Q-Chem (@qchemsoftware.bsky.social)

Development of a Spectroscopic Map to Explain the Broad Raman Peak for Alkynes Solvated in Triethylamine The terminal alkyne C≡C stretch has a large Raman scattering cross section in the “silent” region for biomolecules. Experimental work taking advantage of this property provide an impetus for the development of theoretical tools addressing the vibration. In prior work, we have developed a localized normal mode method for computing terminal alkyne vibrational frequencies using a discrete variable representation of the potential energy surface. Using this method and molecular dynamics simulations, we interpret the unusually broad Raman spectrum of alkynes solvated in triethylamine. Energy decomposition analysis is performed on alkyne-triethylamine dimers to determine that charge transfer, electrostatics, and Pauli repulsion have large effects on the frequency. Molecular dynamics simulations of triethylamine-solvated alkynes are performed and uncover that the terminal alkyne hydrogen interacts strongly with the triethylamine nitrogen. Interactions persist for 3–10 ps. Using this data, a spectroscopic map for terminal alkynes is developed and used to compute Raman spectra for alkynes in triethylamine. We find that the broad experimental spectra result from the combination of a population of alkynes associated with the solvent nitrogens and a population not associated with those nitrogens. This work sets the stage for investigations of alkynes in more complex environments like proteins and nanomaterial surfaces. https://pubs.acs.org/doi/full/10.1021/acs.jpcb.5c05298