Please use this identifier to cite or link to this item: http://hdl.handle.net/10316/17831
Title: Vibrational spectrum and molecular structure of triphenylamine monomer: A combined matrix-isolation FTIR and theoretical study
Authors: Reva, Igor 
Lapinski, Leszek 
Chattopadhyay, Nitin 
Fausto, Rui 
Issue Date: 6-Aug-2003
Publisher: Royal Society of Chemistry
Serial title, monograph or event: Phys. Chem. Chem. Phys
Volume: 5
Abstract: Theoretical optimization of triphenylamine geometry, carried out at DFT(B3LYP) level using 6-31G** and aug-cc-pVDZ basis sets, predicted a propeller-like structure of the compound with D3 overall symmetry. In this structure, the central NCCC atoms are coplanar and the phenyl rings are symmetrically twisted from this plane by 41.5° (6-31G**) or 41.6° (aug-cc-pVDZ). The experimental FTIR spectrum of triphenylamine monomers isolated in an argon matrix was measured and interpreted by comparison with theoretical spectra calculated at the DFT(B3LYP) level with 6-31G** or aug-cc-pVDZ basis sets. The good agreement between the experimental and theoretical spectra allowed a positive assignment of the observed infrared absorption bands. Conformational flexibility of triphenylamine was investigated by carrying out a series of theoretical scans of the potential energy hypersurface of the system. Special attention was granted to the minimal energy pathway between the left-hand rotating and right-hand rotating symmetry identical structures of the compound. A route conserving a C2 symmetry axis was identified as implying an energy barrier of 20 kJ mol−1 only, whereas the calculated barrier for the concerted twist of all the phenyl rings (the route with conservation of the C3 symmetry axis) was as high as 54 kJ mol−1.
URI: http://hdl.handle.net/10316/17831
DOI: 10.1039/B306489A
Rights: openAccess
Appears in Collections:FCTUC Química - Artigos em Revistas Internacionais

Files in This Item:
File Description SizeFormat
PCCP, 5 (2003) 3844.pdf160.43 kBAdobe PDFView/Open
Show full item record

SCOPUSTM   
Citations

46
checked on Nov 7, 2019

WEB OF SCIENCETM
Citations

44
checked on Jun 25, 2019

Page view(s) 50

285
checked on Nov 19, 2019

Download(s) 50

367
checked on Nov 19, 2019

Google ScholarTM

Check

Altmetric

Dimensions


Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.