Quantum Nature of the Proton in Water-Hydroxyl Overlayers on Metal Surfaces

TY - JOUR

T1 - Quantum Nature of the Proton in Water-Hydroxyl Overlayers on Metal Surfaces

AU - Probert, M.I.J.

AU - Xin-Zheng, L.

AU - Alavi, A.

AU - Michaelides, A.

N1 - © 2010 American Physical Society. This is an author produced version of a paper published in Physical Review Letters. Uploaded in accordance with the publisher's self archiving policy.

PY - 2010/2/12

Y1 - 2010/2/12

N2 - Using ab initio path-integral molecular dynamics, we show that water-hydroxyl overlayers on transition metal surfaces exhibit surprisingly pronounced quantum nuclear effects. The metal substrates serve to reduce the classical proton transfer barriers within the overlayers and, in analogy to ice under high pressure, to shorten the corresponding intermolecular hydrogen bonds. Depending on the substrate and the intermolecular separations it imposes, the traditional distinction between covalent and hydrogen bonds is lost partially [e.g., on Pt(111) and Ru(0001)] or almost entirely [e.g., on Ni(111)]. We suggest that these systems provide an excellent platform on which to systematically explore the magnitude of quantum nuclear effects in hydrogen bonds.

AB - Using ab initio path-integral molecular dynamics, we show that water-hydroxyl overlayers on transition metal surfaces exhibit surprisingly pronounced quantum nuclear effects. The metal substrates serve to reduce the classical proton transfer barriers within the overlayers and, in analogy to ice under high pressure, to shorten the corresponding intermolecular hydrogen bonds. Depending on the substrate and the intermolecular separations it imposes, the traditional distinction between covalent and hydrogen bonds is lost partially [e.g., on Pt(111) and Ru(0001)] or almost entirely [e.g., on Ni(111)]. We suggest that these systems provide an excellent platform on which to systematically explore the magnitude of quantum nuclear effects in hydrogen bonds.

KW - PARTIAL DISSOCIATION

KW - PRINCIPLES

KW - MECHANISM

KW - PRESSURE

KW - PLATINUM

KW - HYDROGEN

KW - RU(0001)

KW - ICE

UR - http://www.scopus.com/inward/record.url?scp=76649093610&partnerID=8YFLogxK

U2 - 10.1103/PhysRevLett.104.066102

DO - 10.1103/PhysRevLett.104.066102

M3 - Article

SN - 0031-9007

VL - 104

JO - Physical Review Letters

JF - Physical Review Letters

IS - 6

M1 - 066102

ER -