naa a22 4500 510734529 CHVBK 20180411083005.0 cr unu---uuuuu 180411e20130701xx s 000 0 eng 10.1007/s12039-013-0436-4 doi (NATIONALLICENCE)springer-10.1007/s12039-013-0436-4 Inductive effect of methyl group in a series of methylated indoles: A graph theoretical analysis in the light of density functional theory and correlation with experimental charge transfer transition energies [Elektronische Daten] [AMIT TIWARY, ASOK MUKHERJEE] The inductive effect of methyl group has been quantified by expressing highest occupied molecular orbital (HOMO) and HOMO-1 energies of indole and a series of methylated indoles using a combination of graph theory (GT) and the Coulson-Longuett-Higgins perturbation method. By correlating these expressions with the corresponding Kohn-Sham orbital energies of the indoles obtained by density functional theory (DFT) calculation at the B3LYP/6-31+ +G(d,p) and M06-2X/6-31+ +G(d,p) levels of theory, the inductive effect parameter h Me has been estimated; the Coulomb integral α of π-conjugated carbon atom also comes out from the analysis. A correlation of the GT results with the HOMO and HOMO-1 energies obtained by the HF/STO-3G method yield almost the same values of h Me and α. Finally, when these estimated h Me and α are used to calculate the vertical ionization potentials of the methylated indoles in the series, an excellent correlation with experimental charge transfer transition energies of their molecular complexes with tetracyanoethylene is obtained which complies with Mulliken's theory of charge transfer. Graphical Abstract Inductive effect of methyl group has been quantified and the Coulomb integral α of π-conjugated C-atom has been estimated by comparing the graph theoretically calculated orbital energies of methylindoles with those obtained by HF/STO-3G, DFT/B3LYP/ 6-31++G(d,p) and DFT/M06-2X/6-31++G(d,p) methods. Results correlate well with experimental CT transition energies. Indian Academy of Sciences, 2013 Graph theory nationallicence DFT nationallicence inductive effect nationallicence methyl indoles nationallicence charge transfer nationallicence TIWARY AMIT Department of Chemistry, Netaji Mahavidyalaya, Hooghly 712 601, Arambagh, India aut MUKHERJEE ASOK Digital Computer System, 112, RB Ghosh Road, 713 101, Burdwan, India aut Journal of Chemical Sciences Springer India 125/4(2013-07-01), 905-912 0974-3626 125:4<905 2013 125 12039 https://doi.org/10.1007/s12039-013-0436-4 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/s12039-013-0436-4 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- TIWARY AMIT Department of Chemistry, Netaji Mahavidyalaya, Hooghly 712 601, Arambagh, India aut NATIONALLICENCE 700 1- MUKHERJEE ASOK Digital Computer System, 112, RB Ghosh Road, 713 101, Burdwan, India aut NATIONALLICENCE 773 0- Journal of Chemical Sciences Springer India 125/4(2013-07-01), 905-912 0974-3626 125:4<905 2013 125 12039 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer