Conformers of gaseous cysteine

Jeremiah J. Wilke, Maria C. Lind, Henry F. Schaefer, A. Császár, Wesley D. Allen

Research output: Contribution to journalArticle

89 Citations (Scopus)

Abstract

Structures, accurate relative energies, equilibrium and vibrationally averaged rotational constants, quartic and sextic centrifugal distortion constants, dipole moments, 14N nuclear quadrupole coupling constants, anharmonic vibrational frequencies, and double-harmonic infrared intensities have been determined from ab initio electronic structure computations for conformers of the neutral form of the natural amino acid L-cysteine (Cys). A systematic scan located 71 unique conformers of Cys using the MP2(FC)/cc-pVTZ method. The large number of structurally diverse low-energy conformers of Cys necessitates the highest possible levels of electronic structure theory to determine their relative energies with some certainty. For this reason, we determined the relative energies of the lowest-energy eleven conformers, accurate within a standard error (1γ) of about 0.3 kJ mol -1, through first-principles composite focal-point analyses (FPA), which employed extrapolations using basis sets as large as aug-cc-pV(5+d)Z and correlation treatments as extensive as CCSD(T). Three and eleven conformers of L-cysteine fall within a relative energy of 6 and 10 kJ mol -1, respectively. The vibrationally averaged rotational constants computed in this study agree well with Fourier-transform microwave spectroscopyresults. The effects determining the relative energies of the low-energyconformers of cysteine are analyzed in detail on the basis of hydrogen bond additivity schemes and natural bond orbital analysis.

Original languageEnglish
Pages (from-to)1511-1523
Number of pages13
JournalJournal of Chemical Theory and Computation
Volume5
Issue number6
DOIs
Publication statusPublished - Jun 9 2009

Fingerprint

cysteine
Electronic structure
Cysteine
Dipole moment
Vibrational spectra
Extrapolation
Amino acids
Fourier transforms
Hydrogen bonds
Microwaves
Infrared radiation
energy
Composite materials
electronic structure
Amino Acids
amino acids
extrapolation
dipole moments
quadrupoles
hydrogen bonds

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Computer Science Applications

Cite this

Wilke, J. J., Lind, M. C., Schaefer, H. F., Császár, A., & Allen, W. D. (2009). Conformers of gaseous cysteine. Journal of Chemical Theory and Computation, 5(6), 1511-1523. https://doi.org/10.1021/ct900005c

Conformers of gaseous cysteine. / Wilke, Jeremiah J.; Lind, Maria C.; Schaefer, Henry F.; Császár, A.; Allen, Wesley D.

In: Journal of Chemical Theory and Computation, Vol. 5, No. 6, 09.06.2009, p. 1511-1523.

Research output: Contribution to journalArticle

Wilke, JJ, Lind, MC, Schaefer, HF, Császár, A & Allen, WD 2009, 'Conformers of gaseous cysteine', Journal of Chemical Theory and Computation, vol. 5, no. 6, pp. 1511-1523. https://doi.org/10.1021/ct900005c
Wilke, Jeremiah J. ; Lind, Maria C. ; Schaefer, Henry F. ; Császár, A. ; Allen, Wesley D. / Conformers of gaseous cysteine. In: Journal of Chemical Theory and Computation. 2009 ; Vol. 5, No. 6. pp. 1511-1523.
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