Gas electron diffraction study of the vapour over dimethylamine-gallane leading to an improved structure for dimeric dimethylamidogallane, [Me2NGaH2]2: a cautionary tale

Dimethylamine-gallane is relatively slow to decompose in a closed system and vaporises at low temperature primarily as Me2(H)N.GaH3 molecules which can be trapped in a solid Ar matrix and characterised by their IR spectrum. Under the conditions needed to secure a useful gas electron diffraction (GED) pattern, however, the vapour was found to consist of dimeric dimethylamidogallane molecules, [Me2NGaH2]2, formed from the secondary amine adduct by elimination of H2, and the most reliable structure for which has been determined. Salient structural parameters (r(hl) structure) were found to be: r(Ga-N) 202.6(2), r(Ga-H) 155.6(8), r(N-C) 148.0(3), r(C-H) 111.2(6) pm; Ga-N-Ga 90.7(1), C-N-C 109.3(5), N-C-H 109.9(10) and H-Ga-H 119.4(42) degrees.     

Experimental and theoretical structure and vibrational analysis of ethyl trifluoroacetate,CF3CO2CH2CH3

The molecular structure and conformational properties of ethyl trifluoroacetate, CF₃CO₂CH₂CH₃, were determined in the gas phase by electron diffraction, and vibrational spectroscopy (IR and Raman). The experimental investigations were supplemented by ab initio (MP2) and DFT quantum chemical calculations at different levels of theory. Experimental and theoretical methods result in two structures with C_s (anti–anti) and C₁ (anti–gauche) symmetries, the former being slightly more stable than the latter. The electron‐diffraction data are best fitted with a mixture of 56% anti–gauche and 44% anti–anti conformers. The conformational preference was also studied using the total energy scheme, and the natural bond orbital scheme. Also, the infrared spectra of CF₃CO₂CH₂CH₃ are reported for the gas, liquid and solid states, as is the Raman spectrum of the liquid. The comparison of experimental averaged IR spectra of C_s and C₁ conformers provides evidence for the predicted conformations in the IR spectra. Harmonic vibrational wavenumbers and scaled force fields have been calculated for both conformers. Copyright © 2009 John Wiley & Sons, Ltd.     

CHARACTERIZATION OF NANOSTRUCTURES:TOOLS AND CHALLENGES

Apart from long-known and applied nanostructures like carbon black for tyres or pigments for coatings nanotechnology has created highly sophisticated structures used for nano/molecular electronics,diagnostics,drug delivery, UV-absorbers etc.Often the main question to be solved analytically is the local determination of tiny amounts of chemicals resulting in an ever increasing need for highly sensitive as well as locally resolved techniques.Applications of techniques like mass spectroscopy,transmission el...     

Memoir: My Cambridge Years

The Ramanujan Journal -     

Synthesis of N-(3,5-dichlorophenyl)-2-hydroxysuccinimide-O-sulfate: A potential metabolite of the nephrotoxicant N-(3,5-dichlorophenyl)succinimide

The sulfate conjugate 2 of N-(3,5-dichlorophenyl)-2-hydroxysuccinimide, a potential metabolite of the nephrotoxicant N-(3,5-dichlorophenyl)succinimide, is prepared from the 2-hydroxysuccinimide ( 1 ) by the reaction with chlorosulfonic acid in chloroform and ether mixture at ?78°.     

The gas-phase equilibrium structures of Si8O12(OSiMe3)8 and Si8O12(CHCH2)8

The equilibrium molecular structure of Si(8)O(12)(OSiMe(3))(8) has been determined in the gas phase by electron diffraction (GED). With OSi-containing substituents on the cage silicon atoms, this molecule contains a moiety, which would, if reproduced in a periodic manner, yield a zeolite-type structure. Extensive ab initio calculations were used to identify two conformers of this molecule, with D(4) and D(2) point-group symmetries; the D(4)-symmetric conformer was approximately 1.2 kJ mol(-1) lower in energy. With 132 atoms in each conformer, this is one of the largest studies to be undertaken using gas electron diffraction. Semiempirical molecular-dynamics (SE-MD) calculations were used to give amplitudes of vibration, vibrational distance corrections (differences between interatomic distances in the equilibrium structure and the vibrationally averaged distances that are given directly by the diffraction data), and anharmonic constants. The structure of Si(8)O(12)(CHCH(2))(8) has also been determined by GED. Calculations showed that the vinyl groups are fairly unhindered and rotate between three minimum-energy positions. Ultimately, all possible combinations of the vinyl groups in these low-energy positions were accounted for in the GED model.     

Description of sounds recorded from Longman's beaked whale, Indopacetus pacificus

Sounds from Longman's beaked whale, Indopacetus pacificus, were recorded during shipboard surveys of cetaceans surrounding the Hawaiian Islands archipelago; this represents the first known recording of this species. Sounds included echolocation clicks and burst pulses. Echolocation clicks were grouped into three categories, a 15 kHz click (n?=?106), a 25 kHz click (n?=?136), and a 25 kHz pulse with a frequency-modulated upsweep (n?=?70). The 15 and 25 kHz clicks were relatively short (181 and 144 ms, respectively); the longer 25 kHz upswept pulse was 288 ms. Burst pulses were long (0.5 s) click trains with approximately 240 clicks/s.     

Photochromic and fluorescence properties of coumarin fulgimides

Four new fulgimides possessing a fluorescent coumarin unit were synthesized from the corresponding fulgides, and their photochromic as well as fluorescence properties were investigated. The open-ring forms of coumarin fulgimides were found to exhibit fluorescence in the visible region. Upon exposure to UV light, the fulgimides were transformed into the nonfluorescent closed-ring forms, which can be reverted to the initial fluorescent open-ring forms on exposure to visible light. The efficiency of quenching of fluorescence was as high as 95% at the photostationary state of UV irradiation.