The Photoisomerization of 11-cis-Retinal Protonated Schiff Base in Gas Phase: Insight from Spin-Flip Density Functional Theory

	The Photoisomerization of 11-cis-Retinal Protonated Schiff Base in Gas Phase: Insight from Spin-Flip Density Functional Theory
	Zhou, Panwang; Liu, Jianyong; Han, Keli; He, Guozhong
刊名	journal of computational chemistry
	2014-01-15
卷号	35 期号:2 页码:109-120
关键词	spin-flip density functional theory photoisomerization PSB3 PSB11
通讯作者	韩克利
英文摘要	this extensive theoretical study employed the spin-flip density functional theory (sfdft) method to investigate the photoisomerization of 11-cis-retinal protonated schiff base (psb11) and its minimal model tzt-penta-3,5-dieniminium cation (psb3). our calculated results indicate that sfdft can perform very well in describing the ground- and excited-state geometries of psb3 and psb11. we located the conical intersection (ci) point and constructed the photoisomerization reaction path of psb3 and psb11 by using the sfdft method. to further verify the sfdft results, we computed the energy profiles along the constructed linearly interpolated internal coordinate (liic) pathways by using high-level theoretical methods, such as the eom-ccsd, cr-eom-ccsd(t), caspt2, nevpt2, and xmcqdpt2 methods. the sfdft method predicts that the photoisomerization of psb3 is barrierless, in accordance with previous complete-active-space self-consistent-field (casscf) results. however, an energy barrier is predicted along the liic pathways of psb11. this finding is different from previous casscf results and may indicate that the photoisomerization of psb11 in gas phase is similar to that in solution. however, the higher spin contamination of the sfdft method in the vicinity of the ci point caused the located ci geometry to deviate from that of the real ci. in addition, the liic pathways are only approximations to the minimum energy path (mep). thus, further experimental and theoretical studies are needed to verify the existence of an energy barrier along the photoisomerization reaction path of psb11 in gas phase. (c) 2013 wiley periodicals, inc.
学科主题	物理化学
WOS标题词	science & technology ; physical sciences
类目[WOS]	chemistry, multidisciplinary
研究领域[WOS]	chemistry
关键词[WOS]	retinal chromophore model ; potential-energy surfaces ; excited-state relaxation ; coupled-cluster methods ; multiconfigurational perturbation-theory ; cis-trans isomerization ; ab-initio dynamics ; rhodopsin chromophore ; conical intersection ; femtosecond fluorescence
收录类别	SCI
语种	英语
WOS记录号	WOS:000327853300002
公开日期	2016-05-09
内容类型	期刊论文
源URL	[http://cas-ir.dicp.ac.cn/handle/321008/144226]
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	Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Liaoning, Peoples R China
推荐引用方式 GB/T 7714	Zhou, Panwang,Liu, Jianyong,Han, Keli,et al. The Photoisomerization of 11-cis-Retinal Protonated Schiff Base in Gas Phase: Insight from Spin-Flip Density Functional Theory[J]. journal of computational chemistry,2014,35(2):109-120.
APA	Zhou, Panwang,Liu, Jianyong,Han, Keli,&He, Guozhong.(2014).The Photoisomerization of 11-cis-Retinal Protonated Schiff Base in Gas Phase: Insight from Spin-Flip Density Functional Theory.journal of computational chemistry,35(2),109-120.
MLA	Zhou, Panwang,et al."The Photoisomerization of 11-cis-Retinal Protonated Schiff Base in Gas Phase: Insight from Spin-Flip Density Functional Theory".journal of computational chemistry 35.2(2014):109-120.