Tunneling dynamics in water tetramer and pentamer

被引:76
作者
Gregory, JK [1 ]
Clary, DC [1 ]
机构
[1] UNIV LONDON UNIV COLL,DEPT CHEM,LONDON WC1H 0AJ,ENGLAND
关键词
D O I
10.1063/1.471976
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
We present a theoretical study of the structures, energetics and tunneling dynamics of the cyclic water tetramer and pentamer, both of which have recently been observed experimentally. The very good agreement between vibrationally averaged rotational constants from diffusion quantum Monte Carte calculations and experimental values confirms that the structures are cyclic. We calculate a splitting for a tunneling motion that is a likely cause for doublets observed experimentally in the far infrared spectrum of (D2O)(4). Predictions of tunneling splittings yet to be observed in the water pentamer are made. (C) 1996 American lnstitute of Physics.
引用
收藏
页码:6626 / 6633
页数:8
相关论文
共 69 条
[31]   COOPERATIVE EFFECTS IN EXTENDED HYDROGEN-BONDED SYSTEMS INVOLVING O-H GROUPS - ABINITIO STUDIES OF THE CYCLIC S-4 WATER TETRAMER [J].
KOEHLER, JEH ;
SAENGER, W ;
LESYNG, B .
JOURNAL OF COMPUTATIONAL CHEMISTRY, 1987, 8 (08) :1090-1098
[32]   Vibration-rotation tunneling spectra of the water pentamer: Structure and dynamics [J].
Liu, K ;
Brown, MG ;
Cruzan, JD ;
Saykally, RJ .
SCIENCE, 1996, 271 (5245) :62-64
[33]   FAR-IR VIBRATION-ROTATION TUNNELING SPECTROSCOPY OF THE WATER TRIMER [J].
LIU, K ;
ELROD, MJ ;
LOESER, JG ;
CRUZAN, JD ;
PUGLIANO, N ;
BROWN, MG ;
RZEPIELA, J ;
SAYKALLY, RJ .
FARADAY DISCUSSIONS, 1994, 97 :35-41
[34]   DYNAMICS OF STRUCTURAL REARRANGEMENTS IN THE WATER TRIMER [J].
LIU, K ;
LOESER, JG ;
ELROD, MJ ;
HOST, BC ;
RZEPIELA, JA ;
PUGLIANO, N ;
SAYKALLY, RJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (08) :3507-3512
[35]  
MILLER RE, 1985, J CHEM PHYS, V82, P3554
[36]   TOWARDS AN ACCURATE INTERMOLECULAR POTENTIAL FOR WATER [J].
MILLOT, C ;
STONE, AJ .
MOLECULAR PHYSICS, 1992, 77 (03) :439-462
[37]   STRUCTURE, ENERGETICS, AND DYNAMICS OF SMALL WATER CLUSTERS [J].
OWICKI, JC ;
SHIPMAN, LL ;
SCHERAGA, HA .
JOURNAL OF PHYSICAL CHEMISTRY, 1975, 79 (17) :1794-1811
[38]   THEORETICALLY PREDICTED LOWEST-ENERGY STRUCTURES OF WATER CLUSTERS [J].
PILLARDY, J ;
OLSZEWSKI, KA ;
PIELA, L .
JOURNAL OF MOLECULAR STRUCTURE, 1992, 270 :277-285
[39]   INVESTIGATION OF STRUCTURE AND STABILITY OF SMALL CLUSTERS - MOLECULAR-DYNAMICS STUDIES OF WATER PENTAMERS [J].
PLUMMER, PLM ;
CHEN, TS .
JOURNAL OF CHEMICAL PHYSICS, 1987, 86 (12) :7149-7155
[40]   TOPOGRAPHY OF POTENTIAL-ENERGY SURFACES FOR VAN-DER-WAALS COMPLEXES [J].
POPELIER, PLA ;
STONE, AJ ;
WALES, DJ .
FARADAY DISCUSSIONS, 1994, 97 :243-264