A computational study on molecular adsorption states of nitrogen on a tungsten tetramer
Literature Information
Wataru Yamaguchi, Junichi Murakami
Molecular adsorption states of a dinitrogen (N2) on a free tungsten tetramer (W4) were investigated in detail by using a density functional theory method. It was found that adsorption states with end-on type geometries are the most energetically favorable for molecular adsorption. In the states, interaction between N2 and W4 is weak, and therefore the electronic structure of N2 is not largely modified from that of a free N2. There exist, however, another type of adsorption state with a W–N–N–W bridge-type binding configuration. In the adsorption state of this type, local N (s, p)–W (d) interactions are fairly stronger than in the end-on-type state, and, as a result of this, the adsorbed N2 is significantly activated. The electronic structure of the bridge-type state explains a single-peaked X-ray photoelectron spectrum, previously observed experimentally for N2 adsorbed on supported tungsten nanoclusters. The N 1s spectrum was found in our previous study of low-temperature N2O formation, and therefore, the bridge-type state is a possible candidate for a reaction precursor to the N2O formation under a mild condition.
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