Molecular dynamics simulations and hyperspherical mode analysis of NO in Kr crystals with the use of ab initio potential energy surfaces for the Kr-NO complex

被引:12
作者
Castro Palacio, Juan Carlos [1 ]
Rubayo-Soneira, Jesus
Lombardi, Andrea [2 ]
Aquilanti, Vincenzo [2 ]
机构
[1] Univ Pinar del Rio, Dept Fis, Pinar Del Rio, Cuba
[2] Univ Perugia, Dipartimento Chim, I-06123 Perugia, Italy
关键词
nitric oxide; rare gas solids;
D O I
10.1002/qua.21620
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
The dynamics of structural relaxation of NO doped Kr solids on electronic excitation of the NO molecule has been characterized by molecular dynamics simulations and by normal and hyperspherical mode analysis, with special emphasis on the effects of the anisotropy of the Kr-NO interaction which has been modeled by ab initio potential energy surfaces (PESs). The time evolution of the cage radius and the radial distribution function for the ground and excited states have been calculated for various orientations of the molecular axis with respect the Kr atom matrix with the NO molecule treated as a rigid rotor. The ab initio PESs, considered in previous work, seem to be too repulsive when compared with potentials fitted to spectroscopic data, and this is more evident for the first Ryberg state than for the ground state, where effects of potential anisotropy are less important. The first shell response shows a relative increase, up to similar to 10%, of the excited state equilibrium radius with respect to that of the ground state, while experiments indicate that such an increase should be less than 5%. The kinetic energy power spectrum method, presented in a previous work, has been applied to the total kinetic energy T(t) and to two characteristic quantities of the hyperspherical mode analysis, the hyperradial energy T-rho(t) and the grand angular energy T-Lambda(t) for NO molecular axis orientations of 67 degrees and 90 degrees, respectively, which represent the cases of the largest and smallest lattice distortions in the radial distribution function (RDF) of the atoms in the matrix for the excited state. The band structures of the calculated frequency spectra reveal a blue shift with respect to the case of the isotropic potentials used previously, and this is connected to the different lattice equilibrium structures for 67 degrees and 90 degrees directions. (c) 2008 Wiley Periodicals, Inc.
引用
收藏
页码:1821 / 1830
页数:10
相关论文
共 38 条
[1]   Molecular photodynamics in rare gas solids [J].
Apkarian, VA ;
Schwentner, N .
CHEMICAL REVIEWS, 1999, 99 (06) :1481-1514
[2]   Invariant energy partitions in chemical reactions and cluster dynamics simulations [J].
Aquilanti, V ;
Novillo, EC ;
Garcia, E ;
Lombardi, A ;
Sevryuk, MB ;
Yurtsever, E .
COMPUTATIONAL MATERIALS SCIENCE, 2006, 35 (03) :187-191
[3]   Phase-space invariants for aggregates of particles: Hyperangular momenta and partitions of the classical kinetic energy [J].
Aquilanti, V ;
Lombardi, A ;
Sevryuk, MB .
JOURNAL OF CHEMICAL PHYSICS, 2004, 121 (12) :5579-5589
[4]   Global view of classical clusters: the hyperspherical approach to structure and dynamics [J].
Aquilanti, V ;
Lombardi, A ;
Yurtsever, E .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2002, 4 (20) :5040-5051
[5]  
AQUILANTI V, 2004, PHYS REV LETT, V93
[6]  
Ashcroft N W., 1976, Solid State Physics
[7]   ELECTRONIC-SPECTRA FROM MOLECULAR-DYNAMICS - A SIMPLE APPROACH [J].
BERGSMA, JP ;
BERENS, PH ;
WILSON, KR ;
FREDKIN, DR ;
HELLER, EJ .
JOURNAL OF PHYSICAL CHEMISTRY, 1984, 88 (03) :612-619
[8]   CORE-LEVEL PHOTOELECTRON AND X-RAY-ABSORPTION SPECTROSCOPY OF FREE ARGON CLUSTERS - SIZE-DEPENDENT ENERGY SHIFTS AND DETERMINATION OF SURFACE ATOM COORDINATION [J].
BJORNEHOLM, O ;
FEDERMANN, F ;
FOSSING, F ;
MOLLER, T .
PHYSICAL REVIEW LETTERS, 1995, 74 (15) :3017-3020
[9]  
Bjorneholm O, 1996, J CHEM PHYS, V104, P1846, DOI 10.1063/1.470981
[10]   Lattice response of quantum solids to an impulsive local perturbation -: art. no. 015301 [J].
Bonacina, L ;
Larrégaray, P ;
van Mourik, F ;
Chergui, M .
PHYSICAL REVIEW LETTERS, 2005, 95 (01)