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Entropy-driven population distributions in a prototypical molecule with two flexible side chains: O-(2-acetamidoethyl)-N-acetyltyramine

J. Chem. Phys. 127, 234315 (2007); doi:10.1063/1.2803076

Published 20 December 2007

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V. Alvin Shubert, Esteban E. Baquero, Jasper R. Clarkson, William H. James, III, Jeffrey A. Turk, Alissa A. Hare, Kevin Worrel, and Mark A. Lipton
Department of Chemistry, Purdue University, West Lafayette, Indiana 47907-2084, USA

Daniel P. Schofield and Kenneth D. Jordan
Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, USA

Timothy S. Zwier
Department of Chemistry, Purdue University, West Lafayette, Indiana 47907-2084, USA
Resonant two-photon ionization (R2PI), resonant ion-dip infrared (RIDIR), and UV-UV hole-burning spectroscopies have been employed to obtain conformation-specific infrared and ultraviolet spectra under supersonic expansion conditions for O-(2-acetamidoethyl)-N-acetyltyramine (OANAT), a doubly substituted aromatic in which amide-containing alkyl and alkoxy side chains are located in para positions on a phenyl ring. For comparison, three single-chain analogs were also studied: (i) N-phenethyl-acetamide (NPEA), (ii) N-(p-methoxyphenethyl-acetamide) (NMPEA), and (iii) N-(2-phenoxyethyl)-acetamide (NPOEA). Six conformations of OANAT have been resolved, with S0-S1 origins ranging from 34  536  to  35  711  cm−1, denoted A–F, respectively. RIDIR spectra show that conformers A–C each possess an intense, broadened amide NH stretch fundamental shifted below 3400  cm−1, indicative of the presence of an interchain H bond, while conformers D–F have both amide NH stretch fundamentals in the 3480–3495  cm−1 region, consistent with independent-chain structures with two free NH groups. NPEA has a single conformer with S0-S1 origin at 37  618  cm−1. NMPEA has three conformers, two that dominate the R2P1 spectrum, with origin transitions between 35 580 and 35  632  cm−1. Four conformations, one dominate and three minor, of NPOEA have been resolved with origins between 35 654 and 36  423  cm−1. To aid the making of conformational assignments, the geometries of low-lying structures of all four molecules have been optimized and the associated harmonic vibrational frequencies calculated using density functional theory (DFT) and RIMP2 methods. The S0-S1 adiabatic excitation energies have been calculated using the RICC2 method and vertical excitation energies using single-point time-dependent DFT. The sensitivity of the S0-S1 energy separation in OANAT and NPOEA primarily arises from different orientations of the chain attached to the phenoxy group. Using the results of the single-chain analogs, tentative assignments have been made for the observed conformers of OANAT. The RIMP2 calculations predict that interchain H-bonded conformers of OANAT are 25–30  kJ/mol more stable than the extended-chain structures. However, the free energies of the interchain H-bonded and extended structures calculated at the preexpansion temperature (450  K) differ by less than 10  kJ/mol, and the number of extended structures far outweighs the number of H-bonded conformers. This entropy-driven effect explains the presence of the independent-chain conformers in the expansion, and cautions future studies that rely solely on relative energies of conformers in considering possible assignments. ©2007 American Institute of Physics
History: Received 6 August 2007; accepted 4 October 2007; published 20 December 2007
Permalink: http://link.aip.org/link/?JCPSA6/127/234315/1
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Supplemental Material

KEYWORDS and PACS

Keywords
PACS
  • 33.15.Bh
    General molecular conformation and symmetry; stereochemistry
  • 33.80.Rv
    Multiphoton ionization and excitation to highly excited states in molecules e.g., Rydberg states
  • 33.20.Ea
    Infrared molecular spectra
  • 33.20.Lg
    Ultraviolet molecular spectra
  • 33.15.Mt
    Molecular rotation, vibration, and vibration-rotation constants
  • 33.20.Tp
    Vibrational analysis (molecular spectra)
  • YEAR: 2007

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