 685.1 cm^?1 using the cluster model (El Idrissi, M. I., Liévin, J., Campargue, A. and Herman, M., 1999, J. chem. Phys., 110, 2074). The assignment is discussed also in terms of the very special pressure shift behaviour demonstrated previously for absorption lines reaching these levels (Herregodts, F., Hepp, M., Hurtmans, D., Vander Auwera, J. and Herman, M., 1999, J. chem. Phys., 111, 7961). The experimental information arising from a set-up newly running at ULB, called FT-ICLAS brings decisive information in the assignment process. This set-up is described briefly.     

Application of Brønsted's principle of congruence to n-alkane mixtures

The second virial coefficient of normal methane, ¹²CH₄, has been compared with that of the corresponding deutero compound ¹²CD₄, as well as with the other isotopic molecule, ¹³CH₄. These measurements were performed by means of a differential apparatus over a range of temperature extending from 110°k up to 300°k.     

50 years at the forefront of Physics

Mathemtical Techniques and Physical Applications. By J. Killingbeck and G. H. A. Cole. (Amdemic Press, 1971.) [Pp. xiv + 715.] £7£00. Scope: Textbook; reference. Level: Postgraduate; undergraduate.

Group Theory in Solid-state Physics. By H. W Streitwolf (Macdonald, 1971.) [Pp. 248.] £5·00. Scope: Textbook. Level: Postgraduate.

Statistical Physics. By Ya. P. Terletskii. (North-Holland, 1971.) [Pp xv+279.] $6·30. Scope: Textbook. Level: Postgraduate; undergraduate.

Ubsersichtsbeiträge zur Gasdynamik. Edited by E. Leiter and J. Zierep. (Springer-Verlag, 1971.) [Pp. 386.1 $40·70. Scope: Treatise. Level: Specialist/postgraduate.

Classical Theory of Particles and Melds. Vol. I and Vol. II. By K. H. Ruei. (University Press, Taiwan, Republic of China, 1971.) [Pp.: Vol. I, xxiii + 359; Vol. II, xxvi + 424.] Scope: Textbook. Level: Postgraduate; undergraduate.

Topics in Mathematical Physics. Vol. II: Spectral Theory and Wave Processes. By M. Sh. Birman. (Consultants Bureau, 1971.) [Pp. v + 121.] $14·00. Scope: Treatise. Level: For specialists only.

An Introduction to the Theory of Electromagnetic Waves. By A. C. Hewson. (Longman, 1971.) [Pp. viii+ 115.] £ 1·60. Scope: Textbook. Level: Undergraduate.

Modern Physics and Quantum Mechanics. By Elmer E. Anderson. (W. B. Saunders Co. Ltd., 1971.) [Pp. xi+430.] £6·20. Scope: Textbook. Level: Undergraduate.

Polarized Light and Optical Measurement. By Clarke and Grainqer. (Pergamon Press, 1971.) [Pp. viii+ 187.] £3·50 ($9·50.). Scope: Treatise. Level: Specialist/postgraduate.

Phenomena in Ionized Gases 1971. Edited by R. N. Franklin. (Donald Parsons, 1971.) [Pp. xl+450.] £12·00.

Technology Today. Edited by Edward de Bono. (Routledge &; Kegan Paul Press, 1971.) [Pp. xii+ 144.] Cloth edition £1·75; Paperback 50p. Scope: Survey. Level: General reader.

Diffusion Data. No. 1. Edited by DR. F. H. Wohlbier. (Trans Tech Publications, 1971.) [Pp. 289.] Scope: Library (reference). Level: Specialist/postgraduate.     

The equilibrium geometry of the SC3H radical: an ab initio study

The SC₃H radical is known by experiment to have a linear equilibrium structure, but even rather high-level ab initio computations give a bent equilibrium geometry. A theoretical study of the SCCCH radical has been carried out in order to analyse the influence of several factors in the computed equilibrium structure. Quadratic configuration interaction QCISD(T) and restricted coupled cluster RCCSD(T) computations have been performed in combination with large basis sets. Spin-orbit effects have been taken into account through the Breit-Pauli Hamiltonian using multi-configuration SCF and configuration interaction wavefunctions. Our final results indicate that the equilibrium structure must be linear, in agreement with the experimental studies [McCarthy, M. C., Vrtilek, J. M., Gottlieb, C. A., Wang, W., and Thaddeus, P., 1994, Astrophys. J., 431, L127; Hirahara, Y., Ohshima, Y, and Endo, Y, 1994, J. chem. Phys., 101, 7342]. Both spin-orbit and electron correlation effects appear to be of comparable importance, but an adequate computation of the correlation energy has been much more difficult and has ultimately required basis set extrapolations.     

Synthesis of deuterium-labelled halogen derivatives of L-tryptophan catalysed by tryptophanase

The isotopomers of halogen derivatives of l-tryptophan (l-Trp) (4′-F-, 7′-F-, 5′-Cl- and 7′-Br-l-Trp), specifically labelled with deuterium in α-position of the side chain, were obtained by enzymatic coupling of the corresponding halogenated derivatives of indole with S-methyl-l-cysteine in ²H₂O, catalysed by enzyme tryptophanase (EC 4.1.99.1). The positional deuterium enrichment of the resulting tryptophan derivatives was controlled using ¹H NMR. In accordance with the mechanism of the lyase reaction, a 100% deuterium labelling was observed in the α-position; the chemical yields were between 23 and 51%. Furthermore, β-F-l-alanine, synthesized from β-F-pyruvic acid by the l-alanine dehydrogenase reaction, has been tested as a coupling agent to obtain the halogenated deuterium-labelled derivatives of l-Trp. The chemical yield (～30%) corresponded to that as observed with S-methyl-l-cysteine but the deuterium label was only 63%, probably due to the use of a not completely deuterated incubation medium.     

Evaluation of thermal diffusion factor and diffusion coefficient from measurements on a trennschaukel

Measurements have been taken on a glass trennschaukel of eight tubes for the Ar-He system as a function of composition and with its hot and cold bulbs at 100°c and 0°c. For each mixture, several speeds for the mechanical push-pull motion of the gas which cover a wide enough range were tried. The results have been interpreted to determine the thermal diffusion factor α _T, in conventional fashion as well as on the basis of a theory characterizing the low speed operation, developed here. Four such different possibilities of α _t evaluation are discussed and values compared with the traditional ones obtained from the convection-free two-bulb apparatus. Lastly we discuss also in brief the prospect of estimating the diffusion coefficient as an important byproduct from measurements on trennschaukel runs.     

Improved one-centre wave functions for the hydrogen and methane molecules

Corrections are made to the Joy-Parr hydrogen and the Saturno-Parr methane one-centre wave functions and the functions are accurately reminimized with respect to the energy. The electronic wave functions and total molecular energies are obtained for various internuclear distances and the equilibrium internuclear distance and the breathing force constant determined. Three methods for calculating the force constant are given and compared. The equilibrium bond length for hydrogen is found to be 1·38 a.u. (experimental, 1·40 a.u.) and the force constant 6·33 md/å (experimental, 5·75 md/å). For methane the equilibrium C-H distance is found to be 2·014 a.u. (experimental, 2·05 a.u. and the force constant 25·8 md/å (experimental, 23·5 md/å). The total computed molecular energies for the equilibrium configurations of hydrogen and methane are -1·1605 a.u. (experimental, -1·175 a.u.) and -39·8444 a.u. (experimental, -40·51 a.u.) respectively.     

Spectrophotometric Studies of the Energy Consumed During Oxidative Degradation of D-Fructose

ABSTRACT

Mechanistic investigation of the oxidative degradation of d-fructose (D-Fruc) has been studied by spectrophotometric technique. Molecular mechanics (MM +) calculations suggest that the potential energy (PE/kcal mol^?1) of the d-fruc (opening structure) is at least three (3.71) times more stable than the PE of the cycling structure of the same matrix. The oxidation constant (K _ox) of the anionic form of the d-Fruc (Fruc-NaOH) is about seven times greater than that of the protonated form (Fruc-H₂SO₄). Therefore, the anionic form is more highly oxidizable than is the cationic form of this matrix. The limit of detection can be as low as 18 ppm (mg L^?1) of d-Fruc. This is about 60 times lower than the blood sugar level (BSL) or 100 times lower than that reported previously. The proposed procedure was applied successfully for the oxidation of D-Fruc in uni-fructose powder. The anionic form of D-Fruc (Fruc-NaOH) has the ability to store energy about 744.72 kJ g^?1 h at 608 nm in a condensed lightweight form. Kinetic parameters of the oxidative degradation of the anionic form of D-Fruc at different concentration were deduced. A number of models were used to evaluate the kinetic parameters. The mechanism of the degradation of D-Fruc is explained on the basis of kinetic parameters.     

Paramagnetic resonance in phosphorescent aromatic hydrocarbons

Electron resonance spectra have been recorded of the lowest triplet states of benzene, toluene, triptycene and tribenzotriptycene. The experiments were carried out by ultra-violet irradiation of these molecules in rigid glass solutions both at 77°k and 20°k. From an analysis of the line shape of the spectra, which prove to be strongly temperature dependent, the following conclusions could be drawn.

Benzene in its first triplet state has a configuration of lowest energy which is not a regular hexagon. This finding, supported by the results for toluene, was substantiated by SCF-MO calculations; it is in agreement with a recent analysis by Liehr and Moffitt. Tunnelling between equivalent conformations of benzene is thought to occur at a rate of the order of 10⁹–10¹⁰ sec^-1.

The spectra of the phosphorescent states of triptycene and tribenzotriptycene are dominated by intramolecular excitation transfer between the benzene or naphthalene sub-systems. In triptycene at 77°k transfer occurs at a rate ? 10¹⁰ sec^-1, so that one observes the resonance signal of a triplet exciton. In tribenzotriptycene the transfer is somewhat slower. The rate of excitation transfer decreases with temperature and at 20°k most of the excitation in tribenzotriptycene is effectively trapped in the naphthalene sub-systems.     

The anomalous temperature dependence of the sound velocity in water

The quantum yields of naphthalene vapour fluorescence at 225°c and of phenanthrene vapour fluorescence at 365°c excited by the Hg 313 μ line are independent of concentration up to 0·014 and 0·007 moles/l. respectively; this is attributed to fast dissociation relaxation of the excimer at these temperatures.

The fluorescence of naphthacene vapour excited at temperatures of 355–435°c by the group of Hg lines at 365 μ decreases with increasing pressure at pressures below that at which absorption of the incident radiation is virtually complete, and is attributed to a combination of self-quenching and reabsorption of fluorescence. An analysis of the data for the limiting cases of complete and negligible fluorescence reabsorption provides upper and lower limits for self-quenching constant which are consistent with unit collisional quenching efficiency and a lifetime of 5·3 ± 2·2 + 10^-9 sec at 355°c.     

Reflections on Ernest Roy Davidson: the UW years 1962–1984

In the following research acetylation as an unexplored factor in the anomeric effect in carbohydrate chemistry has been examined. Crystallographic data for methyl glycosides and their acetates have been compared and discussed. Some of the methyl glycosides form hydrogen bonding with the participation of acetal oxygen atoms. This seems to have the most significant influence on the structural diagnostic parameters for anomeric effect.

Abbreviations: Me-α-Glc: methyl α-D-glucopyranoside; Me-β-Glc: methyl β-D-glucopyranoside; Me-α-Gal: methyl α-D-galactopyranoside; Me-β-Gal: methyl β-D-galactopyranoside; Me-α-Man: methyl α-D-mannopyranoside; Me-β-Man: methyl β-D-mannopyranoside; Ac-Me-α-Glc: methyl 2,3,4,6-tetra-O-acetyl-α-D-glucopyranoside; Ac-Me-β-Glc: methyl 2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside; Ac-Me-α-Gal: methyl 2,3,4,6-tetra-O-acetyl-α-D-galactopyranoside; Ac-Me-β-Gal: methyl 2,3,4,6-tetra-O-acetyl-β-D-galactopyranoside; Ac-Me-α-Man: methyl 2,3,4,6-tetra-O-acetyl-α-D-mannopyranoside; Ac-Me-β-Man: methyl 2,3,4,6-tetra-O-acetyl-β-D-mannopyranoside; GIPAW (Gauge Including Projector Augmented Waves) calculations: a DFT based method used for calculating nuclear magnetic resonance parameters; CP/MAS NMR: cross-polarisation (CP) magic angle spinning (MAS) NMR spectroscopy; δ_ss: chemical shift in ¹³C CP/MAS NMR spectrum; δ_t: theoretical chemical shift: as derived from GIPAW DFT; dis: distorted multiplet in ¹H NMR spectrum.     

Structure of the methyl radical

Carbon-13 hyperfine splittings equal to 41±3 gauss have been observed in the paramagnetic resonance of a mixture of C¹²H₃ and C¹³H₃ radicals produced by x-irradiation of CH₃I at 77°k. The observed splitting provides strong evidence that CH₃ is a planar molecule.     

Proton spin-lattice relaxation in aqueous ionic solutions

The proton spin-lattice relaxation time, T ₁, has been measured for aqueous solutions of sodium, potassium, rubidium and magnesium chlorides up to a concentration of about 4N at 25°c. The sodium and the magnesium chloride solutions were also measured at 60°c and 100°c. The variation of 1/T ₁ is not linear with concentration, at least above about ¼N, in contrast with previous reports [1, 2]. The behaviour depends markedly on the nature of the salt and on the temperature. It is shown that almost the whole of the variation of T ₁ as compared with that of water can be directly and simply related to the corresponding changes in the shear viscosity of the solutions. It is noted that the viscosity correction is better the higher the temperature of the solution.     

Intramolecular excitation transfer. The lowest n→π* transitions in pyrazine

In the pyrazine molecule, which has filled non-bonding orbitals para to each other, two orbitally degenerate n→π* transitions are expected, one symmetry forbidden and one symmetry allowed. Interelectronic interactions remove this degeneracy. The lowest pair of (n, π*) triplet states and the corresponding pair of singlet states are studied with a view towards determining the magnitude of such interactions and the ordering of the forbidden and allowed components. Absorption spectra are obtained of pyrazine in crystalline hydrogen and rare gases at 4·2°k, of pure crystalline pyrazine at 4·2°k, and of 42 metres of pyrazine vapour at various pressures. The phosphorescence spectrum of pyrazine in crystalline rare gases at 4·2°k also is studied. The splitting between the two singlet components is found to be approximately 435 cm^?1 with the forbidden component lying lowest. The forbidden singlet-singlet transition gains some of its intensity through vibronic mixing with a (π, π*) state, but vibronic coupling between the two (n, π*) states also may be present. The strongest part of the singlet-triplet absorption spectrum is found to involve the same upper state as the phosphorescence spectrum, and the transition is shown to be symmetry allowed. It is strongly suggested that the ordering of the allowed and forbidden components of the triplet state is inverted from that of the singlet, or the two states may lie very close together. Using an ‘independent systems’ model, a calculation of the splitting, with the inclusion of exchange is made. The theory indicates that the singlet states are indeed split by a coulomb term having roughly the expected magnitude with the forbidden component lying lowest; in addition, there is a very small exchange term with the opposite sign. The splitting between the triplets is shown to involve only the small exchange term, and the order of the allowed and forbidden components becomes reversed. There is no indication of pyrazine fluorescence at 4·2°k in any of the solids used. This fact illustrates the high efficiency of the singlet-triplet radiationless process even under these conditions where the rate might be expected to be a minimum for condensed phases. An interesting alternation of spacing has been discovered in the first few quantum levels of the 600 cm^?1 a _1g ring-bending vibration of the ground electronic state of the molecule.     

Potential energy surfaces for the Walden inversion reaction

A semi-empirical valence bond calculation of potential surfaces for the gas phase reaction between methyl bromide and chloride ion is described. The system is treated in a four participant electron approximation with precautions to include the effects of orthogonalization to the core electrons not involved in bond formation during reaction. The core is taken to include the methyl group as a single fragment whose valence state energy is determined by hybridization at the carbon atom. The qualitative features of the surface are confirmed by a less extensive CNDO calculation.

The lowest potential surface is found to have a central dip, the minimum energy being 0·98 ev below the energy of the reaction products when the C-Cl distance is 3·60 a.u., the C-Br distance 4·11 a.u., and the H-C-Br angle 86°. Analogy with classical two-body scattering suggests that at incident energies of less than 2 ev, the reaction cross section is of the order of 10(1 + 1/E) å ², where E, the initial energy of relative motion, is in ev.     

Singlet–triplet transitions in three-atomic molecules studied by time-dependent MCSCF and density functional theory

Singlet–triplet transition moments and phosphorescence lifetimes have been calculated for the three-atomic molecules HCN, O₃, H₂O, H₂S, GeF₂, GeCl₂ and GeBr₂ by time-dependent density functional theory (DFT) utilizing quadratic response functions in order to qualify DFT which recently has become available for studies of this kind [TUNELL, I., Rinkevivius, Z., VAHTRAS, O., SALEK, P., HELGAKER, T., and ÅGREN, H., 2003, J. chem. phys., 119, 11024]. Comparison with ab initio and experimental data indicates that DFT exhibit results of similar quality as explicitly correlated methods which indicates that it indeed is a viable approach for singlet–triplet transitions. O₃ provides an intriguing example in that a systematic investigation of the singlet–triplet transition moment of its Wulf band indicates a clear advantage of the DFT technique despite the multiconfigurational character of the electronic structure of this molecule. The electronic spin–spin coupling and the hyperfine nuclear coupling constants have also been calculated in order to further characterize the triplet state in the spectra of the investigated systems.     

Ab initio calculation of force constants and equilibrium geometries in polyatomic molecules

The force constants and equilibrium geometry of water were calculated ab initio from Hartree-Fock self-consistent field wavefunctions using the force method, and a 53/31, a 73/3 + 1 and a 95/41 + 2 gaussian lobe basis set. The force method proved to be very economic and numerically accurate.

The calculated values agree well with the experimental ones. Especially good is the agreement for the interaction constant F_rα . Calculated force constants for the 95/41 + 2 basis are: F_r = 9·158 mdyn/å, F_α = 0·8513 mdyn/å, F_rα = +0·3007, F_rr = -0·1724; the experimental values from isotope frequencies are: F_r = 8·456, F_α = 0·762, F_rα = +0·246, F_rr = -0·100 mdyn/å. The agreement in the geometry is also good for the 95/41 + 2 basis r _e = 0·9518 å, α = 107·49°, and the experimental r _e = 0·9572 å, α = 104·52°.

Force constants were found to be quite insensitive to variation in the basis functions, all three sets giving almost the same result. On the other hand, the dipole moment derivative is very sensitive.