First principles determination of the NH2/ND2((A)over-tilde,(X)over-tilde) branching ratios for photodissociation of NH3/ND3 via full-dimensional quantum dynamics based on a new quasi-diabatic representation of coupled ab initio potential energy surfaces

被引：42

作者：

Ma, Jianyi ^{[1
]}

Zhu, Xiaolei ^{[2
]}

Guo, Hua ^{[1
]}

Yarkony, David R. ^{[2
]}

机构：

[1] Univ New Mexico, Dept Chem & Chem Biol, Albuquerque, NM 87131 USA

[2] Johns Hopkins Univ, Dept Chem, Baltimore, MD 21218 USA

来源：

JOURNAL OF CHEMICAL PHYSICS | 2012年 / 137卷 / 22期

基金：

美国国家科学基金会;

关键词：

JET-COOLED AMMONIA; ROVIBRONIC ABSORPTION ANALYSIS; VIBRATIONALLY EXCITED AMMONIA; OPTICAL DOUBLE-RESONANCE; (A)OVER-TILDE STATE; SELECTIVE PHOTODISSOCIATION; WAVE-PACKET; 193.3; NM; PREDISSOCIATION DYNAMICS; DISSOCIATION DYNAMICS;

D O I：

10.1063/1.4753425

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：

The A-band photodissociation of ammonia is an archetypical and long studied example of non-adiabatic dynamics in a polyatomic system. Due to a well-known conical intersection seam, electronically excited NH3 can produce either the ground ((X) over tilde B-2(1)) state or the excited ((A) over tilde (2)A(1)) state of the NH2 fragment. In this work, the non-adiabatic dynamics is investigated using a six-dimensional wave packet method and an improved version of a newly developed diabatic Hamiltonian based on high quality ab initio data. The (A) over tilde (2)A(1)/(X) over tilde B-2(1) branching ratios are in excellent agreement with experimental estimates, thus validating the non-adiabatically coupled Hamiltonian. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4753425]

引用

页数：9

共 3 条

[1] Computational determination of the (A)over-tilde state absorption spectrum of NH3 and of ND3 using a new quasi- diabatic representation of the (X)over-tilde and (A)over-tilde states and full six- dimensional quantum dynamics
Zhu, Xiaolei
Ma, JianYi
Yarkony, David R.
Guo, Hua
JOURNAL OF CHEMICAL PHYSICS, 2012, 136 (23):
[2] Full-Dimensional Quantum Dynamics of Vibrationally Mediated Photodissociation of NH3 and ND3 on Coupled Ab Initio Potential Energy Surfaces: Absorption Spectra and NH2((A)over-tilde2A1)/NH2((X)over-tilde2B1) Branching Ratios
Ma, Jianyi
Xie, Changjian
Zhu, Xiaolei
Yarkony, David R.
Xie, Daiqian
Guo, Hua
JOURNAL OF PHYSICAL CHEMISTRY A, 2014, 118 (51): : 11926 - 11934
[3] Quantum real wave-packet dynamics of the N(4S)+NO((X)over-tilde 2Π)→N2((X)over-tilde 1Σg+)+O(3P) reaction on the ground and first excited triplet potential energy surfaces:: Rate constants, cross sections, and product distributions
Gamallo, P
Sayós, R
González, M
Petrongolo, C
Defazio, P
JOURNAL OF CHEMICAL PHYSICS, 2006, 124 (17):

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