Zero point energy of polyhedral water clusters

被引:14
作者
Anick, DJ [1 ]
机构
[1] Harvard Univ, McLean Hosp, Sch Med, Belmont, MA 02478 USA
关键词
D O I
10.1021/jp045359e
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Polyhedral water clusters (PWCs) are cage-like (H2O)(n) clusters where every 0 participates in exactly three H bonds. For a database of 83 PWCs, 8 <= n <= 20, geometry was optimized and zero point energy (ZPE) was calculated at the B3LYP/6-311++G** level. ZPE correlates negatively with electronic energy (E-0): each increase of 1 kcal/mol in E-0 corresponds to a decrease of about 0.11 kcal/mol in ZPE. For each n, a set of four connectivity parameters accounts for 98% or more of the variance in ZPE. Linear regression of ZPE against n and this set gives an RMS error of 0.13 kcal/mol. The contributions to ZPE from stretch modes only (ZPEs) and from torsional modes only (ZPE(T)) also correlate strongly with E-0 and with each other.
引用
收藏
页码:5596 / 5601
页数:6
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