Premium
The valence and Rydberg excited states of CH 2 : A theoretical exploration
Author(s) -
Li BuTong,
Wei ZiZhang,
Wu HaiShun
Publication year - 2012
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.23075
Subject(s) - rydberg formula , excited state , valence (chemistry) , atomic physics , basis set , atomic orbital , rydberg state , chemistry , sto ng basis sets , complete active space , physics , molecule , ionization , quantum mechanics , ion , electron , organic chemistry
Using the completed active space second‐order perturbation (CASPT2) method, valence and Rydberg excited states of CH 2 molecule are probed with the large atomic natural orbital (ANO‐L) basis set. Five states are optimized and the geometric parameters are in good agreement with the available data in literatures, furthermore, the state of 2 1 B 1 is obtained for the first time. Valence and Rydberg excited states of CH 2 are also calculated for the vertical transitions with the ANO‐L+ basis set that is constructed by adding a set of 1s1p1d Rydberg orbitals into the ANO‐L basis set. Two Rydberg states of the p̃ 3 A 2 and r̃ 3 B 1 at 9.88 and 10.50 eV are obtained for the first time, and the 3a 1 → 3d yz nature of the state p̃ 3 A 2 and the 3a 1 → d x 2 − y 2 nature of the state r̃ 3 B 1 are confirmed. © 2012 Wiley Periodicals, Inc.