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

Gregory A. Chass, Reinard S. Mirasol, David H. Setiadi, Ting Hua Tang, Wutharath Chin, Michel Mons, Iliana Dimicoli, Jean Pierre Dognon, Bela Viskolcz, Sándor Lovas, Botond Penke, Imre G. Csizmadia

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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 languageEnglish
Pages (from-to)5289-5302
Number of pages14
JournalJournal of Physical Chemistry A
Volume109
Issue number24
DOIs
StatePublished - Jun 23 2005

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Phenylalanine
Discrete Fourier transforms
Infrared radiation
Atoms
Molecules
phenylalanine
atoms
molecules
scoring
interactions
critical point
Experiments
orbitals
energy

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 journalArticle

Chass, GA, Mirasol, RS, Setiadi, DH, Tang, TH, Chin, W, Mons, M, Dimicoli, I, Dognon, JP, Viskolcz, B, Lovas, S, Penke, B & Csizmadia, IG 2005, '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', Journal of Physical Chemistry A, vol. 109, no. 24, pp. 5289-5302. https://doi.org/10.1021/jp040720i
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. / 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. In: Journal of Physical Chemistry A. 2005 ; Vol. 109, No. 24. pp. 5289-5302.
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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.",
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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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