Quantum-mechanical approach to predissociation of water dimers in the vibrational adiabatic representation: Importance of channel interactions

	Quantum-mechanical approach to predissociation of water dimers in the vibrational adiabatic representation: Importance of channel interactions
	Mineo, H.1; Niu, Y. L.2; Kuo, J. L.1; Lin, S. H.3,4; Fujimura, Y.3,4,5
刊名	JOURNAL OF CHEMICAL PHYSICS
	2015-08-28
卷号	143 期号:8
英文摘要	The results of application of the quantum-mechanical adiabatic theory to vibrational predissociation (VPD) of water dimers, (H2O)(2) and (D2O)(2), are presented. We consider the VPD processes including the totally symmetric OH mode of the dimer and the bending mode of the fragment. The VPD in the adiabatic representation is induced by breakdown of the vibrational adiabatic approximation, and two types of nonadiabatic coupling matrix elements are involved: one provides the VPD induced by the low-frequency dissociation mode and the other provides the VPD through channel interactions induced by the low-frequency modes. The VPD rate constants were calculated using the Fermi golden rule expression. A closed form for the nonadiabatic transition matrix element between the discrete and continuum states was derived in the Morse potential model. All of the parameters used were obtained from the potential surfaces of the water dimers, which were calculated by the density functional theory procedures. The VPD rate constants for the two processes were calculated in the non-Condon scheme beyond the so-called Condon approximation. The channel interactions in and between the initial and final states were taken into account, and those are found to increase the VPD rates by 3(1) orders of magnitude for the VPD processes in (H2O)(2) ((D2O)(2)). The fraction of the bending-excited donor fragments is larger than that of the bending-excited acceptor fragments. The results obtained by quantum-mechanical approach are compared with both experimental and quasi-classical trajectory calculation results. (C) 2015 AIP Publishing LLC.
收录类别	SCI
语种	英语
公开日期	2015-10-27
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/27649]
专题	化学研究所_高分子物理与化学实验室
作者单位	1.Acad Sinica, Inst Atom & Mol Sci, Taipei 106, Taiwan 2.Chinese Acad Sci, Inst Chem, Beijing 100190, Peoples R China 3.Natl Chiao Tung Univ, Inst Mol Sci, Dept Appl Chem, Shin Chu 300, Taiwan 4.Natl Chiao Tung Univ, Ctr Interdisciplinary Mol Sci, Shin Chu 300, Taiwan 5.Tohoku Univ, Grad Sch Sci, Dept Chem, Sendai, Miyagi 9808578, Japan
推荐引用方式 GB/T 7714	Mineo, H.,Niu, Y. L.,Kuo, J. L.,et al. Quantum-mechanical approach to predissociation of water dimers in the vibrational adiabatic representation: Importance of channel interactions[J]. JOURNAL OF CHEMICAL PHYSICS,2015,143(8).
APA	Mineo, H.,Niu, Y. L.,Kuo, J. L.,Lin, S. H.,&Fujimura, Y..(2015).Quantum-mechanical approach to predissociation of water dimers in the vibrational adiabatic representation: Importance of channel interactions.JOURNAL OF CHEMICAL PHYSICS,143(8).
MLA	Mineo, H.,et al."Quantum-mechanical approach to predissociation of water dimers in the vibrational adiabatic representation: Importance of channel interactions".JOURNAL OF CHEMICAL PHYSICS 143.8(2015).