Optical conversion of conical intersection to avoided crossing

被引:30
作者
Arasaki, Yasuki [1 ]
Takatsuka, Kazuo [1 ]
机构
[1] Univ Tokyo, Dept Basic Sci, Grad Sch Arts & Sci, Tokyo 1538902, Japan
关键词
SCHRODINGER-EQUATION; ELECTRONIC-STRUCTURE; NO2; DYNAMICS; STATES; MODEL; PHOTOISOMERIZATION; PHOTODISSOCIATION; WAVEPACKET; PHASE;
D O I
10.1039/b919504a
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 study a mechanism by which a symmetry-allowed conical intersection is converted to an avoided crossing by external breaking of symmetry. With full quantum dynamics on coupled ab inito potential energy surfaces for an NO2 molecule under a phase controlled far-infrared femtosecond pulse field, we demonstrate that symmetry breaking thus-introduced can indeed convert the conical intersection to an avoided crossing, thereby drastically influencing population transfer through it.
引用
收藏
页码:1239 / 1242
页数:4
相关论文
共 33 条
[1]   Geometric phase effects in the coherent control of the branching ratio of photodissociation products of phenol [J].
Abe, Mayumi ;
Ohtsuki, Yukiyoshi ;
Fujimura, Yuichi ;
Lan, Zhenggang ;
Domcke, Wolfgang .
JOURNAL OF CHEMICAL PHYSICS, 2006, 124 (22)
[2]   Molecular Symmetry Properties of Conical Intersections and Nonadiabatic Coupling Terms: Theory and Quantum Chemical Demonstration for Cyclopenta-2,4-dienimine (C5H4NH) [J].
Al-Jabour, S. ;
Baer, M. ;
Deeb, O. ;
Leibscher, M. ;
Manz, J. ;
Xu, X. ;
Zilberg, S. .
JOURNAL OF PHYSICAL CHEMISTRY A, 2010, 114 (09) :2991-3010
[3]   Solvent effect on the conical intersection of 4-cyclopentadienylidene-1,4-dihydropyridine (CPDHP) [J].
Alfalah, S. ;
Deeb, O. ;
Zilberg, S. ;
Haas, Y. .
CHEMICAL PHYSICS LETTERS, 2008, 459 (1-6) :100-104
[4]   THE EVOLUTION OF THE WAVE-FUNCTION IN A CURVE CROSSING PROBLEM COMPUTED BY A FAST FOURIER-TRANSFORM METHOD [J].
ALVARELLOS, J ;
METIU, H .
JOURNAL OF CHEMICAL PHYSICS, 1988, 88 (08) :4957-4966
[5]  
AMOS RD, 2006, MOLPRO PACKAGE AB IN
[6]   Quantum wavepacket dynamics for time-resolved photoelectron spectroscopy of the NO2 conical intersection [J].
Arasaki, Yasuki ;
Takatsuka, Kazuo .
CHEMICAL PHYSICS, 2007, 338 (2-3) :175-185
[7]   Effect of absolute laser phase on reaction paths in laser-induced chemical reactions [J].
Bandrauk, AD ;
Sedik, EWS ;
Matta, CF .
JOURNAL OF CHEMICAL PHYSICS, 2004, 121 (16) :7764-7775
[8]   Environmental effects on a conical intersection: A model study [J].
Burghardt, I ;
Cederbaum, LS ;
Hynes, JT .
FARADAY DISCUSSIONS, 2004, 127 :395-411
[9]   Excited-state charge transfer at a conical intersection: Effects of an environment [J].
Burghardt, Irene ;
Hynes, James T. .
JOURNAL OF PHYSICAL CHEMISTRY A, 2006, 110 (40) :11411-11423
[10]   Quantum control of internal conversion in 24-vibrational-mode pyrazine [J].
Christopher, P. S. ;
Shapiro, M. ;
Brumer, P. .
JOURNAL OF CHEMICAL PHYSICS, 2006, 125 (12)