The spontaneous synchronized dance of pairs of water molecules

被引:17
作者
Roncaratti, Luiz F. [1 ,2 ]
Cappelletti, David [1 ]
Pirani, Fernando [1 ]
机构
[1] Univ Perugia, Dipartimento Chim Biol & Biotecnol, I-06123 Perugia, Italy
[2] Univ Brasilia, Inst Fis, BR-70910900 Brasilia, DF, Brazil
关键词
BEAM SCATTERING; DYNAMICS; POLARIZABILITY; ORIENTATION; DEPENDENCE; FIELDS; ENERGY;
D O I
10.1063/1.4869595
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
Molecular beam scattering experiments have been performed to study the effect of long-range anisotropic forces on the collision dynamics of two small polar molecules. The main focus of this paper is on water, but also ammonia and hydrogen sulphide molecules have been investigated, and some results will be anticipated. The intermolecular distances mainly probed are of the order of 1 nm and therefore much larger than the molecular dimensions. In particular, we have found that the natural electric field gradient, generated by different spatial orientations of the permanent electric dipoles, is able to promote the transformation of free rotations into coupled pendular states, letting the molecular partners involved in the collision complex swinging to and fro around the field direction. This long-ranged concerted motion manifested itself as large increases of the magnitude of the total integral cross section. The experimental findings and the theoretical treatment developed to shed light on the details of the process suggest that the transformation from free rotations to pendular states depends on the rotational level of both molecules, on the impact parameter, on the relative collision velocity, on the dipole moment product and occurs in the time scale of picoseconds. The consequences of this intriguing phenomenon may be important for the interpretation and, in perspective, for the control of elementary chemical and biological processes, given by polar molecules, ions, and free radicals, occurring in several environments under various conditions. (c) 2014 AIP Publishing LLC.
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页数:6
相关论文
共 35 条
[1]   Glory-scattering measurement of water-noble-gas interactions: The birth of the hydrogen bond [J].
Aquilanti, V ;
Cornicchi, E ;
Teixidor, MM ;
Saendig, N ;
Pirani, F ;
Cappelletti, D .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2005, 44 (16) :2356-2360
[2]   Temperature dependence of chemical and biophysical rate processes: Phenomenological approach to deviations from Arrhenius law [J].
Aquilanti, Vincenzo ;
Mundim, Kleber Carlos ;
Elango, Munusamy ;
Kleijn, Steven ;
Kasai, Toshio .
CHEMICAL PHYSICS LETTERS, 2010, 498 (1-3) :209-213
[3]   Growth of polyphenyls via ion-molecule reactions: An experimental and theoretical mechanistic study [J].
Aysina, Julia ;
Maranzana, Andrea ;
Tonachini, Glauco ;
Tosi, Paolo ;
Ascenzi, Daniela .
JOURNAL OF CHEMICAL PHYSICS, 2013, 138 (20)
[4]   Charge-Transfer Energy in the Water-Hydrogen Molecular Aggregate Revealed by Molecular-Beam Scattering Experiments, Charge Displacement Analysis, and ab Initio Calculations [J].
Belpassi, Leonardo ;
Reca, Michael L. ;
Tarantelli, Francesco ;
Roncaratti, Luiz F. ;
Pirani, Fernando ;
Cappelletti, David ;
Faure, Alexandre ;
Scribano, Yohann .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (37) :13046-13058
[5]   GENERALIZED CORRELATIONS IN TERMS OF POLARIZABILITY FOR VANDERWAALS INTERACTION POTENTIAL PARAMETER CALCULATIONS [J].
CAMBI, R ;
CAPPELLETTI, D ;
LIUTI, G ;
PIRANI, F .
JOURNAL OF CHEMICAL PHYSICS, 1991, 95 (03) :1852-1861
[6]   GENERALIZATION TO ION NEUTRAL SYSTEMS OF THE POLARIZABILITY CORRELATIONS FOR INTERACTION POTENTIAL PARAMETERS [J].
CAPPELLETTI, D ;
LIUTI, G ;
PIRANI, F .
CHEMICAL PHYSICS LETTERS, 1991, 183 (3-4) :297-303
[7]   Revealing Charge-Transfer Effects in Gas-Phase Water Chemistry [J].
Cappelletti, David ;
Ronca, Enrico ;
Belpassi, Leonardo ;
Tarantelli, Francesco ;
Pirani, Fernando .
ACCOUNTS OF CHEMICAL RESEARCH, 2012, 45 (09) :1571-1580
[8]   Stereodynamics of Chemical Reactions 2012 [J].
Carre, B. ;
Poisson, L. ;
Shafizadeh, N. ;
Soep, B. .
JOURNAL OF PHYSICAL CHEMISTRY A, 2013, 117 (34) :8093-8094
[9]   Negative collision energy dependence of Br formation in the OH plus HBr reaction [J].
Che, Dock-Chil ;
Matsuo, Takashi ;
Yano, Yuya ;
Bonnet, Laurent ;
Kasai, Toshio .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2008, 10 (10) :1419-1423
[10]   DIPOLE-DIPOLE SCATTERING IN MOLECULAR BEAMS . VARIATION OF TOTAL CROSS SECTION WITH VELOCITY AND ROTATIONAL OVERLAP [J].
CROSS, RJ ;
GISLASON, EA ;
HERSCHBACH, DR .
JOURNAL OF CHEMICAL PHYSICS, 1966, 45 (10) :3582-+