A NEW APPROACH TO MOLECULAR CLASSICAL OPTIMAL-CONTROL - APPLICATION TO THE REACTION HCN-]HC+N

被引:41
作者
BOTINA, J
RABITZ, H
RAHMAN, N
机构
[1] UNIDO,INT INST PURE & APPL CHEM,I-34012 TRIESTE,ITALY
[2] PRINCETON UNIV,DEPT CHEM,PRINCETON,NJ 08544
关键词
D O I
10.1063/1.469395
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 new method for classical control theory of Hamiltonian systems. This approach is based on a special treatment of the adjoint or Lagrange multiplier equations of motion. The latter function is only asked to preserve the mean of the ensemble of molecular trajectories. In the present case only four such equations are involved greatly simplifying the field design process and making it faster and more stable. Good results are obtained for the selective photodissociation of HCN. The objective is to control the intramolecular reaction HCN→HC+N (i.e., break the stronger bond). Hamilton's equations of motion are employed to model the HCN molecule, initially in its ground state. The control equations are integrated to obtain a high degree of selectivity in the unimolecular dissociation. The robustness of the results to changes in the initial conditions and pulse durations are investigated. An increase of the pulse duration beyond a certain point makes it more difficult to dissociate the N atom due to strong intramolecular coupling. The resultant pulse fields may serve as a basic indicator for future experimental selective dissociation of HCN→HC+N using high power lasers. © 1995 American Institute of Physics.
引用
收藏
页码:226 / 236
页数:11
相关论文
共 40 条
[31]   OPTIMAL-CONTROL OF BOND SELECTIVITY IN UNIMOLECULAR REACTIONS [J].
SHI, S ;
RABITZ, H .
COMPUTER PHYSICS COMMUNICATIONS, 1991, 63 (1-3) :71-83
[32]   QUANTUM-MECHANICAL OPTIMAL-CONTROL OF PHYSICAL OBSERVABLES IN MICROSYSTEMS [J].
SHI, SH ;
RABITZ, H .
JOURNAL OF CHEMICAL PHYSICS, 1990, 92 (01) :364-376
[33]   ON THE FALLIBILITY OF VARIATIONAL CALCULATIONS - ABINITIO VERSUS EMPIRICAL POTENTIAL-ENERGY FUNCTIONS FOR HCN [J].
SMITH, AM ;
KLEMPERER, W ;
LEHMANN, KK .
JOURNAL OF CHEMICAL PHYSICS, 1991, 94 (07) :5040-5050
[34]   THE INTENSITIES OF HCN OVERTONE TRANSITIONS FROM 12 600-18 400 CM-1 [J].
SMITH, AM ;
JORGENSEN, UG ;
LEHMANN, KK .
JOURNAL OF CHEMICAL PHYSICS, 1987, 87 (10) :5649-5656
[35]   CONTROL OF SELECTIVITY OF CHEMICAL-REACTION VIA CONTROL OF WAVE PACKET EVOLUTION [J].
TANNOR, DJ ;
RICE, SA .
JOURNAL OF CHEMICAL PHYSICS, 1985, 83 (10) :5013-5018
[36]   QUANTUM VERSUS CLASSICAL DYNAMICS IN TREATMENT OF MULTIPLE PHOTON EXCITATION OF ANHARMONIC-OSCILLATOR [J].
WALKER, RB ;
PRESTON, RK .
JOURNAL OF CHEMICAL PHYSICS, 1977, 67 (05) :2017-2028
[37]  
WARREN WS, 1993, SCIENCE, V259, P1588
[38]   OPTICAL CONTROL OF MOLECULAR-DYNAMICS - LIOUVILLE-SPACE THEORY [J].
YAN, YJ ;
GILLILAN, RE ;
WHITNELL, RM ;
WILSON, KR ;
MUKAMEL, S .
JOURNAL OF PHYSICAL CHEMISTRY, 1993, 97 (10) :2320-2333
[39]  
YAO K, 1990, CHEM PHYS, V150, P373
[40]   ROBUST OPTIMAL-CONTROL OF QUANTUM MOLECULAR-SYSTEMS IN THE PRESENCE OF DISTURBANCES AND UNCERTAINTIES [J].
ZHANG, H ;
RABITZ, H .
PHYSICAL REVIEW A, 1994, 49 (04) :2241-2254