San-ichiro Mizushima

Infrared absorption spectra of inorganic co-ordination complexes—XVII1: Infrared spectra of platmum(II) and palladium(II) ammine complexes

Abstract The infrared spectra of [Pt(NH 3 ) 4 ]Br 2 , [Pt(NH 3 ) 4 ]Cl 2 , [Pd(NH 3 ) 4 ]Cl 2 , Pt(NH 3 ) 2 C 2 O 4 , Pd(NH 3 ) 2 C 2 O 4 , cis - and trans -Pt(NH 3 ) 2 Cl 2 and cis - and trans -Pd(NH 3 ) 2 Cl 2 , have been measured in the 2–15 μ region. Assignment of the observed absorption bands is reported. Skeletal frequencies have been calculated and the nature of the ligand-to -metal bond is discusaed.

Infrared absorption spectra of inorganic co-ordination complexes—XV: Normal vibrations of sulfamic acid, H3N+—SO3−

Abstract Normal vibrations of the zwitter ion model of sulfamic acid have been calculated. For the skeletal vibrations, the L matrices and the potential energy distribution among symmetry co-ordinates for each normal mode of vibration have been calculated. Based on the result, complete assignment of the infrared and Raman frequencies has been made.

Raman Effect and Free Rotation

THE molecule of ethylene halide, XH2C-CH2X, has an axis C-C, around which the two CH2X groups are capable of rotation, but not all the rotational states are equally probable. The most stable state corresponds to the trans configuration which has a centre of symmetry and no dipole moment. The mean dipole moment of the molecule increases with the decreasing number of molecules in the trans state1. We have made intensity measurements of the Raman lines together with the dipole moments2 and have shown that the intensity ratio I(ω1)/I(ω2) of the two strong Raman lines ω1 and ω2 decreases as the number of molecules in the trans state increases (ω1 = 653, ω2 = 752 for C2H4C12 and ω1 = 551, ω2 = 656 for C2H4Br2). The intensity measurement was also carried out for the solid state and at lower temperatures, and it was observed that the line ω1 disappeared completely, while the line ω2 remained very strong, that is, I(ω1)/I(ω2) = 0.

Molecular Theoretical Investigations on Hydrocarbons and Their Substitution Products. XII

六クロルエタン,五クロルエタン及び非對稱四クロルエタンの氣體に就て行つた電子廻折の實驗によつて之等の化合物の分子形が捩れ形である事を確めた.此の結果は以前著者等が二クロルエタンの〓轉異性體をトランス形,中間形の兩種と定めた事とよく一致する.

Molecular Theoretical Investigations on Hydrocarbons and their Substitution Products. IX

炭素單結合のまわりの分子内部廻轉に關する我々の結論に基いて,一般の鎖状飽和炭化水素の廻轉異性體の分子形態を決定した.而してその結果を三種の表現法によつて表した.尚正セタンの液體のラマン・スペクトルの實測値に基いて之等の廻轉異性體のうち何れが實現されてゐるかを定めた.

Molecular Theoretical Investigations on Hydrocarbons and Their Substitution Products VI

前報までの研究の結果決定し得た分子恒數(慣性能率,基準振動數)を用ひて, 1, 2-二クロルエタンのエントロピーを統計力學的に算出し,第三法則に基いて得られるエントロピーの値と比較した.その結果よりC-C結合を軸とする捩れの振動の波數を決定したところ極めて妥當な値が得られた.

Molecular Theoretical Investigations on Hydrocarbons and Their Substitution Products. Part I

C-C結合を軸とする分子内部廻轉は自由廻轉でない爲に,炭化水素及び其の置換體には一般に幾種かの廻轉異性体を生ずる. XH2C-CH2Y (X, Y=CH3, Cl, Br, I等)なる化學式を有する物質に於てはその分子形熊はトランス形と中間形の2種である.此の結論は從來の我々の研究結果から導かれたものであるが,今囘新に開始した一聯の研究により,之等の廻轉異性体の平衡に於ける混合の割合, C-C結合を軸とする分子内部の捩れの振動,及び之等の物質の分子論的エントロピーが決定せられるに至つた.その結果を豫備的に述べ,且つそれが炭化水素及び其の置換体の化學の諸方面に如何に關聯すべきかに就いて考察する.

Molecular Theoretical Investigations on Hydrocarbons and Their Substitution Products V

1, 2-ニクロルエタン液體のラマン・スペクトルに就て更に精密なる測定を行つた結果新に709cm-1及び223cm-1なる波數の線の存在を確め得た.而して種々の考察の結果,之等をトランス形分子の中心に逆對稱の振動に對應させるのが至當のやうに思はれる.選擇律によれば,之等の振動はラマン効果に現れ得ないのであるが,液體に於ける分子の相互作用等の原因によつて,弱い線として出現したのである.此の中223cm-1の線はエントロピーの計算に際して,極めて重要なる役割を演ずるものである.尚此の研究によつて1, 2-ニクロルエタン分子の骨格振動のすべての波數を實測し得たから,それ等を永年方程式より求め得る計算値と比較して論じた.

Molecular Theoretical Investigation on Cyclohexane-Methylcyclopentane Equilibrium

ラマン効果を應用してシクロヘキサンと,メチルジクロペンタンの平衡を實驗的に研究した.同時に兩物質の分子構造に基いて統計力學的にエントロピー差を計算し,平衡の測定から求められた實驗値とよく一致する結果を得た.

Raman spectra and molecular configurations of solid ethylene dihalides

SummaryThe disappearance of many Raman lines of ethylene dihalides on solidification, which was the most important result of our previous experiment, acquired further confirmation by the more accurate measurement of the present experiment. It was shown by the calculation of normal vibrations as well as by the study of isotopic effect that practically all the molecules of solid ethylene dihalides assume thetrans-form. If, therefore, the thermal transitions observed for these solids (−65°C. for C2H4Cl2 and −24°C. for C2H4Br2) are caused by the onset of molecular rotation, this must take place about only one axis,i.e., that of the zigzag X−C−C−X chain. Such a rotation in one dimension does not contradict the existence of the crystal forces which keep the molecule of the solid in a nearly puretrans-state and is consistent with the small values of heat of transition estimated in thermal measurements.