Abstract
Computational and experimental determinations were carried out in parallel on the conformational probability of N-Acetyl-Phenylalanine-NH2 (NAPA). Ab initio computations were completed at the BLYP/6-311G(df,p), B3LYP/6-31G(d), B3LYP/6-31G(d,p), and B3LYP/6-31+G(d) levels of theory, labeled L/61fp, B/6, B/6p, and B/6+, respectively. Three experimentally identified conformers were compared with theoretical data, confirming their identities as the β L anti, γ L gauche+ and γ L gauche- (BACKBONE SIDECHAIN) conformers. Evidence comes from matching experimental and theoretical data for all three constituent N-H stretches of NAPA, with a A Experimental-Theoretical = ∼1-3 cm -1, ∼0-5 cm -1, and ∼1-6 cm -1, at the L/61fp and B/6+ levels, respectively. Corrected-ZPE relative energies were computed to be 0.14, 0.00, 0.26 and 0.00, 0.67, 0.57 (kcal*mol -1) for the β L anti, γ L gauche+, and γ L gauche- conformers, respectively, at the L/61fp and B/6+ levels, respectively. The MP2/6-31+G(d) level of theory was subsequently found to give similar relative energies. Characterization of the intramolecular interactions responsible for red and blue shifting of the N-H stretches showed the existence of the following intramolecular interactions: C=O [i]- - - HN [i], (Ar [i])-C γ- - -HN [i+1], (Ar [i])-C δ-H- - -O=C [i-1] for β L anti; C=O [i-1]- - -HN [i+l], (Ar [i])-C - H- - -O=C [i] for γ L gauche+; and C=O [i-1]- - -HN [i+1] for γ L gauche-. Each of these interactions were further investigated and subsequently characterized by orbital population and Atoms-In-Molecules (AIM) analyses, with the identity of overlap and bond critical points (BCP) serving as 'scoring criteria', respectively. Experimental and theoretical carbonyl stretches were also compared and showed good agreement, adding further strength to the synergy between experiment and theory.
| Original language | English |
|---|---|
| Pages (from-to) | 5289-5302 |
| Number of pages | 14 |
| Journal | Journal of Physical Chemistry A |
| Volume | 109 |
| Issue number | 24 |
| DOIs | |
| State | Published - Jun 23 2005 |
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All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
Cite this
Characterization of the conformational probability of N-acetyl- Phenylalanyl-NH 2 by RHF, DFT, and MP2 computation and AIM analyses, confirmed by jet-cooled infrared data. / Chass, Gregory A.; Mirasol, Reinard S.; Setiadi, David H.; Tang, Ting Hua; Chin, Wutharath; Mons, Michel; Dimicoli, Iliana; Dognon, Jean Pierre; Viskolcz, Bela; Lovas, Sándor; Penke, Botond; Csizmadia, Imre G.
In: Journal of Physical Chemistry A, Vol. 109, No. 24, 23.06.2005, p. 5289-5302.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Characterization of the conformational probability of N-acetyl- Phenylalanyl-NH 2 by RHF, DFT, and MP2 computation and AIM analyses, confirmed by jet-cooled infrared data
AU - Chass, Gregory A.
AU - Mirasol, Reinard S.
AU - Setiadi, David H.
AU - Tang, Ting Hua
AU - Chin, Wutharath
AU - Mons, Michel
AU - Dimicoli, Iliana
AU - Dognon, Jean Pierre
AU - Viskolcz, Bela
AU - Lovas, Sándor
AU - Penke, Botond
AU - Csizmadia, Imre G.
PY - 2005/6/23
Y1 - 2005/6/23
N2 - Computational and experimental determinations were carried out in parallel on the conformational probability of N-Acetyl-Phenylalanine-NH2 (NAPA). Ab initio computations were completed at the BLYP/6-311G(df,p), B3LYP/6-31G(d), B3LYP/6-31G(d,p), and B3LYP/6-31+G(d) levels of theory, labeled L/61fp, B/6, B/6p, and B/6+, respectively. Three experimentally identified conformers were compared with theoretical data, confirming their identities as the β L anti, γ L gauche+ and γ L gauche- (BACKBONE SIDECHAIN) conformers. Evidence comes from matching experimental and theoretical data for all three constituent N-H stretches of NAPA, with a A Experimental-Theoretical = ∼1-3 cm -1, ∼0-5 cm -1, and ∼1-6 cm -1, at the L/61fp and B/6+ levels, respectively. Corrected-ZPE relative energies were computed to be 0.14, 0.00, 0.26 and 0.00, 0.67, 0.57 (kcal*mol -1) for the β L anti, γ L gauche+, and γ L gauche- conformers, respectively, at the L/61fp and B/6+ levels, respectively. The MP2/6-31+G(d) level of theory was subsequently found to give similar relative energies. Characterization of the intramolecular interactions responsible for red and blue shifting of the N-H stretches showed the existence of the following intramolecular interactions: C=O [i]- - - HN [i], (Ar [i])-C γ- - -HN [i+1], (Ar [i])-C δ-H- - -O=C [i-1] for β L anti; C=O [i-1]- - -HN [i+l], (Ar [i])-C - H- - -O=C [i] for γ L gauche+; and C=O [i-1]- - -HN [i+1] for γ L gauche-. Each of these interactions were further investigated and subsequently characterized by orbital population and Atoms-In-Molecules (AIM) analyses, with the identity of overlap and bond critical points (BCP) serving as 'scoring criteria', respectively. Experimental and theoretical carbonyl stretches were also compared and showed good agreement, adding further strength to the synergy between experiment and theory.
AB - Computational and experimental determinations were carried out in parallel on the conformational probability of N-Acetyl-Phenylalanine-NH2 (NAPA). Ab initio computations were completed at the BLYP/6-311G(df,p), B3LYP/6-31G(d), B3LYP/6-31G(d,p), and B3LYP/6-31+G(d) levels of theory, labeled L/61fp, B/6, B/6p, and B/6+, respectively. Three experimentally identified conformers were compared with theoretical data, confirming their identities as the β L anti, γ L gauche+ and γ L gauche- (BACKBONE SIDECHAIN) conformers. Evidence comes from matching experimental and theoretical data for all three constituent N-H stretches of NAPA, with a A Experimental-Theoretical = ∼1-3 cm -1, ∼0-5 cm -1, and ∼1-6 cm -1, at the L/61fp and B/6+ levels, respectively. Corrected-ZPE relative energies were computed to be 0.14, 0.00, 0.26 and 0.00, 0.67, 0.57 (kcal*mol -1) for the β L anti, γ L gauche+, and γ L gauche- conformers, respectively, at the L/61fp and B/6+ levels, respectively. The MP2/6-31+G(d) level of theory was subsequently found to give similar relative energies. Characterization of the intramolecular interactions responsible for red and blue shifting of the N-H stretches showed the existence of the following intramolecular interactions: C=O [i]- - - HN [i], (Ar [i])-C γ- - -HN [i+1], (Ar [i])-C δ-H- - -O=C [i-1] for β L anti; C=O [i-1]- - -HN [i+l], (Ar [i])-C - H- - -O=C [i] for γ L gauche+; and C=O [i-1]- - -HN [i+1] for γ L gauche-. Each of these interactions were further investigated and subsequently characterized by orbital population and Atoms-In-Molecules (AIM) analyses, with the identity of overlap and bond critical points (BCP) serving as 'scoring criteria', respectively. Experimental and theoretical carbonyl stretches were also compared and showed good agreement, adding further strength to the synergy between experiment and theory.
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U2 - 10.1021/jp040720i
DO - 10.1021/jp040720i
M3 - Article
VL - 109
SP - 5289
EP - 5302
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
SN - 1089-5639
IS - 24
ER -