On diabatization and the topological D-matrix:: Theory and numerical studies of the H+H2 system and the C2H2 molecule

被引:48
作者
Baer, M [1 ]
Ve'rtesi, T
Halász, GJ
Vibók, A
Suhai, S
机构
[1] Univ Debrecen, Dept Theoret Phys, Debrecen, Hungary
[2] Univ Debrecen, Inst Informat, Debrecen, Hungary
[3] German Canc Res Ctr, Dept Mol Biophys, D-69120 Heidelberg, Germany
[4] Soreq Nucl Res Ctr, IL-81800 Yavne, Israel
关键词
D O I
10.1039/b313883f
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
This article is divided into two main parts: ( 1) The theoretical part contains a new derivation of the topological matrix D ( M. Baer and A. Alijah, Chem. Phys. Lett., 2000, 319, 489) which is based, solely, on the spatial dependent electronic manifold. This derivation enables more intimate relations between the adiabatic and the diabatic frameworks as is discussed in detail in the manuscript. ( 2) The numerical part is also divided into two parts: ( a) In the first part we extend our previous study on the H+H-2 system ( G. Halasz, A. Vibok, A. M. Mebel and M. Baer, J. Chem. Phys., 2003, 118, 3052) by calculating the topological matrix for five states ( instead of three) and for configuration spaces four times larger than before. These studies are expected to yield detailed information on the possibility of diabatization of this system. (b) We report on preliminary results concerning the C2H2 molecule. So far we established the existence of one ( 1,2) conical intersection and we have good reasons to believe that this system contains several ( 2,3) and ( 3,4) conical intersections as well.
引用
收藏
页码:337 / 353
页数:17
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