TY - JOUR
ID - Digital.CSIC
A1 - Barragán, Patricia
A1 - Delgado Barrio, Gerardo
A1 - Pérez de Tudela, Ricardo
A1 - Prosmiti, Rita
A1 - Villarreal, Pablo
Y1 - 2011
UR - http://hdl.handle.net/10261/57889
N2 - Classical and path integral Monte Carlo (CMC, PIMC) >on the fly> calculations are carried out to investigate anharmonic quantum effects on the thermal equilibrium structure of the H5 + cluster. The idea to follow in our computations is based on using a combination of the above-mentioned nuclear classical and quantum statistical methods, and first-principles density functional (DFT) electronic structure calculations. The interaction energies are computed within the DFT framework using the B3(H) hybrid functional, specially designed for hydrogen-only systems. The global minimum of the potential is predicted to be a nonplanar configuration of C 2v symmetry, while the next three low-lying stationary points on the surface correspond to extremely low-energy barriers for the internal proton transfer and to the rotation of the H2 molecules, around the C 2 axis of H5 +, connecting the symmetric C 2v minima in the planar and nonplanar orientations. On the basis of full-dimensional converged PIMC calculations, results on the quantum vibrational zero-point energy (ZPE) and state of H5 + are reported at a low temperature of 10 K, and the influence of the above-mentioned topological features of the surface on its probability distributions is clearly demonstrated. © 2011 American Chemical Society.
PB - American Chemical Society
T1 - Internal proton transfer and H2 rotations in the H 5 + cluster: A marked influence on its thermal equilibrium state
ER -