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Nuclear quantum effects of hydrogen bonds probed by tip-enhanced inelastic electron tunneling

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Science  15 Apr 2016:
Vol. 352, Issue 6283, pp. 321-325
DOI: 10.1126/science.aaf2042

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Quantum effects in single hydrogen bonds

Hydrogen bonds are a combination of electrostatics with a nuclear quantum contribution arising from the light mass of hydrogen nuclei. However, the quantum states of hydrogen nuclei are extremely sensitive to coupling with local environments, and these effects are broadened and averaged with conventional spectroscopic or diffraction techniques. Guo et al. show that quantum effects change the strength of individual hydrogen bonds in water layers adsorbed on a salt surface. These effects are revealed in inelastic tunneling spectra obtained with a chlorine-terminated scanning tunneling microscope tip.

Science, this issue p. 321

Abstract

We report the quantitative assessment of nuclear quantum effects on the strength of a single hydrogen bond formed at a water-salt interface, using tip-enhanced inelastic electron tunneling spectroscopy based on a scanning tunneling microscope. The inelastic scattering cross section was resonantly enhanced by “gating” the frontier orbitals of water via a chlorine-terminated tip, so the hydrogen-bonding strength can be determined with high accuracy from the red shift in the oxygen-hydrogen stretching frequency of water. Isotopic substitution experiments combined with quantum simulations reveal that the anharmonic quantum fluctuations of hydrogen nuclei weaken the weak hydrogen bonds and strengthen the relatively strong ones. However, this trend can be completely reversed when a hydrogen bond is strongly coupled to the polar atomic sites of the surface.

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