Electronically excited-state properties and predissociation mechanisms of phosphorus monofluoride: A theoretical study including spin-orbit coupling

	Electronically excited-state properties and predissociation mechanisms of phosphorus monofluoride: A theoretical study including spin-orbit coupling
	Yu, Le 1,2; Bian, Wensheng 1
刊名	journal of chemical physics
	2012-07-07
卷号	137 期号:1
英文摘要	the 51 omega states generated from the 22 lambda - s states of phosphors monofluoride have been investigated using the valence internally contracted multireference configuration interaction method with the davidson correction and the entirely uncontracted aug-cc-pv5z basis set. the spin-orbit coupling is computed using the state interaction approach with the breit-pauli hamiltonian. based on the calculated potential energy curves, the spectroscopic constants of the bound and quasibound lambda - s and omega states are obtained, and very good agreement with experiment is achieved. several quasibound states caused by avoided crossings are found. various curve crossings and avoided crossings are revealed, and with the help of our computed spin-orbit coupling matrix elements, the predissociation mechanisms of the a(1)delta, b(1)sigma(+), e(3)pi, g(1)pi, and (3)(3)pi states are analyzed. the intricate couplings among different electronic states are investigated. we propose that the avoided crossing between the a(3)pi(0+) and b(1)sigma(+)(0+) states may be responsible for the fact that the a(3)pi nu' >= 12 vibrational levels can not be observed in experiment. the transition properties of the a(3)pi - x-3 sigma(-) transition are studied, and our computed franck-condon factors and radiative lifetimes match the experimental results very well. (c) 2012 american institute of physics. [http://dx.doi.org/10.1063/1.4731635]
WOS标题词	science & technology ; physical sciences
类目[WOS]	physics, atomic, molecular & chemical
研究领域[WOS]	physics
关键词[WOS]	configuration-interaction calculations ; quenching rate constants ; correlated molecular calculations ; relaxation rate constants ; gaussian-basis sets ; radiative lifetimes ; wave-functions ; spectroscopic constants ; fine-structure ; ab-initio
收录类别	SCI
语种	英语
WOS记录号	WOS:000306142600026
公开日期	2015-11-10
内容类型	期刊论文
源URL	[http://159.226.238.44/handle/321008/138025]
专题	大连化学物理研究所_中国科学院大连化学物理研究所
作者单位	1.Chinese Acad Sci, Beijing Natl Lab Mol Sci, State Key Lab Mol React Dynam, Inst Chem, Beijing 100190, Peoples R China 2.Chinese Acad Sci, Grad Univ, Beijing 100049, Peoples R China
推荐引用方式 GB/T 7714	Yu, Le,Bian, Wensheng. Electronically excited-state properties and predissociation mechanisms of phosphorus monofluoride: A theoretical study including spin-orbit coupling[J]. journal of chemical physics,2012,137(1).
APA	Yu, Le,&Bian, Wensheng.(2012).Electronically excited-state properties and predissociation mechanisms of phosphorus monofluoride: A theoretical study including spin-orbit coupling.journal of chemical physics,137(1).
MLA	Yu, Le,et al."Electronically excited-state properties and predissociation mechanisms of phosphorus monofluoride: A theoretical study including spin-orbit coupling".journal of chemical physics 137.1(2012).