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Infrared Population Transfer Spectroscopy of Cryo-Cooled Ions: Quantitative Tests of the Effects of Collisional Cooling on the Room Temperature Conformer Populations
journal contribution
posted on 2018-02-20, 23:18 authored by Christopher
P. Harrilal, Andrew F. DeBlase, Joshua L. Fischer, John T. Lawler, Scott A. McLuckey, Timothy S. ZwierThe single-conformation
spectroscopy and infrared-induced conformational
isomerization of a model protonated pentapeptide [YGPAA + H]+ is studied under cryo-cooled conditions in the gas phase. Building
on recent results (DeBlase, A. F.; J. Am. Chem. Soc. 2017, 139, 5481−5493), firm assignments are established for the
presence of two conformer families with distinct infrared and ultraviolet
spectra, using IR–UV depletion spectroscopy. Families (A and
B) share a similar structure near the N-terminus but differ in the
way that the C-terminal COOH group configures itself (cis versus trans) in forming H-bonds with the peptide
backbone. Infrared population transfer (IR-PT) spectroscopy is used
to study the IR-induced conformational isomerization following single-conformer
infrared excitation. IR-induced isomerization is accomplished in both
directions (A → B and B → A) in the hydride stretch
region and is used to determine fractional abundances for the two
conformer families (FA = 0.65 ± 0.04, FB = 0.35 ± 0.04, 2σ error bars).
The time scale for collisional cooling of the room-temperature ions
to Tvib = 10 K by cold helium in the octupole
trap is established as 1.0 ms. Key stationary points on the isomerization
potential energy surface are calculated at the DFT B3LYP/6-31+G(d)
G3DBJ level of theory. Using RRKM theory, the energy-dependent isomerization
rates and populations are calculated as a function of energy. According
to the model, the observed population distribution after collisional
cooling is close to that of the 298 K Boltzmann distribution and is
in near-quantitative agreement with experiment. On the basis of this
success, inferences are drawn for the circumstances that govern the
population distribution in the trap, concluding that, in ions the
size of [YGPAA + H]+ and larger, the observed distributions
will be near those at 298 K.
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Keywords
collisional coolingIR-PTmodel protonated pentapeptidetrapRoom Temperature Conformer PopulationsIR298 K Boltzmann distributionRRKMenergy-dependent isomerization ratespopulation distributionYGPAAconformer familiesIR-inducedspectroscopyInfrared Population Transfer SpectroscopyDFT B 3LYP G 3DBJ levelInfrared population transferhydride stretch regionC-terminal COOH group configures
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