Isotope dependent, temperature regulated, energy repartitioning in a low-barrier, short-strong hydrogen bonded cluster.
We investigate and analyze the vibrational properties, including hydrogen/deuterium isotope effects, in a fundamental organic hydrogen bonded system using multiple experimental (infrared multiple photon dissociation and argon-tagged action spectroscopy) and computational techniques. We note a qualitative difference between the two experimental results discussed here and employ ab initio molecular dynamics simulations to explain these results. A deeper understanding of the differences between the isotopically labeled systems arises from an analysis of the simulated cluster spectroscopy and leads to a system-bath coupling interpretation. Specifically, when a few active modes, involving the shared hydrogen/deuterium stretch, are identified and labeled as "system," with all other molecular vibrational modes being identified as "bath" modes, we find critical differences in the coupling between the system modes for the shared proton and shared deuteron cases. These differences affect the energy repartitioning between these modes resulting in a complex spectral evolution as a function of temperature. Furthermore, intensity borrowing across modes that are widely distributed in the frequency domain plays an important role on the simulated spectra.
Li
Xiaohu
X
Department of Chemistry, Indiana University, 800 E. Kirkwood Ave., Bloomington, Indiana 47405, USA.
Oomens
Jos
J
Eyler
John R
JR
Moore
David T
DT
Iyengar
Srinivasan S
SS
D003903:Deuterium / Q000737:chemistry*; D006860:Hydrogen Bonding; D008968:Molecular Conformation; D056004:Molecular Dynamics Simulation; D013696:Temperature; D013816:Thermodynamics; D014732:Vibration
D003903:Deuterium