THE GEOMETRIC VECTOR POTENTIAL IN MOLECULAR-SYSTEMS WITH ARBITRARILY MANY IDENTICAL NUCLEI

被引:21
作者
KENDRICK, B [1 ]
MEAD, CA [1 ]
机构
[1] UNIV MINNESOTA,DEPT CHEM,MINNEAPOLIS,MN 55455
关键词
D O I
10.1063/1.468544
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
It is known that Born-Oppenheimer electronic wave functions (in systems in which electronic spin plays no role) can acquire a double-valuedness as functions of nuclear coordinates unless the real wave function is multiplied by a phase factor that cancels the sign change that occurs when the nuclear coordinates traverse a closed path enclosing an intersection between two electronic energy levels. We show how such phase factors can be obtained in principle for systems of arbitrary complexity by making use of the cofactors of the adjusted Hamiltonian matrix H-Ej, where Ej is an eigenvalue. The method makes no direct reference to the location of the intersection, and therefore can be used when one is interested in paths that go around the intersection without approaching it closely, bypassing the necessity of costly electronic calculations near the intersection. With appropriate choice of basis functions, the phase factor will cause the electronic wave function to be not only single-valued but invariant under permutations of identical nuclei. Some simple examples are discussed. © 1995 American Institute of Physics.
引用
收藏
页码:4160 / 4168
页数:9
相关论文
共 26 条
[1]   SIGNIFICANCE OF ELECTROMAGNETIC POTENTIALS IN THE QUANTUM THEORY [J].
AHARONOV, Y ;
BOHM, D .
PHYSICAL REVIEW, 1959, 115 (03) :485-491
[2]  
Berry M. V., 1989, GEOMETRIC PHASES PHY
[4]   THE BERRY CONNECTION AND BORN-OPPENHEIMER METHOD [J].
BOHM, A ;
KENDRICK, B ;
LOEWE, ME ;
BOYA, LJ .
JOURNAL OF MATHEMATICAL PHYSICS, 1992, 33 (03) :977-989
[5]   THE BERRY PHASE IN MOLECULAR PHYSICS [J].
BOHM, A ;
KENDRICK, B ;
LOEWE, ME .
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, 1992, 41 (01) :53-75
[6]   FRACTIONAL QUANTIZATION OF MOLECULAR PSEUDOROTATION IN NA-3 [J].
DELACRETAZ, G ;
GRANT, ER ;
WHETTEN, RL ;
WOSTE, L ;
ZWANZIGER, JW .
PHYSICAL REVIEW LETTERS, 1986, 56 (24) :2598-2601
[7]  
HERZBERG G, 1963, DISCUSS FARADAY SOC, V35, P77
[8]   TOWARD A GENERAL-THEORY OF CONICAL INTERSECTIONS IN SYSTEMS OF IDENTICAL NUCLEI [J].
KEATING, SP ;
MEAD, CA .
JOURNAL OF CHEMICAL PHYSICS, 1987, 86 (04) :2152-2160
[9]   CONICAL INTERSECTIONS IN A SYSTEM OF 4 IDENTICAL NUCLEI [J].
KEATING, SP ;
MEAD, CA .
JOURNAL OF CHEMICAL PHYSICS, 1985, 82 (11) :5102-5117
[10]   THE GEOMETRIC PHASE EFFECT SHOWS UP IN CHEMICAL-REACTIONS [J].
KUPPERMANN, A ;
WU, YSM .
CHEMICAL PHYSICS LETTERS, 1993, 205 (06) :577-586