title: Segmentation and additive approach: A reliable technique to study noncovalent interactions of large molecules at the surface of single-wall carbon nanotubes.
abstract: This investigation explores a new protocol, named Segmentation and Additive approach (SAA), to study exohedral noncovalent functionalization of single-walled carbon nanotubes with large molecules, such as polymers and biomolecules, by segmenting the entire system into smaller units to reduce computational cost. A key criterion of the segmentation process is the preservation of the molecular structure responsible for stabilization of the entire system in smaller segments. Noncovalent interaction of linoleic acid (LA, C18 H32 O2 ), a fatty acid, at the surface of a (10,0) zigzag nanotube is considered for test purposes. Three smaller segmented models have been created from the full (10,0)-LA system and interaction energies were calculated for these models and compared with the full system at different levels of theory, namely ωB97XD, LDA. The success of this SAA is confirmed as the sum of the interaction energies is in very good agreement with the total interaction energy. Besides reducing computational cost, another merit of SAA is an estimation of the contributions from different sections of the large system to the total interaction energy which can be studied in-depth using a higher level of theory to estimate several properties of each segment. On the negative side, bulk properties, such as HOMO-LUMO (highest occupied molecular orbital - lowest occupied molecular orbital) gap, of the entire system cannot be estimated by adding results from segment models. © 2016 Wiley Periodicals, Inc.
authors.affiliation: Grupo de Dinámica Cardiovascular, Centro de Bioingeniería, Universidad Pontificia Bolivariana, Bloque 22C, Planta 2a Circular 1a No 73-76, Medellín, Colombia.|Grupo de Termodinámica Computacional, Centro de Investigaciû°n en Materiales Avanzados (CIMAV), Unidad Monterrey, Alianza Norte 202. Parque PIIT, Apodaca, Nuevo León, México.
authors.forename: Ana M
authors.initials: AM
authors.lastname: Torres
authors.affiliation: Department of Chemistry and Biochemistry, Utah State University, Logan, Utah, 84322-0300, USA.
authors.forename: Steve
authors.initials: S
authors.lastname: Scheiner
authors.affiliation: Materials and Manufacturing Directorate, Air Force Research Laboratory, Wright-Patterson Air Force Base, Dayton, Ohio, 45433, USA.
authors.forename: Ajit K
authors.initials: AK
authors.lastname: Roy
authors.affiliation: Grupo de Termodinámica Computacional, Centro de Investigaciû°n en Materiales Avanzados (CIMAV), Unidad Monterrey, Alianza Norte 202. Parque PIIT, Apodaca, Nuevo León, México.
authors.forename: Andrés M
authors.initials: AM
authors.lastname: Garay-Tapia
authors.affiliation: Grupo de Dinámica Cardiovascular, Centro de Bioingeniería, Universidad Pontificia Bolivariana, Bloque 22C, Planta 2a Circular 1a No 73-76, Medellín, Colombia.
authors.forename: John
authors.initials: J
authors.lastname: Bustamante
authors.affiliation: Department of Chemistry and Biochemistry, Utah State University, Logan, Utah, 84322-0300, USA.
authors.forename: Tapas
authors.initials: T
authors.lastname: Kar
keywords: DFT; carbon nanotubes; fatty acid; noncovalent functionalization; segmentation and additive approach; weak interaction