Model for vibrationally enhanced tunneling of proton transfer in hydrogen bond

Abstract

Theoretical analysis of the effect of an external vibration on proton transfer (PT) in a hydrogen bond (HB) is carried out. It is based on the two-dimensional Schrödinger equation with trigonometric double-well potential. Its solution obtained within the framework of the standard adiabatic approximation is available. An analytic formula is derived that provides the calculation of PT rate with the help of elements implemented in {\sl {Mathematica}}. We exemplify the general theory by calculating PT rate constant for the intermolecular HB in the Zundel ion ${\mathrm{H}}_5{\mathrm{O}}_2^{+}$ (oxonium hydrate). This object enables one to explore a wide range of the HB lengths. Below some critical value of the frequency of the external vibration the calculated PT rate yields extremely rich resonant behavior (multiple manifestations of bell-shaped peaks). It takes place at symmetric coupling of the external vibration to the proton coordinate. This phenomenon is absent for anti-symmetric and squeezed mode couplings.

21 p., 5 fig., accepted for publication to Chem.Phys.Lett

References in corpus (6)

• The double well potential in quantum mechanics: a simple, numerically exact formulation
• Analytic description of inversion vibrational mode for ammonia molecule
• Solvent viscosity dependence for enzymatic reactions
• Analytic treatment of IR-spectroscopy data for double well potential
• Calculation of IR absorption intensities for hydrogen bond from exactly solvable Schrödinger equation
• Exactly solvable double-well potential in Schrödinger equation for inversion mode of phosphine molecule

Cited by in corpus (2)

• Schrödinger equation with Pauli-Fierz Hamiltonian and double well potential as model of vibrationally enhanced tunneling for proton transfer in hydrogen bond
• Non-standard quantum algebras and infinite-dimensional PT-symmetric systems