3, 3, 3-Trifluoropropyl(methyl)cyclosiloxanes

The catalytic rearrangement of the cyclopentasiloxanes _mD_5-m, where represents a 3, 3, 3-trifluoropropyl(methyl)siloxane link and D a dimethylsiloxane link, and m=2–5 has been studied by the method described previously [1]. The rate of rearrangement and the rate of formation of a linear polysiloxane rise with an increase in m from 2 to 4. The equilibrium concentration of the linear polysiloxane formed from _mD_5-m and from _mD_4-m (m=0–4) [1] is inversely proportional to the molar fraction of links in the ring and rises with an increase in the total concentration of siloxane links in solution. Results have been obtained on the kinetics of the formation of the cyclosiloxanes _mD_n (where m=0–5, n=0–5, and m+n=3-6) during the rearrangement of the cyclopentasiloxanes _mD_5-m. It has been established that at equilibrium a mixture of cyclosiloxanes _mD_n containing practically constant ratios of tetramers, pentamers, and hexamers (m+n=4, 5, and 6) is obtained, regardless of the composition and structure of the initial cyclosiloxane and of the conditions of rearrangement (polymerization). The cyclopentasiloxanes _mD_5-m are less active in the process of rearrangement than the cyclotetrasiloxanes _mD_4-m. The activity of the cyclosiloxanes in rearrangement in the presence of a base rises in the sequence D₄D_{3 2}D₃<₃D₂<₄D < ₂D₂ < ₃D.For part II, see [1].     

EXAFS Study of Ph3GeMn(CO)5 Structure Evolution on Exposure to X-Radiation

Ge K-edge and Mn K-edge EXAFS spectroscopy was used to study changes in the local environment of germanium and manganese atoms during radiolysis of the Ph₃GeMn(CO)₅ complex. On exposure to X-radiation, the metal complex undergoes a number of transformations depending on the radiant exposure (). It was shown that at = (6–8) × 10⁶ J/m², the initial metal complex decomposes into the [Ph₃Ge] and [Mn(CO) _n ] fragments with partial detachment of the CO groups from Mn atoms. When = 1.3 × 10⁷ J/m², Mn atoms lose completely the CO groups to form finely dispersed metal nanoparticles, which interact with the surrounding atoms (carbon or nitrogen). With further increase in , the local environment of the Mn atoms no longer changes. The Ge atoms remain coordinated to the Ph groups as increases up to 2 × 10⁷ J/m², but starting with = 1.6 × 10⁷ J/m², metal–metal bonds are formed; subsequently, the amount of this phase increases and when = 2.6 × 10⁸ J/m², it becomes predominant. Since manganese and germanium atoms lose their ligands at different values, one can conclude that germanium and manganese nanoparticles are the final products in the radiolysis of Ph₃GeMn(CO)₅.     

Volumes and heat capacities of anionic-nonionic surfactant mixtures

Density, heat capacity and surface tension measurements of sodium decylsulfate (NaDeS)-dodecyldimethylamine oxide (DDAO)-water mixtures were carried out as functions of the surfactants total molality m_t at fixed stoichiometric mixture compositions X_NaDeS. From the surface tension data, the critical micelle concentration of NaDeS-DDAO mixtures as a function of X_NaDeS were obtained. From density and heat capacity data, the apparent molar volume V_,2 and heat capacity C_,2 of NaDeS-DDAO mixtures in water were calculated, respectively. At a given mole fraction, V_,2 and C_,2 monotonically increases and decreases, respectively, with increasing mt. However, anomalies were observed at X_NaDeS=0.1 and 0.3 for both V_,2 and C_,2 vs. mt curves. The nonideal contributions to the thermodynamic properties for the formation of surfactant-surfactant mixed micelles in water by mixing aqueous solutions of pure NaDeS and DDAO micelles were calculated at 0.3 mol-kg^–1 for the micellized surfactants mixture. The excess volume V^exc and heat capacity as functions of X_NaDeS are concave and S-shaped curves, respectively. All the properties are compared to those for sodium dodecylsulfate-DDAO mixture. In addition, to clarify the effect of the change in the hydrophobicity of the surfactants mixtures V^exc for the dodecyltrimethylammonium bromide-decyltrimethylammonium bromide mixture were calculated from literature data.     

VUV-Photolyse von Methanol bei 1236 Å

Zusammenfassung Es wird über die indirekte und die direkte VUV-Photolyse von luftfreiem Methanol in flüssiger Phase bei 1236 Å berichtet. Bei der Bestrahlung von wäßr. 0,01m-Methanol wurden folgende Produkte und Ausbeuten erhalten: (H₂)=1,00, (HCHO)=0,27, (CH₂OH)₂=0,12, (CH₂OH·CHO)=0,04 und (HCOOH)=0,02. Die Photolyse von flüssigem Methanol lieferte die gleichen Produkte, jedoch mit höheren Ausbeuten: (H₂)=1,50, (HCHO)=0,98, (CH₂OH)₂=0,28 und (CH₂OH·CHO)=0,06. Unter Anwendung von Methanol als Radikalfänger konnte auch die Quantenausbeute der Wasserphotolyse bei 1236 Å, (H,OH)=1,025 verifiziert werden. Wahrscheinliche Reaktionsmechanismen werden diskutiert.

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V.U.V.-Photolysis of methanol at 1236 Å

The indirect and the direct v.u.v.-photolysis of air free methanol in liquid phase at 1236 Å is reported. After irradiation of aqueous 0.01M-methanol the following products were obtained: (H₂)=1.00, (HCHO)=0.27, (CH₂OH)₂=0.12, (CH₂OH·CHO)=0.04 and (HCOOH)=0.02. The photolysis of liquid methanol yielded the same compounds, however with higher amount as follows: (H₂)=1.50, (HCHO)=0.98, (CH₂OH)₂=0.28 and (CH₂OH·CHO)=0.06. Using methanol as a scavenger for the H and OH radicals the quantum yield of the water photolysis at 1236 Å could be verified to be (H,OH)=1.025. Probable reaction mechanisms are discussed.

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Herrn Prof. Dr.E. Broda zum 60. Geburtstag gewidmet.     

Seawater—A test of multicomponent electrolyte solution theories. I. The apparent equivalent volume,expansibility, and compressibility of artificial seawater

The apparent equivalent volume _V, expansibility _E, and compressibility _K of an artificial seawater solution containing10 ionic components (Na⁺, Mg²⁺, Ca²⁺, K⁺, Sr²⁺, Cl^–, SO ₄ ^2– , HCO ₃ ^– , Br^–, and F^–) and one nonionic component (H₃BO₃) has been determined from0 to40°C (in5° intervals) and from0.1 to0.8 m ionic strength at1 atm. The concentration dependence (I_v=volume ionic strength) of the _V's, _E's, and _K's have been examined by using a Masson-type equation, = ^° +S'I _V ^1/2, and a Redlich-type equation, = ^° +SI _V ^1/2 +BI _V, where ^° is the infinite-dilution value, S is the empirical Masson slope, S is the theoretical Debye-Hückel slope, and B is an empirical deviation constant. By using Young's rule, = E_i(i), the apparent equivalent volumes, expansibilities, and compressibilities for sea salt have been estimated from the ionic and nonionic components making up the mixture. The estimated apparent molal quantities agree very well with the directly measured values providing the concentration terms, S _i and B_i, are weighted according to the methods of Wood and Reilly.Contribution Number 1599 from the University of Miami.     

De la possibilité d'utiliser une base de Slater uniquement s dans les calculs relatifs aux atomes et aux molécules

A 2p STO may be replaced by a linear combination of 1s and 2s orbitals, = (1s_A-1s_f) + (2s_A-2s_B). Such a should improve LCAO-MO-SCF calculations in minimal STO basis set with simpler programs.     

3, 3, 3-Trifluoropropyl(methyl)cyclosiloxanes

The influence of the number of 3, 3, 3-trifluoropropyl(methyl)siloxane links (/) in the cyclotetrasiloxanes _mD_4-m, where D represents the dimethylsiloxane link and m=0–4, on the rearrangement of these compounds in acetone solution under the action of sodium siloxanolate has been studied. The rearrangement takes place with the formation of a linear polysiloxane the degradation of which yields, in addition to the initial ring, cyclosiloxanes with a different structure. The rate of rearrangement of _mD_4-m and of the formation of a linear polysiloxane rises with an increase in m from 0 to 3. The equilibrium concentration of the linear polysiloxane formed from _mD_4-m is inversely proportional to m. Results have been obtained on the kinetics of the formation of the cyclosiloxanes _mD_n, where m=0–5, n=0–5, and m+n=3–6, in the rearrangement of the rings D₃, ₂D₂, ₃D, and ₄. The reactivity of the siloxane links rises in the sequence (CH₃)₂Si-O-Si(CH₃)₂ < (CF₃CH₂CH₂)-(CH₃) Si-O-Si(CH₃)₂ <(CF₃CH₂CH₂) (CH₃)Si-O-Si(CH₃) (CH₂CH₂CF₃) . Because of the negative inductive effect transferred through the siloxane links, the 3, 3, 3-trifluoropropyl groups strongly activate the siloxane ring with respect to nucleophiiic reagents.For part I, see [3].     

The Influence of Dimerization of Water-Soluble Metalloporphyrins as Photosensitizers on the Efficiency of Generation of Singlet Oxygen

Quantum yields () for the generation of singlet oxygen sensitized by Pd(II) complexes of water-soluble porphyrins: meso-tetrakis(4-N-methylpyridyl)porphine [PdTMPyP]⁴⁺ ( = 0.9), meso-tetrakis(4-N,N,N-trimethylaminophenyl)porphine [PdTTMAPP]⁴⁺ ( = 0.8), meso-tetrakis(4-carboxyphenyl)porphine [PdTCPP]^4– ( = 0.7), and meso-tetrakis(4-sulfonatophenyl)porphine [PdTSPP]^4– ( = 0.5) were determined using a chemical method. It was found that the dimerization and aggregation of metalloporphyrins greatly influence the value. The quantum yields evaluated for the formation of singlet oxygen sensitized by metalloporphyrin monomeric and dimeric forms are _{, M} 0.9 and _{, D} 0.2, respectively, and do not depend on the porphyrin nature.     

Eigenvalues of the real generalized eigenvalue equation perturbed by a low-rank perturbation

The low-rank perturbation (LRP) method solves the perturbed eigenvalue equation (B +V) _k = _k (C +P) _k , where the eigenvalues and the eigenstates of the related unperturbed eigenvalue equationB _i = _i C _i are known. The method is designed for arbitraryn-by-n matricesB, V, C, andP, with the only restriction that the eigenstates _i of the unperturbed equation should form a complete set. We consider here a real LRP problem where all matrices are Hermitian, and where in addition matricesC and (C +P) are positive definite. These conditions guarantee reality of the eigenvalues _k and _i . In the original formulation of the LRP method, each eigenvalue _k is obtained iteratively, starting from some approximate eigenvalue _k . If this approximate eigenvalue is not well chosen, the iteration may sometimes diverge. It is shown that in the case of a real LRP problem, this danger can be completely eliminated. If the rank of the generalized perturbation {V, P} is small with respect ton, then one can easily bracket and hence locate to any desirable accuracy the eigenvalues _k (k = 1, ...,n) of the perturbed equation. The calculation of alln eigenvalues requiresO(² n ²) operations. In addition, if the perturbation (V, P) is local with the localizabilityl p, then onlyO(² n) operations are required for a derivation of a single eigenvalue.     

On a variational method for determining excited state wave functions

A variational method is proposed which results in an approximate wave function for an excited state which has the maximum overlap with the true excited state eigenfunction. The method involves the calculation of the quantities E=¦H¦ and =¦(H-E)²¦, but is free of the constraint that the trial function must remain orthogonal to all states of the same symmetry which lie beneath it. One must know, however, an approximation to the true eigenvalue. A discussion is given on how one might gain the latter information, lacking knowledge of the spectrum, from the repeated application of the method.

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Zusammenfassung Es wird eine Variationsmethode vorgeschlagen, die auf eins genäherte Wellenfunktion für einen angeregten Zustand führt, welche sich maximal mit der wahren Eigenfunktion des angeregten Zustandes überlappt. Die Methode ermöglicht die Berechnung der Größen: E=¦H¦ und =¦(H-E)²¦, ist aber frei von der Nebenbedingung, daß die Versuchsfunktion orthogonal zu allen benachbarten Zuständen mit derselben Symmetrie bleiben muß. — Man will jedoch eine Näherung des wahren Eigenwertes wissen. — Eine Diskussion darüber, wie man durch wiederholte Anwendung der Methode letztere Information gewinnen kann, ohne Kenntnisse über das Spektrum zu besitzen, wird durchgeführt.

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Résumé Méthode variationnelle pour la détermination d'une fonction d'onde d'un état excité présentant le recouvrement maximum avec la fonction d'onde exacte. La méthode implique le calcul de E=¦H¦ et =¦(H-E)²¦ mais ne comporte pas la contrainte d'orthogonalité de la fonction d'essai à tous les états inférieurs de même symétrie. On doit cependant connaître une valeur approchée de la valeur propre exacte. Discussion sur la manière dont on peut obtenir cette valeur approchée sans connaître le spectre, par application répétée de la méthode.

     

Symmetry-adapted cluster f-orbitals and a vector method for generally oriented f-orbital overlaps

The irreducible representations consisting of linear combinations of cluster atomic f-orbitals are obtained for f, f,f and f orbitals in M₃(D _3h ), M₄(D _4h ), M₄(T _d ), M₆(O _h ) and M₈(O _h ) clusters. The charge overlap of any pair of two atoms in a cluster is decomposed in terms of a set of coefficients for the , , , and overlaps, respectively. A vector method is devised for this decomposition which may be extended to any arbitrary orientation and to higher orbitals. The decomposition coefficients represent fundamental geometrical properties of the cluster and are applicable to clusters of arbitrary dimensions.Contribution No. 0004 ITI Basic Research Laboratory. Presented in part at the 187th ACS National Meeting in St. Louis, MO, USA     

Primärprodukte der Wasserphotolyse bei 1849 Å

Zusammenfassung Die Photolyse des Wassers bei 1849 Å wurde unter Verwendung von 0,01m-Formiat als Fänger für die H-Atome und OH-Radikale untersucht. Dabei diente 5m-Äthanol als Aktinometer mit einem korrigierten Wert für (H₂)=0,50. In diesem Fall wurde eine Quantenausbeute der Wasserphotolyse (H, OH)=0,36±0,01 bestimmt. Bezieht man die exper. Daten auf das N₂O-Aktinometer bei (–N₂O)=1,0, dann ist (H, OH)=0,29±0,01. In diesem Wert ist auch die Quantenausbeute der reaktionsfähigen angeregten Wassermoleküle, die mit Formiat reagieren, inbegriffen. Auf Grund von experimentellen Daten wurde ferner die Bildung von solvatisierten Elektronen (e ^–aq) vorgeschlagen. Durch Sättigung der Formiatlösung mit Kohlensäure, die sowohl vone ^–aq als auch von H₂O^* reduziert werden kann, wurde (e ^–aq, H₂O^*)>0,02<0,04 bestimmt.

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Liquid water photolysis at 1849 Å was investigated by using 0,01m-formate as scavenger for the H and OH radicals. 5M-ethyl alcohol serviced as actinometer with a corrected value of (H₂)=0,50. The quantum yield of water photolysis was determined in this case to be (H, OH)=0,36±0,01. When the experimental results are related to N₂O actinometer with (–N₂O)=1,0, a quantum yield of (H, OH)=0,29±0,01 is obtained. This value includes also the quantum yield of the excited water molecules which react with the formate. Based on experimental data the formation of solvated electrons (e ^–aq) is proposed. By saturation of the formate solution with carbon dioxide, which can be reduced bye ^–aq as well as by H₂O^*, (e ^–aq, H₂O^*>0,02<0,04 was determined.

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EDX depths analysis of MIS-structures

Based on experimental energy transfer distributionsdE/dx including the X-ray depth distribution function (x,E ₀,Z) an effective-layer method has been developed in order to homogenize a multilayer target. Effective layer thicknesses are related to real layer thicknesses by means of equal transmission-energy rates. This method has been proved by EDX measurements of Au-SiO₂-Si structures showing good agreement with the real structures.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

Enthalpies of dilution for 1∶3 and 3∶1 electrolytes aqueous solutions

The enthalpies of dilution for aqueous solutions of [Co(cn)₃)]Cl₃, [Co(pn)₃)]Cl₃ and [Co(tn)₃]Cl₃, (whereen=1,2-diaminoethane,pn=1,2-diaminopropane, andtn=1,3-diaminopropane) have been measured at 298.15 K, and up to 1 mol kg^–1+, using a new large isoperibol calorimeter by the long-jump method. Relative apparent molar enthalpies,_291-01, have been extracted as an empirical equation relatingL andm. We have compared our complex salts with the 31 and 13 aqueous systems found in the literature. Theoretical predictions for 13 and 31 electrolytes in the Restricted Primitive Model are also shown.This work was supported in part by CICYT (M.E.C., Spain) under Research Project No.: PB92-0553.     

r 12-Dependent terms in the wave function as closed sums of partial wave amplitudes for large l

The ansatz = (1+1/2r₁₂)+ with the bare nuclear (or screened nuclear) wave function and expanded in products of one-electron functions is explored for second-order perturbation theory and for variational calculations of the ground state of Helium-like ions.The energy increments E _l ⁽²⁾ corresponding to the partial wave expansion of go asymptotically as l^–8, while conventional partial wave increments go as l^–4. is coupled to by a residual interaction U₁₂ that has no singularity for r₁₂=0. With the present ansatz it is sufficient to include l-values up to 5 in order to get the second-order energy accurate to one microhartree. For the same accuracy l4 is sufficient in a CI with correlated reference function while in conventional CI one must go to l50. The surprisingly faster convergence of the variational approach as compared to second-order perturbation theory is explained. The slow convergence of the traditional partial wave expansion is entirely due to the attempt to represent the quantity 1=¦r₁₂r₁₂ ^–1¦ by its partial wave expansion. The best reference function shows very little shielding and resembles closely the eigenstate of the bare nuclear Hamiltonian. The generalization to arbitrary systems is discussed and it is pointed out that the calculation of difficult integrals can be avoided without a significant loss in accuracy.     

An Alternative Method of Introducing Fugacity

In current textbooks fugacity is introduced according to its differential or integral mathematical formulation. In this article an alternative method of explanation is offered. It is suggested that the real state of a pure gas can be described by comparing it to a hypothetical idealized state. The differences between these two states can then be expressed in terms of a function, , defined as (T,P) = _real(T,P) - _ideal(T,P) where _real and _ideal are the chemical potentials of the gas in its real and ideal states, respectively. The function is a molar excess quantity and is expressed as (T,P) = RT1n where is the fugacity coefficient. This approach introduces fugacity deductively through the function, which leads to , the fugacity coefficient. This method is also appropriate for introducing the activity of solution components and the fugacity of a real gas in gaseous mixtures.     

Diffusion in concentrated dispersions: a study with fiber-optic quasi-elastic light scattering (FOQELS)

A fiber-optic, quasi-elastic light-scattering instrument is described using single-mode fiber optical components, including a novel slanted exit face optode. The setup operates with homodyne signal detection. It enables the characterization of diffusion processes in concentrated dispersions up to volume concentrations of 50%.The performance of the instrument is exemplified with results obtained from latex spheres with diameters of 226 nm and 404 nm at volume fractions from =0.01 to =0.5. The correlation functions are analyzed according to the second order cumulants method and the Contin-procedure yielding an average and a distribution function of the short-time self-diffusion coefficient,D _eff ^s , respectively.At high ionic strength the concentration dependence ofD _eff ^s /D ₀ is found to be in close agreement with theoretical predictions based on a multi-body interaction model of hard spheres up to =0.45. With decreasing ionic strength the negative slope of the virial expansion tends to increase, presumably due to enhanced repulsive electrostatic interactions.The described technology offers new experimental means for on-line remote control sensing of particle size in concentrated disperse systems.Presented at the 34. Hauptversammlung der Kolloidgesellschaft e.v., Bochum, Oct. 1–4, 1989     

Viscosities of n-Alkyl Chlorides from 15 to 80°C

The viscosities of n-alkyl chlorides from pentyl to hexadecyl chloride were determined at temperatures between 15 to 80°C at 5°C intervals. The intrinsic volumes of the n-alkyl chlorides were determined by extrapolation of the plot of fluidity against molar volume to zero fluidity. Plots of the logarithm of viscosity vs. reciprocal absolute temperature were almost linear. The energies of activation for viscous flow for the n-alkyl chlorides were calculated and found to increase with increase in chain length. The fluidities, , of the n-alkyl chlorides were found to obey the modified form of Hildebrand's equation. = D[(V-V_o/V_o]\exp(-E_B/RT) where D is a constant, V and V _o are the molar volume and the intrinsic molar volume, respectively, and E _B is an energy term corresponding to the energy required for disrupting the association of the molecules. The activation energy for viscous flow consists of the sum of the energy required for the expansion of the void volume and the energy required to overcome intermolecular interactions. These energies were calculated and discussed.     

Radiolysis of [EtC5H4Mn(CO)2NO]+(PF6)– and Evolution of the Nearest Environment of the Manganese Atoms in the Complex

X-ray emission and EXAFS spectroscopies were used to examine changes in the nearest environment of manganese atoms upon radiolysis of [EtC₅H₄Mn(CO)₂NO]⁺(PF₆)^– at different energy exposures (). It was found that the initial complex loses the CO and NO ligands at = 4.5 × 10⁶ J/m². An increase in to 7.5 × 10⁶ J/m² gives rise to Mn–Mn bonds with lengths characteristic of Mn dimers. At = 9.0 × 10⁶ J/m², Mn nanoparticles are formed; they interact with the carbon atoms of EtC₅H₄ and the fluorine atoms of PF₆ anions. Further increase in = 2.6 × 10⁷ J/m² yields manganese-containing nanoparticles structured like metallic Mn; their surface atoms interact with carbon atoms formed in the disintegration of the EtC₅H₄ ligands. The formation of manganese carbides and fluorides at = 2.6 × 10⁸ J/m² reduces the content of the metal constituent in nanoparticles; this content is zero at = 4.4 × 10⁸ J/m². The final radiolysis products are manganese carbides and fluorides (or fluorocarbides).     

Photochemische Carbonylierung und Oxydation von wässerigem Methanol bei 1470 Å

Zusammenfassung Das photochemische Verhalten von wässerigem Methanol, gesättigt mit Argon, CO bzw. O₂ wurde bei 1470 Å als Funktion der VUV-Dosis und der Methanolkonzentration untersucht. Als Reaktionsprodukte wurden Wasserstoff, Formaldehyd, Glykolaldehyd, Glykol, Ameisensäure und in Gegenwart von Sauerstoff auch Peroxyd nachgewiesen. In 10^–2 m-Methanol, gesättigt mit Argon, betrug (H₂)=0,69 und (HCHO)=0,22, in Gegenwart von 7·10^–4 m-CO war (H₂)=0,10 und (HCHO)=0,29, während bei Sättigung mit O₂ (10^–3 mO₂) (H₂)=0,01, (HCHO)=0,33, (HCOOH)=0,20 und (H₂O₂)=0,22 gefunden wurde. Die -Werte der übrigen Produkte, die unter den angegebenen Bedingungen erhalten wurden, waren <0,07. Durch Erhöhung der Methanolkonzentration bis zu reinem Methanol, gesättigt mit Argon, stieg die Ausbeute von H₂, HCHO und (CH₂OH)₂ entsprechend an, während die von HCOOH und CH₂OHCHO sich praktisch nicht änderte. Bei reinem, mit Argon gesättigtem Methanol war (H₂)=0,89 und (HCHO)=0,73. Das Glykol erreichte bei etwa 2m-Methanol eine Höchstausbeute von =0,38. Reaktionsmechanismen werden diskutiert.

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Photochemical carbonylation and oxidation of aqueous methanol at 1470 Å

The photochemical behaviour of aqueous methanol saturated with argon, CO and O₂, resp., has been investigated at 1470 Å as a function of the v.u.v. dose and the methanol concentration. Hydrogen, formaldehyde, glycolaldehyde, glycol, formic acid and, in the presence of oxygen, also peroxide were detected. In 10^–2 M-CH₃OH saturated with argon (H₂)=0,69 and (HCHO)=0,22 were found; in the presence of 7·10^–4 M-CO the yields are (H₂)=0,10 and (HCHO)=0,29, whereas under saturation with oxygen (10^–3 M O₂) (H₂)=0,01, (HCHO)=0,33, (HCOOH)=0,20 and (H₂O₂)=0,22. The quantum yields of all other products obtained under the conditions mentioned above are <0.07. With increasing methanol concentration up to pure argon saturated methanol, the quantum yields of H₂, HCHO and (CH₂OH)₂ increase correspondingly, whereas the yields of HCOOH and CH₂OHCHO remain practically unchanged. When irradiating pure, argon saturated methanol, (H₂)=0,89 and (HCHO)=0,73 were found. A maximum yield of (CH₂OH)₂=0,38 was achieved using 2M-CH₃OH. Reaction mechanisms are discussed.