A QTAIM approach on poly tetrahydrothiophene molecular wire

  • Srinivasan Ponnusamy Department of Physics, Chikkaiah Naicker College Erode 638 004 Tamilnadu
  • S Palanisamy Kandaswami Kandar’s College, Velur-638182, Namakkal (Dt,)
  • A David Stephen Chikkaiah Naicker College, Erode-638004, Erode (Dt)
  • K Selvaraju Department of Physics, Chikkaiah Naicker College Erode 638 004 Tamilnadu
Keywords: Molecular wire, Density functional theory, HLG, ESP, Dipole moment.


The present investigation of structural, charge density and electrical characteristics of Au and thiol substituted poly tetrahydrothiophene molecular wire by using quantum chemical calculations has been carried out with density functional theory (DFT). The various applied electric field (0.00 – 0.26 VÅ-1) altered the geometrical parameters and the corresponding electrostatic and transport properties of the molecule has been analyzed. Interstingly, the applied electric field is increased from 0 eV, the Au−S bond distance at the right terminal is faintly longer than the left end; this variation is resulted from the gold atom at the left end which practices stronger electric field when compared with at the right end of TET molecule. The variations in the atomic charges (MPA, NPA) of the molecule for the various applied electric fields have been compared. The HOMO-LUMO gap of the molecule for zero bias is 1.96eV, as the field increases this gap decrease to 1.31 eV. The ESP shows the potential difference between charges accumulated of the molecule for various applied electric field. The applied electric field polarizes the DCC molecule; as a result the dipole moment of the molecule rises from 2.47 to 15.33 D.

Author Biographies

Srinivasan Ponnusamy, Department of Physics, Chikkaiah Naicker College Erode 638 004 Tamilnadu
Assistant Professor in Physics, Chikkaiah Naicker College, Erode
S Palanisamy, Kandaswami Kandar’s College, Velur-638182, Namakkal (Dt,)
Department of Physics
A David Stephen, Chikkaiah Naicker College, Erode-638004, Erode (Dt)
Department of Physics
K Selvaraju, Department of Physics, Chikkaiah Naicker College Erode 638 004 Tamilnadu
Department of Physics


. Zade, SS & Bendikov, M (2006) From Oligomers to Polymer: Convergence in the HOMO−LUMO Gaps of Conjugated Oligomers. Organic Letters, 8(23), 5243-5246.

. Curtis, MD, Cao, J & Kampf JW (2004) Solid-State Packing of Conjugated Oligomers: From π-Stacks to the Herringbone Structure. J Amer Chem Soc, 126(13), 4318-4328.

. Bader, RFW (1991) A quantum theory of molecular structure and its applications. Chem Rev, 91(5), 893-928.

. Bagayoko, D (2014) Understanding density functional theory (DFT) and completing it in practice. AIP Advances, 4(12), 127104.

. Frisch, MJ, Trucks, GW, Schlegel, HB, Scuseria, GE, Robb, MA, Cheeseman, JA, Scalmani, G, Barone, V, Petersson, GA, Nakatsuji, H, Li, X, Caricato, M, Marenich, AV, Bloino, J, Janesko, BG, Gomperts, R, Mennucci, B, Hratchian, HP, Ortiz, JV, Izmaylov, AF, Sonnenberg, JL, Williams, F. Ding, Lipparini, F, Egidi, F, Goings, J, Peng, B, Petrone, A, Henderson, T, Ranasinghe, D, Zakrzewski, VG, Gao, J, Rega, N, Zheng, G, Liang, W, Hada, M, Ehara, M, Toyota, K, Fukuda, R, Hasegawa, J, Ishida, M, Nakajima, T, Honda, Y, Kitao, O, Nakai, H, Vreven, T, Throssell, K, Montgomery Jr., JA, Peralta, JE, Ogliaro, F, Bearpark, MJ, Heyd, JJ, Brothers, EN, Kudin, KN, Staroverov, VN, Keith, TA, Kobayashi, R, Normand, J, Raghavachari, K, Rendell, AP, Burant, JC, Iyengar, SS, Tomasi, J, Cossi, M, Millam, JM, Klene, M, Adamo, C, Cammi, R, Ochterski, JW, Martin, RL, Morokuma, K, Farkas, O, Foresman, JB & Fox JD, Gaussian 16 Rev. B.01. 2016: Wallingford, CT.

. Lee, C, Yang, W & Parr, RG (1988) Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phy Rev B, 37(2), 785-789.

. Wadt, WR & Hay PJ (1985) Ab initio effective core potentials for molecular calculations potentials for main group elements Na to Bi. The Journal of Chemical Physics, 82(1), 284-298.

. Cheeseman, J, Keith, TA, & Bader, RFW (1992) AIMPAC Program Package, McMaster University Hamilton, Ontario.

. Volkov, A, Koritsanszky, T, Chodkiewicz, M & King Harry, F (2008) On the basis‐set dependence of local and integrated electron density properties: Application of a new computer program for quantum‐chemical density analysis. Jour of Comp Chem, 30(9), 1379-1391.

. Dennington, R., Keith, TA & Millam, JM (2016) GaussView Version 6. Wallingford, CT.

. Koritsanszky, T, Macchi, P, Gatti, C, Farrugia, L, Mallison, PR, Volkov, A & Richter, T, (2006) XD2006- A computer program package for multipole refinement and analysis of charge densities from diffraction data. .

. O'Boyle Noel, M, Tenderholt Adam, L & Langner Karol, M (2007) cclib: A library for package independent computational chemistry algorithms. Jour of Comp Chem, 29(5), 839-845.

. Burgi, T, (2015) Properties of the gold-sulphur interface: from self-assembled monolayers to clusters. Nanoscale, 7(38), 15553-15567.

. Tachibana, M, Yoshizawa, K, Ogawa, A, Fujimoto, H & Hoffmann, R, (2002) Sulfur−Gold Orbital Interactions which Determine the Structure of Alkanethiolate/Au(111) Self-Assembled Monolayer Systems. Jour of Phy Chem B, 106(49), 12727-12736.

. Bader, R, (1994) Atoms in Molecules: A Quantum Theory (International Series of Monographs on Chemistry). Clarendon Press.

. Silva Lopez, C, & de Lera AR, (2011) Bond Ellipticity as a Measure of Electron Delocalization in Structure and Reactivity. Curr Orga Chem, 15(20), 3576-3593.

. Bader, RFW, & Preston, HJT, (1969) the kinetic energy of molecular charge distributions and molecular stability. Inter Jour of Quant Chemi, 3(3), 327-347.

. Gillespie, RJ, (2001) Electron Densities, Atomic Charges, and Ionic, Covalent, and Polar Bonds. Journal of Chemical Education, 78(12), 1688

. Saha, S, Roy Ram, K, & Ayers Paul, W (2008) Are the Hirshfeld and Mulliken population analysis schemes consistent with chemical intuition?, Inter Jour Quant Chem, 109(9), 1790-1806.

. Reed, AE, Weinstock, RB & Weinhold, F (1985) Natural population analysis. Jour of Chem Phy, 83(2), 735-746.

. Hu, P, Du, K, Wei, F, Jiang, H & Kloc, C (2016) Crystal Growth, HOMO–LUMO Engineering, and Charge Transfer Degree in Perylene-FxTCNQ (x = 1, 2, 4) Organic Charge Transfer Binary Compounds. Crystal Growth & Design, 16(5), 3019-3027.

. Politzer, P, Laurence, PR, & Jayasuriya, K (1985) Molecular electrostatic potentials: an effective tool for the elucidation of biochemical phenomena. Environmental Health Perspectives, 61, 191-202.

. Kirtman, B, Bonness, S, Ramirez-Solis, A, Champagne, B, Matsumoto, H, & Sekino, H (2008) Calculation of electric dipole (hyper) polarizabilities by long-range-correction scheme in density functional theory: A systematic assessment for polydiacetylene and polybutatriene oligomers. Jour of Chem Phy, 128(11), 114108.

. Darancet, P, Widawsky, JR, Choi, HJ, Venkataraman, L & Neaton, JB (2012) Quantitative Current–Voltage Characteristics in Molecular Junctions from First Principles. Nano Letters, 12(12), 6250-6254.

. Landauer, R, (2000) Spatial variation of currents and fields due to localized scatterers in metallic conduction. IBM Journal of Research and Development, 44(1), 251-260.

. Chapter 2 - Electrochemical and Thermodynamic Fundamentals, in Membrane Science and Technology, H. Strathmann, Editor. 2004, Elsevier. p. 23-88.

How to Cite
Ponnusamy, S., Palanisamy, S., Stephen, A. D., & Selvaraju, K. (2018). A QTAIM approach on poly tetrahydrothiophene molecular wire. Boson Journal of Modern Physics, 4(2), 361-383. Retrieved from http://scitecresearch.com/journals/index.php/bjmp/article/view/1567