从头算研究NCN的椭圆π(2)(g) (X(3)Σ(-)(g), 1(1)Δ(g), 1(1)Σ(+)(g)) 电子态。1(1)Δ(g)态中Renner-Teller效应的研究。

Ab Initio Investigation of the ellipsis pi(2)(g) (X(3)Sigma(-)(g), 1(1)Delta(g), 1(1)Sigma(+)(g)) Electronic States of NCN. Study of the Renner-Teller Effect in the 1(1)Delta(g) State.

作者信息

Peric M, Krmar M, Radic-Peric J, Hanrath M

机构信息

Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, Belgrade, 11000, Yugoslavia

出版信息

J Mol Spectrosc. 2000 Dec;204(2):226-234. doi: 10.1006/jmsp.2000.8222.

DOI:10.1006/jmsp.2000.8222

PMID:11148092

Abstract

Large-scale CI calculations are carried out to obtain accurate potential energy surfaces for the ellipsis pi(2)(g) manifold (X(3)Sigma(-)(g), 1(1)Delta(g), 1(1)Sigma(+)(g)) of electronic states of NCN. Separation of the low-lying singlet states from the triplet ground state is computed in close agreement with the results of a recent photoelectron study by T. R. Taylor, R. T. Bise, K. R. Asmis, and D. M. Neumark [Chem. Phys. Lett. 301, 413-416 (1999)]. Vibronic coupling (Renner-Teller effect) in the 1(1)Delta(g) state is studied by means of a perturbative and a variational approach. Results of the present ab initio study confirm explicitly the rho(4) dependence postulated for the splitting of bending potential curves in Delta electronic states at small deviations from linearity. Copyright 2000 Academic Press.

摘要

进行大规模的组态相互作用（CI）计算，以获得NCN电子态的椭圆π(2)(g)多重态（X(3)Σ(-)(g)、1(1)Δ(g)、1(1)Σ(+)(g)）的精确势能面。计算了低激发单重态与三重基态的分离，结果与T. R. 泰勒、R. T. 比斯、K. R. 阿斯米斯和D. M. 纽马克最近的光电子研究结果[《化学物理快报》301, 413 - 416 (1999)]高度吻合。通过微扰法和变分法研究了1(1)Δ(g)态中的振转耦合（伦纳 - 泰勒效应）。本从头算研究的结果明确证实了在与线性稍有偏差时，Δ电子态中弯曲势能曲线分裂所假定的对ρ(4)的依赖性。版权所有2000年，学术出版社。