caa a22 4500 445328126 CHVBK 20180317142728.0 cr unu---uuuuu 170323e20110301xx s 000 0 eng 10.1007/s10953-011-9665-7 doi (NATIONALLICENCE)springer-10.1007/s10953-011-9665-7 Theoretical Study of the Gauche and Trans Conformers of SiH2X-CH2X, SiH2F-CH2Y and SiH2Y-CH2F (X=F,Cl, Br, I and Y [Elektronische Daten] Cl, Br, I) in the Gas and Solution Phases [Benazir Bhonoah, Anusha Ghoorun, Hassan Abdallah, Ponnadurai Ramasami] The gauche and trans rotamers of halogeno(halogenomethyl)silane (XSiH2CH2X; X = F, Cl, Br, I), fluoro(halogenomethyl)silane and halogeno(fluoromethyl)silane (SiH2F-CH2Y and SiH2Y-CH2F; Y = Cl, Br, I) have been studied in the gas phase using theoretical methods. The transition state arising from gauche-trans isomerization has also been modeled. The methods used are density functional theory (DFT) and second-order Møller-Plesset theory (MP2). B3LYP is the functional used for the DFT method. The basis set used is 6-311++G(d,p) for all atoms except that 6-311G(d,p) is used for the iodine atom only. The results indicate that the trans conformers are preferred in the gas phase and both energy difference and rotational barrier height increase as the size of the halogen increases. This study has been extended to include the solvent effect with the dielectric constant of the solvents varying from 2 to 80. The solvent effect was explored using Self-Consistent Reaction Field and the conformers have been fully optimized at the DFT/B3LYP level of theory. The net effect of a solvent is that energy difference decreases but the rotational barrier is not much affected. The findings from this work are explained in terms of different interactions and these are supported by a Natural Bond Orbital analysis. Springer Science+Business Media, LLC, 2011 Halogeno(halogenomethyl)silane nationallicence Fluoro(halogenomethyl)silane nationallicence Halogeno(fluoromethyl)silane nationallicence Molecular structure nationallicence Vibrational spectrum nationallicence Energy difference nationallicence Rotational barrier nationallicence Bhonoah Benazir Department of Chemistry, University of Mauritius, Réduit, Republic of Mauritius aut Ghoorun Anusha Department of Chemistry, University of Mauritius, Réduit, Republic of Mauritius aut Abdallah Hassan School of Chemical Sciences, University Sains Malaysia, Pulau Pinang, Malaysia aut Ramasami Ponnadurai Department of Chemistry, University of Mauritius, Réduit, Republic of Mauritius aut Journal of Solution Chemistry Springer US; http://www.springer-ny.com 40/3(2011-03-01), 430-446 0095-9782 40:3<430 2011 40 10953 https://doi.org/10.1007/s10953-011-9665-7 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/s10953-011-9665-7 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Bhonoah Benazir Department of Chemistry, University of Mauritius, Réduit, Republic of Mauritius aut NATIONALLICENCE 700 1- Ghoorun Anusha Department of Chemistry, University of Mauritius, Réduit, Republic of Mauritius aut NATIONALLICENCE 700 1- Abdallah Hassan School of Chemical Sciences, University Sains Malaysia, Pulau Pinang, Malaysia aut NATIONALLICENCE 700 1- Ramasami Ponnadurai Department of Chemistry, University of Mauritius, Réduit, Republic of Mauritius aut NATIONALLICENCE 773 0- Journal of Solution Chemistry Springer US; http://www.springer-ny.com 40/3(2011-03-01), 430-446 0095-9782 40:3<430 2011 40 10953 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer